Chemistry102

Chapter15

MOLECULARSTRUCTUREANDACIDSTRENGTH
ThestrengthofanaciddependsonhoweasilyaH+ isremovedfromtheH -Xbond.
EaseofH+ lossisdeterminedby2factors
1. ThePolarityoftheH -Xbond
ThepolarityoftheH -Xbonddependsonthe DEN(electronegativitydifference)
betweentheatomsinvolvedinthebond
Thehigher
theE.N.
ofX

The
higher
the DEN

Themore
polar
thebond

Theeasier
tolose
theH+

Thestronger
theacid

2. ThestrengthoftheH -Xbond
ThestrengthoftheH -XbonddependsonthesizeofX(smalleratomsformstronger
bonds)
The
larger
Xis

The
weakerthe
H -Xbond

Theless
tightlythe
Hisheld

Theeasier
tolose
theH+

Thestronger
theacid

TrendsamongBinaryAcids(HX)
RecallthatbinaryacidsdonotcontainOatoms
1.

Acrossaperiodgoingfromlefttoright
ThepolarityoftheH Xbonddeterminesthistrend.
ElectronegativityofXincreases

PolarityoftheH Xincreases
Consequently:
H2OisaweakeracidthanHF
H2SisaweakeracidthanHCl
2.

H2O <HF
H2S <HCl

Goingdownagroup
ThestrengthoftheH -Xbonddeterminesthistrend
F
Cl
Br
I

H -F
Atomic
Size
Increases
(more
electron
shells)

H -Cl
H -Br
H -I
17

Strength
of
Bond
Decreases

Acidic
Strength
Increases

Chemistry102

Chapter15

TrendsamongOxoacids
OxoacidsareOcontainingacids

d+ d-
H O Y
acidicHisalwaysattachedtoanOatom
ThepolarityoftheH Obonddeterminestherelativeacidicstrength
ThepolarityoftheH Obonddependson2factors:
1. TheElectronegativityoftheYatom
Themore
electronegative
Yis

Themore
polarthe
H Obond

Theeasier
tolose
theH+

EN(Cl) =3.16

EN(Br) =2.96

H -O -Cl
>
hypochlorous
acid
(strongest)

H -O -Br
hypobromos
acid

Thestronger
theacid

EN(I) =2.66
>

H -O -I
hypoiodos
acid
(weakest)

ACIDICSTRENGTHINCREASES
2. ThenumberofOatomsbondedtoY (excludingOinOHgroups)
Themore
Oatoms
bondedtoY

Themore
electronegative
Ybecomes

HClO
<
hypochlorousacid
(weakest)

Themorepolar
theH O Y
bondbecomes

HClO2
chlorousacid

<

Thestronger
theacid

HClO3
<
chloricacid

HClO4
perchloricacid
(strongest)

ACIDICSTRENGTHINCREASES
O
H O Cl

H O Cl O

H O Cl O

O
H O Cl O
O

leastpolar

mostpolar
18

Chemistry102

Chapter15

SUMMARY
BINARYACIDS(noO)
AcidicStrengthIncreases
Acidic
Strength
Increases
(H -Xbond
weakens)
(sizeofX
increases)

(H -Xpolarityincreases)

OXOACIDS(HattachedtoY throughO)
Acidic
Strength
Increases
(Polarityof
H -O
increases)

ThemoreOatomsattachedtoY,thestrongertheacid
POLYPROTICACIDS
containmorethanoneacidicH
arestrongerthantheircorrespondinganions

H3PO4

HSO4
weak
acid

H2SO4
strong
acid

>

>

H2PO4-

>

HPO42-

AcidicStrengthIncreases
Reason:

Theacidstrengthofapolyproticacidanditsanion(s)decreaseswithincreasing
negativecharge(itbecomesincreasinglydifficulttoloseaH+)

19

Chemistry102

Chapter15

SELFIONIZATIONOFWATER
PureWaterisgenerallyconsideredanonelectrolyte.
Itisactually avery,veryweakelectrolyte:
H+
H2O (l)

K c =

[H2O]2

H3O+(aq)

H2O(l)

[H 3O +][OH ]
[H 2O]2

Kc isverysmall
Theequilibriumisstronglyshiftedtotheleft

=isessentiallyconstant

[H2O]for1Lofwatercanbecalculatedasfollows:
moles
1000g1mole
? =1L x x 55M
L
1L
18.02g
[H2O]2 xKc =[H3O+][OH-]= Kw =1.0x10-14
Kw

iscalledTHEIONPRODUCTOFWATER

1.0x10-14 at250C(istemperaturedependent)

