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 TheThe CommonCommon IonIon EffectEffect 1 SectionSection 18.218.2 QUESTION:QUESTION: WhatWhat isis thethe effecteffect onon thethe pHpH QUESTION: What is the effect on the pH ofof addingadding NHNH of adding NH 44 4 ClCl toto 0.250.25 MM NHNH Cl to 0.25 M NH 33 3 ((aqaq)?)? (aq)? NHNH ((aqaq)) ++ HH OO ¸¸ NHNH ¸ NH NH 33 3 (aq) + H 22 2 O 44 4 ++ + ((aqaq)) (aq) ++ + OHOH ((aqaq)) OH (aq) -- - HereHere wewe areare addingadding anan ionion COMMONCOMMON toto Here we are adding an ion COMMON to thethe equilibrium.equilibrium. the equilibrium. LeLe ChatelierChatelier predictspredicts thatthat thethe equilibriumequilibrium Le Chatelier predicts that the equilibrium willwill shiftshift toto thethe will shift to the TheThe pHpH willwill gogo The pH will go AfterAfter all,all, NHNH ++ + isis anan acid!acid! is an acid! After all, NH 44 4
 TheThe CommonCommon IonIon EffectEffect 4 SectionSection 18.218.2 Problem:Problem: WhatWhat isis thethe pHpH ofof aa solutionsolution Problem: What is the pH of a solution withwith 0.100.10 MM NHNH with 0.10 M NH 44 4 ClCl andand 0.250.25 MM NHNH Cl and 0.25 M NH ++ 33 3 -- ((aqaq)?)? (aq)? NHNH ((aqaq)) ++ HH OO ¸¸ NHNH ¸ NH NH 33 3 (aq) + H 22 2 O 44 4 + ((aqaq)) (aq) ++ + OHOH ((aqaq)) OH (aq) - WeWe expectexpect thatthat thethe pHpH willwill declinedecline onon We expect that the pH will decline on addingadding NHNH adding NH 44 4 Cl.Cl. Let’sLet’s testtest that!that! Cl. Let’s test that! [NH[NH ]] [NH ] 33 3 [NH[NH [NH 44 4 ++ + ]] ] [OH[OH ]] [OH ] -- - initialinitial initial changechange change equilibequilib equilib
 TheThe CommonCommon IonIon EffectEffect 2 SectionSection 18.218.2 QUESTION:QUESTION: WhatWhat isis thethe effecteffect onon thethe pHpH ofof addingadding NHNH QUESTION: What is the effect on the pH of adding NH toto 0.250.25 MM NHNH ((aqaq)?)? to 0.25 M NH (aq)? 33 3 44 4 ClCl Cl NHNH ((aqaq)) ++ HH OO NH O 33 3 (aq) + H 22 2 ¸¸ ¸ NHNH NH 44 4 ++ + ((aqaq)) (aq) ++ + OHOH ((aqaq)) OH (aq) -- - LetLet usus firstfirst calculatecalculate thethe pHpH ofof aa 0.250.25 MM Let us first calculate the pH of a 0.25 M NHNH NH solution.solution. solution. 33 3 ++ + -- - initialinitial [NH[NH ]] ] [NH 0.250.25 33 3 [NH[NH [NH 00 44 4 ]] ] [OH[OH ]] [OH ] 00 initial 0.25 0 0 changechange change -x-x -x +x+x +x +x+x +x equilibequilib equilib 0.250.25 -- xx 0.25 - x xx x xx x
 TheThe CommonCommon IonIon EffectEffect 5 SectionSection 18.218.2 Problem:Problem: WhatWhat isis thethe pHpH ofof aa solutionsolution Problem: What is the pH of a solution withwith 0.100.10 MM NHNH with 0.10 M NH 44 4 ClCl andand 0.250.25 MM NHNH Cl and 0.25 M NH ++ 33 3 -- ((aqaq)?)? (aq)? NHNH ((aqaq)) ++ HH OO ¸¸ NHNH ¸ NH NH 33 3 (aq) + H 22 2 O 44 4 + ((aqaq)) (aq) ++ + OHOH ((aqaq)) OH (aq) - WeWe expectexpect thatthat thethe pHpH willwill declinedecline onon We expect that the pH will decline on addingadding NHNH adding NH 44 4 Cl.Cl. Let’sLet’s testtest that!that! Cl. Let’s test that! [NH[NH ]] [NH ] 33 3 [NH[NH [NH 44 4 ++ + ]] ] [OH[OH ]] [OH ] -- - initialinitial initial 0.250.25 0.25 0.100.10 0.10 00 0 changechange change -x-x -x +x+x +x +x+x +x equilibequilib equilib 0.250.25 -- xx 0.25 - x 0.100.10 ++ xx 0.10 + x xx x

