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Acids and Bases

7.1TheNatureofAcidsandBases
7.2AcidStrength
7.3ThepHScale
7.4CalculatingthepHofStrongAcidSolutions
7.5CalculatingthepHofweakAcidSolutions
7.6Bases
7.7PolyproticAcids
7.8AcidBasePropertiesofSalts
7.9AcidSolutionsinWhichWaterContributestothe
H+Concentration
7.10StrongAcidSolutionsinWhichWaterContributes
totheH+Concentration
7.11StrategyforsolvingAcidBaseProblems:ASummary

A circle of shiny pennies is created by the


reaction between the citric acid of the lemon
and the tarnish on the surface of the copper.

Source: Fundamental Photos

Arrhenius (or Classical) Acid-Base Definition


Anacidisasubstancethatcontainshydrogenanddissociates
inwatertoyieldahydroniumion:H3O+
Abaseisasubstancethatcontainsthehydroxylgroupand
dissociatesinwatertoyield:OH
NeutralizationisthereactionofanH+(H3O+)ionfromthe
acidandtheOHionfromthebasetoformwater,H2O.
Theneutralizationreactionisexothermicandreleasesapproximately
56kJpermoleofacidandbase.
H+(aq)+OH(aq)H2O(l)H0rxn=55.9kJ

Brnsted-Lowry Acid-Base Definition


Anacidisaprotondonor,anyspeciesthatdonatesanH+ion.
AnacidmustcontainHinitsformula;HNO3andH2PO4aretwo
examples,allArrheniusacidsareBrnstedLowryacids.
Abaseisaprotonacceptor,anyspeciesthatacceptsanH+ion.
AbasemustcontainalonepairofelectronstobindtheH+ion;
afewexamplesareNH3,CO32,F,aswellasOH.
BrnstedLowrybasesarenotArrheniusbases,butallArrhenius
basescontaintheBrnstedLowrybaseOH.
ThereforeintheBrnstedLowryperspective,onespeciesdonatesa
protonandanotherspeciesacceptsit:anacidbasereactionisa
protontransferprocess.
Acidsdonateaprotontowater
Basesacceptaprotonfromwater

Molecularmodel:Twowatermolecules
reacttoformH3O+andOH

Molecularmodel:Thereactionofanacid
HAwithwatertoformH3O+andaconjugatebase.

AcidBaseConjugateConjugate
acidbase

The Acid-Dissociation Constant (Ka)


Strongacidsdissociatecompletelyintoionsinwater:
HA(gorl)+H2O(l)H3O+(aq)+A(aq)
Inadilutesolutionofastrongacid,almostnoHAmolecules
exist:[H3O+]=[HA]initor[HA]eq=0
[H3O+][A]
Qc=
atequilibrium,Qc=Kc>>1
[HA][H2O]
Nitricacidisanexample:HNO3(l)+H2O(l)H3O+(aq)+NO3(aq)
Weakacidsdissociateveryslightlyintoionsinwater:
HA(aq)+H2O(aq)H3O+(aq)+A(aq)
Inadilutesolutionofaweakacid,thegreatmajorityofHA
moleculesareundissociated:[H3O+]<<[HA]initor[HA]eq=[HA]init
[H3O+][A]
Qc=
[HA][H2O]

atequilibrium,Qc=Kc<<1

The Meaning of Ka, the Acid Dissociation Constant


Fortheionizationofanacid,HA:
HA(aq)+H2O(l)H3O+(aq)+A(aq)
Sincetheconcentrationofwateris
+

[H
O
][A
]
3
Kc=
high,anddoesnotchangesignificantly
[HA][H2O]
duringthereaction,itsvalueisabsorbed
Therefore:
intotheconstant.
[H3O+][A] Thestrongertheacid,thehigherthe[H3O+]
Kc=
[HA]
atequilibrium,andthelargertheKa:
Strongeracidhigher[H3O+]largerKa
ForaweakacidwitharelativehighKa(~102),a1Msolution
has~10%oftheHAmoleculesdissociated.
ForaweakacidwithamoderateKa(~105),a1Msolution
has~0.3%oftheHAmoleculesdissociated.
ForaweakacidwitharelativelylowKa(~1010),a1Msolution
has~0.001%oftheHAmoleculesdissociated.

Figure 7.1: Graphical representation


of the behavior of acids of different
strengths in aqueous solution.

AStrongAcid

AWeakAcid

The Extent
of
Dissociation
for Strong
and Weak
Acids

Figure 7.2:
Relationship
of acid
strength and
conjugate
base
strength

TheSixStrongAcids
HydrogenHalides

HClHydrochloricAcid
HBrHydrobromicAcid
HIHydroIodioicAcid
Oxyacids
H2SO4SulfuricAcid
HNO3NitricAcid
HClO4PerchloricAcid

Molecular model: Sulfuric acid

Molecular model: Nitric acid

Molecularmodel:Perchloricacid

The Stepwise Dissociation of Phosphoric Acid


Phosphoricacidisaweakacid,andnormallyonlyloosesoneproton
insolution,butitwillloseallthreewhenreactedwithastrongbase
withheat.Theionizationconstantsaregivenforcomparison.
H3PO4(aq)+H2O(l)H2PO4(aq)+H3O+(aq)
H2PO4(aq)+H2O(l)HPO42(aq)+H3O+(aq)
HPO42(aq)+H2O(l)PO43(aq)+H3O+(aq)

