9.4 - Chemical Monitoring and Management

HSC Stage 6
2 Unit Chemistry
9.4 Chemical Monitoring and Management:

. Construct word and balanced formulae equations of all chemical reactions as they are encountered in this module: EQUATIONS:
Different products under different conditions: Complete combustion: propane + oxygen C3H
!g"
carbon dioxide + water 3C$2 !g" + %H2$ !g"
+ #$2 !g"
Incomplete combustion: propane + oxygen C3H

!g"
carbon + carbon monoxide + water C !s" + 2C$ !g" + %H2$ !g" ammonia + heat
+ 3$2 !g"
aber !rocess: nitrogen + hydrogen &2 !g" + 3H2 !g"
2&H3 !g"
'H ( )*2 +,-mo. barium su./ate + ch.oride
"ulfate Content in #ertili$er: barium ch.oride + su./ate 0aC.2 !a1" + S$%2) !a1"
0aS$% !s" + 2C.) !a1"
ow %$one !rotects &s #rom &' (adiation: $xygen reacts with U23 /orming 2 radica.s: $2 + U2 radiation 2$)
4adica. reacts with oxygen3 /orming o5one: $) + $2 $3
$5one reacts with U23 /orming oxygen and a radica.: $3 + U2 radiation $) + $2
4adica. reacts with o5one3 creating oxygen: $) + $3 2$2
*ll the C#C+(elated ,quations: 6ormation o/ chlorine radical:
Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
CC.262 !g" + U2 radiation 4eaction o/ ozone: =C. !g" + $3 !g"
=C. !g" + =CC.62 !g"
=C.$ !g" + $2 !g"
4egeneration o/ chlorine: =C.$ !g" + $ !g" =C. !g" + $2 !g"
4emo>a. o/ chlorine radical: =C. !g" + CH% !g" HC. !g" + =CH3 !g"
4emo>a. o/ chlorine monoxide radical: =C.$ !g" + &$2 !g" C.$&$2 !g"
6ormation o/ molecular chlorine: HC. !g" + C.$&$2 !g" C.2 !g" + H&$3 !g"
?ecomposition o/ molecular chlorine: C.2 !g" + U2 radiation 2=C. !g"
-he
ea.y+Metal "ulfide -est:
@he su./ide)test is based on the /o..owing e1ui.ibrium: S2) !a1" + 2H3$+ !a1" H2S !a1" + 2H2$ !."
HSC Stage 6
2 Unit Chemistry
/. Much of the wor0 of chemists in.ol.es monitoring the reactants and products of reactions and managing reaction conditions: Outline the role of a chemist employed in a named industry or enterprise identifyin! the "ranch of chemistry underta#en "y the chemist and explainin! the chemical principle that the chemist uses:
S<@A: Bhttp:--wwwCchemCunswCeduCau-4;C<-pro/i.esChtm.D (obert ,.ans: 4obert A>ans is an en>ironmenta. chemistC He is emp.oyed by $rica Etd3 and wor+s at 0otany <ndustria. Far+3 SydneyC ;s an en>ironmenta. chemist at an industria. .ocation3 his main ro.e ensuring the siteGs adherence to AF; !en>ironment protection authority" regu.ationsC @his Hob inc.udes: @he management o/ disposa. o/ contaminated wastes !such as neutra.ising strong.y acidic or basic wastes3 or incinerating toxic wastes"C Ansuring noise .e>e.s comp.y with AF; standards /or industryC <n>estigating reports o/ contamination in soi. or groundwater3 determining the source o/ contamination3 and then correcting the damageC Freparing periodic reports and presentationsC Chemistry: Chemica. princip.es needed /or this ro.e inc.ude: Understanding acid-base reactions !neutra.ising wastes"C Inowing >a.id chemica. samp.ing techni1uesC 2arious techni1ues o/ chemica. ana.ysis o/ samp.es3 inc.uding gra>imetric and >o.umetric ana.ysis3 as we.. as ;;SC Understanding site geo.ogy and groundwater /.ow patternsC
(ole:
Identify the need for colla"oration "et$een chemists as they collect and analyse data:
HSC Stage 6
2 Unit Chemistry
;s chemistry is such a broad /ie.d o/ +now.edge3 peop.e tend to specia.ise within a particu.ar branch3 such as polymer chemistry or analytical chemistryC Howe>er3 in rea.).i/e situations3 many chemica. prob.ems re1uire expertise and in depth +now.edge /rom a wide range o/ chemica. branchesC Hence3 co..aboration between chemists is essentia. /or so.>ing chemica. issues3 or when dea.ing with .arge amounts o/ data being co..ected3 as the chemists pro>ide input and expertise /rom their own particu.ar /ie.d3 /or a common goa.C
;s chemists o/ten wor+ in teams3 co..aboration and communication is re1uired to co..ecti>e.y bene/it the team3 as they co..ect and ana.yse in/ormationC ,1: ;n industria. process wou.d re1uire co..aboration between physica. chemists !/or e1ui.ibrium considerations"3 organic chemists !/or how the reaction occurs" and ana.ytica. chemists !/or monitoring products"C
%escri"e an example of a chemical reaction such as com"ustion $here reactants form different products under different conditions and thus $ould need monitorin!:
Combustion: Chemica. reactions can /orm di//erent products under di//erent conditionsC @a+e3 /or examp.e3 the com"ustion o/ a simp.e hydrocarbon3 propaneC <n an en>ironment with ade1uate amounts o/ oxygen3 propane combusts comp.ete.y3 /orming on.y carbon dioxide and water: propane + oxygen C3H
!g"
carbon dioxide + water 3C$2 !g" + %H2$ !g"
+ #$2 !g"
<n an en>ironment with insu//icient oxygen3 propane combusts incomp.ete.y3 and can /orm a range o/ di//erent products3 such as carbon !soot"3 carbon monoxide3 carbon dioxide and waterC propane + oxygen C3H
!g"
carbon + carbon monoxide + water C !s" + 2C$ !g" + %H2$ !g"
+ 3$2 !g"
Monitoring: Hence3 under di//erent conditions3 chemica. reactions can proceed in di//erent ways3 as seen by the combustion reaction abo>eC Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
Howe>er3 in certain situations !such as in car engines"3 on.y one reaction is desiredC @hus3 the reaction conditions must be monitored to ensure that on.y !or most.y" the wanted reaction occursC
&ather process and present information from secondary sources a"out the $or# of practisin! scientists identifyin!:' the (ariety of chemical occupations: a specific chemical occupation for a more detailed study:
@HA 2;4<A@J $6 CHAK<C;E $CCUF;@<$&S: @he .arge ran!e o/ Hobs a>ai.ab.e in the chemical industry inc.udes: ;na.ytica. chemistryC 0io)mo.ecu.ar chemistryC Co..oid and sur/ace science chemistryC An>ironmenta. chemistryC <ndustria. chemistryC <norganic chemistryC A.ectrochemistryC $rganic chemistryC Fhysica. chemistryC Fo.ymer chemistry C ; SFAC<6<C CHAK<C;E $CCUF;@<$&: ; summary o/ the Hob o/ an en.ironmental chemist: )o" includes re(ie$in! operation of effluent $ater treatment systems and ensurin! compliance $ith !o(ernment en(ironmental re!ulations* +e(ie$in! industry,s compliance $ith !o(ernment en(ironmental noise standards* Assessin! le(els of potential contamination in $astes -e*!* soil. intended for landfill disposal and classifyin! them in accordance $ith !o(ernment !uidelines* /ana!in! disposal of contaminated $astes* In(esti!atin! reports of contamination in soil or !round$ater to determine source and then arran!in! to correct it* %eterminin! $hether
HSC Stage 6
2 Unit Chemistry !as stac# emissions contain unaccepta"le le(els of re!ulated materials* Ad(isin! en!ineers0mana!ers of correcti(e actions needed if any of the a"o(e parameters sho$ faults in systems* Ans$erin! pu"lic or professional performance* en1uiries or complaints re!ardin! en(ironmental
HSC Stage 6
2 Unit Chemistry
2. Chemical processes in industry require monitoring and management to ma3imise production: Identify and descri"e the industrial uses of ammonia:
*mmonia !&H3" is a gas with a strong odour: it has many industria. usesC <t is used to ma+e: So.id and .i1uid /erti.isers !through a reaction with su./uric acid or nitric acid to /orm ammonium su./ate /erti.iser and ammonium nitrate /erti.iser"C &itric acid !through the Ost$ald 2rocess"C Axp.osi>es3 sodium carbonate3 pharmaceutica.s3 househo.d c.eaners3 /ibres and p.astics3 as we.. as re/rigerantsC
Identify that ammonia can "e synthesized from its component !ases nitro!en and hydro!en:
6rom its mo.ecu.ar /ormu.a !&H3" we can see that ammonia is composed o/ nitrogen and hydrogen atomsC Hence3 theoretica..y3 ammonia shou.d be ab.e to be synthesised /rom these gasesC
%escri"e that synthesis of ammonia occurs as a re(ersi"le reaction that $ill reach e1uili"rium:
@he industria. production o/ ammonia is ca..ed the H;0A4 F4$CASSC @he basic chemica. reaction o/ this process is the reaction o/ gaseous hydrogen and nitrogen to /orm ammonia: nitrogen + hydrogen &2 !g" + 3H2 !g" ammonia 2&H3 !g"
6rom the chemica. reaction3 we can see that it is c.ear.y a re>ersib.e reaction3 and hence it does &$@ go to comp.etion3 but reaches a point o/ equilibriumC
Identify the reaction of hydro!en $ith nitro!en as exothermic:

@he reaction o/ hydrogen with nitrogen !3a"er 2rocess" can be represented as: &2 !g" + 3H2 !g" 2&H3 !g" 'H ( )*2 +,-mo. 6rom the chemica. e1uation3 we can see that 'H is .ess that 5ero3 and hence the reaction is an exothermic reactionC
HSC Stage 6
2 Unit Chemistry
Explain $hy the rate of reaction is increased "y hi!her temperatures:

