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AcidsandBases

AnIntroduction
DavidAKatz
DepartmentofChemistry Department of Chemistry PimaCommunityCollege, Tucson,AZ,USA

BasedonaPowerPointbyJohnD.Bookstaver,St.CharlesCommunityCollege,St.Peters, ased on a PowerPoint by John . ookstaver, St. Charles Community College, St. Peters, MOforChemistry,TheCentralScience,10thedition,byTheodoreL.Brown;H.Eugene LeMay,Jr.;andBruceE.Bursten

PropertiesofAcids Properties of Acids


1. Sourtaste (examples:vinegar,citricacid,lemonjuice) 2. Turnslitmusfrombluetored(alsoaffectsother indicators) 3. ReactswithmetalstoliberateH2 4. Reactswithbaselosingitsacidproperties 5. Reactswithsaltstogiveanewacidandanewsalt 6. Conductselectricity(electrolyte)

PropertiesofBases Properties of Bases


1. Bittertaste(examples:bakingsoda,soap) 2. Turnslitmusfromredtoblue(alsoaffectsother indicators bestknownisphenolphthalein) 3. Soapyfeel 4. Reactswithacidlosingitsbasicproperties 5. Conductselectricity(electrolyte)

TheArrheniusTheory The Arrhenius Theory


Svante August Arrhenius (1859 1927) SvanteAugustArrhenius(1859 1927) Acid: Substancethatproduces hydrogenionsinwatersolution. y g HCl(aq) H+(aq) +Cl (aq) Base: Substance that produces Substancethatproduces hydroxideionsinwatersolution. NaOH(aq) Na+(aq) +OH(aq) Anacidneutralizesabase H+( ) + OH( ) H2O(l) (aq) +OH (aq) H

TheArrheniusTheory The Arrhenius Theory


Acid strength depends on the amount of Acidstrengthdependsontheamountof hydrogenionsproduced.
DefinitionincludesacidssuchasHCl,HBr,HI, HNO3,H2SO4,HSO4,HC2H3O2,etc.

Basestrengthdependsonamountof hydroxideionsproduced. h d id i d d
DefinitionincludesbasessuchasNaOH,KOH, Ca(OH)2,Mg(OH)2,Al(OH)3,etc. Mg(OH) Al(OH) etc

TheArrheniusTheory The Arrhenius Theory


Problems with the Arrhenius Theory ProblemswiththeArrheniusTheory
Thesolventislimitedtowater,butwaterisnotinvolved intheacidbasereaction AsolutionofCO2inwaterisacidic,butH2CO3 existsata concentrationlessthan1%oftheCO2 A solution of NH3 in water is basic but NH4OH does not AsolutionofNH inwaterisbasic,butNH OHdoesnot exist(Note:theformulaNH4OHwasinventedby ArrheniustoexplainthebasicnatureofNH3 solutions) ThereactionofHClandNH3 resultsinanacidicsolution

AGeneralizedArrheniusTheory A Generalized Arrhenius Theory


Thesolvent(water)canionizetoproduceH+ andOH ( ) p ions H+(aq) +OH(aq) H2O(l) Acid:Substancethatincreasestheconcentrationof hydrogenionsinsolution. hydrogen ions in solution H+(aq) +Cl (aq) HCl(aq) Astrongacidis100%dissociated Aweakacidisonlyslightlydissociated

AGeneralizedArrheniusTheory A Generalized Arrhenius Theory


Base:Substancethatincreasestheconcentrationof ase Substa ce t at c eases t e co ce t at o o hydroxideionsinwatersolution. NaOH(aq) Na+(aq) +OH(aq) ( q) ( q) ( q)
Astrongbaseis100%dissociated Aweakbaseisonlyslightlydissociated

HydrolysisreactionscanchangeH+ andOH concentrationinwatersolution concentration in water solution CO2 +H2O NH3 + H2O +H O H+ +HCO3 NH4+ + OH +OH CO2isanacid NH3 is a base 3isabase

AGeneralizedArrheniusTheory A Generalized Arrhenius Theory


Solventsotherthanwatercanbeused: Thesolventcanionizetoproducepositiveandnegative ions Example:liquidammonia,NH Example: liquid ammonia, NH3 2NH3 NH4+ +NH2 Acid:Substancethatincreasestheconcentrationofthe Acid Substance that increases the concentration of the positiveioninsolution. HCl +NH3 NH4+ +Cl Base:Substancethatincreasestheconcentrationofthe negativeioninwatersolution. NaOH +NH3 Na+ +NH2 +H2O(l)

AGeneralizedArrheniusTheory A Generalized Arrhenius Theory


Solventsotherthanwater(continued) Solvents other than water (continued) Neutralizationproducesthesolvent: Example:Inliquidammonia,NH Example: In liquid ammonia NH3 NH4+ +NH2 2NH3

