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    GRADE12CHEMISTRY

    OLYMPIADSCHOOL

    WEDNESDAY2:304:30

    FRIDAY4:456.45

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    ,

    and

    pH

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    DifferentcombinationsofstrongArrheniusacidsandbasesreactwiththesameexothermicresult.Measurementsalwaysshowthereleaseof56kJofenergypermoleofwaterformed.Thismakessense,becausethenetionic

    equationisthesameregardlessofthespecificneutralizationreactionthatoccurs.

    TheArrheniustheoryhaslimitations,however.Forexample,H+(aq),abareproton,doesnotexistinwater.Thepositivechargeonaprotonisattractedtotheregionofnegativechargeonthelonepairofelectronsonawater

    moleculesoxygenatom.Thecombinationisahydratedprotoncalleday ron um on, + aq + aq + + aq

    Thehydronium ionformshydrogenbondswithotherwatermolecules.Thus,abetterformulafortheionthatispresentinacidicsolutionsis

    H H2O n +,

    w ere

    n

    is

    usua y

    4

    or

    5.

    For convenience,

    owever,c emists

    usuallyuseasinglehydronium ionwhenwritingequations.

    TheArrheniustheoryalsohaslimitationsforexplainingcertainreactions.Forexample,aqueoussolutionso ammoniaarebasic.Theyreactwithacidsinneutralizationreactions,eventhoughammoniadoesnotcontainthe

    hydroxideion.Manyaqueoussolutionsofsaltswithnohydroxideionsareas c, oo. omereac ons a ep acew ou any qu so ven . orexample,ammoniumchloridecanbeformedbythereactionbetweenammoniaandhydrogenchloride,whicharebothgases:

    g + g s

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    TheBrnstedLowryTheory

    ThelimitationsoftheArrheniustheoryofacidsandbasesareovercomebyamore eneraltheor calledtheBr nstedLowr theor .Thistheor was

    proposedindependently,in1923,byJohannesBrnsted,aDanishchemist,andThomasLowry,anEnglishchemist.Itrecognizesanacidbasereactionasachemicalequilibrium,havingbothaforwardreactionandareversereactionthatinvolvethetransferofaproton.TheBrnstedLowrytheorydefinesacidsandbasesasfollows:

    *Anacidisasubstancefromwhichaprotoncanberemoved.(SomechemistsdescribeBrnstedLowryacidsasprotondonors.)

    *Abaseisasubstancethatcanacceptaproton.(SomechemistsdescribeBrnstedLowr basesas rotonacce tors.

    Notethatthewordprotonreferstothenucleusofahydrogenatom anH+ionthathasbeenremovedfromtheacidmolecule.Itdoesnotrefertoa

    rotonremovedfromthenucleusofanotheratom suchasox enorsulfur,thatmaybepresentintheacidmolecule.Asmentionedpreviously,H+ionsshareelectronswithanyspecies(ionormolecule)thathasalone

    pairofelectrons.Inaqueoussolution,theprotonbondswithawatermoleculetoformthehydronium ion.UnliketheArrheniustheory,however,theBrnstedLowrytheoryisnotrestrictedtoaqueoussolutions.Forexample,thelonepairofelectronsonanammoniamoleculecanbondwith

    +,an qu ammon acanac asa ase.

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    ConjugateAcidBasePairs

    proceedsinbothdirections.Aceticacidisweak,soonlyafewionsdissociate.Thepositionofequilibriumliestotheleft,andthereversereaction is favoured. In the reverse reaction the h dronium ion ives u aprotontotheacetateion.Thus,theseionsareanacidandabase,respectively.Theacidontheleft(CH3COOH)andthebaseontheright(CH3COO)differbyoneproton.Theyarecalledaconjugateacidbasepair.Similarly,H2OandH3O+areaconjugateacidbasepair.

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    Aqueousammoniaisaweakbase,sorelativelyfew

    y rox e

    ons

    orm.

    epos on

    o

    equ r um

    es

    o

    theleft.Intheforwardreaction,thewatermolecule.

    canactasaprotondonor(anacid)inonereactionand

    beamphoteric.(Wateractsasanacidinthepresence,

    strongeracid.

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    StrongAcidsandBases

    Whenastrongacidorbasedissolvesinwater,almosteveryacidorbasemoleculedissociates.Whiletherearemany

    acidsandbases,mostareweak.Thus,thenumberofstrongacidsandstrongbasesisfairlysmall.

    StrongAcids

    Binaryaci st at avet egenera ormu aHX aq ,w ereX=Cl,Br,andI(butnotF):forexample,hydrochloricacid,HCl,

    andhydrobromic acid,HBr (HCl andHBr arehydrohalic

    halogenelements).Oxoacids (acidscontainingoxygenatoms)inwhichthenumberofoxygenatomsexceeds,bytwoormore,thenumberofprotonsthatcanbedissociated:orexamp e,n tr cac , ,su ur c ac , ,

    perchloric acid,HClO4,andchloric acid,HClO3

    Thebinaryacidsofnonmetalsexhibitperiodictrendsin.

    trend:theelectronegativity oftheatomthatisbondedtohydrogen,andthestrengthofthebond.

