3Water is essential for life: - 80% earths surface covered with water- makes up 2/3 of body weight- can live without food for several weeks but can only survive without water for few daysWe take water for granted!!!! When we turn on the tap we expect to have a plentiful supply of clean safe drinking water that we use for cleaning, washing etc. We forget that as a country with piped water system we are in the minority!!!!!
4In this chapter we will study and gain an appreciation for the importance of water in our lives. We will investigate:- water as an important solvent- how substances dissolved in water affect its properties- how water is treated in water treatment plants- water pollution- analyse the composition of water- how sewage is treated
5Hardness In Water Definition: Hard water is water that will not easily form a lather with soap. Hardness in water is caused by the presence of Ca2+ and Mg2+ ions.A grey precipitate (scum) is formed instead
6Hardness caused by dissolved calcium and magnesium salts: - calcium sulphate - CaSO4, magnesium sulphate - MgSO4- calcium chloride - CaCl2, magnesium chloride - MgCl2- calcium hydrogencarbonate - Ca(HCO3)2, magnesium - Mg(HCO3)2One of the most common substances in soap is sodium stearate, C17H35COONa. When soap is added to Hard Water the stearate ion (active part of soap) reacts with the calcium or magnesium ions in the water to form the grey insoluble compound calcium stearate (scum)
7Calcium ion + Stearate ion → Calcium Stearate (scum) Ca C17H35COO- → (C17H35COO)2Ca↓Lather is only formed once all the Ca2+ /Mg2+ ions have been precipitated in the scum – great deal of soap wasted in reaching this stage
8Modern detergents (washing powders, washing up liquids, shampoos etc Modern detergents (washing powders, washing up liquids, shampoos etc.) not affected by hard water as they DO NOT contain soap – made from crude oil
9Types of Hardness:Permanent and TemporaryExpressed as ppm
10Temporary Hardness:Temporary hardness is hardness in water that can be removed by boiling.Caused by:- calcium hydrogencarbonate – Ca(HCO3)2- magnesium hydrogencarbonate – Mg(HCO3)2
11Limestone (calcium carbonate) is insoluble in water thus calcium ions are not immediately available to cause hardnessHowever, limestone does react with carbonic acid:Rainwater + CO → Carbonic AcidH2O + CO2 → H2CO3This acidic solution of carbonic acid reacts with the limestone in the soil to form calcium hydrogencrbonate:Limestone Carbonic Acid → Calcium HydrogencarbonateCaCO H2CO3 Ca(HCO3)2INSOLUBLE SOLUBLE
12Calcium → Calcium Carbonate + CO2 + H2O Hydrogncarbonate The Ca2+ ions cause hardness while the HCO3- ions have no effect. However, if water containing these two ions is heated the water is softened as a chemical reaction occurs which removes the Ca2+ ions from the water:Calcium → Calcium Carbonate + CO2 + H2OHydrogncarbonateCa(HCO3)2 → CaCO3↓ CO H2OSoluble InsolubleHEAT
13An undesirable side effect of this is that the insoluble calcium carbonate precipitate can form a fur/scale that builds up on kettles, boilers, hot water pipes etc. The build up of this limescale can cause problems such as wasting heat, or even explosions due to pipes being completely clogged!!!