CONCLUSION: Kw =[H3O+][OH-]=1.0x10-14 (250C)

InPureWater:

[H3O+]=[OH-]=x
Kw =x2

OH-(aq)

x= K w = 1.0x10 14

[H3O+]=[OH-]=1.0x10-7 M

20

Chemistry102

Chapter15

SolutionofaStrongAcid:
Example:
A0.1MsolutionofHCl
HCl (aq)
0

+H2O(l)

complete

ionization

H3O+ (aq)+ Cl-(aq)

0.1M
0.1M

TheTOTALCONCENTRATIONOFTHE[H3O+]canbethoughtof asthesumofthe:
concentrationof[H3O+]providedbytheacid [H3O+]=1.0x10-1 M
concentrationof[H3O+]providedby theselfionizationofwater [H3O+]=1.0x10-7 M
Actually,thisisevenlessthanthat. Reason:
AccordingtoLeChateliersprinciple,theequilibriumof theselfionizationofwater,is
shiftedtotheleft,by thepresenceoftheexcess[H3O+] providedbytheacid:
H2O(l)

H3O+(aq) + OH-(aq)

+H2O (l)

H3O+(aq)added

Stress:
Response:
NewEquil:increased

increased

TotalConc.of[H3O+] =

increaseddecreased
butslightly

[H3O+]
fromacid

1.0x10-1 M

1.0x10-1 M

[H3O+]
fromselfionizationofwater
lessthan1.0x10-7 M
(negligible)

Concentrationofthe[OH-]cannoweasilybecalculated:
[H3O+][OH-]=1.0x10-14

[OH]=

1.0x10 14 1.0x10 14
=
=1.0x10 13M
+
1
[H 3O ]
1.0x10

CONCLUSION:
Inasolutionofastrongacidtheconcentrationofthe[H3O+]producedbytheselfionization
ofwatercanbeignored.
NOTE:Thesituationisdifferentifthesolutionofthestrongacidisverydilute:
Example: HCl(aq)
1.0x10-7 M
TOTAL[H3O+] = [H3O+]fromacid+[H3O+]fromwater
=
1.0x10-7 M+1.0x10-7 M
(cannotbeignored)
=
2.0x10-7 M
21

Chemistry102

Chapter15

InasolutionofaStrongBase:
Example:
A0.010MsolutionofNaOH
complete

ionization

NaOH(aq)
0

Na+(aq)+OH-(aq)
0.010M
0.010M

TheTOTALCONCENTRATIONOFTHE[OH-]canbethoughtof asthesumofthe:
concentrationof[OH-]providedbythebase [OH-]=1.0x10-2 M
concentrationof[OH-]providedbytheselfionizationofwater [OH-]=1.0x10-7 M
Actually,thisisevenlessthanthat.Reason:
AccordingtoLeChateliersprinciple,theequilibriumoftheselfionizationofwater,is
shiftedtotheleft,by thepresenceoftheexcess[OH]providedbytheacid:
H2O(l)+

H3O+(aq) + OH-(aq)

H2O(l)

OH(aq)added

Stress:
Response:
NewEquil:increased

increased

TotalConc.of[OH] =

decreasedincreased
butslightly

[OH]
frombase

1.0x10-2 M

1.0x10-2 M

[OH]
fromselfionizationofwater
lessthan1.0x10-7 M
(negligible)

Concentrationofthe[H3O+]cannoweasilybecalculated:
+

-14

[H3O ][OH ]=1.0x10

1.0x10 14 1.0x10 14
[H 3O ]=
=
=1.0x10 12
2
[OH ]
1.0x10
+

CONCLUSION:
Inasolutionofastrongbasetheconcentrationofthe[OH-]produced bytheself
ionizationofwatercanbeignored.
NOTE:Thesituationisdifferentifthesolutionofthestrongbaseisverydilute:
Example:
NaOH(aq)
1.0x10-7 M
TOTAL[OH-] =
=
=

[OH-]frombase+[OH-]fromwater
1.0x10-7 M+1.0x10-7 M
(cannotbeignored)
-7
2.0x10 M
22

Chemistry102
CONCLUSIONS:
1.Inaneutralsolution:
2.Inanacidicsolution:

Chapter15

[H3O+]=[OH-]=1.0x10-7 M
[H3O+] >[OH-]
[H3O+] >1.0x10-7 M
[OH-] <1.0x10-7 M

2.Ina basicsolution:

[H3O+] < [OH-]

