ATOLL ie Sat ; ne ence NVIRON ENTAL CHEMISTRY (lp y Gytre We ( ay ic) \ > — Rocks,minerals occurs in outer mantle of the earth os crust and natural gas, oil occurs in deep inner layers ofearth crust. Environmental studies deal with the sum ofall social, Biosphere : economical, biological, physical and chemical | > ([ Allliving species including human beings and animals , sions with our surroundings constitute Biosphere:)) Environment Definition of Terms Environment consists of four segments namely | > Pollutant : A substance present in nature in Atmosphere, Hydrosphere, Lithosphere and creater amounts than natural abundance due to Biogphe: ea ; ; human activity, which has harmful effect on Th Atmosphere (Al organisms and mankind is Called pollutant. Atmosphere is the protective blanket of gases _— saounding the earth. egrCO, ie from the hostile environment ofouter | » These are classified as - On the basis of form — a) Primary pollutant - CO,, SO, NO, Ttoonsists ff4 spheres ¢xtending upto 500 km from ) Secondary pollutant - PAN, “PBN on the basis Beauface ithe cart} of Eco system Teseare Troposphere, Stratosphere, Mesosphere| a) Bio-degradable pollutant Domestic sewage sphere. b) Non bio-degradable pollutant- DDT. Oo Contaminant: A material which does not occur > in nature but is introduced by human activity into the environment and causes adverse effect is called Maintains Ce heat balancel eg: Methyl isocyanate (MIC) (Bhopal trazedy) > Receptor : The medium which is effected by a ‘Absorbs Uv pollutant is called the receptor. rays eg: Eyes in traffic one Yeeeon || > Sink: Themediumwhich retainsand interacts with NO ooraette a long lived pollutant i called the sink. ound wave: egt Trees, oceans are sinks for atmospheric carbon In this regiorl dioxide 0; ,O;N; NO’ ionization of| | > lgases occurs Speciation: The chemical form of pollutant is called Speciation, It is a method of classifying pollutant into inorganic, organic or organo-metallic. Th the region of Troposphere, as the altitude €g: Harmful form of Hg are methyl mercury and — "creases temperature and air density decreases. dimethyl mercury. rosphere (Water): > Threshold Limit Value (TLV) : It is the osphere includes all water sources like Oceans, | Permissible level of a toxic pollutant in the Rivers, Lakes, Streams, Reservoirs,Glaciers | _stmosphere to which a person is exposed during 8 hours to work per day without any harmfal effect. If threshold limit values of X, Y and Z pollutants are 9, 10 and 15 ppm respectively then Z is less toxic, ORE TTENVIRONMENTA\ OY Zor saree lag > Dissolved Oxygen > DOistheamount ofoxygen present in the water. Itis measured in mglit or the number of mg of oxygen dissolved ina litre of HO . > Forthe healthy growth of plants and animals 4-6 mgllit DO is required. Lesser DO indicates greater pollution. Chemical Oxygen Demand (COD): Itis the amount of oxygen required to oxidise the organic substances present in polluted water. > Itisamimportant index forthe amount of the organic substances present in water. COD is determined by oxidising the organic matter with acidified (50%o#7,SO,) potassium dichromate solution. > Biochemical Oxygen Demand (BOD): It is She amount of oxygen used by the suitable micro-organisms present in water during five days vv v qydy 20°C M0 The BOD values of different samples of water —f a) For pure water- | ppm. oat b) Fairly pure water - 3 ppm (obi c)Doubiful purity-5 ppm (lr d) Municipal sewage - 100-4000 ppm. > BOD greater than | 7ppm indicates high pollution ‘no yp om isharmt abit oof mg of O, required I BOD= ~~ orof H,Oinlit Environmental Pollution: > Environmental pollution is the effect of undesirable changes in our surroundings that have harmful effects on plants and animals. Atmospheric Pollution (Air pollution) > Troposphere is the lowest region of atmosphere in which the human beings live along with other organisms. Tropospheric Pollution > — Itoccurs due to the presence of undesirable solid or gaseous particles in the air. A) Gaseous Air Pollutants: These are oxides of sulphur, oxides of nitrogen, oxides of carbon, hydrogen sulphide, hydrocarbons, ozone and other oxidants. B) Particulate Pollutant mist, fumes, smoke, smog etc. ‘hese are dust, Vv A) Gaseous Air Pollutants Oxides of Sulphur : Oxides of sulphur are produced when sulphur containing fossil fuels are burt Sulphur dioxide is a g animals and plants, Evena low concentration of sulphur dioxide causes respiratory diseases like asthma, bronchitis, emphysema. High concentration of SO, leads to stiffness of flower buds which eventually fall off from plants. The presence of particulate matter in polhutedair catalyses the oxidation of sulphur dioxide to sulphur trioxide. 