H3PO4(aq)+3H2O(l)PO43(aq)+3H3O+(aq)

The Conjugate Pairs in Some Acid-Base Reactions


ConjugatePair
Acid+BaseBase+Acid
ConjugatePair
Reaction1HF+H2OF+H3O+
Reaction2HCOOH+CNHCOO+HCN
Reaction3NH4++CO32NH3+HCO3
Reaction4H2PO4+OHHPO42+H2O
Reaction5H2SO4+N2H5+HSO4+N2H62+
2

Identifying Conjugate Acid-Base Pairs


Problem:Thefollowingchemicalreactionsareimportantforindustrial
processes.Identifytheconjugateacidbasepairs.
(a)HSO4(aq)+CN(aq)SO42(aq)+HCN(aq)
(b)ClO(aq)+H2O(l)HClO(aq)+OH(aq)
(c)S2(aq)+H2O(aq)HS(aq)+OH(aq)
Plan:Tofindtheconjugateacidbasepairs,wefindthespeciesthat
donateH+andthosethatacceptit.Theacid(orbase)ontheleft
becomesitsconjugatebase(oracid)ontheright.
Solution:
(a)Theprotonistransferredfromthesulfatetothecyanideso:
HSO4(aq)/SO42(aq)andCN(aq)/HCN(aq)arethetwoacidbasepairs.
(b)Thewatergivesuponeprotontothehypochloriteanionso:
ClO(aq)/HClO(aq)andH2O(l)/OH(aq)arethetwoacidbasepairs.
(c)Oneofwatersprotonsistransferredtothesulfideionso:
S2(aq)/HS(aq)andH2O(l)/OH(aq)arethetwoacidbasepairs.

Autoionization of Water
H2O(l)+H2O(l)H3O++OH
Kc=

[H3O+][OH]
[H2O]2

Theionproductforwater,Kw:
Kc[H2O]2=Kw=[H3O+][OH]=1.0x1014(at25C)
Forpurewatertheconcentrationofhydroxylandhydroniumions
mustbeequal:
[H3O+]=[OH]=1.0x1014=1.0x107M(at25C)
1000g/L
Themolarityofpurewateris:=M
18.02g/mol

Figure 7.3:
The pH
scale and
pH values
of some
common
substances

The pH Values of
Some Familiar
Aqueous
Solutions
[H3O+]
[OH ]=

KW
[H3O+]

[OH]
[H3O+]>
[OH]

[H3O+]<
[OH]
neutral
solution

acidic
solution
basic
solution

[H3O+]=
[OH]

The Relationship Between Ka and pKa


AcidName(Formula)Kaat25oCpKa
Hydrogensulfateion(HSO4)1.02x1021.991
Nitrousacid(HNO2)7.1x1043.15
Aceticacid(CH3COOH)1.8x1054.74
Hypobromousacid(HBrO)2.3x1098.64
Phenol(C6H5OH)1.0x101010.00

Acid and Base Character and the pH Scale


Inacidicsolutions,theprotonsthatarereleasedintosolutionwillnot
remainaloneduetotheirlargepositivechargedensityandsmallsize.
Theyareattractedtothenegativelychargedelectronsontheoxygen
atomsinwater,andformhydroniumions.
H+(aq)+H2O(l)=H3O+(l)
[H+]=[H3O+]
Tohandletheverylargevariationsintheconcentrationsofthehydrogen
ioninaqueoussolutions,ascalecalledthepHscaleisusedwhichis:
pH=log[H3O+]
WhatisthepHofasolutionthatis1012Minhydroniumion?
pH=log[H3O+]=(1)log1012=(1)(12)=12
WhatisthepHofasolutionthatis7.3x109MinH3O+?
pH=log(7.3x109)=1(log7.3+log109)=1[(0.863)+(9)]=8.14
pHofaneutralsolution=7.00
pHofanacidicsolution<7.00
pHofabasicsolution>7.00

Classifying the Relative Strengths of Acids and BasesI


Strongacids.Therearetwotypesofstrongacids:
1.ThehydrohalicacidsHCl,HBr,andHI
2.OxoacidsinwhichthenumberofOatomsexceedsthenumberof
ionizableHatomsbytwoormore,suchasHNO3,H2SO4,HClO4
Weakacids.Therearemanymoreweakacidsthanstrongones.Four
types,withexamples,are:
1.ThehydrohalicacidHF
2.ThoseacidsinwhichHisboundedtoOortohalogen,suchas
HCNandH2S
3.OxoacidsinwhichthenumberofOatomsequalsorexceedsbyone
thenumberofionizableHatoms,suchasHClO,HNO2,andH3PO4
4.Organicacids(generalformulaRCOOH),suchasCH3COOHand
C6H5COOH

Classifying the Relative Strengths of Acids and BasesII


Strongbases.SolublecompoundscontainingO2orOHionsarestrong
bases.Thecationsareusuallythoseofthemostactivemetals:
1)M2OorMOH,whereM=Group1A(1)metals(Li,Na,K,Rb,Cs)
2)MOorM(OH)2,whereM=Group2A(2)metals(Ca,Sr,Ba)
[MgOandMg(OH)2areonlyslightlysoluble,butthesoluble
portiondissociatescompletely.]

