Chang,7thEdition,Chapter16,Worksheet#1

S.B.Piepho,Fall2002

Buffers
AbufferisasolutionthatresistschangesinpH.ThepHofabufferchangesverylittlewhen
smallamountsofastrongacidorstrongbaseareaddedtothebuffer.
Abufferconsistsofapproximatelyequalamountsofaconjugateweakacid/weakbasepairin
equilibriumwitheachother.Strongacidsandtheirconjugatebasesdontproduceabuffersince
strongacidionizationiscomplete:thereisnoequilibrium!
AcidicBuffers
Inanacidicbufferboththeweakacidandconjugatebasearepresentinitiallyinroughlyequal
concentrations.Theequilibriumis
HAH++A
weakacid
conjugatebase
Foraweakacid, K a

[A ]

[H ][A ]
.Thus pH pK log [A ] :
so pK a pH log
a
[HA]
[HA]
[HA]

thisistheHendersonHasselbalchequation.
TheseequationsareusefulforestimatingthepHofabuffer.When[A]=[HA],itfollowsthat
Ka=[H+]andpH=pKa.
AcidicBufferExample:Aceticacid

(HC2H3O2),sodiumacetate(NaC2H3O2)
NaC2H3O2isasolublesaltthatdissolvesinwatertogiveNa+andC2H3O2ions.Na+ionsare
neutralspectatorions,socanbeignored.TheC2H3O2ionsprovidetheconjugatebaseforthe
buffer.Thebufferequilibriumis
HC2H3O2H++C2H3O2
aceticacid
acetateion
Foraceticacid,Ka(HC2H3O2)=1.8x105sopKa=log10Ka=4.74.Thuswhen[HC2H3O2]=
[C2H3O2],pH=pKa=4.74.
BasicBuffers
Inabasicbufferboththeweakbaseandconjugateacidarepresentinitiallyinroughlyequal
concentrations.Theequilibriumis
B+H2OBH++OH
weakbase

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[BH ]
[BH ][OH ]

=
pK

pOH

log
Foraweakbase, K b
so b
[B]
[B]

[BH ]

.Thus pH 14.00 pK log [BH ] .SincepKa=14.00

pK b (14.00 pH) log
b
[B]
[B]

[B]

pKb, pH pKa (BH ) log

.ThisisonceagaintheHendersonHasselbalchequation.
[BH ]
TheseequationsareusefulforestimatingthepHofabuffer.When[BH+]=[B],Kb=[OH].
Consequently,pOH=pKbforthebuffer.ItfollowsthatpH=14.00pKb=pKa(BH+)forthe
buffer.
BasicBufferExample:Ammonia

(NH3),ammoniumchloride(NH4Cl)
NH4ClisasolublesaltthatdissolvesinwatertogiveNH4+andClions.Clionsareneutral
spectatorions,socanbeignored.TheNH4+ionsprovidetheconjugateacidforthebuffer.The
bufferequilibriumis
NH3+H2OOH+NH4+
ammonia
ammoniumion
Forammonia,Kb(NH3)=1.8x105sopKb=log10Kb=4.74.Thuswhen[NH3]=[NH4+],pOH=
4.74andpH=pKa(NH4+)=14.004.74=9.26.
NeutralBuffers
NeutralbuffershaveapHcloseto7.00.AgoodexampleisaNaH2PO4/Na2HPO4buffer.Since
Na+ionsareneutralspectatorions,thisisadihydrogenphosphate/hydrogenphosphate
(H2PO4/HPO42)buffer.Thebufferequilibriumis
H2PO4H++HPO42
dihydrogenphosphateion
hydrogenphosphateion

[H ][HPO 4 2 ]
Here K a
=6.2x108.If[H2PO4]=[HPO42],Ka=[H+]andpH=pKa=7.21.

[H2 PO 4 ]
ResponseofaBuffertotheAdditionofaStrongAcidoraStrongBase
AddedAcid.WhenasmallamountofastrongacidsuchasHClisaddedtoabuffer,theH+from
theacidreactswiththebasicpartofthebuffertogivemoreoftheacidicpartofthebuffer.The
reactionisassumedtogo100%.Thenewconcentrationoftheacidicpartofthebuffer
(increasedfromtheinitialvalue)andthenewconcentrationofthebasicpartofthebuffer
(decreasedfromtheinitialvalue)arethenusedtocalculatethepHofthebuffer.