250, +O, > 2SO, The reaction can also be promoted by ozone and hydrogen peroxide. $09) +05, 2S0,., + On, $0.) +H,0;,, > HSO,,. Oxides of Nitrogen : Dinitrogen and dioxygen are main constituents of air. These gases do not react with each other at a normal temperature. At high altitudes when lightening strikes, they combine to form oxides of nitrogen. NO, is oxidised to nitrate ion, NO; whichis washed into soil, where it serves asa fertilizer. When fossil fuels are bumt in an automobile engines, at high temperature forms nitric oxide (NO) and nitrogen dioxide( NO, Nag * Oy —**> 2NO, ‘NO reacts instantly with oxygen to give 2NO y+ On > 2NO,, The rate of production of NO, is high when nitric oxide reacts with ozone in the stratosphere. NO a Wy ad NOx 2 uy The irritant red haze in the traffic and congested places is due to oxides of nitrogen. Higher concentrations of NO, damage the leaves of plants and retard the rate of photosynthesis. Nitrogen dioxide is a lung irritant that can lead children, Itis toxic to living tissues. Nitrogen dioxide is harmful to various textile fibres and metals. Hydrocarbons : Hydrocarbons are{carcinogenic) i.e, they cause cancer geile hodicaly s that is poisonous to both NO,ATT Leeda ALU , Theyharm plants by causing ageing, breakdown of tissues and shedding of leaves, flowers and twigs. Oxides of Carbon Carbon Monoxide: Carbon monoxide is mainly released into the air by automobile exhaust. » Coal, firewood, petrol, hydro carbons also produce CO oncombustion » CO binds to haemoglobin to form carboxyhaemoglobin, which is about 300 times more stable than the oxyhaemo; 7 » Tn blood, when the concentration of carboxy haemoglobin reaches about 3- 4 % the oxygen carrying capacity of blood is greatly reduced. » Thisoxygen deficiency results into headache, weak eye sight, nervousness and cardiovascular disorders. > Inpregnant women, the increased CO level in blood may induce premature delivery, spontaneous abortions and birth of deformed babies. > The permissible level of CO in atmosphere is 9ppm. > Microbes in soil act as sink for CO 10 2 Loss of vision 100 15 Headache, fatigue 250 32 Un consciousness| 750 60 Death after few hours 000 66 Immediate & death _ Carbon dioxide: ” CO,is liberated largely in to atmosphere byburning offossil fuels, by decomposition of limestone and during volcanic eruptions ” Normally it forms about 0.03% by volume of the , ‘mosphere. Excess of CO, inthe air is removed by green plants, (Photosynthesis) and this maintains an appropriate ‘evel of CO, in the atmosphere. Global Warming & Greenhouse Effect Itis the progessive heating up of earth surface. nce of CO, in atmosphere block a part of te No) Yael ele heat emitted by earth and reflect back. By this earth surface gets heated up. About 75% of solar energy reaching the earth is obserbed by the earth surface. Inaddition to CO,, the green house gases are CFC, Ozone, Nitric oxide, Methane, Water vapour etc. The sources of green house gases - CFC— from S Methane — from paddy fields , coal mines,rotting garbage dumps, fossil fuels Nitric oxide— burning of fossil fuels. Tt leads to melting of polar ice caps and flooding of lowlyingareas all over the ear a Increase in the global temperature increase the incidence of infectious diseases like dengue, malaria, yellow fever, sleeping sicknessetc. Acid Rain When the pH of the rain water drops below 5.6, it is called acid rain. Normally rain water has apH of 5.6 due to the reaction of rain water with carbon dioxide present in the atmosphere. HQy) + COs = HCO sag +HCO, FCO say Fay oa) Acid rain is a byproduct of a variety of humanactivities that emit the oxides ofsulphur and nitrogen in the atmosphere. This causes dry deposits or rain, fog