TheBrnsted LowryTheory The BrnstedLowry Theory


JohannesNicolaus Brnsted (18791947) andThomasMartinLowry(18741936) independentlyproposedtheproton definitionofacidsandbasesin1923 QuotingBrnsted:
"...acidsandbasesaresubstancesthatare capableofsplittingoffortakinguphydrogen capable of splitting off or taking up hydrogen ions,respectively. or Anacidbasereactionconsistsofthetransferof aproton(orhydrogenion)fromanacidtoa base

TheBrnsted LowryTheory The BrnstedLowry Theory


Anacidisaprotondonor An acid is a proton donor
Thatis,anacidisasubstancefromwhicha proton(H )canberemoved. proton (H+) can be removed

ABaseisaprotonacceptor
Thatis,abaseisasubstancethathasanon bondedelectronpairthatcanbondwitha proton(H+)fromanacid.

Nosolventisspecified

TheBrnsted LowryTheory The BrnstedLowry Theory


Ifasubstancecaneitherloseaprotonorgaina If a substance can either lose a proton or gain a proton,thenitis amphiprotic Someexamplesare p HCO3 ,HSO4 ,andH2O UsingHCO Using HCO3: asanacid:HCO3 +H2O H3O+ +CO32 asabase:HCO3 +H3O+ H2CO3+H2O Notethattheproton(H+)iscombinedwith waterformingH3O+ t f i H

TheBrnsted LowryTheory The BrnstedLowry Theory


HCl+H2O H3O+ +Cl
Lookingattheforwardreaction: HClisanacid,becauseithasaprotonavailabletobe transferred. H2Oisabase,sinceitbondswiththeprotonthattheacid lost. lost Lookingatthereversereaction: H3O+ is an acid, because it can give a proton to the Cl isanacid,becauseitcangiveaprotontotheCl Clisabase,sinceitcanbondwiththeprotonfromH3O+ NotethateachpairHClandCl,and,H2OandH3O+ differby oneproton.Thesepairsarecalledconjugateacidbasepairs

TheBrnsted LowryTheory The BrnstedLowry Theory


So,inthereaction:

HCl+H2O
AcidBase Acid Base

H3O+ +Cl
Conjugate Conjugate Acid Base

Oneacid baseconjugatepairisHClandCl One acidbase conjugate pair is HCl and Cl


HClisanacid,andClistheconjugatebaseofHCl

ThesecondacidbaseconjugatepairisH O The second acidbase conjugate pair is H2O andH3O


H2O is a base and H3O+ is the conjugate acid of H2O Oisabase,andH istheconjugateacidofH

TheBrnsted LowryTheory The BrnstedLowry Theory


WhenanAcidDissolves inWater:
Acid1 Base2

WateractsasaBrnsted Lowrybaseandabstractsa proton(H )fromtheacid. proton (H+) from the acid Asaresult,theconjugate base oftheacidanda hydroniumion areformed.

Base1

Acid2

ConjugateAcidsandBases:
FromtheLatinwordconjugare,meaningtojoin together. g Reactionsbetweenacidsandbasesalwaysyield theirconjugatebasesandacids. j g Anotherexampleis:

StrongAcids
HNO3, HCl, H2SO4 and HClO4 are the most commonly known strong acids. l k t id

StrongAcids

This is a submicroscopic artists view

WeakAcids
Weakacidsaremuchlessthan100%ionizedinwater (usually5%ionicorless) (usually 5% ionic or less) Oneofthebestknownweakacidsisaceticacid,CH3CO2H

WeakAcids

StrongBases
AStrongBaseis100%dissociatedinwater. 100%dissociatedinwater.
NaOH(aq) Na+(aq) +OH(aq) aq) aq) aq) OthercommonstrongbasesincludeKOHandCa(OH)2 CaO (lime)+H2O Ca(OH)2(slakedlime)

CaO

WeakBases Weak Bases


AWeakbaseislessthan100%ionizedinwater
Oneofthebestknownweakbasesisammonia NH3(aq) +H2O(l) NH4+(aq) +OH(aq)

WeakBases Weak Bases

StrongAcids Strong Acids


ThesevenstrongacidsareHCl,HBr,HI,HNO3, H2SO4,HClO3,andHClO4. HClO and HClO These are by definition strong electrolytes and Theseare,bydefinition,strongelectrolytesand existtotallyasionsinaqueoussolution(i.e.,they are100%ionicinsolution) Forthemonoprotic strongacids,the concentrationofH3O+ i i fH isequaltothe l h concentrationoftheacid:

[H3O+] = [acid] ]=[acid]

