GRADE12CHEMISTRY

OLYMPIADSCHOOL
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Acids, Acids Bases Bases and pH

TheArrheniusTheoryofAcidsandBases AccordingtotheArrheniustheory(1887),acidsandbasesaredefinedin termsoftheirstructureandtheionsproducedwhentheydissolveinwater. p y *AnacidisasubstancethatdissociatesinwatertoformH+(aq).Twoexamples ofArrheniusacidsarehydrochloricacid,HCl,andsulfuric acid,H2SO4. *A base is a substance that dissociates in water to form OH(aq) Two AbaseisasubstancethatdissociatesinwatertoformOH(aq).Two examplesofArrheniusbasesaresodiumhydroxide,NaOH,andpotassium hydroxide,KOH. TheArrheniustheoryexplainsacidbasereactionsasacombinationof H+(aq)andOH(aq).Itprovidesinsightintotheheatofneutralizationfor thereactionbetweenastrongacidandastrongbase.(Strongacidsand the reaction between a strong acid and a strong base (Strong acids and basesdissociatecompletelyintoionsinsolution.) Considerthefollowing: HCl(aq)+NaOH(aq)NaCl(aq)+H2O(l)H=56kJ l( ) ( ) l( ) (l) k Thetotalionicequationforthisreactionis H+(aq)+Cl(aq)+Na+(aq)+OH(aq)Na+(aq)+Cl(aq)+H2O(l)H=56kJ (aq) C (aq) a (aq) O (aq) a (aq) C (aq) O( ) 56 J Subtractingspectatorionsfrombothsides,thenetionicequationis H+(aq) +OH(aq)H2O()H=56kJ

 DifferentcombinationsofstrongArrheniusacidsandbasesreactwiththe sameexothermicresult.Measurementsalwaysshowthereleaseof56kJof energypermoleofwaterformed.Thismakessense,becausethenetionic equationisthesameregardlessofthespecificneutralizationreactionthat occurs. TheArrheniustheoryhaslimitations,however.Forexample,H+(aq),abare proton,doesnotexistinwater.Thepositivechargeonaprotonisattracted totheregionofnegativechargeonthelonepairofelectronsonawater moleculesoxygenatom.Thecombinationisahydratedprotoncalleda hydroniumion,H3O+(aq)(H+(aq)+H2O()H3O+(aq)) h d i i H3O ( ) (H ( ) H2O() H3O ( )) Thehydronium ionformshydrogenbondswithotherwatermolecules. Thus,abetterformulafortheionthatispresentinacidicsolutionsis [H(H2O)n]+,wherenisusually4or5.For convenience,however,chemists [H(H2O) ] h i ll 4 5 F i h h i usuallyuseasinglehydronium ionwhenwritingequations. TheArrheniustheoryalsohaslimitationsforexplainingcertainreactions. Forexample,aqueoussolutionsofammoniaarebasic.Theyreactwithacids l l f b h h d inneutralizationreactions,eventhoughammoniadoesnotcontainthe hydroxideion.Manyaqueoussolutionsofsaltswithnohydroxideionsare basic,too.Somereactionstakeplacewithoutanyliquidsolvent.For b i t S ti t k l ith t li id l t F example,ammoniumchloridecanbeformedbythereactionbetween ammoniaandhydrogenchloride,whicharebothgases: NH3(g)+HCl(g)NH4Cl(s) NH3( ) HCl( ) NH4Cl( )