Weakbases.Manycompoundswithanelectronrichnitrogenareweak
bases(noneareArrheniusbases).Thecommonstructuralfeature
isanNatomthathasaloneelectronpairinitsLewisstructure.
1)Ammonia(:NH3)
2)Amines(generalformulaRNH2,R2NH,R3N),suchas
CH3CH2NH2,(CH3)2NH,(C3H7)3N,andC5H5N

Figure 7.4: (a) Measuring the pH of


vinegar. (b) Measuring the pH of aqueous
ammonia.

Methods for Measuring the pH of an


Aqueous Solution

(a)pHpaper(b)ElectrodesofapHmeter

Summary:GeneralStrategiesforSolving
(P233)AcidBaseProblems
ThinkChemistry,Focusonthesolutioncomponentsandtheirreactions.Itwillalmost
alwaysbepossibletochooseonereactionthatisthemostimportant.
Besystematic,AcidBaseproblemsrequireastepbystepapproach.
Beflexible.Althoughallacidbaseproblemsaresimilarinmanyways,important
.
differencesdooccur.Treateachproblemasaseparateentity.Donottrytoforceagiven
problemtomatchanyyouhavesolvedbefore.Lookforboththesimilaritiesandthe
differences.
Bepatient.Thecompletesloutiontoacomplicatedproblemcannotbeseenimmediately
inallitsdetail.Picktheproblemapartintoitsworkablesteps.
Beconfident.Lookwithintheproblemforthesolution,andlettheproblemguideyou.
Assumethatyoucanthinkitout.Donotrelyonmemorizingsolutionstoproblems.
Infact,memorizingsolutionsisusuallydetrimental,becauseyoutendtotrytoforcea
newproblemtobethesameasoneyouhaveseenbefore.Understandandthink;dont
justmemorize.

Calculating [H3O+], pH, [OH-], and pOH


Problem:Achemistdilutesconcentratedhydrochloricacidtomake
twosolutions:(a)3.0Mand(b)0.0024M.Calculatethe
[H3O+],pH,[OH],andpOHofthetwosolutionsat25C.
Plan:Weknowthathydrochloricacidisastrongacid,soitdissociates
completelyinwater;therefore[H3O+]=[HCl]init..Weusethe[H3O+]to
calculatethe[OH]andpHaswellaspOH.
Solution:
(a)[H3O+]=3.0MpH=log[H3O+]=log(3.0)=________
14
K
1x10

w
[OH ]===_________________M
3.0
[H3O+]
pOH=log(3.333x1015)=15.0000.477=_______
(b)[H3O+]=0.0024MpH=log[H3O+]=log(0.0024)=_______
Kw
1x1014

[OH ]===________________M
0.0024
[H3O+]
pOH=log(4.167x1012)=12.0000.6198=__________

CalculatethepHofa1.00MHNO2Solution
Problem:CalculatethepHofa1.00MSolutionofNitrousacidHNO2.
Solution:
HNO2(aq)H+(aq)+NO2(aq)Ka=4.0x104
Initialconcentrations=[H+]=0,[NO2]=0,[HNO2]=1.00M
Finalconcentrations=[H+]=x,[NO2]=x,[HNO2]=1.00Mx
[H+][NO2]
(x)(x)
4
Ka==4.0x10 =
[HNO2]
1.00x
Assume1.00x=1.00tosimplifytheproblem.
x2
=4.0x104orx2=4.0x104
1.00
x=2.0x102=0.02M=[H+]=[NO2]
pH=log[H+]=log(2.0x102)=2.000.30=___________

Molecular model: Nitrous acid

Molecular model: HF and H2O

Summary:SolvingWeakAcid
(P237)EquilibriumProblems
Listthemajorspeciesinthesolution.
ChoosethespeciesthatcanproduceH+,andwritebalancedequationsforthe
reactionsproducingH+.
Comparingthevaluesoftheequilibriumconstantsforthereactionsyouhave
written,decidewhichreactionwilldominateintheproductionofH +.
Writetheequilibriumexpressionforthedominantreaction.
Listtheinitialconcentrationsofthespeciesparticipatinginthedominate
reaction.
Definethechangeneededtoachieveequilibrium;thatis,definex.
Writetheequilibriumconcentrationsintermsofx.
Substitutetheequilibriumconcentrationsintotheequilibriumexpression.
Solveforxtheeasywaythatis,byassumingthat[HA] 0x=[HA]0
Verifywhethertheapproximationisvalid(the5%ruleisthetestinthiscase).
Calculate[H+]andpH.

