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AlevelCalculatingthepHofabuffersolution,calculationsofamountsneededGCEASA2chemistryrevisionnotesKS5

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DocBrown'sChemistry
TheoreticalPhysicalAdvancedLevelChemistryEquilibriaChemicalEquilibriumRevisionNotesPART6.4
EquilibriaPart6.4BuffersolutionpHcalculations
HowdoyoucalculatethepHofabuffersolution?
HowdoyoucalculatethequantitiesrequiredtomakeupabuffersolutionofadesiredpH?
GCSE/IGCSEreversiblereactionsequilibriumnotes*

GCSE/IGCSEnotesonacidsandbases

EquilibriaPart6subindex:6.1Salthydrolysis*6.2Acidbaseindicatortheory,pHcurvesandtitrations*6.3
Buffersdefinition,formulationandaction*6.4Buffercalculations*6.5Casestudiesofbufferfunction
AdvancedEquilibriumChemistryNotesPart1.Equilibrium,LeChatelier'sPrinciplerules*Part2.KcandKp
equilibriumexpressionsandcalculations*Part3.Equilibriaandindustrialprocesses*Part4.Partition,solubility
productandionexchange*Part5.pH,weakstrongacidbasetheoryandcalculations*Part6.Salthydrolysis,
Acidbasetitrationsindicators,pHcurvesandbuffers*Part7.Redoxequilibria,halfcellelectrodepotentials,
electrolysisandelectrochemicalseries*Part8Phaseequilibriavapourpressure,boilingpointandintermolecular
forces
6.4BufferpHcalculationstheoreticalcalculationofabuffersolution
6.4.1Calculationsinvolvingabuffermadefromaweakacidanditssaltwithastrongbase.
ConsiderthemixtureismadefromamonobasicweakacidHAandanalkalimetalsaltM+A
e.g.A=CH3COO,M=KorNa
itisreasonabletoassumeforsimpleapproximatecalculationsthat..
1. [A(aq)]=[salt(aq)]sincesaltfullyionisedandM+isaspectatorion,and
2. [HA(aq)]equilib.,=[HA(aq)]initialsincelittleoftheweakacidisionised.
ThereforetheweakacidKaexpressionis...
[H+(aq)][A(aq)]

(i)Ka= moldm3
[HA(aq)]
becomes

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(ii)Ka=

[H+(aq)][salt(aq)]
moldm3
[acid(aq)]

therefore:[H+(aq)]=Ka[acid(aq)]/[salt(aq)]moldm3,andtakinglog10ofbothsidesgives
(iii)pHbuffer=log10(Kax[acid(aq)]/[salt(aq)])
or(iv)pHbuffer=pKa+log10([acid(aq)]/[salt(aq)])
or(v)pHbuffer=pKa+log10([salt(aq)]/[acid(aq)])
whichishowtheequationisusuallyquoted,sometimescalledtheHendersonEquation.
Note:Foragivenconjugatepair(HAandA),thepHofthebufferisdeterminedbytheacid/salt
ratio,thoughthemoreconcentratedthebuffer,thegreateritscapacitytoneutraliselargeramounts
ofadded/formedinareactionmedium.
Anotherpointishowtochoosewhichweakacidisbestforadesiredbuffer?
Theusefulrangeofabufferisdecidedbytheweakacid'sKaandtheratioofthesaltandweak
acidconcentrations.
Thebufferwillbemostusefulwhentheratio[salt]/[acid]isequaltoonei.e.whenbothactive
ingredientsareattheirmaximumconcentrationsatnoexpensetotheotherbytheprinciplesof
relatedchemicalequilibrium,ifyouincreaseoneconcentrationyouwoulddecreasetheother.
Thereforethemaximumbuffercapacityiswhen[salt]=[acid]
NowKa=[H+(aq)]when[salt]=[acid]inequation(i)or(ii)above
thereforetakinglog10ofbothsidesgives...
pKa=pHwhen[salt]=[acid],becauselog10(1)=0inequations(iv)or(v)
andthissimplemathematicalargumentgivesthenecessaryguidance...
Soforexample,supposingyouwantedabuffertocoverapHrangeof4.5to6.0,
andyourchoiceofweakacidpKa'swas2.8,4.2,5.5and6.5,
youwouldchoosetheweakacidwithapKaof5.5becauseitspKaiswellinthedesiredpH
range.
Youwouldthenformulateitwithitssodium(orpotassium)saltnotethatsodiumionandpotassium
ionsaltsareusuallyusedbecausetheyhavevirtuallynoacidicorbasiccharactertocomplicate
matterse.g.thehydratedionsNa+(aq)andK+(aq)donotdonateprotonsintheway,forexample,the
hexaaquaionsofaluminiumcan...
[Al(H2O)6]2+(aq)+H2O(l)