14*Note: Mg2+ ions often come from dolomite rock, which contains a mixture of MgCO3 and CaCO3 (MgCO3.CaCO3)*Demonstration: Test on scale deposits in a kettle
15Permanent Hardness:Permanent hardness is hardness in water that can only be removed by methods other than boiling i.e. ion exchange, distillationCaused by:- sulphates of calcium (gypsum rock) and magnesium- chlorides of calcium and magnesium
16Methods of removing hardness (permanent & temporary) from water: a) Distillationb) Washing Sodac) Ion Exchange Resin/Deionisation
17Distillation:- involves boiling the water and then cooling the vapour- ALL dissolved and suspended solids and dissolved liquids are removed from the water- very pure water- not used on a large scale to soften water due to the expense involved in boiling the water
19b) Washing Soda (Hydrated Sodium Carbonate – Na2CO3.10H2O)Before the development of modern detergents clothes were washed with soap and crystals of this compound were added to the water to soften the water!!!- carbonate ions in the washing soda react with Ca2+ ions in the water and removes them as insoluble calcium carbonate:Ca CO32- → CaCO3↓- Na+ ions (sodium carbonate) remain dissolved in water- bath salts – crystals of washing soda coloured with perfume added
20c) Ion Exchange Resin/ Deionisation (Swap Shop): Easiest way to remove hardness from waterModern ion exchange resins are man-made materials which exchange or ‘swap’ ions that cause hardness (Ca2+, Mg2+) with ions that do not cause hardness (Na+).Ion exchange units used to soften water contain cation (positive ion) exchange resin
21- Ion exchange involves the water being passed through a cation exchange resin.- The resins used are complex sodium compoundsand may be represented as RNa.- The Ca2+ and Mg2+ ions in the hard water swapplaces with the Na+ ions in the resin:Learn:2RNa(s) + Ca2+(aq) → R2Ca(s) + 2Na+(aq)- Eventually the resin loses all of its Na+ ions and itneeds to be regenerated by passing a concentratedsolution of sodium chloride through it
23c) DeionisationIn some cases it is necessary to remove ALL the ions from the water i.e. deionised water. In this case:- the resin used is a mixture of a cation (+ive)exchanger, replaces metal ions in water withhydrogen ions, H+, and an anion (-ive) exchanger,which replaces anions in water with hydroxide ions,OH- - MIXED BED RESIN
24Removal of Na+ and Cl- ions in water using a deioniser: *Learn:- Cation exchange resin, RH, replaces Na+ ions with H+ ions:RH + Na+ → RNa + H+- Anion exchange resin, ROH, replaces Cl- with OH- ions:ROH + Cl- → RCl + OH-- H+ and OH- ions then combine to form water:H+ + OH- → H2O
26Deionised Vs. Distilled (Higher Level)DeionisedEasily and cheaply producedCan contain dissolved gases as well as non-ionic material (organic) dissolved in the waterDistilledExpensive to producePurest form of water as all dissolved and suspended solids as well as dissolved gases have been removed
27Advantages & Disadvantages of Hard Water Provides calcium for teeth and bonesBlocks pipes leaves scale on kettles and boilersNicer tasteWastes SoapGood for brewing and tanningProduces scumStudent Questions:- Bk pg’s Questions- Workbook pg. 48 Question W19.1
28Mandatory Experiment: To determine the total hardness in a water sample (Higher Level) Must understand- theory behind this experiment- theory of experiment- associated calculation- how to determine the concentration of temporary and permanent hardnessStudent Questions:- Bk pg. 289 Questions 19.3 and 19.4, 19.5 (Tricky)- Workbook pg’s Questions W19.2-W19.5
29Water TreatmentWater supplied to houses around the country must fulfil certain criteria. It must be attractive looking, odourless, safe to drink and fluoridated. In order to ensure that the quality of domestic water supplies is of a certain standard it is necessary to carry out certain procedures on the water before going to houses. Water treatment plants have been set up around the country to ensure this standard is reached.
30Stages of Water Treatment: 1. Screening2. Flocculation3. Settlement (Sedimentation)4. Filtration5. Chlorination6. Fluoridation7. pH adjustment
31Screening:Water is first passed through a wire mesh to remove any floating debris – twigs, plastic bags etc.
32Flocculation:Flocculation is the coming together of small ` suspended solids in water to form larger particles (flocs)This is done by adding certain chemicals to the water – flocculating agent Al2(SO4)3A flocculant is a chemical added to water to coagulate suspended particlesThe addition of Al2(SO4)3 causes the suspended solids to stick together to form larger particles, which are allowed to settle out in the settlement stage.
34Settlement (Sedimentation): The flocculated water is pumped into the bottom of large settlement tanks and rises up slowly (allows maximum settlement to take place at bottom of tank) to the surface where clear water is collected in channelsThe suspended particles settle to the bottomApproximately 90% of particles are removed in settlement stage
36Filtration:The water, from top of settlement tanks, is allowed to fall through beds of graded sand and gravelThese filter beds remove any remaining suspended solidsThe sand acts just like a sieve or filter paper in removing the suspended solidsThe water coming out of filter beds is now clear but not yet fit for human consumption
385. Chlorination:Chlorine is added to water in order to sterilise it i.e. kill any harmful micro-organismsChlorine may be added as elemental chlorine or more commonly in the form of sodium hypochlorite (NaOCl) (active disinfecting agent chloric(I) acid)Chlorine requirements in drinking water ppmChlorine requirements in swimming pool water 1- 5ppmAmount of chlorine added must be carefully controlled need enough to give continued protection until use but also not too much as gives water unpleasant taste and smell.