LikeExample7.3(P237)I
CalculatethepHofasolutionthatcontains1.00MHF
(Ka=7.2x104)and5.00MHOCl(Ka=3.5x108).Alsocalculatethe
concentrationsoftheFluorideandHypochloriteionsatequilibrium.
ThreecomponentsproduceH+:
HF(aq)H+(aq)+F(aq)Ka=7.2x104
HOCl(aq)H+(aq)+OCl(aq)Ka=3.5x108
H2O(aq)H+(aq)+OH(aq)Ka=1.0x1014
EventhoughHFisaweakacid,ithasbyfarthegreatestKa,
thereforeitwillbethedominateproducerofH+.
[H+][F]
Ka==7.2x104
[HF]

LikeExample7.3(P236)II
InitialConcentrationEquilibriumConcentration
(mol/L)(mol/L)
[HF]0=1.00[HF]=1.00x
xmolHF

[F ]=0[F
]=x
dissociates
~
+
[H+]=0[H
]=x
[H+][F]
(x)(x)
x2
4
Ka==7.2x10 ==
[HF]
1.00x
1.00

x=2.7x102

2
x=2.7x102usingthe5%rule:x2.7x10
=x100%=2.7%
[HF]0
1.00
Therefore,

[F]=[H+]=x=2.7x102

andpH=___________

LikeExample7.3(P236)III
[H+][OCl]
Ka==3.5x108
[HOCl]

TheconcentrationofH+comes
fromthefirstpartofthis
problem=2.7x102M

[HOCl]=5.00M;[OCl]=x
(2.7x102)[OCl]
3.5x10 =
(5.00x)
8

Assume:5.00x=5.00

8
5.00(3.5x10
)

6
[OCl ]==6.48x10
M
2.7x102

pH=1.56
[F]=2.7x102M;[OCl]=6.48x106M

Molecular model: Hypochlorous acid


(HOC1)

Molecular model: HCN, HNO2, and H2O

Figure 7.5: Effect of dilution on the


percent dissociation and [H+]

Problem:CalculatethePercentdissociationofa0.0100MHydrocyanic
acidsolution,Ka=6.20x1010.
HCN(aq)+H2O(l)H3O+(aq)+CN(aq)
HCNH3O+CN
[H3O+][CN]
Initial0.0100M00Ka= [HCN]
Changex+x+x
(x)(x)
Final0.0100xxx
10
(0.0100x)
Ka==6.20x10
x2
Assume0.0100x=0.0100
0.0100
Ka==6.2x1010
6
x=2.49x10
2.49x106
0.0100
%dissociation=x100%=______________

Runnerstrugglestotopofahill

Source: Corbis

Molecularmodel:HC3H5O3andH2O

Finding the Ka of a Weak Acid from the pH


of its SolutionI
Problem:Theweakacidhypochlorousacidisformedinbleach
solutions.IfthepHofa0.12MsolutionofHClOis4.19,whatisthe
valueoftheKaofthisweakacid.
Plan:Wearegiven[HClO]initialandthepHwhichwillallowustofind
[H3O+]and,hence,thehypochloriteanionconcentration,sowecan
writethereactionandexpressionforKaandsolvedirectly.
Solution:
Calculating[H3O+]:
[H3O+]=10pH=104.19=6.46x105M
Concentration(M)HClO(aq)+H2O(l)H3O+(aq)+ClO(aq)
Initial0.12
Changex+x+x
Equilibrium0.12x+x+x
Assumptions:[H3O+]=[H3O+]HClO
sinceHClOisaweakacid,weassume0.12Mx=0.12M

Finding the Ka of a Weak Acid from the pH of


its SolutionII
HClO(aq)+H2O(l)H3O+(aq)+ClO(aq)
x=[H3O+]=[ClO]=6.46x105M
[H3O+][ClO] (6.46x105M) (6.46x105M)
Ka===348x1010
[HClO]
0.12M
Ka=3.48x108

Intextbooksitisfoundtobe:3.5x108

Checking:
7
1x10
M
+
1.For[H3O ]fromwater:x100=0.155%
6.46x105M
assumptionisOK
6.46x105M
2.For[HClO]dissoc:x100=0.0538%
0.12M

Molecularmodel:Aceticacid

Molecular model: Benzoic acid

Determining Concentrations from Ka and Initial [HA]


Problem:Hypochlorousacidisaweakacidformedinlaundrybleach.
Whatisthe[H3O+]ofa0.125MHClOsolution?Ka=3.5x108
Plan:Weneedtofind[H3O+].Firstwewritethebalancedequationand
theexpressionforKaandsolveforthehydroniumionconcentration.
+

HClO
+H
O
H
O
+ClO
(aq)
2 (l)
3
(aq)
(aq)
Solution:
+

[H
O
][ClO
]
8
3
Ka==3.5x10

[HClO]

Concentration(M)HClOH2OH3O+ClO
Initial0.12500
Changex+x+x
Equilibrium0.125xxx
assume0.125x=0.125
(x)(x)
8
Ka==3.5x10
0.125x
x2=0.4375x108x=0.661x104

Solving Problems Involving Weak-Acid EquilibriaI


Therearetwogeneraltypesofequilibriumproblemsinvolvingweak
acidsandtheirconjugatebases:
1.Givenequilibriumconcentrations,findKa.
2.GivenKaandsomeconcentrationinformation,findtheother
equilibriumconcentrations.
Theproblemsolvingapproach.
1.WritethebalancedequationandKaexpression;thesewilltellyou
whattofind.
2.Definexastheunknownconcentrationthatchangesduringthe
reaction.Frequently,x=[HA]dissoc.,theconcentrationofHAthat
dissociateswhich,throughtheuseofcertainassumptions,also
equals[H3O+]and[A]atequilibrium.
3.Constructareactiontablethatincorporatestheunknown.
4.Makeassumptionsthatsimplifythecalculation,usuallythatxis
verysmallrelativetotheinitialconcentration.