RECALL: 0e/ore any chemica. reactions can occur3 there must be an energy inputC @he acti(ation ener!y o/ a reaction describes the minimum amount o/ energy input necessary /or that reaction to occurC @he rate of reaction is a term used to describe how 6;S@ a reaction occursC @here are 2 reasons why higher temperatures resu.t in a higher rate o/ reaction: ;s temperature is increased3 energy is de.i>ered into the reaction as thermal ener!yC @his therma. energy is con>erted into #inetic ener!y3 and partic.es begin to mo>e /asterC @his causes more co..isions between partic.es3 and hence more reactions occurC ;.so3 i/ the temperature is higher3 there is more chance that co..iding partic.es wi.. ha>e the necessary acti(ation ener!y /or the reaction to ta+e p.aceC 6or the Haber Frocess !and a.. re>ersib.e reactions in genera."3 at higher temperatures3 the rate o/ reaction o/ both the for$ard and re(erse reactions are increased3 and hence e1ui.ibrium is reached /asterC
Explain that the use of a catalyst $ill lo$er the reaction temperature re1uired and identify the catalyst-s. used in the 3a"er process:
; catalyst is a substance that increases the rate o/ reaction o/ a chemica. reaction3 but does not itse./ ta+e part in the reactionC Cata.ysts wor+ by reducing the acti>ation energy o/ reactionsC 6or the Haber Frocess3 the cata.yst used is iron oxide !ma!netite: 6e3$%"C @he cata.yst is /ine.y ground3 to produce a .arge sur/ace area3 and has its sur/ace part.y reduced to e.ementa. ironC
Explain $hy the yield of product in the 3a"er process is reduced at hi!her temperatures usin! 4e Chatelier,s principle:
<n terms o/ industria. re>ersib.e reactions3 the term Lyield o/ productG describes how much product is /ormed at the point o/ e1uili"rium: <t has nothing to do with 4;@A o/ reactionC
HSC Stage 6
2 Unit Chemistry
Since we +now the Haber Frocess is an exothermic reaction3 we can predict the e//ects o/ higher temperatures using Ee Chate.ierGs princip.e: </ an increase in temperature is imposed onto the LsystemG !the reaction" then the LsystemG wi.. shi/t itse./ to counteract this imposed changeC Since the LsystemG wi.. want to cool itse./3 to oppose the heating3 the reaction that is endothermic wi.. be encouragedC @he /orward reaction is exothermic3 hence the re>erse reaction is endothermicC @hus3 at higher temperatures3 the re>erse reaction occurs more 0ut this produces reactants3 not products: thus the yie.d o/ products reducesC
Analyse the impact of increased pressure on the system in(ol(ed in the 3a"er process:
;ccording to Ee Chate.ierGs princip.e3 increasing the pressure wi.. /a>our the side that wi.. reduce the pressure !iCeC has EASS mo.es o/ gas"C <n this reaction3 there are .ess mo.es o/ gas on the product side ! !as ratio is %:2" and hence increasing the pressure wi.. encourage the /orward reactionC <n addition3 higher pressures a.so increase the reaction rate because the gas mo.ecu.es are c.oser and at higher concentrationsC
Explain $hy the 3a"er process is "ased on a delicate "alancin! act in(ol(in! reaction ener!y reaction rate and e1uili"rium:
<n order /or the Haber Frocess to be economica..y >iab.e3 we need to consider yie.d o/ products3 rate o/ reaction3 as we.. as costsC Hence3 a compromise !L"alancin! actG" o/ a.. the abo>e must be made: -emperature: Higher temperatures wi.. produce ammonia faster3 but .ower temperatures wi.. produce more ammoniaC Hence a moderate temperature o/ about #88MC is used3 together with the iron-iron)oxide cata.ystC !ressure: <ncreased pressure wi.. produce more ammonia3 a.so faster3 but it wi.. be expensi>e to bui.d and maintain high)pressure e1uipmentC @he bene/its o/ high pressure outweigh the costs3 and so a pressure o/ 3# KFa is usedC AN@4;: ;nother step ta+en to encourage the economic /ormation o/ products is the continuous .i1ue/action and remo>a. o/ ammonia as it is producedC Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry @his reduces the concentration o/ ammonia3 and hence encourages the /orward reaction3 according to Ee Chate.ierGs princip.eC
Explain $hy monitorin! of the reaction (essel used in the 3a"er process is crucial and discuss the monitorin! re1uired:
Monitoring of (eaction Conditions: @AKFA4;@U4A: the temperature o/ the >esse. must be monitored so that it is +ept within an acceptab.e range !O#88MC"C @his is due to the yie.d and rate considerations3 as abo>eC ;.so3 at excessi>e.y high temperatures3 the iron cata.yst wi.. me.t3 and wi.. be destroyedC F4ASSU4A: the pressure o/ the >esse. must be monitored /or yie.d and rate considerations3 as stated abo>eC ;.so3 i/ pressures read excessi>e.y high .e>e.s3 it wi.. become extreme.y dangerous3 and an exp.osion may occurC Monitoring of (eactants: 4;@<$ o/ 4A;C@;&@S: the ratio o/ the incoming gases has to be monitored so that it is maintained at a constant P:3 !&2 to H2"C @his is because a bui.d)up o/ any gas must be a>oided3 as this may dangerous.y increase the pressureC C$&@;K<&;&@S: the concentration o/ contaminants must be monitored /or >arious reasonsC $2 must be comp.ete.y remo>ed3 as it introduces the ris+ o/ an exp.osi>e reaction with H2C C$3 C$2 and su./ur compounds must be at >ery .ow .e>e.s3 as they a.. poison the cata.ystC Ee>e.s o/ argon and methane must a.so be +ept at .ow concentrations as they .ower the e//iciency o/ the reactionC
&ather and process information from secondary sources to descri"e the conditions under $hich 3a"er de(eloped the industrial synthesis of ammonia and e(aluate its si!nificance at that time in $orld history:
0e/ore the in>ention o/ the industria. Haber Frocess in P*P%3 the g.oba. source o/ nitrates !/or /erti.isers and exp.osi>es" came /rom saltpetre /rom South ;mericaC ?uring QQ<3 RermanyGs supp.ies o/ nitrogen compounds was cut o//: this threatened to cause widespread star>ation3 as we.. as cause Rermany to rapid.y .ose the war !they re.ied on sa.tpetre to ma+e exp.osi>es"C
HSC Stage 6
2 Unit Chemistry
Howe>er3 with the in>ention o/ the Haber Frocess3 Rermany !and .ater the rest o/ the wor.d" had a cheap source o/ nitrates /rom e.ementa. nitrogen and hydrogenC @hus3 the signi/icance o/ this was that it great.y .engthened the QarC
HSC Stage 6
2 Unit Chemistry
4. Manufacture products5 including food5 drugs and household chemicals5 are analysed to determine or ensure their chemical composition: %educe the ions present in a sample from the results of tests:
<ons that are being tested: Cations: 0a2+3 Ca2+3 Fb2+3 Cu2+3 6e2+ and 6e3+ *nions: F$%3)3 S$%2)3 C$32) and C.)
Qhen !i(en a /.owchart3 it is >ery easy to deduce the ion!s" presentC Howe>er3 you need to memorise the tests /or the abo>e ionsC Qe use precipitation reactions to identi/y ions in so.utionC @here are 2 situations possib.e: when there is on.y one ion present in a samp.e3 or when there is a mixture o/ ions in a samp.eC C;@<$&S !when on.y one ion is present": @o determine the ion present3 HC.3 H 2S$% and &a$H is added in that order3 and the /ormation o/ a precipitate wou.d indicate which ion it is:
6irst.y3
Cl !C.) ions" is added to the samp.eC </ a white precipitate /orms3
then the un+nown ion is EA;? !Fb2+": the precipitate is .ead ch.oride !FbC.2"C @o (erify3 add a /ew drops o/ potassium iodide !I<" to a /resh samp.eC Fb 2+ ions /orm a >ibrant ye..ow precipitate with iodide !<)" ionsC &ext3
2
"%4 !S$%2) ions" is added to a 64ASH S;KFEAC </ a precipitate
/orms3 the un+nown ion is either ca.cium !Ca2+" or barium !0a2+":
HSC Stage 6
2 Unit Chemistry
@o distinguish the two ions3 add a /ew drops o/ sodium /.uoride !&a6" to a new samp.eC Ca2+ /orms a precipitate with /.uoride !6)"3 but 0a2+ does notC East.y3 6a% !/or $H) ions" is added to a /resh samp.eC </ a precipitate /orms3 the ion is either copper !Cu2+"3 iron!<<" !6e2+" or iron!<<<" !6e3+": </ the precipitate is b.ue then the ion is Cu2+C @o /urther >eri/y that it is copper3 disso.>e the precipitate in ammonia !&H 3"3 and i/ it is Cu!$H"2 it wi.. /orm a deep)b.ue so.utionC </ the precipitate is &$@ b.ue3 then the ion is either 6e 2+ or 6e3+C Using a /resh samp.e3 add: ; /ew drops o/ potassium thiocyanate !ISC&" so.utionC 6e3+ reacts with thiocyanate ions !SC&)" to /orm a "lood red precipitateC ; /ew drops o/ FU4FEA potassium permanganate !IKn$%" so.utionC 6e2+ deco.ourises the permanganate ion !Kn$%)"3 changing the so.ution /rom purp.e to co.our.essC C;@<$&S !when there is a mi3ture o/ ions": Qhen there is a mixture o/ ions3 there is the ris+ that the test /or one ion wi.. inter/ere with the test /or another ionC $nce a precipitate is /ormed3 the reagent is added unti. no more precipitate wi.. /orm !this is to remo>e a.. traces o/ a speci/ic cation"C @he mixture is then /i.tered or centri/uged to remo>e the precipitate3 and then /urther tests are per/ormed on the remaining so.utionC @he procedure /or identi/ying ions in a mixture: /. 2. ;dd Cl so.ution: i/ a precipitate /orms3 Fb2+ is present in the mixtureC Ieep adding HC. unti. no more precipitate /orms3 then /i.terC ?i>ide the /i.trate into 2 portions: ;dd 6a# to one portion: precipitate indicates the presence o/ Ca2+C ;dd
2
"%4 to the other portion: i/ a precipitate /orms3 0a 2+ or Ca2+
ions are present in the mixtureC Comp.ete.y precipitate out a.. the barium and ca.cium ions3 then /i.terC
HSC Stage 6 4. ;dd 6a%
2 Unit Chemistry so.ution: i/ there is a precipitate3 mix &H 3 into the so.ution
and /i.terC ; presence o/ any b.ue precipitate indicates Cu2+3 whi.e any green or brown precipitate indicates iron ions !to distinguish iron!<<" and iron !<<<"3 use thiocyanate and permanganate tests on new samp.es"C ;&<$&S !when on.y one ion is present": Carbonate !C$32)": ;dd di.ute nitric acid !H&$3": i/ bubb.es o/ a co.our.ess gas /orm !that when passed through .imewater turns it c.oudy" carbonate is presentC </ the so.ution has a pH o/ )PP then carbonate is .i+e.y presentC "ulfate !S$%2)": </ the addition o/ 0a!&$3"2 !barium nitrate" in to an acidi/ied samp.e produces a thic+ white precipitate3 then su./ate is present: ;cidi/y so.utions using di.ute nitric acid !does not /orm precipitates"C </ acidi/ication and addition o/ Fb!&$3"2 !.ead nitrate" produces a white precipitate3 then su./ate is presentC !hosphate !F$%3)": </ the addition o/ 0a!&$3"2 !barium nitrate" to an ;EI;E<&A samp.e produces a white precipitate3 phosphate is presentC Use ammonia !&H3" to ma+e so.utions basicC </ acidi/ication /o..owed by the addition o/ !&H%"Ko$% !ammonium mo.ybdate" so.ution produces a ye..ow precipitate3 phosphate is presentC Chloride !C.)": </ the addition o/ ;g&$3 !si.>er nitrate" to an acidi/ied samp.e produces a white precipitate that disso.>es in ammonia so.ution and dar+ens in sun.ight3 then ch.oride is presentC ;&<$&S !when there is a mi3ture o/ ions present": ;gain3 care must be ta+en not to cause inter/erence between tests: @he procedure: /. ;dd nitric acid: any bubb.ing indicates the presence o/ carbonateC Ieep adding acid unti. a.. bubb.ing stopsC Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6 2. 4. 4.
2 Unit Chemistry ;cidi/y so.ution with more nitric acidC ;dd 0a2+ !through barium nitrate"C </ a precipitate /orms3 su./ate is presentC 6i.ter so.utionC Ka+e the /i.trate a.+a.ine by adding ammoniaC ;dd more 0a2+ ionsC </ a precipitate /orms3 phosphate is presentC 6i.ter so.utionC ;cidi/y so.ution again and add ;g+ ions: precipitate indicates C.) ionsC
%escri"e the use of atomic a"sorption spectroscopy -AAS. in detectin! concentrations of metal ions in solutions and assess its impact on scientific understandin! of trace elements:
**" !;tomic ;bsorption Spectroscopy": ;;S is a method o/ 1uantitati>e.y determining the concentrations o/ meta. ions in so.utions: it is extreme.y sensiti>e and measures to parts)per)mi..ionC <t was de>e.oped by an ;ustra.ian scientist3 ;.an Qa.sh3 and his CS<4$ team in the ear.y P*#8sC ow **" 7or0s:
HSC Stage 6
2 Unit Chemistry
6irst.y3 a so.ution o/ a test samp.e being ana.ysed is /ed into a nebu.i5er !a.so ca..ed an atomiser" where the .i1uid so.ution is made into a spray or mistC @he mist is then mixed with a /ue. and its oxidant !usua..y a mixture o/ oxygen and acety.ene"C @he mixture is combusted into a /.ame: this /.ame gi>es compounds3 mo.ecu.es and ions the energy to become ;@$KSC @hen3 depending on the e.ement being tested /or3 a speci/ic ho..ow)cathode .amp is used !/or examp.e3 i/ coba.t is being tested /or3 a coba.t .amp is used3 where the cathode in the .amp is coba.t meta."C Qhen current is passed into the .amp3 it produces .ight in a spectrum speci/ic to the e.ement !iCeC the e.ementGs emission spectrum"C Qhen this .ight is passed through the /.ame3 the atoms absorb this emission spectrum3 as they are the same e.ement as the cathode in the .amp !there is an exact match o/ emission and absorbance wa>e.engths"C @he atoms in the /.ame absorb the .ight in speci/ic wa>e.engths3 and then this LchangedG .ight is passed into the monochromatorC @his de>ice then se.ects that speci/ic wa>e.ength!s" which are absorbed3 and compares it to a reading without the /.ame-atoms3 and determines a reading ca..ed absorbanceC ;bsorbance is proportiona. to concentration3 and hence the un+nown concentration o/ the e.ement can be determined: L;bsorbanceG is a arbitrary unit3 so the ;;S de>ice must be ca.ibrated using standard solutions !so.utions o/ an e.ement o/ +nown concentration"C
&ses of **": Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
<t is used to monitor concentrations o/ hea>y)meta.s in the en>ironment as we.. as in /ood3 /or hea.th and sa/ety reasonsC ;;S is used as e>en at .ow concentrations3 these meta.s are >ery dangerousC <t is used to measure concentrations o/ micronutrients in soi.sC Used to measure .e>e.s o/ po..utants in water3 soi. and airC <t can determine the concentration o/ trace elements in .i>ing things and hence determine the cause o/ de/iciency)re.ated diseasesC
-he 8mpact of **" %n &nderstanding of -race ,lements: Trace elements are e.ements that are re1uired in .i>ing things in >ery sma.. amounts !in the range o/ P)P88 ppm"C @race e.ements are needed in minute 1uantities /or the proper growth3 de>e.opment3 and physio.ogy o/ organismsC 6or examp.e3 common trace e.ements in humans are 5inc3 coba.t3 copper3 nic+e.3 mo.ybdenum3 iodine and se.eniumC 0e/ore the in>ention o/ ;;S3 ana.ytica. methods were not sensiti>e enough to measure the concentration o/ trace e.ements in organic samp.esC @he presence o/ these e.ements were o/ten unnoticed3 and the causes o/ diseases re.ating to trace)e.ement de/iciency !such as goitre: iodine de/iciency" were un+nownC ;;S showed that not on.y that there were trace amounts o/ e.ements in a.. organisms3 but that these were a.so essentia. /or their we..)beingC Hence3 ;;S had a great impact on the understanding o/ trace e.ements: Axamp.es o/ ;;S use re.ated to trace e.ements: <n coasta. SQ ;ustra.ia3 anima. hea.th was >ery poor e>en though they were gra5ed on seeming.y good pastureC ;;S showed that there were coba.t de/iciencies in the soi. and the pasture3 and this was correctedC ;rid areas o/ 2ictoria cou.d not support .egume crops unti. mo.ybdenum de/iciencies were detected and recti/iedC
HSC Stage 6
2 Unit Chemistry
&ather process and present information to interpret secondary data from AAS measurements and e(aluate the effecti(eness of this in pollution control:
;;S is an extreme.y e//ecti>e too. in po..ution monitoring and managementC <t can be used to measure .e>e.s o/ po..utants in the soi.s3 /ood3 water and has many other app.ications in re.ation to po..ution contro.C ,1: ;;S was used in 0ang.adesh to monitor .e>e.s o/ arsenic in drin+ing waterC ;rsenic is a serious po..utant as it is extreme.y toxicC @he /o..owing ;;S absorbance data was obtained by using standard so.utions o/ arsenic o/ +nown concentration: -otal *rsenic Concentration #8 Sg-E P88 Sg-E P#8 Sg-E @his data was then graphed on a cali"ration cur(e: *bsorbance 8CP2 8C23 8C3#
Samp.es o/ drin+ing water were ta+en their absorbances were measured: "ample Copyright 7 2889: ;hmad Shah <di. *bsorbance
HSC Stage 6
2 Unit Chemistry
P 2 3 concentrations were estimated: Samp.e P !P2% ppb" Samp.e 2 !6P ppb" Samp.e 3 !P63 ppb"
8C2 8CP3 8C3P
@hese absorbances were then p.otted on the graph3 and /rom there the arsenic
;rsenic .e>e.s higher than P88 ppb were considered po..utedC Hence3 ;;S is a >ery e//ecti>e too. in po..ution monitoring and contro.C
&ather process and present information to descri"e and explain e(idence for the need to monitor le(els of specific ions in su"stances used in society:
9ead: Eead needs to be monitored because it is a se>ere neurotoxinC <t retards inte..ectua. de>e.opment in young chi.dren3 causes brain damage and can .ead to neuro.ogica. disordersC Unti. recent.y3 .ead was wide.y used as an additi>e in petro.: it was re.eased in great 1uantities to the atmosphere in >ehic.e exhausts and deposited in the en>ironment near highwaysC Eead a.so used to be /ound in many paints3 as these were o/ten .ead)based pigments: this .ead was re.eased into waterways3 the soi. and air when o.d houses were demo.ishedC Konitoring o/ .ead concentrations o/ soi. near highways3 in water and in the atmosphere is essentia. to ensure that peop.e are not exposed to harm/u. .e>e.s o/ toxic .ead ionsC !hosphate: Fhosphate occurs in natura. waterways at .ow concentrations and is essentia. /or norma. a1uatic p.ant growthC
HSC Stage 6
2 Unit Chemistry
Howe>er3 i/ phosphate .e>e.s become too high3 it cou.d set o// and a.ga. b.oom: this wi.. Lcho+eG the entire waterway3 as the waterway wi.. be comp.ete.y surrounded by a.gae and drained o/ oxygenC @his has many detrimenta. e//ects on the ecosystem .i>ing in the waterC Hence3 by monitoring the .e>e.s o/ phosphates in waterways and in consumer goods that reach waterways !eCgC detergents"3 scientists can guard against the de>e.opment o/ a.ga. b.oomsC
PRACTICAL 5 2erform first'hand in(esti!ations to carry out a ran!e of tests includin! flame tests to identify the follo$in! ions:' Cations: 6arium calcium lead copper and iron:
Anions: 2hosphate sulfate car"onate and chloride: <n this practica.3 students were gi>en >ia.s o/ un+nown so.utions: >ia.s were .abe..ed as Lmixtures o/ ionsG or Lon.y one ionGC Using both precipitation and /.ame tests3 the contents o/ the >ia.s were determinedC !recipitation -ests: F.ease see ;0$2A /or a >ery in)depth co>erage o/ precipitation tests used to determine anions and cations present in a samp.eC #lame -ests: 6.ame tests were on.y used to identi/y cationsC ;nions cannot be identi/ied by /.ame testsC $ut o/ the gi>en .ist o/ cations3 on.y "arium3 calcium3 and copper produce a distincti>e /.ame co.our when sprayed into a /.ame: 0a2+ gi>es a pale'!reen /.ameC Ca2+ gi>es a "ric#'red /.ameC Cu2+ gi>es a "lue'!reen /.ameC
PRACTICAL 5 Identify data plan and select e1uipment and perform first' hand in(esti!ations to measure the sulfate content of la$n fertiliser and explain the chemistry in(ol(ed:
HSC Stage 6
2 Unit Chemistry
<n this practica.3 the su./ate content o/ a .awn /erti.iser was ca.cu.atedC @his is an examp.e o/ gra.imetric analysis: it is a 1uantitati>e ana.ysisC KA@H$?: <n a dry bea+er3 # grams !T8C8PU" o/ /erti.i5er was e.ectronica..y weighedC ;.. the /erti.i5er was care/u..y trans/erred to a mortar and pest.e3 where it was ground into a /ine powderC @he powder was trans/erred into a bea+er: using a wash bott.e with disti..ed water3 a.. the residue was washed into the bea+er up to the 288 mE mar+C #8 mE o/ 8CP K hydroch.oric acid was added3 and the mixture stirred unti. a.. o/ the /erti.i5er disso.>edC @he mixture was then heated to its boi.ing point: the /.ame was turned o//3 and barium ch.oride was added in drops3 which /ormed a precipitate: 0aC.2 !a1" + S$%2) !a1" 0aS$% !s" + 2C.) !a1"
0arium ch.oride was added unti. no more precipitate /ormedC @he mixture was di!ested !heated Hust be.ow boi.ing point" /or 38 minutes3 stirring e>ery now and then3 and then the precipitate was a..owed to sett.eC @he bea+er and its contents was then coo.ed in an ice)bathC Using a sintered)g.ass crucib.e !which had its mass recorded"3 connected to a >acuum pump3 the mixture was /i.teredC @he crucib.e was washed with water3 and then ethano.3 and then dried in an o>en to a constant massC @he di//erence between the crucib.eGs origina. weight and weight a/ter drying !which was the mass o/ 0aS$%" was /ound to be #C*2 gC
C;ECUE;@<&R SUE6;@A C$&@A&@: mass o/ 0aS$% /ormed ( #C*2 g percenta!e o/ su./ate in 0aS$% ( mo.ar mass su./ate - mo.ar mass 0aS$% ( !32CP + %VP6C8" - !P39C3 + 32CP + %VP6C8" ( %PC2 U mass o/ su./ate in 0aS$% ( #C*2 V %PC2 U ( 2C%% g
HSC Stage 6 percenta!e o/ su./ate in /erti.i5er P88 ( 2C%% - #C8 V P88 ( % C* U
2 Unit Chemistry ( mass o/ S$% - mass o/ /erti.i5er V
Analyse information to e(aluate the relia"ility of the results of the a"o(e in(esti!ation and to propose solutions to pro"lems encountered in the procedure:
4AE<;0<E<@J: @he use o/ a >ery precise e.ectronic sca.e ensured accurate measurementC @he /erti.i5er was ground into a powder to ensure that a.. o/ it disso.>ed: i/ some su./ate stayed in so.id /orm3 the measurements wou.d be inaccurateC @he washing o/ the mortar and pest.e into the bea+er was to ensure a.. o/ the /erti.iser was trans/erred into the bea+erC Hydroch.oric acid was added to aid in the disso.>ing o/ the /erti.iserC Slo$ly /orming precipitates !using a dropper" at a hi!h temperature ensures the /ormation o/ .arge partic.esC ;.so3 the mixture was digested /or ha./ an hour to a..ow the partic.es to growC Earge partic.e si5e meant /ewer .oses o/ 0aS$% through the /i.terC @he mixture was coo.ed in ice)water to great.y reduce the so.ubi.ity o/ 0aS$ % to ensure that >irtua..y a.. o/ the su./ate precipitated outC ; sintered)g.ass crucib.e was used instead a /i.ter)paper as /i.ter paper pores are too .arge: they a..ow an unacceptab.e .e>e. o/ 0aS$% throughC @he washing with water and ethano. remo>ed any traces o/ contaminantsC Human errors in measurement were the main source o/ inaccuracies: more care/u. measurement o/ /erti.i5er mass3 wou.d ensure better resu.tsC @here were sma.. .osses o/ barium su./ate due to its >ery sma.. so.ubi.ityC @his was why the bea+er was coo.ed in ice)water be/ore /i.tering !so.ubi.ity decreases at .ow temperatures"C Howe>er3 due to time constraints3 coo.ing did not occur to a great extentC Copyright 7 2889: ;hmad Shah <di. S$EU@<$&S to !roblems ,ncountered:
HSC Stage 6
2 Unit Chemistry
Eonger digestion times wou.d a..ow .arger partic.es to /orm3 and .ess .oss o/ barium su./ate through the /i.ter wou.d occurC @here was possib.y some barium su./ate .e/t on the bea+er wa..s be/ore /i.tering: this wou.d be so.>ed by washing out the bea+er with disti..ed waterC ;n incomp.ete drying o/ the sintered g.ass crucib.e !due to moist en>ironment3 as we.. as time constraints" wou.d be so.>ed by a .onger period o/ heating3 as we.. as by using a dessicatorC
HSC Stage 6
2 Unit Chemistry
4.
uman acti.ity has caused changes in the composition and structure of the atmosphere. Chemists monitor these changes so that further damage can be limited:
%escri"e the composition and layered structure of the atmosphere:

@he atmosphere is a .ayer o/ gas3 288)388 +m thic+3 that surrounds the AarthC C$KF$S<@<$&: @he atmosphereGs main composition o/ gases is: 9 U nitro!enC 2PU oxy!enC 8C*U ar!onC $ther gases that ma+e up an extreme.y sma.. percentage o/ the atmosphere are car"on dioxide3 oxides o/ nitro!en !&$x"3 sulfur compounds !S$2 and H2S"3 car"on monoxide3 neon3 helium3 hydro!en3 ammonia3 ozone !$3" and >o.ati.e organic compounds3 such as methaneC @he atmospheric .e>e.s o/ these .ess abundant gases is measured in the unit ca..ed LppmG !parts per mi..ion"C @he .e>e.s o/ $ater (apour in the atmosphere >aries great.y according to weather3 .ocation3 and other /actors3 and hence is o/ten disregardedC S@4UC@U4A: @he atmosphere is di>ided into .ayers3 each with its own characteristicsC @he /irst .ayer is the troposphere3 /o..owed by the stratosphere3 then the mesosphere3 thermosphere3 ionosphere and then /ina..y the exosphereC 6or this course3 we wi.. /ocus our atmospheric study on the troposphere !ca..ed the L.ower atmosphereG" and the stratosphereC -roposphere: Axtends up /rom the sur/ace o/ the Aarth3 to P# +m highC ;t about P# +m high is the tropopause: it mar+s the end o/ the troposphere3 and is the beginning o/ the stratosphereC @he troposphere is the region where LweatherG is experiencedC
HSC Stage 6
2 Unit Chemistry
Temperature 2rofile: @emperature decreases as a.titude increases !as you go up"C "tratosphere: Axtends /rom P# +m !the tropopause" to #8 +mC ;t about #8 +m high is the stratopause3 where the mesosphere beginsC @he stratosphere has no LweatherGC @he ozone layer is in the stratosphereC Temperature 2rofile: @emperature increase as a.titude increasesC
Identify the main pollutants found in the lo$er atmosphere and their sources:
F$EEU@;@;&@S: Carbon mono3ide: 6rom motor cars3 bush /ires3 cigarettes3 gas sto>e)topsC %3ides of nitrogen !&$ + &$2": 6rom >ehic.es and power stationsC "ulfur dio3ide: combustion and meta. extraction !/rom su./ide ores"C ydrocarbons: 6rom >ehic.es and industria. so.>entsC '%Cs !(olatile or!anic compounds": industria. p.ants3 domestic so.>entsC !articulates !soot as"estos etc*": combustion3 mining3 bush/iresC *irborne lead: .ead sme.ters and .ead)based paint /rom o.d housesC Hot air rises and co.d air /a..sC 6or the troposphere3 its bottom is warmer than its top !because temperature decreases as a.titude increases": hence3 the air /rom the bottom is a.ways rising to the topC @hat is3 there is constant mixing o/ gases !con(ection"C @his means that po..utants re.eased at the AarthGs sur/ace by human acti>ity are rapid.y dispersed throughout the stratosphereC @his is what causes the .ower atmosphere to be so rapid.y po..utedC
R;S K<N<&R:
HSC Stage 6
2 Unit Chemistry
6or the stratosphere3 its bottom is co.der than its top !because temperature increases as a.titude increases": hence3 there is .itt.e mo>ement o/ gasesC @he co.d air at the bottom and hot air at the top simp.y stays thereC @his LprotectsG the stratosphere /rom po..utants re.eased at the sur/ace3 as gas mixing stops at the tropopauseC @he on.y way po..utants enter the stratosphere is by s.ow diffusion o/ gasesC
%escri"e the formation of a coordinate co(alent "ond:

RECALL: @he (alence shell is the outermost e.ectron she.. o/ an atomC Chemica. reactions occur because o/ the acti>ity o/ >a.ence e.ectrons: /or examp.e3 i/ >a.ence e.ectrons are trans/erred /rom one atom to another3 this is a chemica. reaction resu.ting in the /ormation o/ an ionic "ondC @o achie>e chemical sta"ility3 a.. atoms see+ to ha>e an octet ! " o/ e.ectrons in their >a.ence !outermost" she..sC <n a norma. co>a.ent bond3 two atoms SH;4A e.ectrons in order /or both to ha>e a comp.ete she.. o/ eight e.ectrons: ,1: 2 oxygen atoms can share e.ectrons to /orm a co>a.ent bond and ma+e an oxygen mo.ecu.e !$2"C &otice that each oxygen contributes 2 e.ectrons to the co>a.ent bond !the Lbubb.eG":
-8! ) @o count the e.ectrons that be.ong to an atom3 count 0$@H e.ectrons in bonds !a.. o/ them"3 as we.. as the e.ectrons not in bondsC 6or examp.e3 the .e/t oxygen atom in the $ 2 mo.ecu.e as % e.ectrons not in a bond3 as we.. as % e.ectrons in a bondC Hence it has a tota. o/ which ma+es it a stab.e atomC e.ectrons3
Howe>er3 in a coordinate co>a.ent bond between two atoms3 one atom wi.. donate a pair o/ e.ectrons to the other to /orm a bond3 so both can ha>e an octet: 6urther exp.ained in the next dot)pointC
HSC Stage 6
2 Unit Chemistry
%emonstrate the formation of coordinate co(alent "onds usin! 4e$is electron'dot structures:
RECALL: <n EAQ<S e.ectron)dot structures3 atoms are represented by their chemica. symbo.3 surrounded by on.y (alence e.ectrons: eCgC oxygen wi.. be represented as an L$G surrounded by 6 e.ectrons !see ;0$2A"C Use di//erent symbo.s /or the e.ectrons o/ di//erent atoms !eCgC crosses-dots"C ; coordinate'co(alent bond in>o.>es one atom donating a pair o/ e.ectrons to the other to /orm a bond3 so both can ha>e an octet: a.. the e.ectrons in the bond come /rom one atom: ,1: <n the $W$&A !$3" mo.ecu.e3 one o/ the oxygen atoms /orms a coordinate co>a.ent bond with an oxygen atom:
-8! Qhen as+ed to draw a Eewis diagram o/ o5one3 chec+ that a.. oxygen atoms ha>e on.y 6 e.ectrons o/ their own3 but e.ectrons bonded a.together: Ee/t: % unbonded e.ectrons + % e.ectrons in co>a.ent bond ( Kidd.e: 2 unbonded + % in co>a.ent bond + 2 in coordinate co>a.ent ( 4ight: 6 unbonded + 2 in coordinate co>a.ent (
Compare the properties of the oxy!en allotropes O 7 and O8 and accounts for them on the "asis of molecular structure and "ondin!:
RECALL: Allotropes are di//erent structura. /orms o/ the same e.ementC 6or examp.e3 a..otropes o/ carbon are graphite and diamondC ;..otropes can exhibit >ery di//erent physica. ;&? chemica. propertiesC
$xygen has 2 stab.e a..otropes: oxygen gas !$2" and o5one gas !$3"C @hese two a..otropes exhibit di//erent many di//erent properties3 and these can be exp.ained in terms o/ mo.ecu.ar structure and bonding: Colour: $2 is co.our.ess3 whi.e $3 is a pa.e b.ue gas:
HSC Stage 6
2 Unit Chemistry
&o exp.anation a>ai.ab.eC :oiling !oint: @he boi.ing point o/ $ 2 is P 3XC3 whi.e $3 has one o/ PPPXC: @he boi.ing point o/ $2 is .ower than that o/ o5one as $2 has a .ower mo.ecu.ar mass3 hence re1uiring .ess energy in the boi.ing processC "olubility in 7ater: $2 has >ery .ow so.ubi.ity in water compared to $3: &on)po.ar $2 does not /orm strong intermo.ecu.ar /orces in the po.ar waterC $5one has a bent structure3 which creates a s.ight po.arity in the mo.ecu.e3 a..owing it to ha>e intermo.ecu.ar interactions with waterC Chemical "tability: $5one is much .ess stab.e than $2: @o decompose oxygen3 its doub.e bond has to be bro+en: this re1uires considerab.e amounts o/ energyC Howe>er3 the sing.e bond !coordinate co>a.ent bond" in o5one re1uires much .ess energy to be bro+en3 and hence o5one is much .ess stab.e !readi.y decomposes to $2"C %3idising "trength: $2 is a moderate.y strong oxidising agent3 whi.e $3 is an extreme.y strong oxidising agent: @he oxidising strength o/ o5one comes /rom the wea+ness o/ the sing.e bond: it easi.y re.eases an oxygen which can then oxidise a compoundC
Compare the properties of the !aseous forms of oxy!en and the oxy!en free radical:
6ree radica.s are atomic or mo.ecu.ar species with unpaired e.ectronsC @hey are &$@ ionsC @he oxygen /ree radica. has two pairs o/ e.ectrons3 as we.. as two unpaired e.ectrons !see diagrams": these unpaired e.ectrons are high.y reacti>eC <t is basica..y an oxygen atom: they ha>e the same e.ectron con/igurationC @he oxygen /ree radica. can be made either by passing e.ectrica. current through oxygen gas to decompose it3 or by exposure to UC2C radiation: $2 2$) Copyright 7 2889: ;hmad Shah <di. ,1: @he oxy!en /ree radica.:
HSC Stage 6
2 Unit Chemistry
@he oxygen radica. is >ery short).i>ed3 and wi.. instant.y react with other radica.s3 and so it cannot be compared to oxygen gas in terms o/ physica. properties such as boi.ing point or co.ourC
Howe>er3 a comparison can be made in terms o/ reacti>ity: @he oxygen /ree radica. is much more reacti>e than oxygen gasC
%escri"e ozone as a molecule a"le to act "oth as an upper atmosphere U9 radiation shield and a lo$er atmosphere pollutant:
@he action o/ o5one !as we.. as its >a.ue" depends great.y on where it is .ocatedC <n the upper atmosphere !stratosphere" o5one is /ound as the Lo5one .ayerGC <t is extreme.y crucia. part to .i/e on AarthC Howe>er3 in the .ower atmosphere !troposphere"3 o5one is a serious air po..utantC %$one in the &pper *tmosphere: $5one in the stratosphere3 in the /orm o/ an ozone layer protects us /rom harm/u. u.tra>io.et radiation !U2 .ight": @here are 3 /orms o/ U2 .ight: U2);3 U2)0 and U2)CC @he o5one).ayer b.oc+s the harm/u. U2)0 and U2)C rays /rom passing through the atmosphere: these can cause many cancers and se>ere sunburnC @he use/u. U2); !needed /or photosynthesis" can sti.. pass throughC @he /o..owing e1uations show how o5one is /ormed and destroyed as we.. as how it protects us /rom harm/u. U2 radiation: $2 + U2 radiation $) + $2 $3 $) + $2 2$)
$3 + U2 radiation $) + $3 2$2
A>ery time an oxygen-o5one reacts with U2 .ight3 it absorbs itC Hence o5one can be said to be an upper atmosphere U2 radiation shie.dC Howe>er3 when o5one is /ound in the .ower atmosphere ! troposphere"3 it is considered a serious air po..utantC Copyright 7 2889: ;hmad Shah <di.
%$one in the 9ower *tmosphere:
HSC Stage 6
2 Unit Chemistry
@his is because o5one can cause serious hea.th and en>ironmenta. prob.emsC HA;E@H <SSUAS: $5one is poisonous to humans: as a strong oxidant3 it can react with body tissue3 especia..y with sensiti>e mucous membranes when breathed inC $5one causes breathing di//icu.ties3 aggra>ates respiratory prob.ems and produces headaches and premature /atigueC FH$@$CHAK<C;E SK$R: Qhen o5one is /ound as a component o/ smo! it is a serious po..utant3 and can be >ery ha5ardous /or hea.thC Sun.ight sp.its nitrogen dioxide and the /ree radica. produced Hoins with oxygen to /orm o5one: &$2 &$ + $)C ;.so3 hydrocarbons and F;& !peroxyacyl nitrates" can be present in the smogC
@hus o5one is both as a maHor po..utant3 and a U2 radiation shie.dC
Identify and name examples of isomers -excludin! !eometrical and optical. of haloal#anes up to ei!ht car"on atoms:
aloal0anes are compounds /ormed when one o/ the hydrogens o/ an a.+ane is rep.aced by a halo!en atom !63 C.3 0r or <"C Namin! 3aloal#anes: @here is a systematic <UF;C method o/ naming ha.oa.+anesC ,1: &ame this ha.oa.+ane:
/. 2.
6irst.y3 count the number carbons in the .ongest carbon chain: in this case3 there are 33 so the parent a.+ane is F4$F;&AC &ext identi/y3 name and number the ha.ogens3 using L fluoro'G3 Lchloro',3 L"romo'G and Liodo'G as pre/ixes instead o/ chemica. namesC Say we ta+e the .e/t)most carbon as carbon)P !C P": then3 there are 3 ch.orines !2 on CP and P on C3"3 and there are 3 /.uorines !P on CP and 2
HSC Stage 6
2 Unit Chemistry on C3"C 6or mu.tip.e ha.ogens3 use the pre/ixes di'3 tri)3 and tetra'C Hence3 so /ar we ha>e propane3 P3P33)trich.oro) and P3333)tri/.uoroC
4. 4.
@o ma+e the /u.. name3 p.ace the parent a.+ane at the end3 and p.ace the ha.ogens in alpha"etical order: P3P33)trich.oro)P3333)tri/.uoropropaneC &ow CHACI: say instead we too+ the right)most carbon as C PC <n that case3 the name wou.d be P3333)trich.oro)P3P33)tri/.uoropropaneC Jou KUS@ ta+e the name with the lo$er sum o/ numbersC
;.
<n this case3 both names ha>e an e1ua. sumC </ this occurs3 you gi>e the .ower numbers to the more e.ectronegati>e ha.ogen !6 D C. D 0r D <"C Hence3 the correct name is : 8 8'trichloro': : 8'trifluoropropaneC
<somers: 8somers are compounds that ha>e the same chemical /ormu.a3 but di//erent structural /ormu.aC Carbon compounds3 such as haloal#anes are ab.e to /orm many di//erent isomers: the .onger the chain3 the more isomers are possib.eC ,1: ?raw % isomers o/ C%H9C.62 and name them using <UF;C nomenc.ature:
2)ch.oro)P33)di/.uorobutaneC
%)ch.oro)P3P)di/.uorobutaneC
P)ch.oro)P3P)di/.uorobutaneC
HSC Stage 6
2 Unit Chemistry
P)ch.oro)P3P)di/.uoro)2)methy.propaneC
Identify the ori!ins of chlorofluorocar"ons -C;Cs. and halons in the atmosphere:

C#Cs: Chlorofluorocar"ons are compounds that contain $&EJ carbon3 /.uorine and ch.orine: &$ hydrogen atoms !eCgC C6C)P2 is CC.262"C C6Cs were introduced in the P*38Gs !+nown as freons" as rep.acements /or ammonia in re/rigeration: @his was because had the re1uired pressure)dependent properties that re/rigerants needed3 as we.. as that they were odour.ess3 non)/.ammab.e3 non)toxic and inert3 much un.i+e the toxic3 /ou.)sme..ing ammoniaC C6Cs were >ery wide.y used as: 4e/rigerants in /ridges and air)conditionersC Frope..ants in aeroso. spray cansC 6oaming agents in the manu/acture o/ /oam p.astics .i+e po.ystyreneC C.eaning agents in e.ectronic circuitryC @hese many uses re.eased C6Cs direct.y into the .ower atmosphereC ;s they were >ery inert and inso.ub.e in water !rain"3 they remained in the troposphere3 where air con>ection spread them throughout the atmosphereC 2ery s.ow.y3 the C6CGs began to di//use through the tropopause and into the stratosphere3 where prob.ems began to occurC alons: 3alons are compounds that contain carbon and bromine3 as we.. as other ha.ogens: they are basica..y C6CGs that a.so contain bromine !no hydrogen"C @hey are dense3 non)/.ammab.e .i1uids that were wide.y used as e//ecti>e /ire) extinguishers !ca..ed 0C6 /ire)extinguishers"C ;s they were used onto /ires3 the ha.ons were re.eased direct.y into the atmosphere3 where they too s.ow.y di//used into the stratosphereC
HSC Stage 6
2 Unit Chemistry
%iscuss the pro"lems associated $ith the use of C;Cs and assess the effecti(eness of steps ta#en to alle(iate these pro"lems:
@he biggest prob.em associated with the use o/ C6Cs is the destruction o/ stratospheric o5one !iCeC depletion of the ozone layer": ;s stated abo>e3 C6Cs are >ery inert3 and are not washed out by rainC ;s a resu.t3 C6Cs remain in the troposphere /or many years3 and e>entua..y di//use into the stratosphere3 where they dep.ete the o5one .ayerC @his .eads to more U2 radiation reaching Aarth3 which great.y increases the chances o/ mutations and damage !especia..y cancer" in .i>ing thingsC ow C#Cs Destroy -he %$one 9ayer: 6irst.y3 short wa>e.ength U2 radiation !that has not been remo>ed by the o5one .ayer" attac+s the C6C mo.ecu.e and brea+s o// a ch.orine atom: CC.262 !g" + U2 radiation a ch.orine monoxide radica. !C.$": =C. !g" + $3 !g" =C.$ !g" + $2 !g" =C. !g" + =CC.62 !g"
@his ch.orine atom !radical" then reacts with o5one3 /orming oxygen gas3 and
@he ch.orine monoxide radica. then reacts with an oxygen radica.3 and the ch.orine radica. is re!enerated: =C.$ !g" + =$ !g" =C. !g" + $2 !g"
@he net resu.t is that an o5one mo.ecu.e and an oxygen radica. ha>e been con>erted into 2 oxygen mo.ecu.es ;&? the ch.orine has not been used upC @he ch.orine radica. can then attac+ another o5one mo.ecu.e and repeat the who.e process thousands o/ times: this is a chain reactionC ; >ery sma.. amount o/ C6C in the stratosphere can do signi/icant damageC ow Chlorine (adicals *re (emo.ed: ;ccording to the abo>e3 theoretica..y3 a sing.e ch.orine atom cou.d destroy the entire o5one).ayer: howe>er certain natura. reactions remo>e this radica.C @he ch.orine atom reacts with stratospheric methane3 ending the chain reaction: =C. !g" + CH% !g" HC. !g" + =CH3 !g"
HSC Stage 6
2 Unit Chemistry
&either HC. nor the methy.)radica. has any e//ect on o5oneC ;nother important reaction /or stopping o5one dep.etion in>o.>es the =C.$ species reacting with nitrogen dioxide3 /orming chlorine nitrate: =C.$ !g" + &$2 !g" C.$&$2 !g" ole:
-he *ntarctic "pring %$one
@here is a serious periodic dep.etion o/ the o5one).ayer that occurs e>ery spring o>er ;ntarctica: it is ca..ed the L$5one Ho.eGC @his is due to the conditions o/ ;ntarctica in winter3 as we.. as springC ;ntarctic $inters are perpetua..y dar+: the co.d conditions3 as we.. as so.id particu.ate cata.ysts in the air3 encourage the /o..owing reaction to occur: HC. !g" + C.$&$2 !g" C.2 !g" + H&$3 !g"
@his has 5ero e//ect on o5one .e>e.s during the winterC Howe>er during ear.y spring3 the Sun begins to rise3 and the situation changes dramatica..y: sun.ight is ab.e to sp.it ch.orine mo.ecu.es: C.2 !g" + U2 radiation 2=C. !g"
Hence in spring there is another source o/ ch.orine radica.s to destroy more o5one: the concentration o/ o5one is reduced dramatica..y3 causing a ho.eC A>entua..y3 the /ixed amount o/ C.2 created o>er the winter is b.own away by ;ntarctic winds and the o5one .ayer s.ow.y regeneratesC
Dealing 7ith -he C#C !roblem: @he on.y way to stop o5one dep.etion is to S@$F re.easing C6Cs o/ any /ormC <&@A4&;@<$&;E ;R4AAKA&@S: @he main way the C6C prob.em is being dea.t with is by internationa. agreements based on the common goa. o/ phasing out C6CsC @he Kontrea. Frotoco. on Su"stances That %eplete the Ozone 4ayer !P* 9" is an internationa. treaty designed to protect the o5one .ayer by phasing out the production o/ a number o/ substances be.ie>ed to be responsib.e /or o5one dep.etionC <ts goa.s inc.ude ceasing the manu/acturing and banning the use o/ C6Cs and certain ha.oa.+anes by P**63 the end o/ ha.on use by P**%3 the phasing Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry out o/ HC6Cs3 as we.. as the pro>ision o/ /inancia. assistance to de>e.oping nations in order to he.p them reach the goa.s o/ Kontrea.C
C6C 4AFE;CAKA&@S: 6inding a.ternati>e compounds to /u./i. the ro.es o/ C6Cs is a maHor step /orward in pre>enting o5one dep.etionC @his is examined in greater detai. be.owC
%ealin! <ith Increased U9 +adiation: <ncreasing U2 .e>e.s ha>e meant that more U2 inhibitors need to be inc.uded in po.ymers !such as F2C" and Cancer Counci.s ha>e ad>ised the use o/ on.y sunscreens with a rating o/ SF6 38+ or greaterC
,ffecti.eness of -hese "olutions: @he Kontrea. Frotoco. is on.y e//ecti>e i/ member nations rati/y the protoco. and adhere to its regu.ations: so /ar3 the Kontrea. Frotoco. has been a huge success in internationa. agreement and en>ironmenta. hea.thC Certain C6C rep.acements are not as e//ecti>e as the C6Cs themse.>es: /uture techno.ogica. ad>ancement hopes to /ind better rep.acementsC @here are sti..3 howe>er3 signi/icant .e>e.s o/ C6Cs in the atmosphere3 and current techno.ogy has no way o/ remo>ing themC
-he 1reenhouse !roblem: ; .ess ta.+ed about issue o/ C6Cs and HC6Cs is that they contribute great.y to the increased !reenhouse effect !thousands o/ times more than C$2"C @his may .ead to c.imate change3 and is the /ocus o/ the Iyoto Frotoco.C
2resent information from secondary sources to $rite the e1uations to sho$ reactions in(ol(in! C;Cs and ozone to demonstrate the remo(al of ozone from the atmosphere:
;.. the C#C)re.ated e1uations /rom a"o(e: 6ormation o/ chlorine radical: CC.262 !g" + U2 radiation 4eaction o/ ozone: =C. !g" + =CC.62 !g"
HSC Stage 6
2 Unit Chemistry
=C. !g" + $3 !g"
=C.$ !g" + $2 !g"
4egeneration o/ chlorine: =C.$ !g" + $ !g" =C. !g" + $2 !g"
4emo>a. o/ chlorine radical: =C. !g" + CH% !g" HC. !g" + =CH3 !g"
4emo>a. o/ chlorine monoxide radical: =C.$ !g" + &$2 !g" C.$&$2 !g"
6ormation o/ molecular chlorine: HC. !g" + C.$&$2 !g" C.2 !g" + H&$3 !g"
?ecomposition o/ molecular chlorine: C.2 !g" + U2 radiation 2=C. !g"
2resent information from secondary sources to identify alternati(e chemicals used to replace C;Cs and e(aluate the effecti(eness of their use as a replacement for C;Cs:
*mmonia: Earge sca.e !industria." re/rigeration has re>erted bac+ to using ammonia as a re/rigerant3 as was done prior to the disco>ery o/ C6CsC Howe>er3 great care is exercised3 as ammonia is dangerous and toxicC C#Cs: 3ydrochlorofluorocar"ons are C6Cs that contain hydrogenC @hese were the /irst rep.acements /or C6CsC HC6Cs contain CH bonds that are susceptib.e to attac+ by reacti>e radica.s in the troposphere and so are decomposed rapid.y to a signi/icant extentC @his means that on.y a >ery sma.. proportion e>er reaches the stratosphereC HC6Cs rep.aced C6Cs in domestic re/rigeration3 as prope..ants in spray cans3 as an industria. so.>ent and as a /oaming agentC A//ecti>eness: Sma.. amounts o/ HC6Cs do reach the stratosphere3 and hence they are a.so o5one)dep.eting !P8U the o5one)dep.eting potentia. o/ C6Cs"C Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
@hey are seen as on.y a temporary so.utionC HC6Cs a.so contribute massi>e.y to the greenhouse e//ect3 and so their use is being phased out !comp.ete ban by 2838"C #Cs: 3ydrofluorocar"ons are compounds that contain on.y carbon3 hydrogen and /.uorine !&$ ch.orine or bromine"C @hey are wide.y seen as a >iab.e C6C and HC6C a.ternati>e3 as they contain reacti>e CH bonds !so they degrade in troposphere" as we.. as the /act that they do not contain any ch.orine !and hence cannot /orm =C. radica.s"C @heir o5one dep.eting potentia. is 5eroC H6Cs are >ery wide.y used in re/rigeration and air)conditioning app.icationsC A//ecti>eness: ;s they ha>e 5ero o5one)dep.eting potentia.3 H6Cs are a good a.ternati>e to using C6Cs in terms o/ atmospheric hea.thC Howe>er3 they are not as e//ecti>e re/rigerants as C6Cs3 and are s.ight.y more expensi>eC @hey are a.so strong greenhouse gases3 and so /urther research is re1uiredC
Analyse the information a(aila"le that indicates chan!es in atmospheric ozone concentrations descri"e the chan!es o"ser(ed and explain ho$ this information $as o"tained:
ow *re %$one 9e.els Measured< Stratospheric o5one .e>e.s are measured /rom ground)based instruments3 /rom instruments in sate..ites and /rom instruments in weather)ba..oonsC $5one .e>e.s are measured in ?obson Units !?U"C @he measurements made indicate that changes in o5one .e>e.s ha>e occurredC R4$U&?)0;SA?: @he !round'"ased instruments used are U2 spectrophotometers that are ab.e to measure the intensity o/ .ight at speci/ic wa>e.engthsC
HSC Stage 6
2 Unit Chemistry
@hese instruments are pointed direct.y upwards towards the s+y and are set to measure .ight intensity at the wa>e.engths o/ .ight at which o5one absorbs !such as U2)0 and U2)C" and at wa>e.engths on either side !/or .ight which o5one does not absorb"C ; comparison o/ these 2 measurements gi>es a measure o/ the tota. o5one in the atmosphere per unit o/ area o/ Aarth sur/ace at that .ocationC 0;EE$$&)0;SA?: @hese spectrophotometers can a.so be p.aced in high)a.titude weather ba..oons that can rise abo>e the stratosphereC @he instruments are pointed downwards3 and measure o5one /rom abo>eC S;@AEE<@A)0;SA?: ;n instrument ca..ed the @$KS !total ozone mappin! spectrophotometers" ha>e been p.aced on se>era. US sate..itesC @hey wor+ simi.ar.y to the U2 spectrophotometers as abo>e3 but as the sate..ites orbit the Aarth3 the @$KS is ab.e to scan the entire g.obe and measure o5one concentrations as a /unction o/ a.titude and geographica. .ocationC -he Changes %bser.ed: Keasurements o/ the tota. amount o/ o5one in a co.umn o/ atmosphere ha>e been recorded since P*#9C @he main dep.etion o/ o5one has occurred o>er the ;ntarcticC Scientists identi/ied that a dramatic dec.ine in springtime o5one occurred /rom the .ate P*98s o>er the entire ;ntarcticC @he dec.ine reached approximate.y 38U by P* #C <n some p.aces3 the o5one .ayer had been comp.ete.y destroyedC @he o5one dec.ine o>er ;ntarctica during springtime is now not so dramatic3 but o/ten exceeds #8UC
PRACTICAL &ather process and present information from secondary sources includin! simulations molecular modellin! #its or pictorial representations to model isomers of haloal#anes:
HSC Stage 6
2 Unit Chemistry
<n this experiment3 molecular modelling 0its were used to show di//erent isomers o/ a ha.oa.+aneC @he c.ass was di>ided into groups3 and each group was pro>ided with a +itC Aach group was pro>ided with a ha.oa.+ane3 which they were re1uire to draw structura. /ormu.a /or3 and then using the +it3 3 di//erent isomers were /ormedC =&"-8#> the method: @he mode.s created a good >isua. 3? representation o/ a chemica. property: that is3 isomerismC
(,"&9-": 6our isomers o/ C%H9C.62 with their <UF;C names:
2)ch.oro)P33)di/.uorobutaneC
%)ch.oro)P3P)di/.uorobutaneC
P)ch.oro)P3P)di/.uorobutaneC
P)ch.oro)P3P)di/.uoro)2)methy.propaneC
HSC Stage 6
2 Unit Chemistry
;.
uman acti.ity also impacts on waterways. Chemical monitoring and management assists in pro.iding safe water for human use and to protect the habitats of other organisms:
Identify that $ater 1uality can "e determined "y considerin!:' concentrations of common ions: total dissol(ed solids: hardness: tur"idity: acidity: dissol(ed oxy!en and "iochemical oxy!en demand:
Concentration of Common 8ons: Usua..y3 the concentration o/ a.. the ions in a so.ution is considered as a who.e: this is ca..ed the total dissol(ed solidsC Howe>er3 certain common ions ha>e their concentrations indi>idua..y measured: the resu.ts o/ these tests indicate di//erent aspects o/ water 1ua.ityC <mportant ions whose concentrations are indi>idua..y measured inc.ude meta. cations such as sodium !&a+"3 ma!nesium !Kg2+"3 calcium !Ca2+" and anions such as chloride !C.)" and the po.yatomic phosphate !F$%3)" and nitrate !&$3)"C @he concentrations o/ sodium and ch.oride are important indicators o/ the salinity o/ water system: any signi/icant change in sa.inity !whether increase or decrease" can great.y a//ect any a1uatic .i/eC /a!nesium and calcium ions are measured to indicate water hardness3 which is co>ered in more detai. "elo$C Fhosphate and nitrate ions are essentia. to a1uatic .i/e: howe>er3 excess .e>e.s o/ these ions .eads to eutrophication and a.ga. b.ooms3 destroying waterwaysC KA;SU4<&R <$&S: @he concentration o/ the metal cations in samp.es is >ery 1uic+.y and easi.y measured using spectroscopic methods such as ;;SC