    , , .Theyhaveonlyasinglehydrogenatomthatdissociatesinwater.Someacidshavemorethanonehydrogenatomthatdissociates.Theseacidsarecalledpolyprotic acids.

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    StrongbasesareconfinedtotheoxidesandhydroxidesfromGroups1(IA)and2(IIA).

    rong asesAlloxidesandhydroxidesofthealkalimetals:forexample,

    , , ,

    Alkalineearth(Group2(IIA))metaloxidesandhydroxides

    belowberyllium:forexample,calciumhydroxide,Ca(OH)2,andbariumhydroxide,Ba(OH)2

    Thestrongbasicoxideshavemetalatomswithlowe ec ronega v y. us, e on ooxygen s on can srelativelyeasilybrokenbytheattractionofpolarwatermolecules.Theoxideionalwaysreactswithwatermoleculestoproducehydroxideions.O2(aq)+H2O() 2OH(aq)

    Magnesiumoxideandmagnesiumhydroxidearenotveryso u e. eyares rong ases, owever, ecause esma amountthatdoesdissolvedissociatesalmostcompletelyintoions.Ber lliumoxideisaweakbase. Itistheexce tionin

    Group2(IIA).)Itisarelativelysmallatom,sothebondtooxygenisstrongandnoteasilybrokenbywatermolecules.

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    CalculationsThatInvolveStrongAcidsand

    Bases enas rongac ssoc a escomp e e y n o ons

    inwater,theconcentrationofH3O+(aq)isequaltotheconcentrationofthestrongacid.Similarly,when

    astron basedissociatescom letel inwater,the

    concentrationofOH(aq)isequaltothe.

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    TheEquilibriumofWeakAcidsandBases

    solutionproducesionsthatinteractwithwater.ThepHoftheaqueoussolutionisdeterminedbythepositionofequilibriuminreac ons e ween e ons a arepresen nso u onan ewatermolecules.Purewatercontainsafewions,producedbythe

    dissociationofwatermolecules:2H2O() H3O+(aq)+OH(aq)

    At25C,onlyabouttwowatermoleculesinonebilliondissociate,.

    neutralwater,at25C,theconcentrationofhydronium ionsisthesameastheconcentrationofhydroxideions:1.0 107mol/L.

    eseconcentrat onsmust et esame ecauset e ssoc at onofwaterproducesequalnumbersofhydronium andhydroxide

    ions.Becausethisisanequilibriumreaction,andbecausethepositionofequilibriumofallreactionschangeswithtemperature,[H3O+]isnot1.0 107mol/Latothertemperatures.Thesameistrueof OH .

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    TheIonProductConstantforWater

    Theequilibriumconstant,Kc,forthedissociationofwaterisgivenbythefollowingexpression.

    Sofewionsformthattheconcentrationofwaterisessentiallyconstant.TheproductKc[H2O]2 isequaltotheproductoftheconcentrationsofhydronium ions

    andhydroxideions.TheequilibriumvalueoftheconcentrationionproductH3O+ OH at25 Cisca e t e onpro uctconstant orwater.Itisgivent e

    symbolKw.

    Kc[H2O]2=[H3O+][OH]=1.0 107mol/L 1.0 107mol/L=1.0 1014=Kw

    eun tsarecommon y roppe ,as not erequ r umexpress onsyou ave

    encountered.TheconcentrationofH3O+inthesolutionofastrongacidisequaltotheconcentrationofthedissolvedacid,unlessthesolutionisverydilute.Consider

    + . .dissociateinwater,formingahydronium ionconcentrationthatequals0.1mol/L.Theincreased[H3O+]pushesthedissociationreactionbetweenwatermoleculesto

    theleft,inaccordancewithLeChteliers principle.Consequently,theconcen ra ono y ron um ons a resu s rom e ssoc a ono wa er sevenlessthan1 107mol/L.This[H3O+]isnegligiblecomparedwiththe0.1mol/Lconcentrationofthehydrochloricacid.Unlessthesolutionisverydilute(about1

    [H3O+]ofastrongacid.

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    Similarly,theconcentrationofhydroxideionscanbe

    thesolutionisastrongbase,youcanignorethedissociationofwatermoleculeswhendetermining[OH],unlessthe

    . known,youcanusetheionproductconstantforwater,Kw,to

    determinetheconcentrationoftheotherion.Althou hthevalueofKw forwateris1.0 1014at25Conly,youcanusethisvalueunlessanothervalueisgivenforadifferent

    .

    Inanacidicsolution,[H3O+]isgreaterthan1.0 107mol/L

    and[OH]islessthan1.0 107mol/L.Inaneutralsolution,both[H3O+]and[OH]areequalto1.0 107mol/L.Inabasicsolution,[H3O+]islessthan1.0 107mol/Land[OH]

    . .