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 TheThe CommonCommon IonIon EffectEffect 3 SectionSection 18.218.2 QUESTION:QUESTION: WhatWhat isis thethe effecteffect onon thethe pHpH ofof addingadding NHNH QUESTION: What is the effect on the pH of adding NH toto 0.250.25 MM NHNH ((aqaq)?)? to 0.25 M NH (aq)? 33 3 44 4 ClCl Cl NHNH ((aqaq)) ++ HH OO NH O 33 3 (aq) + H 22 2 ¸¸ ¸ NHNH NH 44 4 ++ + ((aqaq)) (aq) ++ + OHOH ((aqaq)) OH (aq) -- - K b 1.8 x 10 -5 = [NH 4 + ][OH - ] = x 2 0.25 - x [NH 3 ] AssumingAssuming xx isis <<<< 0.25,0.25, wewe havehave [OH[OH -- ]] == xx == [K[K bb (0.25)](0.25)] 1/21/2 == 0.00210.0021 MM ThisThis givesgives pOHpOH == 2.672.67 andand soso pHpH == 14.0014.00 -- 2.672.67 == 11.3311.33 forfor 0.250.25 MM NHNH 33
6
TheThe CommonCommon IonIon EffectEffect
SectionSection 18.218.2
Problem:Problem: WhatWhat isis thethe pHpH ofof aa solutionsolution withwith 0.100.10 MM NHNH
Problem: What is the pH of a solution with 0.10 M NH
ClCl
Cl
44
4
andand 0.250.25 MM NHNH ((aqaq)?)?
and 0.25 M NH (aq)?
33
3
NHNH ((aqaq)) ++ HH OO ¸¸ NHNH
++
NH
(aq) + H
O
¸ NH
+
((aqaq))
(aq)
++
+
OHOH ((aqaq))
--
OH (aq)
-
33
3
22
2
44
4
[NH 4 + ][OH - ]
x(0.10 + x)
1.8 x 10 -5
=
=
K b
[NH 3 ]
0.25 - x
[OH[OH -- ]] == xx == (0.25(0.25 // 0.10)K0.10)K bb == 4.54.5 xx 1010 -5-5 MM
ThisThis givesgives pOHpOH == 4.354.35 andand pHpH == 9.659.65
pHpH dropsdrops fromfrom 11.3311.33 toto 9.659.65 onon
 7 Buffer Solutions BufferBuffer SolutionsSolutions HClHCl isis addedadded toto purepure water.water. HClHCl isis addedadded toto aa solutionsolution ofof aa weakweak acidacid HH 22 POPO 44 -- andand itsits conjugateconjugate basebase HPOHPO 44 2-2- 10 BufferBuffer SolutionsSolutions ConsiderConsider HOAcHOAc//OAcOAc -- toto seesee howhow buffersbuffers workwork CONJ.CONJ. BASEBASE USESUSES UPUP ADDEDADDED HH ++ HOAcHOAc ++ HH 22 OO ¸¸ OAcOAc -- ++ HH 33 OO ++ hashas KK aa == 1.81.8 xx 1010 -5-5 Therefore,Therefore, thethe reversereverse reactionreaction ofof thethe WEAKWEAK BASEBASE withwith addedadded HH ++ hashas KK reversereverse == 1/1/ KK aa == 5.65.6 xx 1010 44 KK reversereverse isis VERYVERY LARGE,LARGE, soso OAcOAc -- completelycompletely snarfssnarfs upup HH ++ !!
 8 BufferBuffer SolutionsSolutions TheThe functionfunction ofof aa bufferbuffer isis toto resistresist changeschanges inin thethe pHpH ofof aa solution.solution. BuffersBuffers areare justjust aa specialspecial casecase ofof thethe commoncommon ionion effect.effect. BufferBuffer CompositionComposition WeakWeak AcidAcid ++ ConjConj BaseBase HOAcHOAc ++ OAcOAc -- HH 22 POPO 44 -- ++ HPOHPO 44 2-2- WeakWeak BaseBase ++ ConjConj AcidAcid NHNH 33 ++ NHNH 44 ++ 11 BufferBuffer SolutionsSolutions Problem:Problem: WhatWhat isis thethe pHpH ofof aa bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand [[OAcOAc -- ]] == 0.6000.600 M?M? HOAcHOAc ++ HH 22 OO ¸¸ OAcOAc -- ++ HH 33 OO ++ KK aa == 1.81.8 xx 1010 -5-5 [[HOAcHOAc]] [[OAcOAc -- ]] [H[H 33 OO ++ ]] initialinitial 0.7000.700 0.6000.600 00 changechange -x-x +x+x +x+x equilibequilib 0.7000.700 -- xx 0.6000.600 ++ xx xx