40Fluoridation:Involves adding small quantities (1ppm) of fluorine compounds to waterFluoridation of water is carried out because it has been shown that the presence of fluoride ions in water can help prevent tooth decay – strengthens enamel of teethSources of fluoride ions:- sodium fluoride, NaF- hexafluorosilicic acid, H2SiF6
42pH Adjustment:It may be necessary to adjust the pH of water before it leaves treatment plantOptimum pH of water for distribution – pH 7-9If water supply slightly acidic (due to original source or chemicals added) can lead to corrosion of pipes so calcium hydroxide (lime) added to raise pH above 7If water supply slightly basic (due to added softeners-sodium carbonate) sulphuric acid added to lower pH.
44Mandatory Experiment: To determine the total suspended solids (p.p.m) of a sample of water by filtrationthe total dissolved solids (p.p.m) of a sample of water by evaporationthe pH of a sample of waterMust understand:- theory of experiment- associated calculations
47Dissolved Oxygen:Dissolved oxygen in rivers, lakes and the sea is vital for the survival of fish and other forms of life.Although oxygen (non-polar) is only slightly soluble in water aquatic life cannot exist without it.The solubility of oxygen in water is dependent on the temperature of the water – the solubility of gases in water decreases with increase in temperature - when water is heated bubbles of air are seen to come out of solution.
48Another factor affecting the amount of dissolved oxygen in water is the discharge of organic waste (domestic sewage, animal slurry, silage effluent etc.) into waterways.When organic waste is discharged into the water, the bacteria and other organisms which are naturally present in the water are provided with nutrients.These nutrients cause the organisms to multiply into large numbers. As the organisms break down the waste (aerobic respiration) into compounds like CO2 and water, they use up the oxygen dissolved in the water:Organic Matter + Oxygen CO2 + H2O
50If a considerable amount of organic waste is present, it is possible that the dissolved oxygen level in the water will be reduced so much that fish life in the water will start to decline e.g. trout and salmon require 5 p.p.m of dissolved oxygen in order to survive.If the dissolved oxygen level drops to low levels such as zero concentration, anaerobic bacteria will take over and start producing H2S gas leaving the river with a foul smell!!!!Such POLLUTION results in the death of vast amounts of fish and other aquatic life!!!!!
51Biochemical Oxygen Demand (B.O.D.) (Higher Level): The Biochemical Oxygen Demand (B.O.D.) test was developed to determine the level of pollution in our waterways:Biochemical Oxygen Demand is defined as:- the amount of dissolved oxygen- consumed by biological action- when a sample of water is kept at 20oC- in the dark- for five days*Note: B.O.D. is measured in mg/L of oxygen
52This process involves collecting two water samples from the same area This process involves collecting two water samples from the same area. The dissolved oxygen in bottle A is measured immediately using a titration called The Winkler Method (or using a dissolved oxygen meter). Bottle B is incubated in the dark at 20oC for five days:- kept in the dark to prevent the production of oxygen by photosynthesis that might be carried out by any plant life present.- amount of oxygen dissolved in water depends on temperature, experiment is carried out at a fixed temperature to allow the valid comparison of the BOD values of different water samples.
53- the Winkler method of measuring dissolved - the Winkler method of measuring dissolved oxygen is carried out on the sample of water in bottle B at the end of the 5 day period. The difference between the dissolved oxygen level for bottle A and the dissolved oxygen level for bottle B is the B.O.D. This B.O.D. value represents the amount of oxygen required by bacteria and other micro-organisms to break down organic material over the five day test period.
54- if the sample is very polluted, (effluents with - if the sample is very polluted, (effluents with BOD greater than 9mg/L) it must be diluted by a fixed amount with well-oxygenated water. This ensures that the dissolved oxygen present does NOT run out before the end of the 5 day test period and that a measureable amount of oxygen (at least 2 p.p.m) will be left after the five day period. When the B.O.D. calculation is carried out, the result is multiplied by the dilution factor to get the true B.O.D. value.- The higher the B.O.D. value the more polluted the water. A high B.O.D. value means that there is a large amount of organic waste in the water and as this organic waste is acted on by bacteria, the level of oxygen decreases.