Solving Problems Involving Weak-Acid EquilibriaII


5.SubstitutethevaluesintotheKaexpressionandsolveforx.
6.Checkthattheassumptionsarejustified.Wenormallyapplythe
5%rule;ifthevalueofxisgreaterthan5%ofthevalueitis
comparedwith,youmustusethequadraticformulatofindx.
Thenotationsystem.Molarconcentrationsofspeciesareindicatedby
usingsquarebracketsaroundthespeciesofinterest.Bracketswithno
subscriptrefertothemolarconcentrationofthespeciesatequilibrium.
Theassumptions.Thetwokeyassumptionstosimplifythe
arithmeticare:
1.The[H3O+]fromtheautoionizationofwaterisnegligible.Infact,
thepresenceofacidfromwhateverisputintosolutionwillhinder
theautoionizationofwater,andmakeitevenlessimportant.
2.AweakacidhasasmallKa.Therefore,itdissociatestosuchasmall
extentthatwecanneglectthechangeinitsconcentrationtofindits
equilibriumconcentration.

Tanks in Miami, Florida

Source: Visuals Unlimited

LikeExample7.5(P243)
CalculatethepHofa2.0x103MsolutionofNaOH.
SinceNaOHisastrongbase,itwilldissociate100%inwater.
NaOH(aq)Na+(aq)+OH(aq)
Since[NaOH]=2.0x103M,[OH]=2.0x103M
Theconcentrationof[H+]canbecalculatedfromKw:
14
Kw
1.0x10
12
[H ]===5.0x10
M

3
[OH ]
2.0x10
+

pH=log[H+]=log(5.0x1012)=12.000.70=_________

Amines:BaseswiththeNitrogenAtom
..
..
N
N
H3C H H
H3C H CH3
..
N
Methylamine
Dimethylamine
..
N
H3C CH CH3

Pyridine

..
N

Trimethylamine

H H C2H5

Ethylamine

Determining pH from Kb and Initial [B]I


Problem:Ammoniaiscommonlyusedcleaningagentinhouseholdsand
isaweakbase,withaKbof1.8x105.WhatisthepHofa1.5MNH3
solution?
Plan:Ammoniareactswithwatertoform[OH]andthencalculate
[H3O+]andthepH.ThebalancedequationandKbexpressionare:
NH3(aq)+H2O(l)NH4+(aq)+OH(aq)
[NH4+][OH]
Kb=
[NH3]
Concentration(M)NH3H2ONH4+OH
Initial1.500
Changex+x+x
Equilibrium1.5xxx
makingtheassumption:sinceKbissmall:1.5Mx=1.5M

Determining pH from Kb and Initial [B]II


SubstitutingintotheKbexpressionandsolvingforx:
[NH4+][OH]
(x)(x)
Kb===1.8x105
1.5
[NH3]
x2=2.7x105=27x106
x=5.20x103=[OH]=[NH4+]
CalculatingpH:
14
K
1.0x10
w
12
[H3O+]===1.92x10
5.20x103
[OH]

pH=log[H3O+]=log(1.92x1012)=12.0000.283
pH=___________

Molecularmodel:Na+andOHandH2O

Molecular model: CH3NH2 and H2O

The Relation Between Ka and Kb of a Conjugate


Acid-Base Pair
AcidHA+H2OH3O++A
BaseA+H2OHA+OH
2H2OH3O++OH
+

[H
O
][A
]
3
+

[H3O ][OH ]=x


[HA]

[HA][OH]
[A]

Kw=KaxKb
Ka=4.5x104
4
11
15
K
xK
=(4.5x10
)(2.2x10
)=9.9x10
ForHNO2
a
b
15
14
11
or~10x10
=1x10
=Kw
K =2.2x10
b

Molecular model: H+, HSO4-, and H2O

Molecular model: Phosphoric acid

Molecular model: H3PO4 and H2O

LikeExample7.7(P2478)I
CalculatethepHofa5.0MH3PO4solutionanddetermine
equilibriumconcentrationsofthespecies:H3PO4,H2PO4,HPO42,
andPO43.
Solution:
H3PO4(aq)H+(aq)+H2PO4(aq)
[H+][H2PO4]
Ka=7.5x103=
[H3PO4]
InitialConcentration(mol/L)EquilibriumConcentration(mol/L)
[H3PO4]0=5.0[H3PO4]=5.0x
[H2PO4]0=0[H2PO4]=x
[H+]0=0[H+]=x
+

[H
][H
PO
]
(x)(x) ~
2
4
3
Ka1=7.5x10 ===
5.0x
[H3PO4]

x2
5.0

LikeExample7.7(P2478)II
1
~
Solvingforx=1.9x10
Since1.9x101islessthan5%of5.0,the
approximationisacceptableand:

[H+]=x=0.19M=[H2PO4],pH=0.72[H3PO4]=5.0x=4.8M
TheconcentrationofHPO42canbeobtainedfromKa2:
[H+][HPO42]
Ka2=6.2x10 =
[H2PO4]
8

where:[H+]=[H2PO4]=0.19M;[HPO42]=Ka2=6.2x108M
Tocalculate[PO43],weusetheexpressionforKa3,andthevalues
obtainedfromtheothercalculations:
+
3
3
[H
][PO
]
0.19[PO
]
4
4
13
Ka3=4.8x10 ==
[HPO42]
6.2x108
13
8
(4.8x10
)(6.2x10
)
3
[PO4 ]==_______________M
0.19

