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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
Molecularmodel:Twowatermolecules
reacttoformH3O+andOH
Molecularmodel:Thereactionofanacid
HAwithwatertoformH3O+andaconjugatebase.
AcidBaseConjugateConjugate
acidbase
atequilibrium,Qc=Kc<<1
[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.
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
Molecularmodel:Perchloricacid
H3PO4(aq)+3H2O(l)PO43(aq)+3H3O+(aq)
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]
Weakbases.Manycompoundswithanelectronrichnitrogenareweak
bases(noneareArrheniusbases).Thecommonstructuralfeature
isanNatomthathasaloneelectronpairinitsLewisstructure.
1)Ammonia(:NH3)
2)Amines(generalformulaRNH2,R2NH,R3N),suchas
CH3CH2NH2,(CH3)2NH,(C3H7)3N,andC5H5N
(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.
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=___________
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
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
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
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
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
pH=log[H3O+]=log(1.92x1012)=12.0000.283
pH=___________
Molecularmodel:Na+andOHandH2O
[H
O
][A
]
3
+
[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
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
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
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.
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=___________
Increasingacidity
11
w
KbofNO2 ===1.4x10
KaofHNO2 7.1x104
SinceKaofFe3+>KbofNO2,thesolutionisacidic.
..
B+H+BH+
TheproductofanyLewisacidbasereactioniscalledanadduct,a
singlespeciesthatcontainsanewcovalentbond:
ALewisbaseisalonepairofelectronstodonate.
ALewisacidisavacantorbital
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
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;
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.