55B.O.D (mg/L)Source of sample1-2Clean Water20-40Treated Sewage100Polluted Water (fish die)30,000Pig slurry54,000Silage EffluentMost fish kills in Ireland are caused by slurry and silage effluent into rivers and lakes
56Example 1:To find the B.O.D. of a sample of polluted river water, 25cm3 of the water was diluted to one litre with well-oxygenated pure water. Two bottles, A and B, were filled with the diluted water and their dissolved oxygen concentrations were determined. The analysis was carried out immediately for bottle A and five days later for bottle B. The results obtained were 12.8 p.p.m and 8.2 p.p.m respectively.Why dilute polluted river water? What was advantage in using well oxygenated water for this purpose?Under what conditions should bottle B have been kept for the five days before it was analysed? In the case of one of these conditions explain why it is necessary.iii) What was the B.O.D. of the polluted river water?
58Example 2:Why is it necessary to analyse the sample of water in bottle A immediately???Example 2 Solution:So that oxygen content does not increase due to photosynthesisSo that the oxygen content does not decrease due to respirationSo that the oxygen content does not increase/decrease due to activity of organisms
59Example 3:A sample of polluted water was analysed, in order to determine the amount of dissolved oxygen in the water, using the Winkler method. The main reactions may be represented as follows:4Mn(OH)2 + O2 → 2Mn2O3 + 4H2OMn2O3 + 2I- + 6H+ → 2Mn2+ + I2 + 3H2OA 50cm3 sample of the water was diluted to one litre with pure well-oxygenated water. 300cm3 of this diluted solution were analysed by the Winkler method and 14.7cm3 of 0.02M sodium thiosulphate were required. A second 300cm3 sample was stored in the dark at 20OC for five days and then analysed for dissolved oxygen. The liberated iodine required 4.8cm3 of 0.02M sodium thiosulphate. Calculate the amount of dissolved oxygen in each sample of water. Express your answers in p.p.m. Hence find the B.O.D. of the water.
62Mandatory Experiment: To measure the amount of dissolved oxygen in a sample of water by means of a redox titration (Winkler Method)Must understand:- reaction equations- theory of experiment- associated calculations (calculating amount of dissolved oxygen in water in p.p.m.
63Eutrophication:Another process which results in the reduction of the amount of dissolved oxygen in water is EUTROPHICATION.Defnition:Eutrophication is the enrichment of water with nutrients, which leads to excessive growth of algae
64This is caused when water is overloaded with plant nutrients, in particular nitrate ions (NO3-) and phosphate ions (PO43-). This is caused by untreated or partially treated sewage or by run off from farmland of slurry or fertilisers.As the nitrate and phosphate levels rise, many plants and floating algae undergo population explosions.The algae are short lived.As the algae decay, micro-organisms use up much of the dissolved oxygen in the water, leading to the death of many forms of animal life.
65‘Algal Bloom’ covers much of the surface of the water with a green scum
66Eutrophication may occur artificially or naturally Higher LevelEutrophication may occur artificially or naturallyNatural Eutrophication:- occurs mainly in lakes- when sediments build up in a lake leads to a gradual increase in nitrogen and phosphorous levels.Artificial Eutrophication:- caused by a sudden increase in nutrients- source of these nutrients – artificial fertilisersbeing washed into rivers and lakes or by domestic sewage/waste from farming entering waterways
67There is some concern about the levels of nitrate ions in water There is some concern about the levels of nitrate ions in water. It is thought that high levels of nitrates may cause stomach cancer and also death in babies.
68Heavy Metal Pollution (Higher Level): Water pollution is also caused by the release of toxic metal ions into the water e.g. lead ions (Pb2+) , mercury ions (Hg2+) and cadmium ions (Cd2+)These elements considered cumulative poisons i.e. frequent exposure causes a build up in the body, with consequent serious health damage.Quantities of these elements can be found in rivers and lakes as a result of the discharge of industrial effluents or the dumping of batteries that contain these metals.Consequently they can enter drinking water!!!!!