and smog SO, and NO, after oxidation and reaction with water form acid rain. Particulate matter catalyse this oxidation, 2801p) + Ong + 2H O11) NOs + Ong + 2H 30.) > 4HNO a9) Adverse Effects: Acid rain changes p' of the soil and effects fertility Acid rain is harmful for agriculture, trees and plants as it dissolves and washes away nutrients needed for their growth, It causes respiratory ailments in human beings and animals. It affects plants and animal life in aquatic ecosystem. It corrodes water pipes resulting in the leaching of heavy metals such as iron, lead and copper into the drinking water. ~> 2H, SOx.) iali ENVIRONMENTAL CHEMISTRY Acid rain damages buildings and other structures made of stone of metal The Taj Mahal in India has been affected by acid rain, ” The resulting acid rain reacts with marble, CaCO, ofTajMahal_causing damage to this wonderful quent ) Particulate Pollutants ulate pollutants are the minute solid particles liquid droplets in air. These are two types : Inne Y NING) 1) The viable particulates are bacteria, fungi, algae. These are responsible for causing allergy in human NIN LIVING enon Viable particulates are ‘Smoke particulates- Cigarette smoke, smoke ‘burning of fossil fuel 2) ~ produced during crushing, grinding. ~~ gMists - Sulphuric acid mist and herbicides and > re v v cides. Fumes — Organic solvents, metals and metallic oxides. The effect of particulate pollutants are largely dependent on the particle size. Particulate pollutants bigger than 5 microns are likely tS Todge n the nasal passage, W about 10 micron enter into lungs easily. Gea’ used to be a major air pollutant emitted by vehicles. Lead (> 50 ppb) is carcinogenic This problem has now been overcome by using unleaded petrol in most of the cities in India Smog: ‘Smog is derived from smoke and fog. There are two types of smog ) Classical smog ~ present in cool humid i) It is amixture of smoke, fog andfulphur dione Chemically it isa reducing mixture and so it is called as reducing smog or London smog— ) Photochemical smog ~ present in warm, dry and ‘sunny climate. It contains unsaturated hydrocarbons and nitrogen oxides. ; Photochemical smog has high concentration of oxidising agents called as oxidising smog. Formation of photo chemical smog: When fossil fuels are burnt, two pollutants (NO) are emitted into atmosphere. The formation of photo chemical smog are : sun light. oxygen atom. NO,,, —*-» NO, + O,,, with the O, in air to produce Oy, * Ory Oy, 4) Regeneration of NO,NO,,+Oyy>NOs,,+0;, > Ozone s a toxic gas and both NO, and O,are strong oxidising agents. They react with the unburnt hydrocarbons in the polluted air to produce formaldehyte, acroleinand peroxyacety| nitrate (PAN), 1) 3CH,+20,-» 3CH,=O0 +3H30 Formaldehyde (CH,= CH-CHO) ((CH;COONO; ) 2) Acrolein 3) Peroxyacetyl nitrate oO Effects of photochemical smog: > Photochemical smog causes serious health problems. Both ozone and PAN act as powerful eye irritants, > — Ozone and nitric oxide irritate the nose and throat and their high concentration causes headache, chest pain, dryness of the throat, cough and difficulty in breathing. Photochemical smog leads to cracking of rubber and extensive damage to plant life Italso causes corrosion of metals, stones, building materials, rubber and painted surfaces. Control of photochemical smog: > — Bycontrolling the pollutants like (primary precursors of phtochemical smog) such as NO, hydrocarbons, the activity of ozone and PAN (the secondary precursors) will be automatically reduced, > — Catalytic converters in automobiles, prevent the release of nitrogen oxide and hydrocarbons > Planting Pinus, Juniparus, Quercus, Pyrus and Vitis can metabolise nitrogen oxide. Stratospheric Pollution Formation and Break down of Ozone The upper stratosphere consists of considerable amount of ozone (O,), which protects us fromthe harmful violet (UV) radiations (A. 255m) coming fromthe sun. > Ozone in the stratosphere is'a product of UV radiations acting on dioxygen (O,) molecules. v vi v ultra uw Or4@) > a) +e) Ww. Oe) + On) =O 5) > Themainreason ofozone layer depletion i believed to be the release of chloroftuoracarbon compounds (CFCs) also known as freon,, > , El Se LL Re Nate aia CFCs are released in the atmosphere, they mix with the normal atmospheric gases and eventually reach the stratosphere. Instratosphere, they get broken down by powerful UV radiations, releasing chlorine free radical. CFC13(@) “5 Ci(g)+CRCI(g) The chlorine free radical then reacts with stratospheric ozone to form chlorine monoxide radicals and molecular oxygen. Ci(g)+0,(¢) + C10(e)+0.