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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.
Sec/Tert Interface 2009
Dissolved oxygen Hardness Alkalinity Chloride ion Hypochlorite in bleach solutions Phosphate 3 7 11 14 16 18
Sec/Tert Interface 2009
ions reduce Mn3+ to Mn2+. I2 + II3- In the titration reaction. American Water Works Association and Water Environmental Federation. thus causing an error. American Public Health Association. The analysis of DO is a key test in water pollution and waste treatment process control. Interferences The presence of oxidising or reducing materials in the sample may cause interference with the standard method given here. the brown colour due to the triiodide ion fades as the iodine is reduced by the thiosulfate. iodine is then reduced by thiosulfate I2 + 2 S2O322 I+ S4O62- As the titration proceeds. The iodometric method is the most precise and reliable titrimetric procedure for DO analysis.1. Mn2+ ions (from MnSO4) form a precipitate of Mn(OH)2. chemical. forming a blue complex with I2. L. Rice. 2 Mn3+ + 2I2 Mn2+ + I2 I2 molecules.1 Introduction Dissolved oxygen (DO) levels in natural and wastewaters depend on the physical. Standard Methods for the Examination of Water and Wastewater 21st edition. are oxidised by O2 to Mn3+ forming Mn(OH)3.and liberates free Mn3+ ions. O2 + 4 Mn(OH)2 + 2 H2O 4 Mn(OH)3 Addition of acid neutralises OH.0 Dissolved Oxygen (Winkler/iodometric method) (adapted from Eaton. so starch is added as the brown colour fades. and biochemical activities in the water body. A number of modifications are available to minimise interference. Washington) 1. Mn2+ ions (in equilibrium with Mn(OH)2 precipitate). A 2005. combine with iodide ions in a reversible reaction to form the brown. It is based on the sequence of reactions given below. Certain oxidising agents liberate I2 from iodides (positive interference) and certain reducing agents reduce I2 to iodides (negative interference). The endpoint is signalled by the disappearance of the blue colour of the starch-iodine complex.Bergmann 3 Sec/Tert Interface 2009 . soluble tri-iodide ion. The permanganate modification is used in the presence of Fe2+. A. which are not soluble in water. The azide modification removes interference due to nitrite (common in effluents and incubated BOD samples). Mn(OH)3 + 3H+ Mn3+ + 3 H2 O I. liberating I2 equivalent to the original DO content. Most organic matter is oxidised partially when the oxidised manganese precipitate is acidified. The disappearance of the triiodide is a difficult endpoint to detect. Reaction sequence of iodometry In the presence of excess OH-. E. E and Greenberg. Clesceri.
3 Safety Latex gloves.4 Analysis 1. Once O2 has been consumed.4. You need to ensure a smooth flow of water into the bottle here. Cap the bottle underneath the water surface so that no bubbles are present in the sample bottle. temperature. time. Since dissolved oxygen will be measured back in the laboratory. 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. 1. Chemical and biochemical activity may consume O2. see 1.e.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 1.2M MnSO4 10 mL alkaline KI reagent (0. general description of site). care must be taken to prevent the loss or addition of oxygen to the sample once it is collected. place.4.Bergmann 4 Sec/Tert Interface 2009 . (after formation of I3-) treated samples can be transported back to the laboratory for titration. E. Ideally.2 Sampling The reliability of the results depends heavily upon the sampling method.4. remember that the KI reagent and conc. It is most important that you measure the temperature of the water where you have collected your sample.9 M KI and 12.5) 10 mL 1% starch suspension 1 L water sample 1.025M Na2S2O3 (can be standardised with KIO3. pH.2 Reagents (The following should be enough to do 4 titrations of a single water sample.5M KOH) 10 mL conc H2SO4 60 mL 0. safety glasses. Because the amount of dissolved O2 is also temperature dependent.) 10 mL 2.5 should be performed immediately after sample collection.1. the temperature of the sample should also be maintained (or stored at a lower temperature).4. You should endeavour to collect the water sample on the same day that you intend to do the DO assay.3 On-site measurements Record all information regarding the sample (i. 1. Steps 1 . H2SO4 are both extremely corrosive. to avoid aeration.
