Chemistry: The Central Science

Fifteenth Edition

Chapter 17
Aqueous Equilibria: Buffers,
Titrations, and Solubility

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17.1 The Common-Ion Effect
• “Whenever a weak electrolyte and a strong electrolyte
containing a common ion are together in solution, the
weak electrolyte ionizes less than it would if it were alone
in solution.”
• The equilibrium constant does not change.
• The relative concentrations or reactant and product in the
equilibrium expression change.
• Changes follow the Le Chatelier Principle.

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Effect of Acetate on the Acetic Acid
Equilibrium (1 of 2)
• Acetic acid is a weak acid:
– CH3COOH aq  ƒ H aq   CH3COO aq 

• Sodium acetate is a strong electrolyte:

– NaCH3COO aq   Na aq   CH3COO aq 
• The equations have a common acetate ion.
• Calculations will be done using the acetic acid equation
and K a .

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Effect of Acetate on the Acetic Acid
Equilibrium (2 of 2)
• The presence of acetate from sodium acetate in an acetic
acid solution will shift the equilibrium left, according to Le
Châtelier’s principle:

– CH3COOH aq  € H aq   CH3COO  aq 

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Weak Bases Work the Same Way
• The common-ion effect applies to weak bases the same
way.
• If a solution contains a weak base and a salt of its
conjugate acid, the base won’t dissociate as much as if it
is alone in solution. Equilibrium shifts left.

NH3 aq   H2O l  ƒ NH4  aq   OH aq 

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Calculating pH for a Common Ion (1 of 3)
• What is the pH of a solution made by adding 0.30 mol of e

acetic acid and 0.30 mol of sodium acetate to enough

e

water to make 1.0 L of solution?

iter

• Assume the salt dissociates 100%.

• Focus on the acetic acid equilibrium.

1) CH3COOH aq  ƒ H aq   CH3COO  aq 

2) K a   H+   CH3COO   CH3COOH  1.8  10  5

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Calculating pH for a Common Ion (2 of 3)
3) CH3COOH(aq ) ƒ H (aq )  CH3COO  (aq )

Initial (M) 0.30 0 0.30

Change (M) x +x +x
negative X

Equilibrium (M) (0.30  x ) x (0.30  x )

left parenthesis 0.30 + x right parenthesis

left parenthesis 0.30 minus x right parenthesis

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Calculating pH for a Common Ion (3 of 3)
4) 1.8 10  5   x 0.30  x  0.30  x 
Assume that adding or subtracting x from 0.30 will not
change 0.30 enough to matter and the equation
becomes

1.8 10 5

 x 0.30 
0.30 
5 
which results in: x 1.8 10 M   H 


So: pH   log 
   4.74
H

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17.2 Buffers
• Solutions of a weak conjugate
acid–base pair that resist
drastic changes in pH are
called buffers.
• These solutions contain
relatively high concentrations
(10 3 M or more) of both the
acid and base. Their
concentrations are
approximately equal.

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Ways to Make a Buffer
1) Mix a weak acid and a salt of its conjugate base or a
weak base and a salt of its conjugate acid.
2) Add strong acid and partially neutralize a weak base or
add strong base and partially neutralize a weak acid.

• For laboratory work, prepackaged buffers at specific pH

may be purchased.

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How a Buffer Works

• Adding a small amount of acid or base only slightly

neutralizes one component of the buffer, so the pH
doesn’t change very much.
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Deriving the Henderson-Hasselback
Equation (1 of 2)
 H   A  
• For a weak acid: K a 
HA 
• Take  log of both sides:
  A  
 log K a   log  H    log    
 HA  
 

• Rearrange:
  A  
 log  H    log K a  log    
 HA  
 
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Deriving the Henderson-Hasselback
Equation (2 of 2)
• Which is:   A  
pH  pK a  log    
 HA  
 
• This equation is known as the Henderson–Hasselbalch
equation.
– This applies to cases of weak acids/bases and their
respective salts.
– There are four variables. If three variables are
known, the fourth variable may be calculated.
– This equation is used for buffers and for weak
acid/weak base titration calculations.
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Example Using the Henderson–Hasselback
Equation to Find pH
• What is the pH of a buffer that is 0.12 M in lactic acid,
CH3CH OHCOOH, and 0.10 M in sodium lactate?

K a for lactic acid is 1.4 10  4.

  A  
 pH  pK a  log    
 HA  
 
 0.10 M  
 4
  log 1.4 10  log   
 0.12 M 
 3.85   0.08  3.77
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Buffer Capacity and pH Range
• The amount of acid or base the buffer can neutralize before p H
begins to change to an appreciable degree.
– Using the Henderson–Hasselback equation, p H will be the
same for a conjugate acid–base pair of 1.0 M each or 0.1
M each.
– The buffer that is 1 M can neutralize more acid or base
before the pH changes than a 0.1 M buffer

• Buffers usually have a useable p H range 1 pH unit from pK a .

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Addition of a Strong Acid or a Strong
Base to a Buffer (1 of 2)
Addition of the strong acid or base is a neutralization
reaction.
1) Calculate like a stoichiometry problem to find HA  and  A  

when all of the added acid or base reacts. This is a

limiting agent situation.