StrongBases Strong Bases


Strongbasesarethesolublehydroxides,whichare thealkalimetalandheavieralkalineearthmetal h lk li l dh i lk li h l hydroxides(Ca2+,Sr2+,andBa2+). Strongbasesdissociatecompletelyinaqueous solution(i.e.,theyare100%ionicinsolution). solution (i e they are 100% ionic in solution) F Foramonohydroxy strongbase,theconcentration h d t b th t ti ofOH isequaltotheconcentrationofthebase:

[OH] [b ] ]=[base]

WeakAcids Weak Acids


Acetic acid, HC2H3O2,isaweakacid

HC2H3O2(aq) +H2O(l) 2(aq)

H3O+(aq) +C2H3O2(aq) (aq)

AcetateisastrongerbasethanH2O,sothemolecular form(theleftsideoftheequation)isfavored. form (the left side of the equation) is favored. Onlyabout1%oftheaceticacidisionic.

PolyproticAcids
Havemorethanoneionizable H Acommonpolyprotic acidissulfuricacid,H A common polyprotic acid is sulfuric acid H2SO4 Thedissociationofapolyprotic acidiswrittento takeplaceinsteps: take place in steps: H2SO4(aq)+H2O(l) HSO4(aq)+H2O(l) HSO4(aq)+H3O+(aq) SO42(aq)+H3O+(aq)

For a weak acid or weak base all the ions shown in Foraweakacidorweakbase,alltheionsshownin theequationarepresentinsolution.

PolyproticAcids

PolyproticAcids Polyprotic Acids

AutoionizationofWater Autoionization of Water


Waterisamphoteric. Inpurewater,afewmoleculesactasbases andafewactasacids.

H2O(l)+H2O(l)

H3O+(aq)+OH(aq)

Thisprocessisreferredtoasautoionization.

AutoionizationofWater
TheproductoftheconcentrationsofH3O+ andOH is givenbytheequation: i b h i

Kw =[H3O+][OH]=1.00x1014 at25oC
Inaneutralsolutiontheconcentrations[H ]=[OH In a neutral solution the concentrations [H3O+] = [OH] so[H3O+]=[OH]=1.00x107 M

p pH
Acommonwaytoexpressacidityand basicityiswithpH
p pHisdefinedasthenegativelogarithm(tothebase g g ( 10)ofthehydrogenion(hydronium)concentration

pH= log[H pH = log [H3O+]


Inaneutralsolution, [H3O+]=[OH]=1.00x107 at25oC pH=log(1.00x107) = (7)=7

pH
Therefore in pure water Therefore,inpurewater, pH=log(1.0 107)=7.00 An acid has a higher [H3O+] than pure water so Anacidhasahigher[H ]thanpurewater,so itspHis<7 [ ] p , Abasehasalower[H3O+]thanpurewater,soits pHis>7.

p pH
TheconceptofpHwasfirstintroducedbyDanishchemist SrenPederLauritzSrensen(18681939),theheadofthe CarlsbergLaboratorysChemicalDepartment,in1909 Dr.SrensendevelopedthepHscaleduringhispioneering researchintoproteins,aminoacidsandenzymes thebasis oftodaysproteinchemistryinapapertitledEnzyme StudiesII.TheMeasurementandMeaningofHydrogenIon ConcentrationinEnzymaticProcesses:
The value of the hydrogen ion concentration will accordingly be expressed by the hydrogen ion based on the normality factor of the solution used, and this factor will have the form of a negative power of 10 10. Since in the following section I usually refer to this, I will explain here that I use the name "hydrogen ion exponent" and the designation PH for the numerical value of the exponents of this power.

Srensen and the Carlsberg Chemistry Department

p pH
Today,werefertopHasmeaningthepowerofhydrogen. ThepHscaleprovidesasimpleanduniversalmeasurementofthe p p p amountofhydrogenionsinasolution,whichaffectsitsacidityand howitreactschemically. EachvalueofpHmeanstheH+ concentrationchangesbyafactorof p g y 10 AstheH+ concentrationdecreases,theOH concentrationincreases

pH 1
strong acid weak acid

pH 7
neutral weak base

pH 14
strong base

The pH scale according to the late Dr. Hubert Alyea, Princeton University

pHvalues forsome for some common substances

TheLevelingEffect
ThepHscalerangesfrom0to14 CananacidorbasehaveapHlowerthan0orhigher p g than14? Whenastrongacid,suchasHCl,isdissolvedinwater,it reactstoformH reacts to form H3O+ in the follo ing reaction inthefollowingreaction: HCl( ) + H2O(l) (aq)+H (l) H3O+( ) + Cl( ) (aq)+Cl (aq)

AnyacidthatisstrongerthanH3O+ reactswithH2Oto formH3O+;therefore,noacidcanbestrongerthanH3O+ f H th f id b t th H inH2O.

