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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

Page 1

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
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
addingadding aa commoncommon ion.ion.
 

7

 

Buffer Solutions

BufferBuffer SolutionsSolutions

HClHCl isis addedadded toto purepure water.water. HClHCl isis addedadded toto aa

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 4 4 2 - 2 -

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

     

Page 2

 

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

0.7000.700 andand 0.600,0.600, wewe havehave [H 3 O + ](0.600) 1 . 8 x 1 0

[H 3 O + ](0.600)

andand 0.600,0.600, wewe havehave [H 3 O + ](0.600) 1 . 8 x 1 0 -

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
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

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 (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
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
acidacid andand thenthen adjustedadjusted byby thethe ratioratio ofof acidacid andand
conjugateconjugate base.base.

17

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 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

Page 3

 

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 AddingAdding anan AcidAcid toto aa BufferBuffer WhatWhat isis thethe pHpH whenwhen 1.001.00 mLmL ofof
20
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 --
[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
TheThe pHpH hashas notnot changedchanged onon addingadding HClHCl toto thethe
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.

Page 4

 

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

25 Preparing a Buffer Preparing Preparing a a Buffer Buffer BufferBuffer preparedprepared fromfrom HCOHCO 3 3

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-