Add 2. Accurately weigh approximately 0.4. 2.4 Method 1. Ideally you should not have any air bubbles after adding the first 2 reagents and capping the solution. repeat the inversions. 2 I.) 2. take 203 mL from the flask and transfer to a 500 mL conical flask. 6.Bergmann 5 Sec/Tert Interface 2009 .) It does not matter that the solution is now open to the air (why not?) 7. (The 203 mL allows for the addition of the other reagents and is equivalent to 200 mL of the original water sample.+ 6 S4O62. 5. A precipitate of manganese(II) hydroxide will form. 3.4.1. adding starch as colour fades to straw yellow. When the precipitate settles.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.+ 6 H2O E. You should leave a space at the top that will accommodate about 5 mL of reagents. Pipette out 25 mL of this solution and add 10 mL of 10% sulfuric acid solution and 2 g of KI.0 mL MnSO4 solution. Carefully fill a 250 mL conical flask (with a stopper) to nearly full with water from your sampling site. Repeat steps 1 – 7 for further aliquots.0 mL of conc H2SO4 (wearing latex gloves) by allowing the acid to run down the neck of the flask. Using a 2 mL pipette. quickly add 2.+ 12 H+ + 12 S2O32Method 1. Using a 250 mL measuring cylinder. leaving about 100 mL of clear supernatant. Titrate with thiosulfate solution. Record the final volume of sodium thiosulfate in the burette. THEN add starch indicator (~0. (The starch reacts with iodine to give a deep blue colour.) Continue the titration to the first disappearance of blue colour. (Check with tap water before you start. Allow the precipitate to settle so that about 100 mL of clear solution is produced. Record the initial volume of sodium thiosulfate in the burette.5 Standardisation of thiosulfate solutions Thiosulfate solutions can be standardised by reaction with iodate. Pour the sample water down the side of the flask in order to minimise bubbles.0 mL of the alkaline KI reagent. Molarity of iodate solution should be about one-sixth that of the thiosulfate being used. Calculate volume of thiosulfate used. mix and then add 2. 4. Stopper the flask and invert several times to mix and bring about the reaction with the O2(aq). The overall reaction is as follows: 2 IO3. 3. 8. 1.5 mL). Titrate with this thiosulfate to a pale straw yellow colour. Stopper the flask and invert/mix several times until all the precipitate dissolves.
92 7. Temp (˚C) 0 1 2 3 4 5 6 7 8 9 10 DO (ppm) 14.013 x 103 kPa and a partial pressure of oxygen of 0.3 E.54 9. 8.48 13.77 7.83 8. 1mL of sodium thiosulfate solution (0. then the DO of the sample is 8.025 M) is equivalent to 1 mg/L (1ppm) dissolved oxygen in the sample.87 11. 2.74 9.80 12.22 8.38 8.17 8.15 9.13 12.53 8.99 Temp (˚C) 22 23 24 25 26 27 28 29 30 31 32 DO (ppm) 8.37 10. (b) Make some suggestions about any differences between your results and the saturation values given in the table.35 9.7 mL of sodium thiosulfate was used.e.17 11.7 ppm.68 8. Table 1.7 6. Compare your results with the Oxygen Solubility Data (Table 1).23 13.8 6.62 14.3 7.7mg/L i.83 10. 3. (If 8. Calculate the molarity of the thiosulfate from the solution standardisation procedure.1.84 13.0 6.4 Temp (˚C) 33 34 35 36 37 38 39 40 41 42 43 DO (ppm) 7.33 Temp (˚C) 11 12 13 14 15 16 17 18 19 20 21 DO (ppm) 11.60 10.9 6.95 9.08 10. (a) Calculate the percentage saturation of your sample.213 x 103kPa.5 6.7 7.4.6 6.6 Calculations and Discussion 1. The water is in equilibrium with water-saturated air at a total pressure of 1.4 6. Calculate the Dissolved Oxygen (check your notes for some help) for your sample.59 11.2 7. Oxygen Solubility Reference Table The following values refer to the solubility of oxygen in chloride-free water at various concentrations.5 7.1 7.Bergmann 6 Sec/Tert Interface 2009 .48 12.07 7. Shortcut (if thiosulfate concentration is accurate): When a 200 mL water sample is used.