TheBrnstedLowryTheory ThelimitationsoftheArrheniustheoryofacidsandbasesareovercomeby amoregeneraltheory,calledtheBrnstedLowrytheory.Thistheorywas g y, y y y proposedindependently,in1923,byJohannesBrnsted,aDanishchemist, andThomasLowry,anEnglishchemist.Itrecognizesanacidbasereaction asachemicalequilibrium,havingbothaforwardreactionandareverse reactionthatinvolvethetransferofaproton.TheBrnstedLowrytheory definesacidsandbasesasfollows: *Anacidisasubstancefromwhichaprotoncanberemoved.(Somechemists f p ( describeBrnstedLowryacidsasprotondonors.) *Abaseisasubstancethatcanacceptaproton.(Somechemistsdescribe BrnstedLowrybasesasprotonacceptors.) y p p ) Notethatthewordprotonreferstothenucleusofahydrogenatom an H+ionthathasbeenremovedfromtheacidmolecule.Itdoesnotrefertoa p protonremovedfromthenucleusofanotheratom,suchasoxygenor , yg sulfur,thatmaybepresentintheacidmolecule.Asmentionedpreviously, H+ionsshareelectronswithanyspecies(ionormolecule)thathasalone pairofelectrons.Inaqueoussolution,theprotonbondswithawater moleculetoformthehydronium ion.UnliketheArrheniustheory,however, theBrnstedLowrytheoryisnotrestrictedtoaqueoussolutions.For example,thelonepairofelectronsonanammoniamoleculecanbondwith H+,andliquidammoniacanactasabase. H d li id i t b

ConjugateAcidBasePairs The dissociation of acetic acid in water is an equilibrium reaction because it Thedissociationofaceticacidinwaterisanequilibriumreactionbecauseit proceedsinbothdirections.Aceticacidisweak,soonlyafewions dissociate.Thepositionofequilibriumliestotheleft,andthereverse reactionisfavoured.Inthereversereaction,thehydronium iongivesupa reaction is favoured. In the reverse reaction, the hydronium ion gives up a protontotheacetateion.Thus,theseionsareanacidandabase, respectively.Theacidontheleft(CH3COOH)andthebaseontheright (CH3COO)differbyoneproton.Theyarecalledaconjugateacidbasepair. y p y j g p Similarly,H2OandH3O+areaconjugateacidbasepair.

 Aqueousammoniaisaweakbase,sorelativelyfew hydroxideionsform.Thepositionofequilibriumliesto h d id i f Th iti f ilib i li t theleft.Intheforwardreaction,thewatermolecule givesupaprotonandactsasanacid.Asubstancethat gives up a proton and acts as an acid A substance that canactasaprotondonor(anacid)inonereactionand aprotonacceptor(abase)inanotherreactionissaidto a proton acceptor (a base) in another reaction is said to beamphoteric.(Wateractsasanacidinthepresence ofastrongerbase,andasabaseinthepresenceofa of a stronger base and as a base in the presence of a strongeracid.

StrongAcidsandBases Whenastrongacidorbasedissolvesinwater,almostevery acidorbasemoleculedissociates.Whiletherearemany acidsandbases,mostareweak.Thus,thenumberofstrong id db k h h b f acidsandstrongbasesisfairlysmall. StrongAcids BinaryacidsthathavethegeneralformulaHX(aq),whereX= Bi id h h h lf l HX( ) h X Cl,Br,andI(butnotF):forexample,hydrochloricacid,HCl, andhydrobromic acid,HBr (HCl andHBr arehydrohalic acids:acidsthathavehydrogenbondedtoatomsofthe acids: acids that have hydrogen bonded to atoms of the halogenelements).Oxoacids (acidscontainingoxygen atoms)inwhichthenumberofoxygenatomsexceeds,by twoormore,thenumberofprotonsthatcanbedissociated: forexample,nitricacid,HNO3,sulfuric acid,H2SO4, f l i i id HNO3 lf i id H2SO4 perchloric acid,HClO4,andchloric acid,HClO3 Thebinaryacidsofnonmetalsexhibitperiodictrendsin theiracidstrength.Twofactorsareresponsibleforthis their acid strength Two factors are responsible for this trend:theelectronegativity oftheatomthatisbondedto hydrogen,andthestrengthofthebond. AcidssuchasHCl,CH3COOH,andHFaremonoprotic acids. Acids such as HCl, CH3COOH, and HF are monoprotic acids. Theyhaveonlyasinglehydrogenatomthatdissociatesin water.Someacidshavemorethanonehydrogenatomthat dissociates.Theseacidsarecalledpolyprotic acids.