(e) Reaction of chlorine monoxide radical with atomic ‘oxygen produces more chlorine radicals. C10(g)+0(g) +Cl(g)+0,(g) The chlorine radicals are continuously regenerated and cause the breakdown of ozone The Ozone Hole: Depletion ofozone yer commonly knownas ozone hole, whichis first observed over the South Pole Ingummer season, nitrogen dioxide and methane react with chlorine monoxide and chlorine atoms forming chlorine sinks, preventing much ozone letion. - Whereas in winter, special type of clouds called polar stratospheric clouds are formed over Antarctica. These polar stratospheric clouds provide surface on which chlorine nitrate formed. It reacts with hydrogen chloride produced to give ‘molecular chlorine. C10,.)+ NO, sj») 2 CIONO ,,) Cl) + CH yg) 2 CH yy) + HC) CIONO,,,, + H,0,,, > HOCI,) + HNO\,, CIONO, + HCl p) > Chg) + HNOys) ‘When sunlight returns to the Antarctica in the spring, the sun's warmth breaks up the clouds, then HOC! and CI, are photolysed by sunlight. HOCI,,, Samad o Ay t Chy Cy) —92C hy The chlorine radicals thus formed, initiate the chain . for ozone depletion. Aya a) Effects of Depletion of the Ozone Layer UV radiations lead to ageing of skin, cataract, sunburn, skin cancer, killing of many phytoplanktons, damage to fish productivity etc. Plant proteins get easily affected by UV radiations which leads to the harmful mutation of cells. It increases evaporation through the stomata of the leaves and decreases the moisture content of the soil. Increase in UV radiations damage paints and fibres, causing themto fade faster. Water Pollution Imbalance in the quality of water so as to cause adverse effect on the living organisms is called “Water pollution” Water gets polluted in several ways by human activities, eg. municipal and industrial discharge, agricultural run offacid rain, drainage. jicro-organisms __ [Domestic sewage [Domestic sewage, | janimal excreta and |Organic waste ste, decaying animals jand plants, discharge lfrom food processing fact Plant nutrients chemical fertilizers ‘Toxic heavy metals _ [Industries and chemi {factories Erosion of soil by Sediments agriculture and strip. | ‘Chemical used for killing insects, Pesticides. fungi and weeds |Radioactive Mining of uranium eubstances lcontaining minerals Heat Water used for cooling in industries Causes of Water Pollution a) Pathogens ‘These are disease causing agents. ‘They inchide bacteria and other organisms that enter water from domestic sewage and animal excreta Human excreta contain bacteria such as Escherichia coli and Streptococcus faecalis wb cause gastrointestinal diseases. avv b) Organic Wastes The major water pollutant is organic matter suchas Excessive phytoplankton growth within water is also ¢ of water pollution, Th biodegradable. In cold water, dissolved oxygen (DO) concentration up to 10 ppm (parts per Where as oxygen in air That is why even a moderate amount of organic matter when decomposes in water can deplete the water ofits dissolved oxygen. Ifthe concentration of dissolved oxygen of water is below 6 ppm, the growth of fish gets inhibited. The anaerobic bacteria (which do not require oxygen) begin to break down the organic waste and produce chemicals that have a foul smell and are harmful to human health. Aerobic (oxygen requiring) bacteria degrade these organic wastes and keep the water depleted in dissolved oxygen. c) Chemical Pollutants Water soluble inorganic metals such as cadmium, mercury, nickel etc are the important pollutants. Alll these metals are dangerous to humans because our body cannot excrete them. These metals can damage kidneys, central nervous system, liver ete. Acids (like sulphuric acid) from mine drainage and salts from many different sources including raw salt used to melt snow and ice in the colder climates (sodium and calcium chloride) are water soluble