forming an octahedral complex. the pH used in this titration experiment and in most hardness tests. scale formation continues to be a problem. Calcium and magnesium carbonates are two of the few common salts whose solubility decreases with increasing temperature. N atoms are protonated and two of the carbonyl groups are deprotonated. 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. as in the zwitter-ion of amino acids. A simplified representation of the neutral form of EDTA. et al. In fact. however. The tetra-anion form of EDTA exists at high pH and is able to form 6 bonds to a central metal ion. There are no known adverse health effects of hard or soft water. especially those of calcium and magnesium. Thus. Note the lone pairs of electrons on the two nitrogens. However. The chemical structure of EDTA is shown below. The advent of synthetic detergents has significantly reduced the problems associated with hard water and the “lack of foaming”. E. However. This is due to the removal of dissolved CO2 as temperature increases. Both are organic compounds which can form a complex with divalent metal ions. A. water hardness was defined as a measure of the capacity of water to precipitate soap.2. 0 Water Hardness by Complexation Titration (Adapted from Greenberg.Bergmann 7 Sec/Tert Interface 2009 . Current laboratory practices. The method described below relies on a “competition” between EDTA and an indicator (Eriochrome Black T). the value reported for hardness includes all divalent ions in a water sample. expressed in terms of mgCaCO3/L. combined with the dissociated carboxyl groups. create a 1:1 hexadentate complex with each divalent ion in solution. define total hardness as the sum of divalent ion concentrations. the complexation constant is a function of pH. Washington) 2. American Public Health Association.E.1 Introduction In the past. 1975 Standard methods for the examination of water and wastewater 14th edition. Virtually all common divalent ions will be complexed at pH values greater than 10. These.
Both Ca2+ solutions and EDTA are colourless so an indicator is needed to signal the reaction completion. In this analysis you will be titrating Ca2+ in a standard solution and water samples with EDTA. T.5 x 105 K = 7. and one EDTA forms 6 bonds to each divalent metal ion – hence it’s said to be a hexadentate ligand.0 x 107 (Aylward. the remaining H+ ions are removed from the carboxyl groups.Bergmann 8 Sec/Tert Interface 2009 . (Na+)2H2EDTA2-. each of the 4 carboxyl groups will be deprotonated as will the N atoms (being in a basic solution). (Calcium ions are “better” at bonding to EDTA than magnesium. The indicator then returns to a sky-blue form signaling the end-point. as well as on O of each carboxylate anion. In the presence of excess OH. the ions dissociate. Australia Limited) E. the EDTA is “better” at bonding with magnesium ions than the indicator is.ions. so H2EDTA2.133). EDTA is supplied as the disodium salt. The EDTA is said to act as a ligand or chelate. This has lone pairs on the 2 N atoms of the amino groups.1 x 108 K = 1. Stability constants for the formation of each complex ion are as follows: [CaEDTA]2[CaEBT]2+ [MgEDTA]2[MgEBT]2+ log K = 10.ions are free in solution. When all of the Ca2+ (and any other divalent metal ions present) has been removed from solution by reaction with EDTA. to form the tetra-anion. forming a di-anion. G. SI Chemical Data 5th edition (pp. These are able to form co-ordinate covalent bonds with empty valence orbitals of metal ions. In solution. So at the end point the indicator is not bound to any metal ion.85 log K = 7 K = 4. The indicator of choice is Eriochrome Black T (EBT) which forms a wine-red complex with Mg2+. so the EDTA will exist in this solution as a tetra-anion.4 log K = 8.At high pH (>10). 132 . the Mg2+ originally bound to the indicator will combine with the EDTA.65 log K = 5. A very small amount of Mg2+ will be bound to the indicator through most of the titration.5 x 1010 K = 2. and Findlay. and when there are no free calcium ions left. John Wiley and Sons. in which 2 protons have been removed. This can be related to the K values (stability constants) for the formation of each complex with EDTA and with EBT given below.
2. (If Mg salt of EDTA is not available. Mix. Stopper. If 0.00 mL. as required.01M CaCl2 1.1 Preparation of a standard solution of 0.18g of MgSO4.5 g of the dye with 4.5 g of the dye and 100 g NaCl For a solution: mix 0. this standard is equivalent to 1.2H2O). Accurately weigh approximately 0.2 Reagents 250 mL 0.01M EDTA solution (Weigh approximately 0. Store in a plastic bottle.1) 250 mL 0.2500 g of dried anhydrous CaCO3.5 g of hydroxylamine hydrochloride.g.3 Standardisation of EDTA Solution 2.) pH 10 buffer containing Mg2+ (Dissolve 16. (1000 ppm) If a slightly different amount of CaCO3 is used. record its mass and quantitatively transfer to a 250 mL Erlenmeyer flask.3.2432/0. dissolve in distilled water.2. Transfer quantitatively to a 250 mL volumetric flask and fill to the mark with distilled water.25 g of the Mg salt of EDTA.2500) E.2 Analysis 2. Continue adding HCl dropwise until the solution is clear.5 50 mL pipette (or measuring cylinder) 2. add another drop of HCl.2. 5. 0.1 Apparatus 20 mL pipette and filler 50 mL burette 250 mL conical flask pH meter or indicator strips to give pH 10 – 10. Store in a labelled plastic bottle. Add 50 mL distilled water and boil for a few minutes to expel CO2. 3. dissolve 1. then 2 mL of 6M HCl.2.Bergmann 9 Sec/Tert Interface 2009 .6H2O in 50 mL H2O and add to buffer solution. then a factor must be applied e.) Eriochrome Black T indicator (For a powder: mix 0. 4.2500 g of CaCO3 is used. Make up to 250 mL with distilled water. and if the mixture remains cloudy. and dilute to 250 mL.) 2. 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. then dissolve in 100 mL of 95% ethyl or isopropyl alcohol. Place a funnel in the neck of the flask and add approximately 25 mL of distilled water. tightly stoppered.9 g of AR grade disodium ethylenediamine tetraacetate dihydrate (Na2H2C10H12O8N2.9 g NH4Cl in 143 mL conc NH4OH.7H2O or 645mg of MgCl2.01M CaCl2 solution (see Section 2. to which has been added 1. Cool.3.2.2. invert 10 – 15 times to mix thoroughly.00 mg CaCO3/1. 2.