70Associated problems:- lead in drinking water - old houses containing lead plumbing- mercury poisoning – metallic mercury is dangerous when inhaled but less dangerous when swallowed as most of it passes out of body within a few days However, it is a build up of mercury salts which can pose serious health risks! – Minamata Bay 1950’s – birth defects and death
71Before the effluent is run into a waterway, the metal ions are removed by means of precipitation – lead ions are reacted with dilute HCl:Pb Cl- → PbCl2↓
72EU and Water QualityWater quality is controlled by EU legislation. Heavy metal limits have to be set because of the toxic effects of metals like mercury, cadmium and lead. Limits on phosphates and nitrates help to reduce the occurrence of eutrophication in waterways. Limits are also set for chemical species dissolved in drinking water.Cadmium – 5 mg/LMercury – 1 mg/LLead – 10 mg/LNitrates – 50 mg/L
74For many years, domestic sewage running untreated into rivers, lakes and the sea has been one of the most serious causes of pollution in Ireland. In general a small quantity of a pollutant would not pose a problem as it would be degraded quickly, posing no threat to the environment. However, large quantities of sewage cannot be broken down in a reasonable period of time and so constitutes serious pollution.Sewage may consist of organic waste, inorganic waste and various gases. If this were simply dumped into a local river or lake there would be such a high demand on the dissolved oxygen that the water would become very polluted!!!
75The essential purpose of a sewage treatment plant is to reduce the B.O.D. of the sewage before it is discharged into the local river or lake.There are three recognised stages in sewage treatment:- Primary Treatment- Secondary Treatment- Tertiary Treatment
76Primary Treatment (Mechanical Process): Involves screening and settlingScreening: sewage passes through steel bars that remove large floating solids and physically break up sewage. Sewage is then slowly passed through grit channels in which pebbles, grit etc. settle and are removed periodically.Sewage flows into bottom of primary settling tanks where it remains for a few hours.Settlement (Sedimentation): suspended solids settle to the bottom of the tank and form a sludge. Scraper at bottom of tank removes sludge periodically.
77Liquid on top (supernatant liquid) flows away to secondary treatment. Removes approx 1/3 B.O.D. in sewageDefinition:Primary treatment involves screening and settlement, and is a physical process.
78Secondary Treatment (Biological Oxidation of Sewage): involves biological process which reduces the levels of suspended and dissolved organic materials – ACTIVATED SLUDGE PROCESSconsists of an aeration tank followed by a settling tank.Aeration Tank: The sewage is fed continuously into an aerated tank that is kept oxygenated by mechanical agitators. Micro-organisms present in the tank oxidise most of the organic matter (activated sludge)*Note: function of aeration tank is to breakdown organic matter without letting the concentration of dissolved oxygen in the liquid drop too low.
79After the biological stage the sewage flows into a settling tank where it undergoes further settlement.Settling: some of the sludge (rich in nutrients) is removed and used as fertiliser or further converted to methane. Some of the sludge is recycled back into the aeration tank to come in contact with fresh sewage.Thus the micro-organisms are continually decomposing the organic waste in the sewage into compounds like carbon dioxide, nitrates etc.
80After secondary treatment about 95% of the B. O. D After secondary treatment about 95% of the B.O.D. of the original sewage is removed.Effluent may now be discharged into waterways, however, still contains compounds of phosphorous and nitrogen – moves to tertiary treatment.Definition:Secondary treatment is a biological process involving the oxidation by micro-organisms of the nutrients present in the sewage.
82Tertiary Treatment:Involves chemical and biological processesInvolves the removal of phosphates (household detergents) and nitrates (organic materials) from the effluent resulting from secondary treatmentRemember nitrates and phosphates cause pollution by eutrophicationPhosphates removed by precipitation. Reacted with a compound such as aluminium sulphate producing an insoluble salt – aluminium phosphate. Other additives used are iron(III) chloride and lime. Insoluble phosphate compounds allowed to settle before effluent discharge.
83Nitrates present in the form of ammonia, nitrite compounds, nitrate compounds or organic compounds containing nitrogen.Nitrates removed by biological denitrification.Bacteria is used to reduce nitrates to nitrogen gas. The removal of all nitrogen compounds can be very difficult and quite expensive.Effluent may now be discharged into waterways!!!
84Definition:Tertiary treatment involves the removal of phosphates and nitrates from the effluent
86*Notes on separate handout* A) pH meterB) Atomic Absorption SpectrometryC) Colorimetry*Notes on separate handout*
87Mandatory Experiment: To estimate the concentration of free chlorine in swimming pool water or bleach using a comparatorMust understand:- theory of experimentStudent Questions:Book – pg.290 No’sWorkbook – pg.49 W19.9