 Strongbasesareconfinedtotheoxidesandhydroxidesfrom Groups1(IA)and2(IIA). St StrongBases B Alloxidesandhydroxidesofthealkalimetals:forexample, sodiumhydroxide,NaOH,andpotassiumhydroxide,KOH sodium hydroxide NaOH and potassium hydroxide KOH Alkalineearth(Group2(IIA))metaloxidesandhydroxides belowberyllium:forexample,calciumhydroxide,Ca(OH)2, y p y ( ) andbariumhydroxide,Ba(OH)2 Thestrongbasicoxideshavemetalatomswithlow electronegativity.Thus,thebondtooxygenisionicandis electronegativity Thus the bond to oxygen is ionic and is relativelyeasilybrokenbytheattractionofpolarwater molecules.Theoxideionalwaysreactswithwatermolecules y toproducehydroxideions.O2(aq)+H2O()2OH(aq) Magnesiumoxideandmagnesiumhydroxidearenotvery soluble.Theyarestrongbases,however,becausethesmall l bl Th t b h b th ll amountthatdoesdissolvedissociatesalmostcompletelyinto ions.Berylliumoxideisaweakbase.(Itistheexceptionin y ( p Group2(IIA).)Itisarelativelysmallatom,sothebondto oxygenisstrongandnoteasilybrokenbywatermolecules.

CalculationsThatInvolveStrongAcidsand Bases
Wh Whenastrongaciddissociatescompletelyintoions t id di i t l t l i t i inwater,theconcentrationofH3O+(aq)isequalto theconcentrationofthestrongacid.Similarly,when g p y , astrongbasedissociatescompletelyinwater,the concentrationofOH(aq)isequaltothe concentrationofthestrongbase. concentration of the strong base

TheEquilibriumofWeakAcidsandBases
The dissociation of an acidic or basic compound in aqueous Thedissociationofanacidicorbasiccompoundinaqueous solutionproducesionsthatinteractwithwater.ThepHofthe aqueoussolutionisdeterminedbythepositionofequilibriumin reactionsbetweentheionsthatarepresentinsolutionandthe ti b t th i th t ti l ti d th watermolecules.Purewatercontainsafewions,producedbythe dissociationofwatermolecules: 2H2O() H3O+(aq)+OH(aq) At25C,onlyabouttwowatermoleculesinonebilliondissociate, whichiswhypurewaterissuchapoorconductorofelectricity.In which is why pure water is such a poor conductor of electricity In neutralwater,at25C,theconcentrationofhydronium ionsisthe sameastheconcentrationofhydroxideions:1.0 107mol/L. Theseconcentrationsmustbethesamebecausethedissociation Th i b h b h di i i ofwaterproducesequalnumbersofhydronium andhydroxide ions.Becausethisisanequilibriumreaction,andbecausethe positionofequilibriumofallreactionschangeswithtemperature, [H3O+]isnot1.0 107mol/Latothertemperatures.Thesameis trueof[OH]. [ ]

TheIonProductConstantforWater Theequilibriumconstant,Kc,forthedissociationofwaterisgivenbythefollowing expression.

Sofewionsformthattheconcentrationofwaterisessentiallyconstant.The productKc[H2O]2 isequaltotheproductoftheconcentrationsofhydronium ions andhydroxideions.Theequilibriumvalueoftheconcentrationionproduct [H3O+][OH]at25Ciscalledtheionproductconstantforwater.Itisgiventhe [H3O ][OH ] 25C i ll d h i d f I i i h symbolKw. Kc[H2O]2=[H3O+][OH]=1.0 107mol/L 1.0 107mol/L=1.0 1014=Kw Theunitsarecommonlydropped,asinotherequilibriumexpressionsyouhave Th i l d d i h ilib i i h encountered.TheconcentrationofH3O+inthesolutionofastrongacidisequalto theconcentrationofthedissolvedacid,unlessthesolutionisverydilute.Consider [H3O+]inasolutionof0.1mol/Lhydrochloricacid.AllthemoleculesofHCl [H3O+] in a solution of 0.1 mol/L hydrochloric acid. All the molecules of HCl dissociateinwater,formingahydronium ionconcentrationthatequals0.1mol/L. Theincreased[H3O+]pushesthedissociationreactionbetweenwatermoleculesto theleft,inaccordancewithLeChteliers principle.Consequently,the concentrationofhydronium i t ti fh d i ionsthatresultsfromthedissociationofwateriseven th t lt f th di i ti f t i lessthan1 107mol/L.This[H3O+]isnegligiblecomparedwiththe0.1mol/L concentrationofthehydrochloricacid.Unlessthesolutionisverydilute(about1 10 7mol/L),thedissociationofwatermoleculescanbeignoredwhendetermining 107 mol/L), the dissociation of water molecules can be ignored when determining [H3O+]ofastrongacid.