If the volumes of EDTA agree to within 0.Bergmann 10 Sec/Tert Interface 2009 . recording all data. 3. then reduce the volume of water in the flask. Rinse a 50 mL burette with distilled water then with the EDTA solution.5 Calculations 1. the volume of water can be varied for water with more or less calcium. Consider both your laboratory procedures and other factors. 2. Add pH 10 buffer solution to give a pH of 10 – 10. If your water is very hard. as the blue colour does not develop immediately).1. 4.2. EDTA and Ca2+ react in a 1:1 ratio.2 Standardisation of 0. 3. Record the volume required to titrate the CaCl2 sample.3) and repeat the titration. Prepare a second portion of CaCl2 in the same way as above (steps 2 . Express this result both as a molarity and as mg CaCO3 per litre (ppm). Measure100 mL of tap water into a 250mL flask. Keep the first sample as a colour reference. to bring pH to 10 – 10. and in each 20. and hence calculate EDTA concentration. Determine the moles of CaCO3 (moles Ca2+) in the 250 mL of standard solution. 2. 5. 2. Mix well. proceed to the next section.2.01M EDTA solution 1.4 Determination of water hardness 1. E.1 as above) and 5 drops of Eriochrome Black T.4 mL. Add pH 10 buffer (about 5 times the volume you added to the standard. (100 mL of SEQ water should give a titre of around 10 mL.2.00mL aliquot. Calculate the average volume of EDTA which reacted with the standard solution. and 2 drops of Eriochrome Black T indicator. Rinse a pipette with distilled water then with CaCl2.) 2. Titrate the sample in the flask with the EDTA. The Brisbane City Council website states that the average total hardness of Brisbane tap water is 100mg as sCaCO3/L. Pipette 20 mL of the CaCl2 solution into a rinsed 250 mL Erlenmeyer flask. Fill with EDTA.2. What colour should the solution be at this point? 4. from the time the buffer is added to endpoint. slowing additions (as red becomes more purple) as you near the sky-blue endpoint (wait 3–5 seconds between additions. suggest possible reasons for the difference. If not.4 mL. and hence calculate the concentration of calcium (and other divalent ions) in the water. Mix well. Repeat until you have 2 titres which are in agreement as Step 5 above. Calculate the average volume of EDTA which reacted completely with the tap water sample. Titrate with the standardised EDTA solution. How closely does your result agree with this value? If it does not. Your titration should not take longer than 5 minutes.3. 2. repeat the titration until 2 or more titres agree within 0.