[Al(H2O)5(OH)]+(aq)+H3O+(aq)

becausethepolarisingpowerofthecentralmetalions,Na+orK+istoosmalltoeffectthis
process.
6.4.2Buffercalculations
CalculatingthepHofabuffercalculatingamountsofsaltandacidneeded
Buffercalculationexample6.4.2a
Abuffersolutionwaspreparedwhichhadaconcentrationof0.20moldm3inethanoicacidand0.10mol
dm3insodiumethanoate.IftheKaforethanoicacidis1.74x105moldm3,calculatethetheoretical
hydrogenionconcentrationandpHofthebuffersolution.
Ka=[H+(aq)][salt(aq)]/[acid(aq)]
1.74x105=[H+(aq)]x0.10/0.20
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[H+

5
5
3
(aq)]=1.74x10 x0.20/0.10=3.48x10 moldm

pH=log(3.48x105)=4.46
Buffercalculationexample6.4.2b
Inwhatratioshoulda0.30moldm3ofethanoicacidbemixedwitha0.30moldm3solutionofsodium
ethanoatetogiveabuffersolutionofpH5.6?
Kaforethanoicacidis1.74x105moldm3
[H+(aq)]=10pH=105.6=2.51x106moldm3
Ka=[H+(aq)][salt(aq)]/[acid(aq)]
[salt]/[acid]=Ka/[H+(aq)]=1.74x105/2.51x106=6.93
Thereforevolumeratiois6.93:1forsalt:acid,e.g.6.93cm3of0.30Msodiumethanoateismixedwith
1.0cm3of0.30MethanoicacidtogiveabuffersolutionofpH5.6.
NotethatthepHisdeterminedbytheratioofconcentrations,butthebufferingcapacityofthesolutioncan
beincreasedbyincreasingtheconcentrationsofbothcomponentsinthesamemolarconcentrationratio.
Buffercalculationexample6.4.2c
WhatisthepHofabuffersolutionmadefromdissolving2.0gofbenzoicacidand5.0gofsodium
benzoatein250cm3ofwater?
Kabenzoicacid=6.3x105moldm3,Ar's:H=1,C=12,O=16,Na=23
Molecularmasses:Mr(C6H5COOH)=122,Mr(C6H5COONa+)=144,250cm3=0.25dm3
molesacidC6H5COOH=2.0/122=0.0164mol,molarity=0.0656moldm3
molessaltC6H5COONa+=5.0/144=0.0347mol,molarity=0.139moldm3
[H+(aq)]=Ka[acid(aq)]/[salt(aq)]
[H+(aq)]=6.3x105x0.0656/0.139=2.97x105moldm3
pH=log[H+(aq)]=log(2.97x105)=4.53
Buffercalculationexample6.4.2d
CalculatethepHofabuffermadebymixing100cm3ofa0.40Msodiumpropanoateand50cm3of0.2M
propanoicacidsolution.
Kapropanoicacid=1.3x105moldm3,totalvolumeofbuffer=150cm3
molaritiesinthemixture:
[salt]=0.40x100/150=0.267moldm3
[acid]=0.20x50/150=0.0667moldm3
[H+(aq)]=Ka[acid(aq)]/[salt(aq)]
[H+(aq)]=1.3x105x0.0667/0.267=3.24x106moldm3
pH=log[H+(aq)]=log(3.24x106)=5.48
Buffercalculationexample6.4.2e
UsingtheHendersonequation
pHbuffer=pKa+log10([salt(aq)]/[acid(aq)])
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CalculatethepHofbuffersolutionmadebymixingtogether100cm3of0.100Methanoicacidand50cm3
of0.400Msodiumethanoate,
giventhatKaforethanoicacidis1.74x105moldm3
Nowbecausethevolumesarenotequal,therealconcentrationsinthemixturemustbeworkedout.
Thetotalvolumeis150cm3,thereforethedilutionsaregivenby
[acid]=0.1x100/150=0.06667
[salt]=0.4x50/150=0.1333
SubstitutingintheHendersonEquationgives
pHbuffer=log10(1.74x105)+log10(0.1333/0.0667)
pHbuffer=log10(1.74x105)+log10(2)
pHbuffer=4.76+0.3010
pHbuffer=5.06

EquilibriaPart6subindex:6.1Salthydrolysis*6.2Acidbaseindicatortheory,pHcurvesandtitrations
6.3Buffersdefinition,formulationandaction*6.4Buffercalculations*6.5Casestudiesofbufferfunction

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