[H3O+] <1.0x10-7 M
[OH-] >1.0x10-7 M

23

Chemistry102

Chapter15

Examples:
1. Whatistheconcentrationofthe[H3O+]and[OH-]ina0.25MsolutionofBa(OH)2?
Ba(OH)2(aq)
0

Ba2+(aq)
0.25M

2OH-(aq)
2x0.25M

[OH-]=0.50M
[H3O+]=

2. Whatistheconcentrationofthe[H3O+]and[OH-]ina0.040MsolutionofHNO3?

3. Identify eachofthefollowingsolutionsareacidic,basicorneutral:
a)

[OH]=1.0x105 M

b)

[H3O+]=3.8x109 M

c)

[H3O+]=6.2x103 M

d)

[OH]=4.5x1010 M

24

Chemistry102

Chapter15

pHSCALE
pHisanimportantchemicalquantityintroducedbySorensen,tosimplifyhandlingofnegative
exponents,whenexpressingtheacidityorbasicityofaqueoussolutions
pHcanbeloosely referredtoaspowerofhydrogen)
BySorensensdefinition,widelyacceptedtoday:
pH= -log[H3O+]
Foraneutralsolution:

orsimply:

pH= -log[H+]

[H3O+]=1.0x10-7 M
pH= -log(1.0x10-7)=7.00

Foranacidicsolution: [H3O+] >1.0x10-7 M

pH<7.00
Forabasicsolution:

[H3O+] <1.0x10-7 M
pH>7

pHcalculationscanbegreatlysimplifiedbyarearrangementoftheexpression:
[H3O+][OH-]=1.0x10-14
Takinglogsofbothsides:
log[H3O+]+log[OH-]=log(1.0x10-14)
-pH - pOH= -14.00
pH

+pOH

=14.00

pOH= -(log[OH-])

NOTE:

ApHorseshoe
[H+]

[OH-]
Uparrowsindicatechangingthesign
andthencalculatinginverselog

Downarrowsindicatecalculatinglog
andthenchangingthesign
pH

pH+pOH=14

25

pOH

Chemistry102

Chapter15

Examples:
1. ObtainthepHcorrespondingtoahydroxideionconcentrationof 2.7x10-10 M.
pOH= -log(2.7x10-10)=9.568
pH=14.00 -9.568 =4.43
2. Awinewastestedforacidity,anditpHwasfoundtobe3.85at25 C. Whatisthe
hydroniumionconcentration?
log[H3O+]= -pH= -3.85
[H3O+]=antilog(3.85)=10-3.85 =1.4x10-4 M
3. A1.00Laqueoussolutioncontains6.78gofBa(OH)2. WhatisthepHofthesolution?
First:CalculatethemolarityoftheBa(OH)2 solution:
moles6.78gBa(OH)2 1molBa(OH)2
? = x =0.03956MBa(OH)2
L
1.00Lsolution 171.4gBa(OH)2
2molesOH-
[OH-]=0.03956MBa(OH)2 x =0.07912M
1moleBa(OH)2
1.0x10-14
[H3O+]= =1.264x10-13 M
0.07912M
pH= log(1.264x10-13 M)=12.90
4. WhatisconcentrationofasolutionofKOHwithapHof11.89?

26

Chemistry102

Chapter15

MEASUREMENTOFpH
AcidBaseIndicators
AcidBaseindicatorschangecolorwithinasmallrange.
Reason:Indicatorsestablishanequilibriumbetweentheiracidform andtheirbaseform,
respectively:
HIn
In-

=acidformofindicator
=baseformofindicator

ThesetwoformsoftheIndicatorhavedifferentcolors(notnecessarilyredandblue)
HIn(aq)
Example:

H3O+(aq)

H2O(aq)

Phenolphthalein:

In-(aq)

HIn (aq)iscolorless In-(aq)ispink

Whenabaseisaddedtotheacidicsolutionofphenolphthalein:
HIn (aq)

H3O+(aq)

+H2O (l)

In-(aq)

OH reactswithH3O+(aq)toproduceH2O
Equilibriumshifts >
In-(aq) isproduced. Solutionturnspink
PhenolphthaleinbeginstoturnpinkataboutpH=8.0
UniversalpHpaper
Thispaperisimpregnatedwithseveralindicators
ItgivesdifferentcolorstodifferentpHranges(tothenearestintegervalue)
pHmeter
Consistsoftwoelectrodes(oronecombinationelectrode)dippedintothesolutionwhosepHis
tobemeasured.
Measuresthevoltagethatisgeneratedbetweentheelectrodes.
ThisvoltagedependsonpHandisreadonametercalibrateddirectlyinpHunits.

27