Rice. American Water Works Association and Water Environmental Federation.4 Sample preservation Samples should be collected in glass or plastic bottles with no entrapped air if possible. Samples may be subject to microbial action and to loss or gain of gases when exposed to air. A 2005. 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. American Public Health Association. 20 mL microburette pH meter 250 mL beaker magnetic stirrer E.1.5 end point using bromocresol green-methyl red indicator solution.2 Analysis 3.2 Summary of Test Method The total alkalinity is determined by titrating a portion of sample with standardised sulfuric acid to pH 4. For groundwaters.Bergmann 11 Sec/Tert Interface 2009 . A.1.1.3. or for samples with pH greater than 8. the main source of carbonate and bicarbonate is rocks through which the water has passed. so they should be analysed without delay.3 end point using phenolphthalein indicator. it can be used as an indicator of the concentrations of these components.0 Alkalinity (adapted from Eaton. Standard Methods for the Examination of Water and Wastewater 21st edition. If stored at 0-4˚C immediately upon receipt. To overcome this. samples can be kept for up to 24 hours prior to analysis.3. Avoid sample agitation and prolonged exposure to air. a smaller aliquot of sample may be used or the procedure for low alkalinity may be followed. E and Greenberg. 3. 50 mL pipette For low alkalinity procedure.3 Interferences Strongly coloured or turbid samples may hinder end point detection.1 Apparatus 150 or 250 mL Erlenmeyer Flasks 50 mL burette 10 mL pipette. 3. Do not filter samples. bicarbonate and hydroxide. “Phenolphthalein Alkalinity” to pH 8.1.1 Introduction This procedure could be taught in conjunction with work on equilibrium and buffers with specific reference to the carbonate/bicarbonate equilibrium. 3. As neutralising capacity depends mainly on carbonate. Clesceri.2. Sample alkalinity less than 20 mg CaCO3/L can only be reported if the low alkalinity procedure is used. Washington) 3. L. 3.
5 +/.01M H2SO4 Make up a 0. 3. strong pink. pH 5. 1. Dry 3 to 5 g of primary standard Na2CO3 at 250C for 4 hours and cool in a desiccator.Bergmann 12 Sec/Tert Interface 2009 .2. An indicator blank should be titrated as well. greenish blue. Calculations 1. 4. Weigh 2. and titrate as above.025M Na2CO3 solution. transfer to a 1L volumetric flask.3 Method 3. 2. (VH2SO4) 5.0.1 Standardisation of 0.0. then the volume should be subtracted from the volume used in the standardization titration before determining concentration of sulfuric acid. 3.8. pH 4.methyl red indicator solution (Dissolve 100 mg bromocresol green and 20 mg methyl red into 100 mL 95% ethyl or isopropyl alcohol. light pink grey with bluish cast. light pink.2. Add 5 drops of indicator to 10mL of the water. or 100mg bromocresol green sodium salt and 20mg methyl red sodium salt in 100 mL water.1 for standardisation procedure) • mixed bromocresol green . Use this value to calculate the molarity of the H2SO4 solution.3. fill flask to the mark with distilled water.2 Reagents • 0. pH 4.01M sulfuric acid (see 3. Find the number of moles of Na2CO3 (nNa2CO3) weighed out to make up the standard solution.3. and below pH 4.) • phenolphthalein solution (Dissolve 1 g phenolphthalein in 100 mL 95% ethyl or isopropyl alcohol and add 100 mL distilled water.5. Write the balanced equation for the reaction between Na2CO3 and H2SO4.2. 2. Subtract the value for the indicator blank from the average volume of acid that was added to the Na2CO3 solution.01M H2SO4 using 5 drops of the bromocresol green–methyl red indicator.) Note: The colour response of the mixed bromocresol green-methyl red is approximately as follows: above pH 5. and dissolve and mix reagent. 4. Titrate 10 mL of this solution with the 0. Do not keep longer than a week. light blue with lavender grey.2g (to the nearest mg).2. Calculate the molarity of the Na2CO3 solution (M Na2CO3). to ensure that this result is not being affected by residual alkalinity of the distilled water used to make up the standard solution. 5. E. Repeat the titration as necessary.3. If this value is significant.0. 3.2.
2.2.3 proceed as in Total Alkalinity above. at the end point. Over a white surface. 3. Pipette 50 mL of sample (or less if alkalinity is high) into an Erlenmeyer flask. 3. 2.3.2. then proceed as follows: 1. calculations are based on the reaction between CaCO3 and H2SO4. Repeat steps 1 – 3 as required. 3. 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. As the stoichiometric ratio is 1:1. If it is above 8. Add approximately 5 drops of mixed indicator to the sample.3.3.3 Phenolphthalein alkalinity If solution pH is greater than 8.01M H2SO4 to a persistent colour change characteristic of the equivalence point (this can be found by making a pH buffer solution to pH 4.3.4 Calculations As alkalinity is reported as the equivalent mass of CaCO3.3.5 and adding 5 drops of mixed indicator).2 Total alkalinity •Test the pH of the sample before beginning titration.4 Low alkalinity samples Use a 200 mL sample volume. If below 8. V = volume of solution or sample) E. and titrate using a 20 mL microburette and the pH 4. M = molarity.5 endpoint procedure. substituting phenolphthalein for the mixed indicator.Bergmann 13 Sec/Tert Interface 2009 . 3. n(CaCO3) = n(H2SO4).2. then you must use the phenolphthalein procedure. of moles. 4. titrate with 0.3.