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 9 BufferBuffer SolutionsSolutions ConsiderConsider HOAcHOAc//OAcOAc -- toto seesee howhow buffersbuffers workwork ACIDACID USESUSES UPUP ADDEDADDED OHOH -- WeWe knowknow thatthat OAcOAc -- ++ HH 22 OO ¸¸ HOAcHOAc ++ OHOH -- hashas KK bb == 5.65.6 xx 1010 -10-10 Therefore,Therefore, thethe reversereverse reactionreaction ofof thethe WEAKWEAK ACIDACID withwith addedadded OHOH -- hashas KK reversereverse == 1/1/ KK bb == 1.81.8 xx 1010 99 KK reversereverse isis VERYVERY LARGE,LARGE, soso HOAcHOAc completelycompletely snarfssnarfs upup OHOH -- !!!!!!!!

12

BufferBuffer SolutionsSolutions

Problem:Problem: WhatWhat isis thethe pHpH ofof aa bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM

andand [[OAcOAc -- ]] == 0.6000.600 M?M?

++

HOAcHOAc

HH 22 OO ¸¸ OAcOAc --

++ HH 33 OO ++

KK aa == 1.81.8 xx 1010 -5-5

[[HOAcHOAc]]

[[OAcOAc -- ]]

[H[H 33 OO ++ ]]

equilibequilib

0.7000.700 -- xx

0.6000.600 ++ xx

xx

AssumingAssuming thatthat xx <<<< 0.7000.700 andand 0.600,0.600, wewe havehave

[H 3 O + ](0.600)

1.8 x 10 -5

[H[H 33 OO ++ ]] == 2.12.1 xx 1010 -5-5 andand pHpH == 4.684.68

0.700

=

K a

13
BufferBuffer SolutionsSolutions
NoticeNotice thatthat thethe expressionexpression forfor calculatingcalculating thethe
HH ++ concconc ofof thethe bufferbuffer isis
Orig. conc. of HOAc
[H 3 O
]
K a
Orig. conc. of OAc -
[Acid]
[Base]
[H 3 O
]
[OH
]
[Conj. base] •K a
[Conj. acid] •K b
NoticeNotice thatthat thethe HH ++ oror OHOH -- concsconcs dependdepend onon
KK andand thethe ratioratio ofof acidacid andand basebase concsconcs

16

WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof 1.001.00 MM HClHCl isis addedadded toto

 a)a) 1.001.00 LL ofof purepure waterwater (after(after HClHCl,, pHpH == 3.00)3.00) b)b) 1.001.00 LL ofof bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand

[[OAcOAc -- ]] == 0.6000.600 MM (pH(pH beforebefore == 4.68)4.68)

SolutionSolution toto PartPart (b)(b)

StepStep 11 —— dodo thethe stoichiometrystoichiometry

HH 33 OO ++ (from(from HClHCl)) ++ OAcOAc -- (from(from buffer)buffer) --->--->

HOAcHOAc (from(from buffer)buffer)

TheThe reactionreaction occursoccurs completelycompletely becausebecause KK isis

veryvery large.large.