TheLevelingEffect
Inthesameway,abasewhichisstrongerthanthe conjugatebaseofwater,suchassodiumoxide,willreact withwatertogivetheweakerbasewhichisthehydroxide ion,OH: Na2O(s)+ H2O +H O 2OH(aq)+ 2Na+(aq) +2Na
Note:Theactualbasehereistheoxideionsincethesodiumionisanextremelyweakacidorbase.

Allbaseswhicharestrongerthanthehydroxideionwill reactwithwatertoproducehydroxideion. react with water to produce hydroxide ion Althoughoxideion,amideion,ethoxideion,and methoxideionareallstrongerbasesthanhydroxideion, theirstrengthinaqueoussolutionisleveledtothatof hydroxideion. Any base that is stronger than OH reacts with H2O to form AnybasethatisstrongerthanOH reactswithH Otoform OH;therefore,nobasecanbestrongerthanOH inH2O.

TheLevelingEffect
Canthestrengthsofstrongacidsorbasescanbe differentiated? Thelevelingeffectoperatesinanyprotonicsolvent.Ifa solventotherthanwaterisused,differencesbetween strengthsofstrongacidsorbasescanbemeasured. strengths of strong acids or bases can be measured Inliquidammonia,forexample,allacidsarelevelledto thestrengthoftheammoniumion,NH4+,andallbases areleveledtothestrengthoftheamideion,NH2. NH4+ +NH2 2NH3
Manyoftheacidswhichareweakinwateractasstrongacidsin liquidammoniabecausetheyarestrongerthanammoniumion. Notallofthebaseswhicharestronginwaterarealsostrongin N ll f h b hi h i l i liquidammonia.

TheLevelingEffect
Glacialaceticacidisanotherprotonicsolventinwhich thelevelingeffecttakesplace.

HC2H3O2

H+ +C2H3O2

Glacialaceticacidcanbeusedtoshowthathydrogen y g chlorideisaweakeracidthanisperchloricacid,since hydrogenchloridebehavesasaweakacidinglacial aceticacid. acetic acid Methanolisalsoaprotonicsolventinwhichsomeof theacidswhicharestrong(completelydissociated)in waterarefoundpartiallyinmolecularform

pHandpOH pH and pOH


Previouswesaw: P i [ [H3O+][OH]=Kw =1.0 1014 ][ ] Ifwetakethenegativelogof[H3O+]and[OH] log[H3O+]+log[OH]=logKw =14.00 or,inotherwords, i th d p pH+pOH=pKw =14.00 p p

MeasuringpH Measuring pH
Forasimpleacidorbasedeterminationweusean indicatorknownasLitmuspaper i di k Li
Litmusisawatersolublemixtureofdifferentdyesextractedfromlichens,especially Roccellatinctoria. Th ThenamelitmuscomesfromMiddleEnglishlitemose(ofScandinavianorigin;akin lit f Middl E li h lit ( f S di i i i ki toOldNorselitmosi,dyer'sherbs:litr,color,dye+mosi,bog,moss)andMiddle Englishlykemose(fromMiddleDutchlijkmoes,variantoflcmoes:lken,todrip+ moes,moss).

Red litmus paper turns blue above ~pH = 8 pH Blue litmus paper turns red below ~pH = 5

MeasuringpH Measuring pH
pH test papers are made pHtestpapersaremade usingamixtureofdyesto indicatepHvaluesovera widerangeor,formore accuratemeasurements, thereareshortrange th h t papers.

MeasuringpH
Indicatorsaredyesormixturesofdyesthatcanbeaddedto solutionsofacidsorbasestodeterminepH. Somecommonindicatorsandtheircolorchangesareshownin thechartbelow:

MeasuringpH Measuring pH
Formoreaccurate measurements,apH meterisused. Usingspecialglass electrodes,themeter measuresthevoltageof th lt f thesolutionasa functionoftheactivityof thehydrogenionsnear thetipoftheelectrode.

ThepHMeter
FirstpHmeterwasconstructedin1934byArnold Beckman(19002004). AglasspHelectrodethathadapotentialdependenton activityofH+ ionshadbeenconstructedin1906byFritz HaberandZygmuntKlemensiewicz,buttherewere technicaldifficultiesduetoalargeinternalresistanceof h i l diffi l i d l i l i f glasselectrodes.Toobtainreliableresultsonewas forcedtouseverysensitivegalvanoscope expensive anddifficulttomaintain. and difficult to maintain ToovercometheproblemArnoldBeckmanproposedto usesimplehighgainamplifiermadeusingtwovacuum tubes.Amplifiedcurrentwasmucheasiertomeasure tubes Amplified current was much easier to measure withcheapmiliamperometers.
Beckmans first pH meter, 1934 (middle photo) The Model G pH meter, the first successful marketed pH meter, 1936 (bottom photo)