5 M H2SO4 1. Clesceri. Add AgNO3 solution until a definite red precipitate is formed.0 mg NaCl (dried at 140˚C) in distilled water and dilute to 1000 mL 0. s = 1.0141 M. Rice.1 Apparatus 250 mL flask 50 mL burette pH probe or indicator strips for pH range 7 . 0.66 x 10-5 M) 4.is present in the portion titrated.15 to 10 mg of Cl.(aq) 2Ag+(aq) + CrO42.(aq) AgCl(s) (Ksp = 1.395 g AgNO3 in distilled water and dilute to 1000 mL. A 2005.3. Let stand for 12 hours. Chloride ions are quantitatively precipitated as AgCl before the red silver chromate precipitate is formed. 0 Chloride ion titration by Mohr (argentometric) method (adapted from Eaton. filter (Whatman No. Standard Methods for the Examination of Water and Wastewater 21st edition. (Dissolve 824.0M NaOH E.6 x 10-12.8 x 10-10.Bergmann 14 Sec/Tert Interface 2009 . Standardise against NaCl by the procedure described below. A. L. Ag+(aq) + Cl.) standard silver nitrate titrant.3. American Water Works Association and Water Environmental Federation.10 1 mL pipette 100 mL pipette or measuring cylinder 4.34 x 10-5 M) Ag2CrO4(s) (Ksp = 2.) standard NaCl solution. American Public Health Association. s = 8.0141 M (Dissolve 2. Maximum sample portion required for a single titration is 100 mL.2 Reagents K2CrO4 indicator solution (Dissolve 50 g K2CrO4 in a little distilled water.4. 4. Store in a brown bottle. E and Greenberg. 0. Washington) 4. The titrant is a standardised solution of AgNO3.1 Introduction The method is suitable for the analysis of chloride ion concentrations in relatively clean water when 0.2 Sample collection Collect samples in clean chemically resistant glass or plastic bottles. 42) and dilute to 1 L with distilled water.3 Analysis 4.
5M H2SO4 or 1M NaOH as necessary.4.3.3 Method 4. E.3 Titration 1. Chloride ion concentration of sample is reported as mg Cl.0 mL K2CrO4 indicator solution.3.3. Titrate with standard AgNO3 solution to a pinkish yellow end point as for the standardisation above. Be consistent in end point recognition. Titrate 20 mL of the standard NaCl solution with the AgNO3 to a pinkish yellow end point. Subtract the reagent blank value from the titre and use the difference to calculate the concentration of the AgNO3.3. 4.10 with 0. Use a 100 mL sample or a suitable portion diluted to 100mL if chloride ion concentration is high.3. Establish a reagent blank value by titrating 100mL of distilled water plus 1. Test pH of sample.Bergmann 15 Sec/Tert Interface 2009 .2 Sample preparation 1.3.per L (ppm). 2.1 Standardisation of AgNO3 titrant 1. Adjust sample pH to 7 .3.0 mL of K2CrO4 indicator with the AgNO3 titrant. Add1. 3. 4. 2. 2.
so the I2 product is titrated with thiosulfate. 20 mL and 25 mL and filler burette (50 mL) 100 mL volumetric flask 250 mL conical flasks 5.5.2 Analysis 5. so it is advisable to dilute the bleach by a factor of 1 in 10. This reaction produces I2.+ I2 2 I+ S4O62(2) From equations (1) and (2).reacts to form 1 mole I2. As the iodine is used. starch can be added. Hence.+ H2O (brown) (1) We can’t detect an end-point for the reaction above. and then disappears. the brown colour due to the triiodide ion fades to yellow. Starch forms a blue complex with I2.6 g NaI or 14.1 Introduction Note: Standard titrimetric methods for determination of free chlorine (hypochlorite ion. 5.2 M Na2S2O3 solution acidified NaI or KI solution (12. 2 S2O32.7M).2 Reagents bleach (freshly purchased) 0.Bergmann 16 Sec/Tert Interface 2009 . 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.0 Sodium hypochlorite (free chlorine) levels in Bleach 5.25% NaClO by mass (approx 0.2. This is a hard endpoint to detect.1 Apparatus pipettes 10 mL. (This in turn combines with iodide ion to form the very visible soluble brown triiodide ion I3-. which consumes 2 moles of S2O32-.) ClO(faint yellow) + 2I(colourless) + 2 H+ I2 + Cl. Typical bleach concentrations are quoted as 35 g/L available Cl as sodium hypochlorite (approx 1M) or approximately 5. it can be seen that 1 mole of ClO.0 g KI + 40 mL glacial acetic acid in 1 L) 1% starch suspension E. or to investigate the effect of factors such as UV light or addition of organic materials to pool water. hypochlorous acid and chlorine) are not sensitive enough for the analysis of municipal water supplies. so when the brown starts to fade to yellow. This method is suitable for the analysis of pool water.2. and this colour disappears when the stoichiometric amount of thiosulfate has been added to the flask. 1 mole of hypochlorite is equivalent to 2 moles of thiosulfate.
