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Henderson­HasselbalchProblems

AreminderoftheHenderson­Hasselbalchequation:

AreminderoftheHenderson­Hasselbalchequation: Problem#1: pK a forphenophthaleinis9.3atroomtemp.

Problem#1:pK a forphenophthaleinis9.3atroomtemp.

a)CalculateratioofitsanionicformtoacidformatpH8.2andatpH10.

b)Usingthesevalues,explainthecolourchangewithinthispHrange.

Solutiontopart(a):

1)AtpH=8.2:

8.2=9.3+log(baseform/acidform)

log(baseform/acidform)=­1.1

ratioofbaseformtoacidform=0.0794to1(callit8to100)

2)AtpH=10.:

10=9.3+log(baseform/acidform)

log(baseform/acidform)=0.7

ratioofbaseformtoacidform=5.01to1(callit500to100)

Solutiontopart(b):

1)Keyfact:

it'stheanionic(orbase)formthatiscoloredpink.Theacidformiscolorless.

2)AtpH=8.3:

thepinkformisintheminorityatthispH.Forevery100acid(colorless)forms,thereareonly8

base(pink)forms.

3)AtpH=10.:

thecolorlessformisintheminority.Forevery100acid(colorless)formspresent,therearenow

500base(pink)formspresent.

4)Thismeans:

FrompH=8.3topH=10.,therehasbeena6250%increaseinpinkforms(from8:100to

500:100).

Whiletheremightbeaslightpinkcolor(viewedagainstawhitebackground)atpH8.3,the

populationofpinkformshasgreatlyincreasedbypH=10.,tothepointwherethepinkcoloris

noweasilyseen,evenwithouttheaidofawhitebackground.

Problem#2:AspirinhasapK a of3.4.WhatistheratioofA¯toHAin:

(a)theblood(pH=7.4)

(b)thestomach(pH=1.4)

Generalcommentaboutthesolutions:YouhavetofindtheratiobetweenA¯andHAsotheconcentrations

arenotneeded

Solutiontopart(a):

pH=pK a +log[A¯]/[HA]

7.4=3.4+log[A¯]/[HA]

7.4­3.4=4=log[A¯]/[HA]

10 4 =10000=[A¯]/[HA]

Solutiontopart(b):

1.4=3.4+log[A¯]/[HA]

1.4­3.4=­2.0=log[A¯]/[HA]

10 ­2 =0.01=[A¯]/[HA]

1.4­3.4=­2.0=log[A¯]/[HA] 10 ­ 2 =0.01=[A¯]/[HA] Problem#3:

Problem#3:CalculatethepHofthesolutionthatresultsfromtheadditionof0.040molesofHNO 3 toa

buffermadebycombining0.500Lof0.380MHC 3 H 5 O 2 (K a =1.30x10¯ 5 )and0.500Lof0.380M NaC 3 H 5 O 2

Assumeadditionofthenitricacidhasnoeffectonvolume.

Solution:

1a)ThenitricacidwillreducetheamountofNaC 3

(0.380mol/L)(0.500L)=0.190molofNaC

H

5

3

H

O 2

5 O

:

2

0.190mol­0.040mol=0.150molNaC 3 H 5 O 2 remaining

1b)Thereactionin1awillincreasetheamountofHC 3 H 5 O 2 :

theincreasewillbebythesameamountofthedecrease

0.190mol+0.040mol=0.230molofHC 3 H 5 O 2

2)CalculatethenewpH:

pH=pK a +log[base]/[acid]

pH=4.886+log(0.150/0.230)

pH=4.700

Note:theratioofthemolesisthesameastheratioofthemolarities.Youcandemonstratethattoyourselfby

calculatingthenewmolaritiesin0.500L,themaddingthetwosolutionstogether,therebycuttingthe

molaritiesinhalf.Then,insertthemintotheHenderson­HasselbalchEquation.Youwillget4.700foryour

answer.

Problem#4:YouneedtoproduceabuffersolutionthathasapHof5.27.Youalreadyhaveasolutionthat

contains10.0mmol(millimoles)ofaceticacid.Howmanymillimolesofsodiumacetatewillyouneedtoadd

tothissolution?ThepK a ofaceticacidis4.75.

Solution:

1)SubstituteintotheHenderson­HasselbalchEquationandsolve:

5.27=4.75+log(x/10)

log(x/10)=0.52

x/10=3.3113

x=33.1millimolesofsodiumacetate

log(x/10)=0.52 x/10=3.3113 x=33.1millimolesofsodiumacetate Problem#5: WhatisthepHwhen25.0mLof0.200MofCH 3

Problem#5:WhatisthepHwhen25.0mLof0.200MofCH 3 COOHhasbeentitratedwith35.0mLof

0.100MNaOH?