chemical pollutants. The organic chemicals are another group of | substances that are found in polluted water. eg : Petroleum products, major oil spills in oceans. Industrial chemicals like polychlorinated biphenyls, PCBs) which are used as cleansing solvents, ‘detergents and fertilizers add to the list of water pollutants PCBs are suspected to be carcinogenic. Fertilizers contain phosphates as additives. The addition of tes in water enhances algae growth, Profuse growth of algae, covers the water surface and reduces the oxygen concentration in water. ‘se Wastes are mnreach a illion) about 2,00,000 ppm. > wi v Vv DV CHEM-VOL The proce: Lupport adense plant population, which kills animal life by depriving it of oxygen and results in subsequent loss of biodiversity is known as Eutrophication. / i) Fluoride: | (up>rets ] The deficiency of f° indrinking water is harmful and causes tooth decay. Soluble fuorideis often added to drinking water tg bring its concentration upta ) ppm or(1 fig Mim) F ionconcentration above 2 ppm causes br6%n mottling of teeth, The F ions make the enamel on teeth much harder by converting hydroxyapatite, [3(Ca (PO), Ca(OH),}, the enamel on the surface of the teeth, into much harder fluorapatite, [3Ca,(PO,),,CaF} ‘The addition of F- decreases the colour of zirconium alizarin-S dye solution by removing zirconium from. the dye in the form of colourless zirconium fluoride. It is used to detect F Excess fluoride (>10 ppm) causes harmful effect to bonesand teeth (Fluorosis) Defluoridation : Itis the process of removal of excess F- ion from water. Can be re Activated generated by carbon method] carbon (charcoal)| 4% NaOH+1%4 HPO, Fis precipitated as calcium aluminum fluoride egloner Drinking water gets contaminated with lead when lead pipes are used for transportation of water. ‘The prescribed upper concentration limit of lead in drinking water is about 50 ppb. Lead can damage kidney, liver, reproductive system etc, Nalgonda [Bleaching technique |powder+ lime+alum A Pots M WSaudyl Atduius _VION MUSEUMS Sie iii) Sulphate: picviseo Excessive sulphate (>S00 ppm) in drinking water ative effect. At moderate levels it is iv) Nitrate: ) Themaximum limit ofnitrate in drinking water is 50 m. Excess nitrate in drinking water can cause disease such as methemoglobinemia (‘blue baby’ syndrome). — y) Other metals: The maximum concentrations of metals can be present in drinking water. 380 w pyr mn 0.005 Soil Pollution = The insecticides, pesticides and herbicides cause soi pollution. i) Pesticides and Herbicides : Prior to World War II, nicotine was used as pest controlling substance. DDT was found to be of great use in the control of malaria insect-borne diseases. It is used in agriculture to control the damages caused by insects, rodents, weeds and various crop diseases. Pesticides are basically synthetic toxic chemicals with ecological repercussions. eg: Aldrin and Dieldrin Most ofthe organic toxins are water insoluble and non-biodegradable. The process of transformation of persistent toxins from lower trophic level to higher trophic level through food chain is called bio-amplification . Theconcentration of toxins in higher animals reach a level which causes serious metabolic and physiological disorders. Recently less persistent or more bio-degradable organo-phosphates and carbamates have been introduced, Cadmivn) ‘These chemicals are also severe nerve toxins and hence more harmful to humans. > \ v wo | y ore) el ie) mel Now a days less harmful herbicides such as sodium chlorate (NaC'1O, ), sodium arsinite (Na AsO,) and many others are introduced instead of pesticides. Herbicides are toxic to mammals but are not as persistent as organo-chlorides. Some herbicides cause birth defects. Corn-fields sprayed with herbicides are more prone to insect attack and plant disease than fields that are weeded manually. ii) Industrial Waste : Biodegradable wastes are generated by cotton, paper, textile and food processing industries. > Non-biodegradable wastes are generated by w wer, steel, metallurgical plants. |X eg{ily ash)slag, mud, tailings and gypsum. Nowadays, fly ash and slag from the steel industry are utilised by the cement industry. Large quantities of toxic