 Similarly,theconcentrationofhydroxideionscanbe determinedfromtheconcentrationofthedissolvedbase.If determined from the concentration of the dissolved base. If thesolutionisastrongbase,youcanignorethedissociation ofwatermoleculeswhendetermining[OH],unlessthe solutionisverydilute.Wheneither[H3O+]or[OH]is solution is very dilute When either [H3O+] or [OH ] is known,youcanusetheionproductconstantforwater,Kw,to determinetheconcentrationoftheotherion.Althoughthe g valueofKw forwateris1.0 1014at25Conly,youcanuse thisvalueunlessanothervalueisgivenforadifferent temperature. temperature [H3O+] and [OH] in Aqueous Solutions at 25C [H3O+]and[OH ]inAqueousSolutionsat25 C Inanacidicsolution,[H3O+]isgreaterthan1.0 107mol/L and[OH]islessthan1.0 107mol/L.Inaneutralsolution, both[H3O+]and[OH]areequalto1.0 107mol/L.Ina basicsolution,[H3O+]islessthan1.0 107mol/Land[OH] isgreaterthan1.0 10 7mol/L. is greater than 1 0 107 mol/L

pHandpOH
Youcandescribetheacidityofanaqueoussolutionquantitativelybystating ou ca desc be t e ac d ty o a aqueous so ut o qua t tat e y by stat g theconcentrationofthehydronium ionsthatarepresent.[H3O+]isoftena verysmallnumber.ThepHscalewasdevisedasaconvenientwayto representacidity(and,byextension,basicity).Thescaleislogarithmic, t idit ( d b t i b i it ) Th l i l ith i basedon10.Thinkoftheletterpasamathematicaloperationrepresenting log.ThepHofasolutionistheexponentialpowerofhydrogen(or g p p p f y g ( hydronium)ions,inmolesperlitre.Itcanthereforebeexpressedas follows:pH=log[H3O+] Th ThepracticalrangeofthepHscaleisfrom0to14.Asolutionofastrong i l f h H l i f 0 14 A l i f acidthatismoreconcentratedthan1.0mol/LwouldgiveanegativepH. Sinceyoucandetermine[H3O+]ofsuchsolutionsdirectlyfromthe y [ ] y concentrationoftheacid,thepHscaleoffersnoadvantage.Similarly,the pHofastrongbasethatismoreconcentratedthan1.0mol/Lisgreaterthan 14.NotethatpHisadimensionlessquantity.Inotherwords,ithasnounits. 14 N t th t H i di i l tit I th d it h it YoucancalculatethepOH (thepowerofhydroxideions)ofasolutionfrom the[OH ].pOH log[OH ] the [OH]. pOH =log[OH] Kw=[H3O+][OH]=1.0 1014at25C pH+pOH =14