HSC Stage 6
2 Unit Chemistry
Ch.oride .e>e.s can be measured by titrating the samp.e against si.>er nitrate3 with potassium chromate as the indicatorC @he methods used to determine phosphate and nitrate .e>e.s in water samp.es are co>ered "elo$ !see LKonitoring AutrophicationG"C -otal Dissol.ed "olids: @?S !tota. disso.>ed so.ids" is the tota. mass o/ a.. so.ids disso.>ed in a gi>en >o.ume o/ waterC <t is gi>en as either mg-E or ppm !both mean the same thing"C @he disso.>ed so.ids are main.y composed o/ sa.ts !ionic compounds"C @?S is re.ated to the 1ua.ity o/ water because c.ean water is re.ati>e.y /ree o/ contaminants: a .arge amount o/ disso.>ed so.ids indicates unc.ean waterC KA;SU4<&R @?S: ; gra>imetric method /or determining @?S is by /irst /i.tering the water samp.e to obtain a c.ear so.ution3 then e(aporatin! the samp.e dryness3 and weighing the so.idsC @his method is >ery .aborious and prone to inaccuracies3 and hence e.ectrochemica. methods are pre/erredC 0ecause most o/ the disso.>ed so.ids are ions3 the electrical conducti(ity o/ the water samp.e can be used to measure @?SC ;.though conducti>ity tests gi>e a measure o/ tota. disso.>ed sa.ts3 this is 1uite an accurate approximation /or @?SC ardness: Hard)water is water with high .e>e.s o/ calcium and ma!nesium ionsC Hardness is an issue /or water 1ua.ity because hard)water creates Lsca.eG deposits o/ CaC$3 and KgC$3 on sin+s and bathtubsC ;.so soap does not wor+ in hard water3 and /orms scum)precipitates which can stain /abricsC KA;SU4<&R H;4?&ASS: @he .e>e.s o/ these ions can be measured by titration against a compound +nown as A?@; !ethy.ene)diamine)tetra)acetic)acid"C Hardness is then expressed as mg-E o/ CaC$3C ;.ternati>e.y3 the .e>e.s o/ Kg2+ and Ca2+ can be measured using ;;SC
HSC Stage 6 -urbidity: Qater tur"idity means a Lc.oudinessG o/ the waterC
2 Unit Chemistry
@urbidity is caused by the presence o/ suspended so.ids that are su//icient.y sma.. so that they do not sett.e upon standing and remain suspendedC @urbidity gi>es water an undesirab.e appearance as we.. as a unp.easant tasteC High .e>e.s o/ turbidity can a//ect the penetration o/ .ight through the water3 which then reduces the rate o/ photosynthesis3 reducing disso.>ed oxygenC KA;SU4<&R @U40<?<@J: @urbidity is measured using a turbidity tubeC ; tur"idity tu"e is a .ong ho..ow p.astic cy.inder that has a mar+ !usua..y a b.ac+ cross" inscribed onto its /.at bottomC Qater is poured into the tube unti. the mar+ is no .onger >isib.eC @he height o/ water at which this occurs is the turbidity measurement o/ the waterC @urbidity is measured in &@U !nephe.ometric turbidity units"C
*cidity: @he pH o/ a water system is a good indicator o/ its hea.thC ;nything outside the norma. range o/ 6C#) C# indicates a po..uted system3 caused by the discharge o/ some chemica. into the waterC Rreat changes in acidity-a.+a.inity great.y a//ect the usabi.ity o/ waterC KA;SU4<&R pH: @he pH o/ water is measured using indicators3 pH strips or a pH meterC
Dissol.ed %3ygen: ?$ !disso.>ed oxygen" re/ers to the .e>e.s o/ molecular oxygen !$2" that are disso.>ed in a water samp.eC A>en though $2 has >ery .ow so.ubi.ity in water3 this sma.. amount is crucia. to a1uatic .i/e: this oxygen is extracted and used /or respirationC Eow oxygen .e>e.s !.ower than # ppm" wi.. cause many a1uatic species to dieC @he water body wi.. decay and de>e.op undesirab.e characteristicsC KA;SU4<&R ?$:
HSC Stage 6
2 Unit Chemistry
?isso.>ed oxygen can be measured using a chemica. titration +nown as the <in#ler /ethodC <n this method3 the disso.>ed oxygen oxidises manganese /rom Kn2+ to Kn!<2" in a.+a.ine so.utionC Kn!<2" then oxidises iodide !< )" ions to iodine !<2" in acidic conditionsC <odine is then titrated against sodium thiosu./ate !&a2S2$3" using starch as in indicatorC ;.ternati>e.y3 an e.ectronic oxygen sensor can be usedC :iological %3ygen Demand: @he 0$? !bio.ogica. oxygen demand" o/ a water body is a measure o/ the concentration o/ disso.>ed oxygen that is needed /or the comp.ete brea+down o/ the organic matter in the water by anaerobic bacteriaC @hat is3 it measures how /ast bacteria !or other organisms" use up oxygenC High 0$? .e>e.s indicate .arge amounts o/ organic matter in the water3 which wi.. drain the water o/ oxygen: sewage has >ery high .e>e.s o/ 0$?C KA;SU4<&R 0$?: @wo samp.es o/ water must be ta+en: the disso.>ed oxygen is measured in one o/ the samp.es immediate.y3 whi.e the other samp.e is p.aced in a sea.ed air)/ree container and incubated at 28MC /or /i>e daysC ;/ter #)day incubation3 the second samp.eGs oxygen .e>e.s are measured and the di//erence in disso.>ed oxygen .e>e.s is the 0$?C
Identify factors that affect the concentrations of a ran!e of ions in solution in natural "odies of $ater such as ri(ers and oceans:
@he concentrations o/ a range o/ ions is bodies o/ water !such as ri>ers and oceans" is a//ected by a number o/ /actors3 both natural and unnatural: <t can be said that the source o/ water /or a.. water)bodies is rainC 4ain contains >ery /ew ions !on.y >ery .itt.e &a+ and C.) /rom sea)spray" and so any increased .e>e.s o/ ions in water bodies is a resu.t o/ what occurs in between rain/a.. and when the water /.ows into the water)bodyC &$@A that the ion .e>e.s in ri>ers and .a+es are much susceptib.e to change compared to oceans3 which ha>e much greater >o.umes o/ waterC 6atural "ources of 8ons: Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
</ rain /a..s on bush.and3 and then runs)o// into streams and ri>ers3 it wi.. on.y pic+ up sma.. amounts o/ nitrates and phosphates /rom sur/ace nutrients3 as we.. as some Kg2+ and Ca2+ /rom minera.s: @?S wi.. be .ow !Y#8"C </ rain soa+s into the ground and /.ows into a1uifers !.ayers o/ permeab.e roc+" and then into ri>ers3 the water wi.. ha>e increased .e>e.s o/ Ca 2+3 Kg2+3 C.)3 S$%2) and C$32) which are disso.>ed /rom the soi.s and roc+s the water /.ows throughC @?S wi.. be moderate !O288"C </ water seeps down into roc+s !percolates" in deep underground basins !artesian "asins. and on.y reaches the sur/ace centuries .ater3 then the .e>e.s o/ the abo>e ions wi.. increase massi>e.y3 as may contain other ions !such as 6e3+3 Kn2+3 Cu2+ and Wn2+C @?S >a.ues are >ery high !DP888"C
9and Clearing: Qhen .and is c.eared o/ >egetation3 the soi. .oses the stabi.ising e//ects o/ p.ant roots and so soi. is easi.y mo>ed and disp.acedC </ rain /.ows o>er c.eared .and3 it wi.. disturb dirt and sediment and carry it into the water body it /.ows into !this wi.. great.y increase @U40<?<@J"C @he .e>e. o/ disso.>ed so.ids and ions !@?S" wi.. increase3 due to high .e>e.s o/ minera. ions in the soi.s !such as &a+3 I+ etcC"
*griculture: Qhen rain /.ows o>er .and used /or the growing o/ crops and pasture).and it .eads to increased .e>e.s o/ phosphates and nitrates due to /erti.i5er run)o//C @he turbidity wi.. a.so increase3 as we.. as the 0$?3 as organic matter !such as anima. /aeces" enters the water)waysC
(aw "ewage and %ther ,ffluents: +a$ se$a!e3 i/ discharged direct.y into the water3 wi.. great.y increase the .e>e.s o/ many ions !especia..y nutrient ions such as nitrates and phosphates"C Sewage can increase a water)wayGs @?S by 288 or more: it a.so great.y increases turbidity3 0$? and pathogen .e>e.sC Storm$ater run)o// in urban areas can a.so carry high .e>e.s o/ ionsC
HSC Stage 6
2 Unit Chemistry
Industrial effluent as we.. as leachin! /rom rubbish dumps can increase the .e>e.s o/ dangerous HA;2J)KA@;E ions in water !such as Hg2+ and Cd2+"C
%escri"e the desi!n and composition of microscopic mem"rane filters and explain ho$ they purify contaminated $ater:
; membrane /i.ter is basica..y a thin /i.m o/ synthetic polymer throughout which there are sma.. pores o/ uni/orm si5eC Common po.ymers used are polypropylene and polytetrafluoroethylene !F@6A"C 6i.ters are c.assi/ied according to the si5e o/ their pores3 as this determines what type o/ partic.es can pass throughC 6<E@A4 ?AS<R&: @here are many designs in which the /i.ter can be /ormed: this depends on the purpose /or which the /i.ter was madeC $ne simp.e design in>o.>es a thin sheet o/ /i.ter)membrane that is /o.ded around a ho..ow core !such as a thin tube" and surrounded by a casingC Qhen water is passed o>er the membrane3 c.ean water passes through and exits >ia the ho..ow coreC ;nother design in>o.>es /orming the membranes into capi..aries !tiny tubes" with a diameter o/ about #88 Sm: these are ca..ed hollo$ fi"re /i.tersC Earge numbers o/ these capi..aries are bounded together to /orm a /i.tering unit that has a >ery .arge sur/ace areaC Qater is passed o>er the sur/ace o/ the capi..ary and c.ean water passes through to the midd.e o/ the capi..ary and /.ows outC
%escri"e and assess the effecti(eness of methods used to purify and sanitise mass $ater supplies:
Monitoring Catchment: @he /irst step to ensure water used /or human use is c.ean is to ensure that the area the water flo$s o>er !the C;@CHKA&@ area" is +ept c.eanC @his in>o.>es banning any .and)c.earing3 industry or agricu.ture in the entire catchment area3 to pre>ent sediment3 anima. waste or bacteria to bui.d up in water supp.iesC Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
A66AC@<2A&ASS: @his is a >ery cheap and e//ecti>e way o/ ensuring the purity o/ water /or human use: by remo>ing the sources o/ contamination3 purity is ensuredC
"creening: 0e/ore the water /rom catchment areas is a..owed to enter treatment p.ants or storage dams3 it is passed through meta. screens that remo>e .arge debris such as stic+s3 .ea>es3 trash and other .arge partic.es which may inter/ere with subse1uent puri/ication steps A66AC@<2A&ASS: @his step is e//ecti>e /or its purpose3 but more treatment is neededC
Clarification and #locculation: Certain suspended partic.es !ca..ed colloidal particles" cause water to become turbid3 but are too sma.. to be remo>ed by con>entiona. /i.trationC <n this step3 these partic.es are coagu.ated together to /orm .arge partic.es3 which can then be remo>ed: this is ca..ed L/.occu.ationGC 6irst.y3 the pH o/ the water is increased3 as this encourages the /ormation o/ precipitates: this is achie>ed by adding .imeC &ext3 an e.ectro.yte is added to /orce the partic.es to precipitate: iron!<<<" hydroxide or a.uminium ch.oride is used !a.though ;. 3+ ions are pre/erred as they .ea>e no meta..ic a/tertaste in the water3 as 6e3+ does"C @he precipitate is /irst /ormed as >ery tiny partic.es3 but as the water is gent.y agitated or stirred3 the partic.es /.occu.ate into .arger partic.esC A66AC@<2A&ASS: 6.occu.ation remo>es most o/ the suspended partic.es3 as we.. as bacteria3 which are caught up in the partic.e aggregatesC <t is >ery cost)e//ecti>e3 and re.ati>e.y /astC
"edimentation: Qater that has been /.occu.ated is then a..owed to settle in .arge tan+s: this causes the dirt and other partic.es to /a.. to the bottom o/ the tan+ as a s.udge3 where it is remo>edC
HSC Stage 6
2 Unit Chemistry
@he c.ear water is then pumped to the /i.tration systemsC A66AC@<2A&ASS: Sedimentation emp.oys a natura. /orce !iCeC gra>ity" to separate the s.udge /rom c.ean water3 and so reduces p.ant running costsC @he s.ow speed o/ sedimentation may a//ect its e//ecti>enessC
#iltration: Qater /rom the sett.ing tan+ is then passed through a /i.ter bed o/ /ine sand and gra>e.: this remo>es the rest o/ the particu.ate matter3 as we.. as the materia. that did not sett.e to the bottom o/ the tan+C Sometimes anthracite !metamorphic coa." is added to the /i.ter beds3 as it adsorbs organic matter and remo>es odoursC A66AC@<2A&ASS: Sand /i.tration remo>es a high proportion o/ the particu.ate matter that aggregated during /.occu.ation3 howe>er extreme.y sma.. partic.es are not remo>ed !such as some bacteria and >iruses"C <t is suitab.e /or pro>iding water to urbanised areasC
Chlorination: East.y3 be/ore water is pumped to homes3 ch.orine gas is bubb.ed through the water: this /orms the hypoch.orite ion !$C. )" which can +i.. disease causing agents3 such as bacteria and some >irusesC A66AC@<2A&ASS: Ch.orination is an e//ecti>e way o/ remo>ing most pathogenic organisms3 but3 it is not so e//ecti>e at +i..ing >iruses ;.so3 ch.orine may impart an unp.easant odour on the waterC
;.ternati>e ) Membrane #ilters: ;.. the abo>e are the steps ta+en to saniti5e water in most ;ustra.ian p.antsC ;.ternati>e.y3 membrane /i.ters can be used3 which wou.d rep.ace many o/ the steps used abo>eC Kembrane /i.ters wou.d remo>e the need /or /.occu.ation3 sedimentation3 sand /i.tration and a.so ch.orination3 because: Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