wastes are usually destroyed by controlled incineration, whereas small quantities are burnt along with factory garbage in open bins. Strategies to Control Pollution a) Waste Management : Collection and Disposal: Domestic wastes are collected in small bins, by private or municipal workers. Biodegradable wastes are deposited in land fills and are converted into compost. Non-biodegradable materials suchas plastic, glass, metal scraps etc. are sent for recycling. Polythene bags, ifswallowed by cattle can cost their lives also. b) Green Chemistry : adie Lhe tép fps Green chemistry is a production process that would bring about minimum pollution or deterioration to the environment. Organic solvents such as benzene, toluene, carbon tetrachloride ete., are highly toxic. ‘No chemical pollutants will be introduced into the environment, ifin a chemical reaction, reactants are fully converted to environmental friendly products. Green Chemistry in Every Day Life i) Dry Cleaning of Clothes : Tetra chloroethene (C/,C=CC1,), earlier used as solvent for dry cleaning, is carcinogenic. Now itis replaced by liquified carbondioxide, with a suitable detergent whichis less harm to ground _water__—_— eeNiels ces > —H,0,isused for the purpose of bleaching cloth the process of laundary, which gives better res er amount of water. Bleaching of Paper : > — Chlorine gas was used earlier for bleaching paper. > Hydrogen peroxide (HO, with suitable catalyst, romotes the bleaching action now a days. iii) Synthesis of Chemicals : > Ethanal (CH CHO) is now commercially prepared. by one step oxidation of ethene in the presence of ionic catalyst inaqueous medium witha yield of 90%. CH, =CH, +0, > ‘Pr’ catalytic converters used to reduce the effect ofexhaust fumes from vehicles contain the coating, of metal over ceramic honey comb. Worked Out Examples W.E.1:Dissolved oxygen values of four water samples A, B, C and D are respectively 1 ppm, 3 ppm, 5 ppm and 7 ppm. Which is more polluted? Sol: Lesser the DO value, greater the extent of pollution of water. Thus, Ais the most polluted water sample. iochemical oxygen demand values offour water samples A, B, C and D are respectively 50 ppm, 100 ppm, 150 ppm and 40 ppm. Arrange them in the descending order of their purity. Sol :More the BOD value, more the extent of pollution and less the purity of water. Thus purity of water samples is in the order D>A>B>C. W.E,3:100 ml of a sample of water requires 1.96 mg of potassium dichromate in the presence of 50% H.SO, for the oxidation of dissolved organic matter in it. Calculate the chemical cute pia Gathnmenay ? CH CHO(90%) WW. oxygen demand. Sol: One gram equivalent of any oxidant can give, 6 equivalent weight of oxygen (8g) ¢ 49 K,0;0, >8g O, 1.96 K,Cr,0, >? 8x1.96 Chemical oxygen demand of the given 100 ml sample of water =922 = 3.2ppm :.4:DO value of a water sample is 6 ppm. Calculate the weight of dissolved oxygen present in 100 kg of water sample. Sol :DO value 6 ppm means, 10° g of water contains 6g of dissolved oxygen. 10° g water > 6g0, 100g (10° g Jat» tO 06g Amount of dissolved oxygen in water = 0.6 g. 5: The COD value of a water sample is 40 ppm. Calculate the amount of acidified K,Cr,0, required to oxidise the organic matter present in 500 ml of that water sample. :COD value is 40 ppm. It means 10°g of water sample require 40 g of oxygen to oxidise the organic matter Sol 500 water > aon 2x10 gofO, 500 mL water sample requires 2 x 107g of O,, to oxidise the organic matter present in it. 49x2x107 8 Amount of K,Cr,O, required to oxidise the organic ‘matter present in the water sample is 0.1225g. W.E.6: Ozone is harmful in the environment segment ‘x’ but it is useful in the environment segment ‘y’. What are x and y? Sol :'x’ is troposphere (In this ozone acts as green house gas). ° *y’is stratosphere (In this ozone absorbs harmful UV radiation) Le uvensics LEVEL-I(C.W) ronmental Segments,Definitions & Terms Environment consists of A) Atmosphere B) Hydrosphere 2x10? g of O, = g of K,Cr,0, vw V ©) Biosphere NE A&B 2)B&C 3) C&A\AFA,B,C Bhopal gas tragedy in 1984 was caused by Methyl isocyanide_ hyl isocyanate Contaminant is 1)SO, 2)COCI, 3) prgerry isocyanate (E - 2007,2011, M-2013 1)co Hie [ Vea n , fet