TheAcidDissociationConstant Manycommonfoods(suchascitrusfruits),pharmaceuticals,andsome vitaminsareweakacids.Whenaweakaciddissolvesinwater,itdoesnot , completelydissociate.Theconcentrationofthehydronium ions,andthe concentrationoftheconjugatebaseoftheacidthatisformedinsolution, dependontheinitialconcentrationoftheacidandtheamountofacidthat dissociates.Youcanrepresentanyweakmonoprotic acidwiththegeneral formulaHA.Theequilibriumofaweakmonoprotic acidinaqueoussolution canbeexpressedasfollows: HA(aq)+H2O(aq) H3O+(aq)+A(aq) TheequilibriumexpressionforthisreactionisKc =[H3O+][A]/[HA][H2O] Indilutesolutions,theconcentrationofwaterisalmostconstant. In dilute solutions the concentration of water is almost constant Multiplyingbothsidesoftheequilibriumexpressionby[H2O]givesthe productoftwoconstantsontheleftside.Thisnewconstantiscalledthe aciddissociationconstant,Ka. , Kc[H2O]=Ka=[H3O+][A]/[HA] YoucandeterminethevalueofKaforaparticularacidbymeasuringthepH ofasolution. of a solution WeakacidshaveKavaluesthatarebetween1andabout1 1016.Very weakacidshaveKavaluesthatarelessthan1 1016.Thesmallerthe valueofKa,thelesstheacidionizesinaqueoussolution. value of Ka the less the acid ionizes in aqueous solution

TheBaseDissociationConstant Manycompoundsthatarepresentinplantsareweakbases. Caffeineincoffeeandpiperidine i bl k C ff i i ff d i idi inblackpepperaretwo t examples.Aweakbase,representedbyB,reactswithwater toformanequilibriumsolutionofions. q B(aq)+H2O() HB+(aq)+OH(aq) Theequilibriumexpressionforthisgeneralreactionisgiven q p g g asfollows: Kc =[HB+][OH]/[B][H2O] Theconcentrationofwaterisalmostconstantindilute solutions.Multiplyingbothsidesoftheequilibrium expressionby[H2O]givestheproductoftwoconstantson expression by [H2O] gives the product of two constants on theleftside.Thenewconstantiscalledthebasedissociation constant,Kb. Kc[H2O]=[HB+][OH]/[B]=Kb NitrogencontainingcompoundsareBrnstedLowrybases, becausethelonepairofelectronsonanitrogenatomcan because the lone pair of electrons on a nitrogen atom can bondwithH+fromwater.

AcidsandTheirConjugateBases Thereisanimportantrelationshipbetweenthedissociationconstantforan acid,Ka,andthedissociationconstantforitsconjugatebase,Kb.Consider , , f j g , aceticacidanditsdissociationinwater. CH3COOH(aq)+H2O(aq) H3O+(aq)+CH3COO(aq) Kaisgivenbythefollowingexpression:Ka=[CH3COO][H3O+]/[CH3COOH] Ka is given by the following expression: Ka = [CH3COO][H3O+]/[CH3COOH] Theacetateionistheconjugatebaseofaceticacid.Asolublesaltofthe conjugatebase,suchassodiumacetate,formsacetateionsinsolution.The solutionactsasabasewithwater. solution acts as a base with water CH3COO(aq)+H2O(aq) CH3COOH(aq)+OH(aq) Kbisgivenbytheexpression:Kb=[CH3COOH][OH]/[CH3COO] TheproductKaKb givesaninterestingresult. KaKb =[H3O+][CH3COO]/[CH3COOH] [CH3COOH][OH]/[CH3COO] =[H3O+][OH ]=Kw = [H3O+][OH] = Kw Thus,foranacidanditsconjugatebase(orabaseanditsconjugateacid), KaKb =Kw.Oneinterpretationoftheresultisthestrongeranacid,the weakeritsconjugatebasemustbe.Thismakessensechemically,becausea weaker its conjugate base must be This makes sense chemically because a strongacidgivesupaprotonfromeachmolecule.Therefore,itsconjugate basedoesnotbondwiththeproton.Insummary,then,thestrengthofan acidanditsconjugatebaseareinverselyrelated.Theconjugateofastrong acid and its conjugate base are inversely related. The conjugate of a strong acidisalwaysaweakbase,and,conversely,theconjugateofastrongbase isalwaysaweakacid.

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