Solution:

1)DeterminemolesofaceticacidandNaOHbeforemixing:

CH 3 COOH:(0.200mol/L)(0.0250L)=0.00500mol

NaOH:(0.100mol/L)(0.0350L)=0.0035mol

2)Determinemolesofaceticacidandsodiumacetateaftermixing:

CH

CH

3

3

COOH:0.00500mol­0.00350mol=0.00150mol

COONa:0.0035mol<.blockquote>

Theabovecomesfromconsiderationofthisreaction:

CH 3 COOH+NaOH<===>CH 3 COONa+H 2 O

3)UsetheHenderson­HasselbalchEquation:

pH=4.752+log[(0.00350mol/0.060L)/(0.0015mol/0.060L)]

pH=4.752+log2.333

pH=4.752+0.368=5.120

Problem#6:Asolutioncontaining50.00mLof0.1800MNH 3 (K b =1.77x10 ­5 )isbeingtitratedwith

0.3600MHCl.CalculatethepH:

a.initially

b.Aftertheadditionof5.00mLofHCl

c.Aftertheadditionofatotalvolumeof12.50mLHCl

d.Aftertheadditionofatotalvolumeof25.00mLofHCl

e.Aftertheadditionof26.00mLofHCl

Anexampleofthesolutiontechniqueforpart(a)isprovidedhere.Theanswerforourexampleis11.252.

Solutiontopart(b):

1)DeterminemolesofNH 3 andHClbeforemixing:

NH 3 :(0.1800mol/L)(0.0500L)=0.00900mol

HCl:(0.3600mol/L)(0.0050L)=0.00180mol

2)Determinemolesofammoniaandammoniumionaftermixing:

NH 3 :0.00900mol­0.00180mol=0.00720molNH 3 remaining

NH

4 + :0.00180molproduced

Theabovecomesfromconsiderationofthisreaction:

NH 3 +HClNH 4 Cl

3)UsetheH­HEquation:

pH=pK a +log(base/acid)

pH=9.248+log[(0.0072/0.055)/(0.0018/0.055)]

pH=9.850

NotethatthepK a wasused,NOTthepK b NotealsothattheadditionofacidcausedthepHofthe(now) buffertodecrease,thatistobecomemoreacidic.Thisiswhatweexpecttohappen.Lastly,notetheinclusion

ofthenewvolume,0.055L.Boththesevaluescancelout,sothenewvolumeisratherinconsequential.In

fact,whenIcalculatedtheanswerforthisproblem(March23,2010),Iactuallydivided72by18.

Solutiontopart(c):

1)DeterminemolesofNH 3 andHClbeforemixing:

NH 3 :(0.1800mol/L)(0.0500L)=0.00900mol

HCl:(0.3600mol/L)(0.01250L)=0.00450mol

2)Determinemolesofammoniaandammoniumionaftermixing:

NH 3 :0.00900mol­0.00450mol=0.00450molNH 3 remaining

NH

4 + :0.00450molproduced

3)UsetheH­HEquation:

pH=pK a +log(base/acid)

pH=9.248+log(0.0045/0.0045)

pH=9.248

Solutiontopart(d):

1)DeterminemolesofNH 3 andHClbeforemixing:

NH 3 :(0.1800mol/L)(0.0500L)=0.00900mol

HCl:(0.3600mol/L)(0.02500L)=0.00900mol

2)Determinemolesofammoniaandammoniumionaftermixing:

NH 3 :0.00900mol­0.00900mol=zeromolNH 3 remaining

NH

4 + :0.00900molproduced

3)Thissolutionisnolongerabuffer.Itisnowthesaltofaweakbaseanditssolutionwillbeacidic.TheH­

HEquationisnotusedtodeterminethepHofthesolution.Anintroductiontothesolutiontechniquecanbe

foundhere.Theactualmolarityisimportantanditis0.120M(0.00900mol/0.0750L).ThepHis5.084.

Solutiontopart(e):

Thissolutionisnowasolutionofastrongacid(thepresenceoftheweakacidNH 4 + maybeignored).

1)LetusdeterminethenewmolarityoftheHCl:

M 1 V 1 =M 2 V 2

(0.36)(1.00mL)=(x)(76.00mL)

x=0.004736842M(Ikeptsomeguarddigits.)