A Drexel University
Chemist shows that
a new form of concrete
called ZeoTech
(on the right)
can withstand soaking
in sulfuric acid for 30
days

Source: AP/Wide World Photos

LikeExample7.9(P2512)
CalculatethepHofa3.00x103MSulfuricacidsolution.
InitialConcentration(mol/L)EquilibriumConcentration(mol/L)

Xmol/LHSO4
[HSO4]0=0.00300[HSO
4 ]=0.00300x
dissociates
2
[SO42]0=0[SO
]=x
4
toreach
+
equilibrium
[H+]0=0.00300[H
]=0.00300+x

FromdissociationofH2SO4

Assume
[H+][SO42] (0.00300+x)(x)
Ka2=1.2x10 ==
x<<0.00300
(0.00300x)
[HSO4]
Whenwesolveforxwegetx=1.2x102,whichiscloseto0.00300
thereforetheapproximationisnotvalid,andwemustsolvewith
thequadraticformula.Multiplyingtheexpressionoutweget:
0=x2+0.015x3.6x105
b+ b24ac x=2.10x103
x=
2a
a=1,b=0.015
c=3.6x105
[H+]=0.00300+x=0.00510pH=2.29
2

Figure 7.6: A plot of the fractions of


H2CO3, HCO-3 and CO32-

The Effect of
Atomic
and Molecular
Properties on
Nonmetal
Hydride Acidity

EffectsofSaltsonpHandAcidity
Saltsthatconsistofcationsofstrongbasesandtheanionsof
strongacidshavenoeffectonthe[H+]whendissolvedinwater.
Examples:NaCl,KNO3,Na2SO4,NaClO4,KBr,etc.

Foranysaltwhosecationhasneutralproperties(suchasNa+or
K+)andwhoseanionistheconjugatebaseofaweakacid,the
aqueoussolutionwillbebasic.
Examples:NaF,KCN,NaC2H3O2,Na3PO4,Na2CO3,K2S,
Na2C2O4,etc.
Asaltwhosecationistheconjugateacidofaweakbaseproduces
anacidicsolutionwhendissolvedinwater.
Examples:NH4Cl,AlCl3,Fe(NO3)3,etc.

Molecular model: Na+, C2H3O2-, and H2O

LikeExample7.11(P255)I
CalculatethepHofa0.45MNaCNsolution.TheKavalueforHCN
is6.2x1010.
Solution: SinceHCNisaweakacid,theCyanideionmusthave
significantaffinityforprotons.
CN(aq)+H2O(l)HCN(aq)+OH(aq)
[HCN][OH]
Kb=
[CN]

ThevalueofKbcanbecalculated
fromKwandtheKavalueforHCN.

Kw
1.0x1014
5
Kb===1.61x10

10
6.2x10
Ka(forHCN)
InitialConcentration(mol/L)EquilibriumConcentration(mol/L)

[CN]0=0.45[CN
]=0.45x
Xmol/LCNreactswith
[HCN]0=0[HCN]=x
H2Otoreachequilibrium
[OH]0=0[OH]=x

LikeExample7.11(P255)II
Thus:

[HCN][OH]
(x)(x) ~ x2
Kb=1.61x10 ===
[CN]
0.45x
0.45
5

~
3
x=2.69x10

Althoughthisisnotexactlyvalidbythe
5%rule,itisonlyoffby1%,sowewill
useitfornow!

x=[OH]=2.69x103M
pOH=log[OH]=30.43=2.57
pH=14.002.57=____________

LikeExample7.12(P2556)I
CalculatethepHofa0.010MAlCl3solution.TheKavalueforthe
Al(H2O)63+ionis1.4x105.
Solution:
SincetheAl(H2O)63+ionisastrongeracidthanwater,thedominate
equilibriumwillbe:
Al(H2O)63+(aq)Al(OH)(H2O)52+(aq)+H+(aq)
2+
+
[Al(OH)(H
O)
][H
]
2
5
5
1.4x10 =Ka=
[Al(H2O)63+]
InitialConcentration(mol/L)EquilibriumConcentration(mol/L)

Xmol/L
3+
[Al(H2O)63+]0=0.010[Al(H
2O)6 ]=0.010x
2+
[Al(OH)(H2O)52+]=0[Al(OH)(H
Al(H2O)63+
2O)5 ]=x
~
+
+
Dissociates
[H ]0=0[H
]=x
toreach
equilibrium

LikeExample7.12(P2556)II
Thus:

2+
+
[Al(OH)(H
O)
][H
]
2
5
5
1.4x10 =Ka==
[Al(H2O)63+]

(x)(x)
Ka==
0.010x

x2
0.010

x=3.7x104
Sincetheapproximationisvalidbythe5%rule:
[H+]=x=3.7x104MandpH=___________

Ka Values of Some Hydrated Metal Ions at 25oC


IonKa
Fe3+(aq)6x103
Sn2+(aq)4x104
Cr3+(aq)1x104
Al3+(aq)1x105
Be2+(aq)4x106
Cu2+(aq)3x108
Pb2+(aq)3x108
Zn2+(aq)1x109
Co2+(aq)2x1010
Ni2+(aq)1x1010