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    pHandpOH Youcandescribetheacidit ofana ueoussolution uantitativel b statin

    theconcentrationofthehydronium ionsthatarepresent.[H3O+]isoftenaverysmallnumber.ThepHscalewasdevisedasaconvenientwayto

    represen ac y an , yex ens on, as c y . esca e s ogar m c,

    basedon10.Thinkoftheletterpasamathematicaloperationrepresenting

    log.ThepHofasolutionistheexponentialpowerofhydrogen(orhydronium)ions,inmolesperlitre.Itcanthereforebeexpressedasfollows:pH= log[H3O+]

    T epractica rangeo t epHsca eis rom0to14.Aso utiono astrong

    acidthatismoreconcentratedthan1.0mol/LwouldgiveanegativepH.

    Since oucandetermine H3O+ ofsuchsolutionsdirectl fromthe

    concentrationoftheacid,thepHscaleoffersnoadvantage.Similarly,the

    pHofastrongbasethatismoreconcentratedthan1.0mol/Lisgreaterthan

    . o e a p sa mens on essquan y. no erwor s, asnoun s.

    YoucancalculatethepOH (thepowerofhydroxideions)ofasolutionfrom

    =

    Kw=[H3O+][OH]=1.0 1014at25C pH+pOH =14

    Th A id Di i i C

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    TheAcidDissociationConstant

    Manycommonfoods(suchascitrusfruits),pharmaceuticals,andsomevitaminsareweakacids.Whenaweakaciddissolvesinwater itdoesnot

    completelydissociate.Theconcentrationofthehydronium ions,andtheconcentrationoftheconjugatebaseoftheacidthatisformedinsolution,dependontheinitialconcentrationoftheacidandtheamountofacidthatdissociates.Youcanrepresentanyweakmonoprotic acidwiththegeneralformulaHA.Theequilibriumofaweakmonoprotic acidinaqueoussolution

    canbeexpressedasfollows:HA(aq)+H2O(aq) H3O+(aq)+A(aq)

    TheequilibriumexpressionforthisreactionisKc =[H3O+][A]/[HA][H2O]

    , .

    Multiplyingbothsidesoftheequilibriumexpressionby[H2O]givestheproductoftwoconstantsontheleftside.Thisnewconstantiscalledtheaciddissociationconstant Ka.Kc[H2O]=Ka=[H3O+][A]/[HA]

    YoucandeterminethevalueofKaforaparticularacidbymeasuringthepH.

    WeakacidshaveKavaluesthatarebetween1andabout1 1016.VeryweakacidshaveKavaluesthatarelessthan1 1016.Thesmallerthe

    , .

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    The Base Dissociation Constant

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    TheBaseDissociationConstant

    Manycompoundsthatarepresentinplantsareweakbases.

    a e ne

    nco ee

    an

    p per ne n

    ac

    pepper

    are

    wo

    examples.Aweakbase,representedbyB,reactswithwatertoformane uilibriumsolutionofions.

    B(aq)+H2O() HB+(aq)+OH(aq)

    Theequilibriumexpressionforthisgeneralreactionisgivenasfollows:

    Kc =[HB+][OH]/[B][H2O]

    Theconcentrationofwaterisalmostconstantindilutesolutions.Multiplyingbothsidesoftheequilibrium

    theleftside.Thenewconstantiscalledthebasedissociationconstant,Kb.

    Kc[H2O]=[HB+][OH]/[B]=Kb

    NitrogencontainingcompoundsareBrnstedLowrybases,

    bondwithH+fromwater.

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    AcidsandTheirConjugateBases

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    j g

    Thereisanimportantrelationshipbetweenthedissociationconstantforanacid Ka andthedissociationconstant oritscon u atebase Kb.Consider

    aceticacidanditsdissociationinwater.CH3COOH(aq)+H2O(aq) H3O+(aq)+CH3COO(aq)

    Theacetateionistheconjugatebaseofaceticacid.Asolublesaltofthe

    conjugatebase,

    such

    as

    sodium

    acetate,

    forms

    acetate

    ions

    in

    solution.

    The

    .

    CH3COO(aq)+H2O(aq) CH3COOH(aq)+OH(aq)

    Kbisgivenbytheexpression:Kb=[CH3COOH][OH]/[CH3COO]

    TheproductKaKb givesaninterestingresult.

    KaKb =[H3O+][CH3COO]/[CH3COOH] [CH3COOH][OH]/[CH3COO]

    = =

    Thus,foranacidanditsconjugatebase(orabaseanditsconjugateacid),KaKb =Kw.Oneinterpretationoftheresultisthestrongeranacid,the

    . ,strongacidgivesupaprotonfromeachmolecule.Therefore,itsconjugatebasedoesnotbondwiththeproton.Insummary,then,thestrengthofan

    acidisalwaysaweakbase,and,conversely,theconjugateofastrongbase

    isalwaysaweakacid.

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