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AddedBase.Whenasmallamountofastrongbaseisaddedtoabuffer,theOHreactswiththe
acidicpartofthebuffertogivemoreofthebasicpartofthebuffer.Thereactionisassumedto
go100%.Thenewconcentrationoftheacidicpartofthebuffer(decreasedfromtheinitial
value)andthenewconcentrationofthebasicpartofthebuffer(increasedfromtheinitialvalue)
arethenusedtocalculatethepHofthebuffer.

Exercises
1.Identifywhichofthefollowingmixedsystemscouldfunctionasabuffersolution.Foreach
systemthatcanfunctionasabuffer,writetheequilibriumequationfortheconjugateacid/base
pairinthebuffersystem
(a)KF/HF(b)NH3/NH4Br(c)KNO3/HNO3(d)Na2CO3/NaHCO3
Answer:
(a) Buffer:HFH++F
(b) Buffer:NH3+H2ONH4++OH(orNH4+H++NH3)
(c) NotabuffersinceHNO3isastrongacid.Itis100%ionized.
(d) Buffer:HCO3H++CO32

2.WhatisthepHofa1Lsolutioncontaining0.240molHC2H3O2and0.180molNaC2H3O2?
Ka(HC2H3O2)=1.8x105.HINT:Beginbyfillingouttheequilibriumtablebelow.
BalancedEquation
HC2H3O2
H++ C2H3O2
InitialConcentration(M)
Change(M)
EquilibriumConcentration(M)

Answer:
BalancedEquation
InitialConcentration(M)
Change(M)
EquilibriumConcentration(M)

H++

HC2H3O2
0.240
x
0.240x

0
x
x

C2H3O2
0.180
x
0.180+x

[H ][C2 H3 O2 ]
x (0.180 x) x (0.180)
.ThisapproximationisOKifthe%
Ka
1.8 105

[HC2 H3 O2 ]
(0.240 - x)
0.240
ionizationis<5%;itisinthiscase.Thusx=2.4x105=[H+].pH=4.62.

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3.WhatwouldbethepHofthebufferfrom#2aboveif0.010molofHClwereaddedperliterof
thebuffer?

Answer:
Thenewinitialconcentrationsare:
[C2H3O2]=(0.1800.010)M=0.170M(basicpartdecreases)
[HC2H3O2]=(0.240+0.010)M=0.250M(acidicpartincreases)

[H ][C2 H3 O2 ]
x (0.170 x) x (0.170)
Thus K a
.Thusx=[H ]=2.647x10
1.8 105

[HC 2 H3 O2 ]
(0.250 - x)
0.250
+

;pH=

4.58.NotethatthepHhas

decreased

verylittle!!

4.WhatwouldbethepHofthebufferfrom#2aboveif0.010molNaOHwereaddedperliterof
thebuffer?

Answer:
Thenewinitialconcentrationsare:
[C2H3O2]=(0.180+0.010)M=0.190M(basicpartincreases)
[HC2H3O2]=(0.240.010)M=0.230M(acidicpartdecreases)

[H ][C2 H3 O2 ]
x (0.190 x) x (0.190)
Thus K a
.Thusx=[H+]=2.179x105;pH
1.8 105

[HC 2 H3 O2 ]
0.230 - x
0.230
=4.66.NotethatthepHhas

increased

verylittle!!

5.WhatwouldbethepHof0.010MHClwithoutthebuffer?

Answer:
HClisastrongacidandistherefore100%ionized.Thus[H+]=0.010M,sothepH=2.00.
NotehowmuchlowerthepHisthanitwaswiththebufferin#3above(pH=2.00hereversus4.58in#3above)!

6.WhatwouldbethepHof0.010MNaOHwithoutthebuffer?
Answer:

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S.B.Piepho,Fall2002

NaOHisastrongbaseandistherefore100%ionized.Thus[OH]=0.010M,sothepOH=2.00.ThuspH=14.00
pOH=12.00.
NotehowmuchhigherthepHisthanitwaswiththebufferin#4above(pH=12.00hereversus4.66in#4above)!

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