Increasingacidity

Molecular model: C1-, A1(H2O)63+, H2O

A pH meter showing that the


pH of 0.1 M AICI3 is 2.93

Predicting the Relative Acidity of Salt Solutions


Problem:Determinewhetheranaqueoussolutionofiron(III)nitrite,
Fe(NO2)3,isacidic,basic,orneutral.
Plan:Theformulaconsistsofthesmall,highlycharged,andtherefore
weaklyacidic,Fe3+cationandtheweaklybasicNO2anionoftheweak
acidHNO2,Todeterminetherelativeacidityofthesolution,wewrite
equationsthatshowthereactionsoftheionswithwater,andthenfindKa
andKboftheionstoseewhichionreactstoformtoagreaterextent.
Solution:Writingthereactionswithwater:
Fe(H2O)63+(aq)+H2O(l)Fe(H2O)5OH2+(aq)+H3O+(aq)
NO2(aq)+H2O(l)HNO2(aq)+OH(aq)
ObtainingKaandKboftheions:ForFe3+(aq)Ka=6x103.
ForNO2(aq),Kbmustbedetermined:
14
K
1.0x10

11
w
KbofNO2 ===1.4x10
KaofHNO2 7.1x104
SinceKaofFe3+>KbofNO2,thesolutionisacidic.

Electron-Pair Donation and the Lewis Acid-Base Definition


TheLewisacidbasedefinition:
Abaseisanyspeciesthatdonatesanelectronpair.
Anacidisanyspeciesthatacceptsanelectronpair.
ProtonsactasLewisacidsinthattheyacceptanelectronpairinall
reactions:

..

B+H+BH+
TheproductofanyLewisacidbasereactioniscalledanadduct,a
singlespeciesthatcontainsanewcovalentbond:
ALewisbaseisalonepairofelectronstodonate.
ALewisacidisavacantorbital

Metal Cations as Lewis Acids


M2++4H2O(l)M(H2O)42+
Metalionscanacceptelectronpairsfromwatermoleculestoform
complexes.Anexampleisnickelwhichformsanadductwithwaterto
formthehexaaquacomplex:
Ni2++6H2O(l)Ni(H2O)62+(aq)

AmmoniaisastrongerLewisbasethanwaterbecauseitdisplaceswater
fromhydratedionswhenaqueousammoniaisadded.
Ni(H2O)62+(aq)+6NH3(aq)Ni(NH3)62+(aq)+6H2O(aq)
ManyessentialbiomoleculesareLewisadductswithcentralmetal
ions.ChlorophyllisaLewisadductofacentralMg2+ion.VitaminB12
hasasimilarstructurewithacentralCo3+,asdoeshemewithacentral
Fe2+ion.OthermetalssuchasZn2+,Mo2+,andCu2+areboundtothe
activesiteinenzymesandparticipateinthecatalyticactionbyvirtueof

The Mg2+ Ion as a Lewis


Acid in the Chlorophyll
Molecule

Identifying Lewis Acids and Bases


Problem:IdentifytheLewisacidsandbasesinthefollowingreactions:
(a)F+BF3BF4
(b)Co2++6H2OCo(H2O)62+
(c)NH3+H+NH4+
Plan:Weexaminethespeciestoseewhichspeciesacceptstheelectron
pair(Lewisacid)andwhichdonatesit(Lewisbase)inthe
reactions.
Solution:
(a)TheBF3acceptedanelectronpairfromthefluorideion.
BF3istheacidandFisthebase.
(b)TheCo2+ionacceptedtheelectronpairsfromthewatermolecules.
Co2+istheacidandH2Oisthebase.
(c)TheH+ionacceptedtheelectronpairfromtheammoniamolecule.
H+istheacidandwateristhebase.

Example7.14(P259)
Predictwhetheranaqueoussolutionofeachofthefollowingsalts
willbeacidic,basic,orneutral.
a)NH4C2H3O2b)NH4CNc)Al2(SO4)3
Solution:
a) Theionsaretheammoniumandacetateions,KaforNH4+is
5.6x1010,andKbforC2H3O2is5.6x1010.Sincetheareequal
thesolutionwillbeneutralandthepHcloseto7.
b) Thesolutionwillcontaintheammoniumandcyanideions,the
KavalueforNH4+is5.6x1010,and
Kw

Kb(forCN )==1.6x105
Ka(forHCN)
SinceKbforCNismuchlargerthanKaforNH4+,thissolution
willbebasic.
c)ThissolutioncopntainsthehydratedAluminumionandthesulfate
ion.KaforAl(H2O)63+=1.4x105,forsulfate,Kb=8.3x1013;

Molecular model: Na+, F-, H2O

Molecular model: C1-, NH4+, and H2O

A pH meter showing that the


pH of 0.1 M HN4CI is 5.13

Table7.6(P259)I
AcidBasePropertiesofAqueousSolutionsofVariousTypesofSalts
TypeofSaltExamplesCommentpHofSolution
CationisfromNeitheractsas
strongbase;KCl,KNO3anacidoraNeutral
anionisfromNaCl,NaNO3base
strongacid
CationisfromAnionactsas
strongbase;NaC2H3O2abase;cationBasic
anionisfromKCN,NaFhasnoeffect
weakacidonpH
CationisconjugateCationactsas
acidofweakbase;NH4Cl,anacid;anionAcidic
anionisfromNH4NO3hasnoeffect