14
Henderson-Henderson-HasselbalchHasselbalch EquationEquation
[Acid]
[H 3 O
]
[Conj. base] •K a
TakeTake thethe negativenegative loglog ofof bothboth sidessides ofof thisthis
equationequation
[Acid]
pH
pK a - log
[Conj. base]
pK a + log [Conj. base]
pH
[Acid]
TheThe pHpH isis determineddetermined largelylargely byby thethe pKpK aa ofof thethe
conjugateconjugate base.base.

17

WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof 1.001.00 MM HClHCl isis addedadded toto

 a)a) 1.001.00 LL ofof purepure waterwater (pH(pH == 3.00)3.00) b)b) 1.001.00 LL ofof bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand

[[OAcOAc -- ]] == 0.6000.600 MM (pH(pH == 4.68)4.68)

SolutionSolution toto PartPart (b):(b): StepStep 1—1—StoichiometryStoichiometry

 [H[H 33 OO ++ ]] ++ [[OAcOAc -- ]] --->---> [[HOAcHOAc]] BeforeBefore rxnrxn 0.001000.00100 0.6000.600 0.7000.700 ChangeChange -0.00100-0.00100 -0.00100-0.00100 +0.00100+0.00100 AfterAfter rxnrxn 00 0.5990.599 0.7010.701

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 15 AddingAdding anan AcidAcid toto aa BufferBuffer Problem:Problem: WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof 1.001.00 MM HClHCl isis addedadded toto a)a) 1.001.00 LL ofof purepure waterwater (before(before HClHCl,, pHpH == 7.00)7.00) b)b) 1.001.00 LL ofof bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand [[OAcOAc -- ]] == 0.6000.600 MM (pH(pH == 4.68)4.68) SolutionSolution toto PartPart (a)(a) CalcCalc [[HClHCl]] afterafter addingadding 1.001.00 mLmL ofof HClHCl toto 1.001.00 LL ofof waterwater MM 11 •V•V 11 == MM 22 •• VV 22 MM 22 == 1.001.00 xx 1010 -3-3 MM pHpH == 3.003.00 18 AddingAdding anan AcidAcid toto aa BufferBuffer WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof 1.001.00 MM HClHCl isis addedadded toto a)a) 1.001.00 LL ofof purepure waterwater (pH(pH == 3.00)3.00) b)b) 1.001.00 LL ofof bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand [[OAcOAc -- ]] == 0.6000.600 MM (pH(pH == 4.68)4.68) SolutionSolution toto PartPart (b):(b): StepStep 2—Equilibrium2—Equilibrium HOAcHOAc ++ HH 22 OO ¸¸ HH 33 OO ++ ++ OAcOAc -- [[HOAcHOAc]] ¸¸ [H[H 33 OO ++ ]] ++ [[OAcOAc -- ]] BeforeBefore rxnrxn 0.7010.701 00 0.5990.599 ChangeChange -x-x +x+x +x+x AfterAfter rxnrxn 0.701-x0.701-x xx 0.5990.599 ++ xx
 19 AddingAdding anan AcidAcid toto aa BufferBuffer WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof 1.001.00 MM HClHCl isis addedadded toto a)a) 1.001.00 LL ofof purepure waterwater (pH(pH == 3.00)3.00) b)b) 1.001.00 LL ofof bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand [[OAcOAc-]-] == 0.6000.600 MM (pH(pH == 4.68)4.68) SolutionSolution toto PartPart (b):(b): StepStep 2—Equilibrium2—Equilibrium HOAcHOAc ++ HH 22 OO ¸¸ HH 33 OO ++ ++ OAcOAc -- [[HOAcHOAc]] ¸¸ [H[H 33 OO ++ ]] ++ [[OAcOAc -- ]] AfterAfter rxnrxn 0.701-x0.701-x 0.599+x0.599+x xx BecauseBecause [H[H 33 OO ++ ]] == 2.12.1 xx 1010 -5-5 MM BEFOREBEFORE addingadding HClHCl,, wewe againagain neglectneglect xx relativerelative toto 0.7010.701 andand 0.599.0.599. 22 Preparing a Buffer PreparingPreparing aa BufferBuffer YouYou wantwant toto bufferbuffer aa solutionsolution atat pHpH == 4.304.30 oror [H[H 33 OO ++ ]] == 5.05.0 xx 1010 -5-5 MM POSSIBLEPOSSIBLE ACIDSACIDS KK aa HSOHSO 44 -- // SOSO 44 2-2- 1.21.2 xx 1010 -2-2 HOAcHOAc // OAcOAc -- 1.81.8 xx 1010 -5-5 HCNHCN // CNCN -- 4.04.0 xx 1010 -10-10 BestBest choicechoice isis aceticacetic acidacid // acetate.acetate.
20
WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof 1.001.00 MM HClHCl isis addedadded toto
a)a)
1.001.00 LL ofof purepure waterwater (pH(pH == 3.00)3.00)
b)b)
1.001.00 LL ofof bufferbuffer thatthat hashas [[HOAcHOAc]] == 0.7000.700 MM andand
[[OAcOAc-]-] == 0.6000.600 MM (pH(pH == 4.68)4.68)
SolutionSolution toto PartPart (b):(b): StepStep 2—Equilibrium2—Equilibrium
HOAcHOAc
++
HH 22 OO ¸¸ HH 33 OO ++
++ OAcOAc --
[HOAc]
0.701
[H 3 O
]
•K a
0.599 •(1.8 x 10 -5 )
[OAc - ]
[H[H 33 OO ++ ]] == 2.12.1 xx 1010 -5-5 MM
------>------> pHpH == 4.684.68
buffer!buffer!
23
Preparing a Buffer
PreparingPreparing aa BufferBuffer
YouYou wantwant toto bufferbuffer aa solutionsolution atat pHpH == 4.304.30 oror
[H[H 33 OO ++ ]] == 5.05.0 xx 1010 -5-5 MM
[H 3 O
]
5.0 x 10 -5 = [HOAc]
(1.8 x 10 -5 )
[OAc - ]
2.78
SolveSolve forfor [[HOAcHOAc]/[]/[OAcOAc -- ]] ratioratio
1
Therefore,Therefore, ifif youyou useuse 0.1000.100 molmol ofof NaOAcNaOAc
andand 0.2780.278 molmol ofof HOAcHOAc,, youyou willwill havehave pHpH ==
4.30.4.30.