2)CalculatethepHintheusualmanner:

pH=­log[H + ]

pH=2.324

Problem#7:Abeakerwith100.0mLofanaceticacidbufferwithapHof5.000issittingonabenchtop.

Thetotalmolarityofacidandconjugatebaseinthisbufferis0.1000M.Astudentadds7.300mlofa0.3600

MHClsolutiontothebeaker.HowmuchwillthepHchange?ThepK a ofaceticacidis4.752.

Solution:

1)UseH­HEquationtodetermineratioofbasetoacid:

pH=pK a +log(base/acid)

5.000=4.752+log(x/1)

IwanttheratioofbasetoacidwhichiswhyIusedx/1

logx=0.248

x=1.77

mybase:saltratiois1.77:1

2)Determinemolesofbaseandmolesofacidin0.0100moleoftotalsolute:

letx=molesofacid

x=0.00361moles(thisistheacid)

base=0.00639mol

3)Addstrongacid,whichwillprotonatethebase:

(0.360mol/L)(0.00730L)=0.002628molofstrongacidadded

base:0.00639­0.002628=0.003762mol

acid:0.00361+0.002628=0.006238mol

pH=4.752+log(0.003762/0.006238)

pH=4.752+(­0.220)

pH=4.532

Note:IusedmolesinthelastH­Hexpressionratherthanusingthenewvolumeof0.1073Ltogetmolarities.

Sincetherewouldbea0.1073Linthenumeratorandthedenominator,Ijustskippedthatstep.

Problem#8:1.00Lofasolutioncontaining0.0500moleofHOAcand0.100moleofNaOAcisprepared.

Ignoretheautoionizationofwaterforthepurposesofthisproblem.TheK a ofHAcequals1.77x10 ­5 .

(a)Calculatethenumericalvalueofthereactionquotient,Qfortheinitialcondition. (b)Whichwaywillthereactionshift?

(c)Calculateto3significantdigitsthepHofthissolution.

Note:Thechemicalreactiontoconsideris:

HAcH + +Ac¯

Solutionto(a):

1)WritethereactionquotientfortheabovereactionandsolveforQ:

Q a =([H + ] o [Ac¯] o )/[HAc] o

Q a =[(1.00x10¯ 7 )(0.100)]/0.0500

Q a =2.00x10¯ 7

NoticethatIdidusethevalueforthe[H + ]derivedfromtheautoionizationofwater.The instructioninthequestionisintendedforusewhenthepHiscalculated.

Solutionto(b):

SinceQ a <K a ,thereactionshiftsright,inordertoincreasethevalueforQ a uptothevaluefor K a .

Solutionto(c):

1)WritetheK a expressionandsolveit:

K a =([H + ][Ac¯])/[HAc]

1.77x10¯ 5 =[(x)(0.100)]/0.0500

x=8.85x10¯ 6 M

2)CalculatethepH:

pH=­log8.85x10¯ 6 =5.053

NoticethatIdidnotusetheHenderson­Hasselbalchequation.Ah,butIdid!TheH­Hequationissimplya rearrangementoftheK a expression.

Problem#9:CalculatetheratioofCH 3 NH 2 toCH 3 NH 3 ClrequiredtocreateabufferwithpH=10.14

Solution:

1)WeneedtheK a ofthemethylammoniumion:

K b ofCH 3 NH 2 =4.4x10 ­4

K a forCH 3 NH 3 Cl=1.00x10 ­14 /4.4x10 ­4 =2.27x10 ­11

2)WritethechemicalequationandtheHenderson­Hasselbalchequation:

CH 3 NH 3 + +H 2 O<==>H 3 O + +CH 3 NH 2

pH=pK a +log(base/acid)

3)Substituteandsolveforthebase/acidratio:

10.14=10.644+log(base/acid)

log(base/acid)=­0.504

base/acidratio=0.313

Problem#10:FiftypercentofaweakacidisinanionizedforminasolutionwithpHof5.000,whatisthe

pK a valuefortheweakacid?

Solution:

1)Ifoundthisansweron­line:

"LetussupposetheacidisHAanditsionicanionisA¯.Then,fora50%ionizedsolution,pH=

pK a because,athalf­neutralization,[HA]/[A¯]=1.Sincelog(1)=0,thepHathalf­ neutralizationisnumericallyequaltopK a .

2)Comments:

a)IdecidedtoputtheansweramongHenderson­Hasselbalchquestionsbecauseofthereference tothelogtermoftheH­Hequation. b)Thehalf­neutralizationpoint,where[HA]=[A¯],isanimportantoneintitrationandisa techniquewherebythepK a ofaweakacidcanbeobtained.