Add 50 mL of the acidified iodide solution to the bleach in the flask. Titrate with thiosulfate solution.5. 3. E. 3.2 Part B titration of bleach solution 1. Repeat titrations. 5. Prepare the diluted bleach solution by pipetting 10 mL into a 100 mL volumetric flask and filling to the mark with distilled water.2. Use the stoichiometric information given above to find the molarity of your diluted bleach solution.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.3 Calculations 22.214.171.124. Rinse a 20 mL (or 25 mL) pipette with the bleach solution. The overall reaction is as follows: 2 IO3. 5.+ 6 H2O 1.Bergmann 17 Sec/Tert Interface 2009 . Add a few drops of starch indicator. Rinse and fill the burette with Na2S2O3 solution.3 Method 5.2. It should go brown. If it does not.2. Stopper and invert several times to mix. adding starch as colour fades to straw yellow. Molarity of iodate solution should be about one-sixth that of the thiosulfate being used.+ 6 S4O62. Calculate the molarity of the neat bleach. Pipette out 25 mL of this solution and add 10 mL of 10% sulfuric acid solution and 2 g of KI. A blue starch-iodine complex should form. 4. 6. 2. 5. Continue adding Na2S2O3 to the flask until the blue colour disappears. Accurately weigh approximately 0. and titrate until the brown colour fades to a straw yellow. check the bleach – it decomposes over time. and transfer an aliquot to a conical flask. 2. 2.1 Part A standardisation of thiosulfate Thiosulfate solutions can be standardised by reaction with iodate.+ 12 H+ + 12 S2O322 I.3.
or in the bodies of aquatic organisms. A. ammonium molybdate reacts under acid conditions to form a heteropoly acid. (ii) colorimetric determination of dissolved orthophosphate. condensed phosphates (polyphosphates) and organically bound phosphates. Standard Methods for the Examination of Water and Wastewater 21st edition. This method oxidises all nitrogen compounds to nitrate and all phosphorus compounds to orthophosphate. Small amounts of orthophosphate or certain condensed phosphates are added to some water supplies during treatment. Organic phosphates are formed primarily by biological processes. both as precipitated inorganic forms and incorporated into organic compounds. because these materials are major constituents of many commercial cleaning preparations.and macroorganisms in nuisance quantities. These are classified as orthophosphates (phosphate PO43-).1 Introduction Phosphorus occurs in natural waters and in wastewaters almost solely as phosphates. American Public Health Association. (ii) nitric acid-sulfuric acid can be used for most samples. They occur in solution. Orthophosphates applied to agricultural or residential cultivated land as fertilisers are carried into surface waters with storm runoff. the discharge of raw or treated wastewater. Clesceri. L. A 2005.0 Colorimetric Phosphate Determination (stannous chloride method) (adapted from Eaton. agricultural drainage. but the simplest is (iii) persulfate oxidation. in particles or detritus. In this colorimetric determination of phosphate concentration. American Water Works Association and Water Environmental Federation.6. Rice. E and Greenberg. Phosphates also occur in bottom sediments and in biological sludges. molybdophosphoric acid. Washington) 6. This is then reduced by stannous chloride to intensely coloured moleybdenum blue.Bergmann 18 Sec/Tert Interface 2009 . The concentration of the orthophosphate is then determined colorimetrically. The digestion can be accomplished in 3 ways: (i) perchloric acid recommended only for difficult samples such as sediments. In instances where phosphate is a growth-limiting nutrient. Larger quantities of the same compounds may be added during laundering or other cleaning. Analysis of phosphorus involves 2 steps: (i) digestion or conversion of the phosphorus to dissolved orthophosphate. E. Phosphorus is essential to the growth of organisms and can be the nutrient that limits the primary productivity of a body of water. These forms of phosphate arise from a variety of sources. or certain industrial wastes to that water may stimulate the growth of photosynthetic aquatic micro. They are contributed to sewage by body wastes and food residues.