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 21 Preparing a Buffer PreparingPreparing aa BufferBuffer YouYou wantwant toto bufferbuffer aa solutionsolution atat pHpH == 4.30.4.30. ThisThis meansmeans [H[H 33 OO ++ ]] == 1010 -pH-pH == 5.05.0 xx 1010 -5-5 MM ItIt isis bestbest toto choosechoose anan acidacid suchsuch thatthat [H[H 33 OO ++ ]] isis aboutabout equalequal toto KK aa (or(or pHpH pKpK aa ).). —then—then youyou getget thethe exactexact [H[H 33 OO ++ ]] byby adjustingadjusting thethe ratioratio ofof acidacid toto conjugateconjugate base.base. [H 3 O ] [Acid] [Conj. base] •K a

24

Preparing a Buffer

PreparingPreparing aa BufferBuffer

AA finalfinal pointpoint ——

CONCENTRATIONCONCENTRATION ofof thethe acidacid andand conjugateconjugate

basebase areare notnot important.important.

ItIt isis thethe RATIORATIO OFOF THETHE NUMBERNUMBER OFOF MOLESMOLES

ofof each.each.

Result:Result: dilutingdiluting aa bufferbuffer solutionsolution doesdoes

notnot changechange itsits pHpH

25

Preparing a Buffer

PreparingPreparing aa BufferBuffer

BufferBuffer preparedprepared fromfrom

 HCOHCO 33 -- weakweak acidacid COCO 33 2-2- conjugateconjugate basebase

HCOHCO 33 -- ++ HH 22 OO

¸¸ HH 33 OO ++ ++ COCO 33 2-2-