Table7.6(P259)II

AcidBasePropertiesofAqueousSolutionsofVariousTypesofSalts
TypeofSaltExamplesCommentpHofSolution
CationisconjugateCationactsasAcidicif:
acidofweakbaseNH4C2H3O2anacid;anionKa>Kb
anionisconjugateNH4CNactsasabaseBasicif:
baseofweakacidKb>Ka
Neutralif:
Ka=Kb
CationishighlyHydratedcation
chargedmetalion;Al(NO3)3,actsasanacid;Acidic
anionisfromFeCl3anionhasno
strongacideffectonpH

ValueofKaI
WestartwiththeexpressionforthevalueofKa,fortheweakacid
HA:Fromtheconservationofchargeequation:
[H+][A]
[H+]=[A]+[OH]
Ka=
[HA]
FromtheKwexpressionforwater:
Kw

[OH ]= +
[H ]
Thechargebalanceequationbecomes:
Kw
[Kw]
+

+
or:
[H ]=[A ]+
[A ]=[H ]
+
[H ]
[H+]
Thematerialbalanceequationis:
[HA]0=[HA]+[A]or[HA]=[HA]0[A]
Since:

Kw

+
[A ]=[H ]
[H+]

Wehave:

Kw
[HA]=[HA]0([H ])
[H+]
+

ValueofKaII
Nowwesubstitutetheexpressionsfor[A]and[HA]intoKa:
Kw
[H ]([H ])
+

[H ][A ]
[H+]
Ka===
[HA]
Kw
[HA]0([H+])
[H+]
+

Ka=

[H+]2Kw
[HA]0

[H+]2Kw
[H+]

Simplified,thisequationbecomes:
[H+]2
Ka= [HA] [H+]
0

LikeExample7.16(P2645)I
Calculatethe[H+]in:a)1.0MHOClandb)1x104MHOCl
forhypochlorousacidHOCl,Ka=3.5x108
a)Firstdotheweakacidprobleminthenormalway.
2
x2x

8 ~
=3.5x10 =
1.0x1.0

X=1.87x104M=[H+]

b)Firstwedotheweakacidprobleminthenormalway.
2
x2x

8 ~
=3.5x10
=
1.0x104x1.0x104

X=1.87x106M=[H+]

InthisverydilutesolutionofHOClweshouldusethefull
equationtoobtainthecorrectH+concentration.
Ka=3.5x10 =
8

[H+]21014
+ 2
14
[H
]
10
4
1.0x10
[H+]

LikeExample7.16(P2645)II

Tosolvethiswewillusesuccessiveapproximations,firstsubstituting
thevalueweobtainedinthenormalway:1.87x106MTodothiswe
addinthecorrectionforwaterionization,1.0x107M,givingasan
approximation:1.97x106MforH+.
[H+]21014
Ka=3.5x10 =
6 2
14
(1.97x10
)
1.0x10
4
1.0x10
1.97x106
+ 2
14
+ 2
14
[H
]
10
[H
]
10
3.5x108==
9.8x105
1.0x1041.97x106
8

[H+]2=3.44x1012[H+]=1.85x106
Substituting1.85x106intotheequationinplaceof1.97x106yields
1.85x106Msotheapproximationyieldsthesameanswer,sothe
finalansweris1.85x106M.
pH=log(1.85x106)=__________

Summary:ThepHCalculationsforanAqueous
SolutionofaWeakAcidHA
(majorspeciesHAandH2O)
Thefullequationforthiscaseis:

[H+]2Kw
Ka=
[H+]2Kw
[HA]0
[H+]
Whentheweakacidbyitselfproduces[H+]>106M,thefullequation
becomes:
Thiscorrespondstothetypical
[H+]2
Ka=
weakacidcase:
[HA]0[H+]
When:

[H+]2Kw thefullequation
[H+]2Kw
[HA]0>>
Ka=
+
becomes:
[H ]
[HA]0

Whichgives:

[H+]=Ka[HA]0+Kw

Summary:SolvingAcidBaseEquilibriaProblems
Listthemajorspeciesinsolution.
Lookforreactionsthatcanbeassumedtogotocompletion,suchasastrong
aciddissociatingorH+reactingwithOH.
Forareactionthatcanbeassumedtogotocompletion:
a)Determinetheconcentrationsoftheproducts.
b)Writedownthemajorspeciesinsolutionafterthereaction.
Lookateachmajorcomponentofthesolutionanddecidewhetheritisanacid
orabase.
PicktheequilibriumthatwillcontrolthepH.Useknownvaluesofthe
dissociationconstantsforthevariousspeciestodeterminethedominant
equilibrium.
a)Writetheequationforthereactionandtheequilibriumexpression.
b)Computetheinitialconcentrations(assumingthatthedominantequilibrium
hasnotyetoccurredforexample,therehasbeennoaciddissociation).
c)Definex.
d)Computetheequilibriumconcentrationsintermsofx.
e)Substitutetheconcentrationsintotheequilibriumexpression,andsolveforx.
f)Checkthevalidityoftheapproximation.
g)CalculatethepHandotherconcentrationsasrequired.