@heir pore si5e is su//icient.y sma.. to remo>e suspended partic.esC Kembranes are >ery thin and a..ow the use o/ pressuri5ation: this great.y speeds up the process3 and hence remo>es the need /or sedimentationC Sand /i.tration is a s.ow process that membrane /i.tration supersedesC Kembrane /i.ters can remo>e a.. bacteria ;&? >iruses3 as these organisms are much too .arge to /it through the pores o/ a membrane /i.terC Howe>er3 membrane /i.ters are considerab.y more expensi(e than current methods used3 and so their use is .imited by costsC
&ather process and present information on the ran!e and chemistry of the tests used to: identify hea(y metal pollution of $ater monitor possi"le eutrophication of $ater$ays
ea.y Metals: 3ea(y metals are the transition meta.s in addition to .ead and arsenicC @he hea>y meta.s that are o/ the most concern due to their extreme.y detrimenta. e//ects on hea.th !and hence shou.d be monitored /or the most" are mercury3 lead3 cadmium3 chromium and arsenic* @he .e>e.s o/ these hea>y meta.s is most easi.y 1uantitati>e.y measured by using ;;S3 as their .e>e.s are usua..y >ery .owC $ne o/ the most common 1uantitati>e tests /or the presence o/ hea>y meta.s is the sulfide'test: ; water samp.e is acidi/ied3 and then a /ew drops o/ sodium su./ide !&a 2S" is addedC </ a precipitate /orms3 then one o/ the /o..owing ions is present: 4ead sil(er mercury copper cadmium or arsenic* </ no precipitate /orms in acidi/ied conditions3 then the samp.e is made a.+a.ineC </ this produces a precipitate3 then one o/ the /o..owing is present: Chromium3 zinc3 iron3 nic#el3 co"alt3 man!anese or aluminiumC CHAK<S@4J: @he su./ide)test is based on the /o..owing e1ui.ibrium:
HSC Stage 6 S2) !a1" + 2H3$+ !a1"
2 Unit Chemistry
H2S !a1" + 2H2$ !."
Qhen in acidic so.ution3 e1ui.ibrium .ies great.y to the right3 and there is on.y a sma.. amount o/ su./ide: this sma.. amount is enough to precipitate the /irst group o/ hea>y meta.s3 but not the secondC <n a.+a.ine so.ution3 the e1ui.ibrium .ies to the .e/t: there are !as we.. as the Pst group: this is why the acidic test is done /irst"C $ther simp.e 1uantitati>e techni1ues to identi/y the presence o/ hea(y metals inc.udes other precipitation tests3 /.ame tests !eCgC /or copper"C $ther 1ua.itati>e tests !besides ;;S" inc.udes >o.umetric and gra>imetric ana.yses3 co.orimetry !using co.orimeter de>ices" and chromatographyC ,utrophication: Eutrophication is the process by which a water body becomes enriched with nutrients !S$%2) Z &$32)" to such an extent that an al!al "loom is >ery .i+e.yC Autrophication is not the same as a.ga. b.ooms3 but EA;?S to a.ga. b.oomsC Qaterways need to be monitored /or possib.e eutrophication in order to stop a.ga. b.ooms /rom occurring* ;.ga. b.ooms need to be pre>ented because: 0.ue)green a.gae !cyano"acteria" in a.ga. b.ooms produce poisons that can +i.. humans as we.. as .i>estoc+C Qater becomes unsuitab.e /or norma. recreationa. uses as it is c.ogged up with a.gae3 which can co>er ri>ers /or +i.ometres ;.gae can star>e ri>ers o/ oxygen3 +i..ing a.. the a1uatic .i/eC @o monitor waterways /or eutrophication3 the .e>e.s o/ nitrates and phosphates needs to be measured !1uantitati(e testing on.y"C &<@4;@AS: Kethods to measure the nitrate .e>e.s in water usua..y in>o.>e measuring the total nitro!en .e>e.s in the samp.eC @wo methods are used: =>eldahl di!estion3 and co.orimetric methodsC @he chemistry o/ IHe.dah. digestion: Copyright 7 2889: ;hmad Shah <di. .arge amounts o/ su./ide3 and hence the 2nd group o/ hea>y meta.s precipitates
HSC Stage 6
2 Unit Chemistry @he samp.e is heated with concentrated su./uric acid to LdigestG any organic nitrogen compounds into ammonium su./ateC @his is then reacted with sodium hydroxide to /orm ammoniaC @he .e>e.s o/ ammonia are then measured by bac+ titration against a standardised so.ution o/ hydroch.oric acidC
@he chemistry o/ the co.orimetric method: <n this method3 the samp.e is comp.ete.y digested3 as abo>e3 except the samp.e is then treated with &ess.erGs reagent3 a chemica. that reacts with nitrogenous compounds to /orm a ye..ow compoundC @he co.orimeter then measures the intensity o/ the ye..ow co.our to ca.cu.ate the concentration o/ nitratesC </ the .e>e.s o/ nitrate reaches too high3 the water is ca..ed eutrophicC FH$SFH;@AS: ;s abo>e3 techni1ues to measure phosphates actua..y measure the .e>e.s o/ total phosphorus present in the water samp.eC @he main techni1ue used is a co.orimetric methodC @he chemistry o/ the co.orimetric method: <n this method3 a measured 1uantity o/ ammonium moly"date is added to the samp.e and comp.ete.y disso.>edC ; measured 1uantity o/ so.id !powdered" ascor"ic acid is then added3 and this /orms an intense.y b.ue comp.ex o/ a compound +now as Lmo.ybdenum b.ueGC @he intensity o/ the b.ueness is measured by a co.orimeter and this p.aces a >a.ue on the concentration o/ phosphateC </ phosphate .e>e.s reach greater than 8C8# ppm !or mg-E"3 than the water is eutrophic and an a.ga. b.oom is extreme.y .i+e.yC
&ather process and present information on the features of the local to$n $ater supply in terms of:' catchment area:
HSC Stage 6
2 Unit Chemistry
possi"le sources of contamination in this catchment: chemical tests a(aila"le to determine le(els and types of contaminants: physical and chemical processes used to purify $ater: chemical additi(es in the $ater and the reasons for the presence of these additi(es:
6or the .oca. Sydney area3 the water is supp.ied by 7arragamba DamC C;@CHKA&@ ;4A;: Qarragamba ?am is Sydney[s main water storage dam3 and one o/ the .argest domestic water supp.y dams in the wor.dC @he dam .ies on the Qarragamba 4i>er3 /or which it is namedC Catchment areas are areas o/ .and /rom which rain water drains toward a common water)bodyC @he Qarragamba catchment has an area o/ about *888 +m 2 and extends /rom south o/ Rou.burn3 north to Eithgow3 east to Qerombi and Kittagong3 and west to part o/ the Croo+we.. .oca. go>ernment areaC S$U4CAS $6 C$&@;K<&;@<$&: Eand C.earing: Qithin the catchment area3 there are >arious .ogging and .and)c.earing acti>ities occurring to ma+e way /or more agricu.tura. .andC @his has .ead to increased turbidity in the water /.owing into the dam !especia..y during hea>y)/.ow periods"C Higher .e>e.s o/ disso.>ed so.ids in the water a.so occursC ;gricu.ture: @here are >arious patches o/ .and within the catchment area that are used /or agricu.tura. purposes such as growing crops or raising catt.eC 4un)o// /rom agricu.tura. .and contains high .e>e.s o/ phosphates and nitrates as a resu.t o/ .eeching /erti.i5ers /rom the soi. and cropsC
HSC Stage 6
2 Unit Chemistry
Eow).e>e.s o/ pesticides !such as organoch.orins and organophosphates" ha>e been detected in the run)o// /rom agricu.tureC Qater that runs o>er .and used /or catt.e)gra5ing !pasture).and" can carry with it anima. /aeces !detected by high /aeca. co.i/orm .e>e.s": this contamination .eads to the growth o/ bacteria3 as we.. as a high 0$?C Kining: Qithin the catchment area are abandoned mines which water can /.ow intoC Qhen water .ea+s into meta. mines and /.ows out3 it .eaches out with it certain ions such as Wn2+ and Cu2+ which are hea>y meta. po..utants3 as we.. as su./ides /rom the meta. ores3 which ma+e the water acidicC Coa. mining occurs in the outer catchment area: possib.e contamination o/ the water in>o.>es disposa. o/ mining wastes direct.y into water)waysC &atura. Soi.: @he natura. soi. and roc+ strata around the catchment area ha>e high .e>e.s o/ iron and manganese in themC 4ain water can .each out these minera.s3 in the /orm o/ 6e3+ and Kn2+ ionsC @his .eads to water with a co.oured tinge and a meta..ic tasteC Sewage: ;t certain p.aces a.ong the sewage .ine are p.aces ca..ed Lo(erflo$ pointsGC ?uring times o/ hea>y /.ooding the sewage treatment p.ants cannot hand.e the hea>y input o/ stormwater /.ows3 and so 4;Q untreated sewage is a..owed to /.ow out o/ these o>er/.ow pointsC @his .eads to contamination o/ the water with bacteria and excess ionsC ;nima.s: Certain /era. and nati>e anima.s may contaminate the water with their /aeces direct.y3 or by dying and decaying within the waterC @his can .ead to serious contamination o/ the water with pathogensC @his was the cause o/ the &iardiasis and Cryptosporidium scare o/ P** C @AS@<&R 6$4 C$&@;K<&;&@S: Copyright 7 2889: ;hmad Shah <di.
HSC Stage 6
2 Unit Chemistry
@he testing /or contaminants /or Qarragamba ?am occurs in a >ariety o/ .ocations: using mu.tip.e testing sites ensures that a wide range o/ in/ormationC Kost chemica. tests are used to detect the .e>e.s common ions3 and ensure that they remain be.ow sa/e thresho.ds: this is especia..y true /or nutrient ionsC @he chemica. tests a>ai.ab.e to determine .e>e.s and types o/ contaminants ha>e a.ready been described in greater detai. !see a"o(e"C <n summary: @he test /or common ions uses e.ectrica. conducti>ity: the test /or hea>y meta. ions is the su./ide)test3 but ;;S is used to determine 1uantities: the test /or nitrates is IHe.dah. digestion: phosphates detection in>o.>es mo.ybdenum co.orimetry and 0$? is measured using the Qin+.er methodC
Q;@A4 FU4<6<C;@<$&: @he puri/ication o/ water that is caught in the Qarragamba catchment area is puri/ied using the method described a"o(eC <t is a cost)e//ecti>e method /or saniti5ing water to an acceptab.e degreeC <n summary: Qater is /irst screened to remo>e .arge debris: /.occu.ation then occurs using 6e3+ or ;.3+ e.ectro.ytes3 /o..owed by sha+ing to encourage precipitate /ormation: this is then .e/t in a sedimentation tan+ to sett.e: s.udge is scooped out and the c.ean water is .ed onto a sand)bed /i.ter: this /i.ter consists o/ .ayers o/ sand and gra>e. and the water comes out c.eanC
CHAK<C;E ;??<@<2AS: @he 2 main chemica. additi>es in Sydney water are chlorine and fluorideC Chlorine !C.2" is added to the water supp.y as a disin/ecting agent: ch.orine gas is bubb.ed through the water Hust be/ore it exits the p.antC Hypoch.orite ions are /ormed3 and these +i.. bacteria and some >iruses3 saniti5ing the waterC ;luoride !6)" is added to the water because it is be.ie>ed to strengthen tooth ename. in growing chi.drenC 6.uoride ions are added in the /orm o/ sodium /.uoride at a contro..ed concentration o/ P ppmC
HSC Stage 6
2 Unit Chemistry
PRACTICAL 2erform first'hand in(esti!ations to use 1ualitati(e and 1uantitati(e tests to analyse and compare the 1uality of $ater samples:
<n this practica.3 water samp.es were ta+en /rom the .oca. Coo+Gs 4i>er and using a LStream<atchG +it the water 1ua.ity tests were per/ormed on)siteC Qater samp.es were ta+en /rom >arious parts o/ the ri>er3 and the resu.ts were compared to the same tests per/ormed on disti..ed waterC !ollutants: @his was a 1ua.itati>e test per/ormed on the water samp.es to detect po..utionC ;ny sort o/ co.ouration o/ the water !any de>iation /rom Lc.earG" indicated the presence o/ a /orm o/ po..ution: any Lrainbow strea+sG meant hydrocarbonsC @he water was sme.t to detect any odours !another sign o/ po..ution"C ; samp.e bott.e was /i..ed ha./)way with samp.e water3 and another bott.e was /i..ed with disti..ed water: both were sha+en at the same time /or e1ua. periods o/ timeC </ the bubb.es remained .onger on the samp.e3 this indicated the presence o/ detergentsC @he presence o/ hea>y meta. po..ution was per/ormed in the .aboratory: P mE o/ sodium su./ide was p.aced in # mE o/ samp.e waterC ;ny precipitate indicated the presence o/ a hea>y meta.C -urbidity: @his test was a re.ati>e.y 1uantitati>e test3 with turbidity measured in &@UC 6irst.y3 disti..ed water was poured into the turbidity tube3 and it was c.ear a.. the way to the top o/ the tubeC <t was gi>en a turbidity o/ BP8 &@UC @he samp.e water was co..ected in a bott.e using a te.escoping hand.e3 and this water was poured into the tube: it had a much higher turbidity3 and c.ouded the >iew o/ the cross on the bottom o/ the tubeC -emperature: ; thermometer !with a rubber hand.e" was p.aced direct.y into the water way to accurate.y measure the temperature o/ the water: it was /ound to be within acceptab.e rangesC p :
HSC Stage 6
2 Unit Chemistry
pH o/ water samp.es was done using strips o/ pH paperC 6irst.y3 the pH o/ disti..ed water was measured and /ound to be 9C @he pH o/ the water samp.e was then measured and /ound to be 9C#C @he tota. disso.>ed so.ids was measured using an e.ectrica. conducti>ity meter that measured in SS-cm !mircosie>erts per centimetre"C @he samp.e water had on.y s.ight.y more ions that disti..ed waterC @he .e>e.s o/ disso.>ed oxygen was easi.y measured using an oxygen sensing metre /ound in the StreamQatch +itC @wo samp.e bott.es were /i..ed: one was capped air)/ree and sea.ed tight.y3 and the ?$ .e>e. in the other was measured immediate.yC @he other samp.e had the .e>e.s o/ ?$ measured # days .ater3 and the di//erence was the 0$?C ardness:
-D":
D%-:%D:
6or hardness3 a titration method was usedC @o a P88 mE samp.e3 P mE o/ bu//er so.ution !pH P8" was added3 and 2)3 drops o/ Ariochrome 0.ac+ @ indicator was addedC @his red)>io.et so.ution was titrated against a so.ution o/ A?@; unti. a permanent b.ue co.our occurredC ; .ac+ o/ de/inite change in co.our meant there were no magnesium ionsC