H2SO4 to 400 mL distilled water.0 µg phosphorus.0 ppm.1 Part A persulfate digestion • phenolphthalein indicator solution • strong acid solution (slowly add 300 mL conc H2SO4 to 600 mL distilled water.2. solid • 1.Bergmann 19 Sec/Tert Interface 2009 .) E.4H2O in 175 mL of distilled water.5 mg anhydrous KH2PO4 and dilute to 1 L (1. Cautiously add 280 mL conc.2.3 Part C Standard curve • standard phosphate solution (Dissolve in distilled water 126.96.36.199 Reagents 6.2. add molybdate solution.) • stannous chloride reagent (Dissolve 2. When cool.) • sulfuric acid solution (Carefully add 300mL conc H2SO4 solution to approx 600 mL distilled water and dilute to 1L with distilled water. and dilute to 1 L.6. K2S2O8.0 mL conc HNO3 and dilute to 1L. solid or ammonium persulfate.2 Analysis 6. add 4.2.1 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 6.00 mL = 50.5 g fresh SnCl2.) 6.) • potassium persulfate.2. (NH4)2S2O8 .2. Cool.0M sodium hydroxide 6.2 Part B Colour development • phenolphthalein indicator solution • strong acid solution (as above) • ammonium molybdate reagent (Dissolve 25 g of (NH4)6Mo7O24. This reagent is stable and requires neither preservative nor special storage. Heat in a water bath and stir with a glass rod to hasten dissolution.2H2O in 100 mL of glycerol. or P concentration is 50.
Use 50 mL or a suitable portion of a thoroughly mixed sample. a precipitate may form at this stage. using a distilled water blank.25 mL (5 drops) is required.5g of solid K2S2O8. Prepare at least one standard with each set of samples or once each day that tests are made.0 mL molybdate reagent and 0.3. Use a calibration curve prepared as described in Part C below to find the concentration of P. 2. take a smaller sample and dilute to 100 mL with distilled water after first discharging the pink colour with acid. Because the colour at first develops progressively and later fades. and neutralise to a faint pink colour with NaOH.05 mL (1 drop) of phenolphthalein indicator solution. dilute to 30 mL with distilled water. • Colour measurement After 10 minutes.6. add strong acid solution dropwise to discharge the colour. add 0. hold samples. 4. measure colour photometrically at 690 nm. Then add 1 mL H2SO4 solution and either 0. but before 12 minutes. add 0. using the same specific interval for all determinations. each 1˚C increase producing about 1% increase in colour.2. Cool.Acid persulfate digestion (for each water sample and for the calibration curve standards) 1. shake well. Add 0. If more than 0. • Colour development Add. 6.Bergmann 20 Sec/Tert Interface 2009 . The calibration curve may deviate from a straight line at the upper concentrations of the 0.05 mL (1 drop) of phenolphthalein indicator. 3. maintain equal timing conditions for samples and standards.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. Always run a blank on reagents and distilled water. Make up to 100 mL with distilled water. Hence.0 mg/L range. with thorough mixing after each addition. but do not filter. E.3. If sample turns pink. The precipitate (which is possibly a calcium phosphate) redissolves under the acidic conditions of the colorimetric reactive phosphorus test. In some samples.3 to 2. 6. Rate of colour development and intensity of colour depend on temperature of the final solution.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. If sample turns pink.1 Part A . Rinse with distilled water.2. Boil gently on a preheated hotplate for 30 to 40 minutes or until a final volume of 10 mL is reached.5 mL (10 drops) of stannous chloride reagent.4 g solid (NH4)2S2O8 or 0.2. For any subsequent subdividing of the sample. standards and reagents within 2˚C of one another and the temperature range between 20 and 30˚C. add strong acid solution dropwise to just discharge the colour.05 mL (1 drop) of phenolphthalein indicator.
mg/L or µg/mL) 5 4 3 2 1 0 Volume of 5ppm solution (mL) 25 20 15 10 5 0 Volume of water (mL) 0 5 10 15 20 25 • To prepare each standard solution for colorimetric measurement. Concentration of P (ppm.6. apply the persulfate digestion and colorimetric development procedures as given above. • Prepare the calibration curve.3. E. prepare a range of standards from 0 .3 Part C Preparation of calibration curve • Prepare a 5 ppm P standard solution by pipetting 10.Bergmann 21 Sec/Tert Interface 2009 .0 mL of the stock (50ppm P) solution into a 100 mL volumetric flask and making up to 100 mL.2.5 ppm according to the volumes given below. • From this.
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