9.4 - Chemical Monitoring and Management

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9.4 - Chemical Monitoring and Management

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HSC Stage 6

9.4 Chemical Monitoring and Management:

carbon dioxide + water 3C$2 !g" + %H2$ !g"

Incomplete combustion: propane + oxygen C3H

aber !rocess: nitrogen + hydrogen &2 !g" + 3H2 !g"

'H ( )*2 +,-mo. barium su./ate + ch.oride

0aS$% !s" + 2C.) !a1"

4adica. reacts with oxygen3 /orming o5one: $) + $2 $3

$5one reacts with U23 /orming oxygen and a radica.: $3 + U2 radiation $) + $2

4adica. reacts with o5one3 creating oxygen: $) + $3 2$2

*ll the C#C+(elated ,quations: 6ormation o/ chlorine radical:

Copyright 7 2889: ;hmad Shah <di.

CC.262 !g" + U2 radiation 4eaction o/ ozone: =C. !g" + $3 !g"

=C. !g" + =CC.62 !g"

=C.$ !g" + $2 !g"

4egeneration o/ chlorine: =C.$ !g" + $ !g" =C. !g" + $2 !g"

?ecomposition o/ molecular chlorine: C.2 !g" + U2 radiation 2=C. !g"

ea.y+Metal "ulfide -est:

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

carbon dioxide + water 3C$2 !g" + %H2$ !g"

carbon + carbon monoxide + water C !s" + 2C$ !g" + %H2$ !g"

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

Identify the reaction of hydro!en $ith nitro!en as exothermic:

Copyright 7 2889: ;hmad Shah <di.

Explain $hy the rate of reaction is increased "y hi!her temperatures:

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

Cl !C.) ions" is added to the samp.eC </ a white precipitate /orms3

"%4 !S$%2) ions" is added to a 64ASH S;KFEAC </ a precipitate

/orms3 the un+nown ion is either ca.cium !Ca2+" or barium !0a2+":

Copyright 7 2889: ;hmad Shah <di.

"%4 to the other portion: i/ a precipitate /orms3 0a 2+ or Ca2+

Copyright 7 2889: ;hmad Shah <di.

HSC Stage 6 4. ;dd 6a%

Copyright 7 2889: ;hmad Shah <di.

&ses of **": Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

8C2 8CP3 8C3P

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

HSC Stage 6 percenta!e o/ su./ate in /erti.i5er P88 ( 2C%% - #C8 V P88 ( % C* U

2 Unit Chemistry ( mass o/ S$% - mass o/ /erti.i5er V

Copyright 7 2889: ;hmad Shah <di.

%escri"e the composition and layered structure of the atmosphere:

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

%escri"e the formation of a coordinate co(alent "ond:

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

%$one in the 9ower *tmosphere:

@hus o5one is both as a maHor po..utant3 and a U2 radiation shie.dC

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

Identify the ori!ins of chlorofluorocar"ons -C;Cs. and halons in the atmosphere:

Copyright 7 2889: ;hmad Shah <di.

Copyright 7 2889: ;hmad Shah <di.

-he *ntarctic "pring %$one

Copyright 7 2889: ;hmad Shah <di.

=C. !g" + $3 !g"

=C.$ !g" + $2 !g"