2) Use the Henderson–Hasselbalch equation to find pH.

The equilibrium calculation is simplified by using this
equation.

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Addition of a Strong Acid or a Strong
Base to a Buffer (2 of 2)

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Example of pH Calculation for Buffer
after Strong Base Addition (1 of 2)
• A buffer is made by adding 0.300 mol HC2H3O 2 and
0.300 mol NaC2H3O 2 to enough water to make 1.00 L. iter..

0.020 mol of NaOH is added.

1) Stoichiometry table  limiting reactant calculation

CH3COOH(aq )  OH (aq )  H2O( l )  CH3COO  (aq )

Before reaction (mol) 0.300 0.020 - 0.300

Change (limiting reactant) (mol)  0.020  0.020 - +0.020

negative 0.020
negative 0.020

After reaction (mol) 0.280 0 - 0.320

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Example of pH Calculation for Buffer
after Strong Base Addition (2 of 2)
2) Henderson–Hasselbalch equation:
  A  
pH  pK a  log    
 HA  
 
Since this is a buffer, the volume for each concentration
is the same, so the ratio of molarity can be calculated
using a ratio of moles.

  nA -    0.320 
pH  pK a  log   A   pH  4.74  log   4.80
 HA
nHA    0.280 
 

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Contrast Base Addition on pH for Buffer
versu s Water ersu

What is the pH if 5.00 m L of 4.0 M NaOH is added to: a)

illi iters

1.000 L of a buffer that is 0.300 M CH3COOH and 0.300 M

iter

CH3COO  ; b) 1.000 L of water iter

a) Buffer calculations require moles

CH3COOH(aq )  OH (aq )  H2O( l )  CH3COO  (aq )
Before reaction (mol) 0.300 0.020 - 0.300

Change (limiting reactant) (mol)  0.020  0.020 - +0.020

negative 0.020
negative 0.020

After reaction (mol) 0.280 0 - 0.320

 0.302 

pH  log 1.8 10 5
  log  0.320  4.75
0.280
 0.298 
4.80
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Contrast Base Addition on pH for Water
versu s Buffer
ersu

b) Pure water (4.0 mol/L) 5.00 10  3 L 2.0 10  2 mol

2.0 10  2 mol / 1.005 L 0.0199 M
pOH  log  OH   log (0.0199) 2.70
pH 14.00  1.70 12.30

pH change minimized using buffer:

Adding base to buffer: 4.80 to 4.75 is 0.05 units
Adding base to water: 7.00 to 12.30 is 5.30 units

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17.3 Acid–Base Titrations
• An acid (or base) solution of
known concentration is slowly
added to a base (or acid)
solution of unknown
concentration.
• A pH meter or indicators are
used to determine when the
solution has reached the
equivalence point.
– The amount of acid equals
the amount of base.

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Titration of a Strong Acid with a Strong
Base
• Plot pH versu s mL of strong
ersu

base.
• From the start of the titration to
near the equivalence point, the
pH goes up slowly.
• Just before (and after) the
equivalence point, the pH rises
rapidly.
• At the equivalence point, pH =
7.
• As more base is added, the pH
again levels off.

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Titration of a Strong Base with a Strong
Acid
• It appears to be a “flipped
over” curve of the strong
acid being titrated by a
strong base.
• Start with a high pH (basic
solution).
• pH = 7 at the equivalence
point.
• Adding more acid, pH
levels off.

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Titration of a Weak Acid with a Strong
Base
• There are four distinct regions:
1. Initial pH uses K a calculation.
2. Between initial pH and
equivalence point (excess
acid) uses limiting reactant
then Henderson-Hasselback.
3. At the equivalence point.
4. After the equivalence point
(excess base).

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Calculating pH When Some Weak Acid is
Neutralized—Excess Acid
• Calculate the moles of weak acid and strong base.
• Write the neutralization equation.
• Track limiting reactant change using the table. Gives you
moles of remaining acid and the moles of anion formed.
• Substitute into the Henderson-Hasselbalch equation to
find pH.

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Calculating pH for a Weak Acid Strong
Base Titration at the Equivalence Point
• The pH is Not 7.00 at the equivalence point.
• Calculate the moles of weak acid and strong base.
• Write the neutralization equation.
• Substitute into table.
• All moles of weak acid react with strong base. Only anion
of weak acid remains.
• Find molarity of weak acid using the new volume.
• Use the equations of either the K b of the anion or the K a
of the weak acid to determine the pH (like in Chapter 16).
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Ways That a Weak Acid Titration Differs
from a Strong Acid Titration
1) A solution of weak acid has a
higher initial pH than a strong
acid.
2) The pH change near the
equivalence point is smaller
for a weak acid.
3) The pH at the halfway to the
equivalence point is the pK a
4) The pH at the equivalence
point is greater than 7 for a
weak acid.
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Titrations with an Acid–Base Indicator
• Indicators are weak acids that have a different color than their
conjugate base form.
– Each indicator has its own pH range over which it changes color.
– Can be used to determine the equivalence point in a titration as
long as it changes color in the small volume change region
where the pH rapidly changes.

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Titrations of Polyprotic Acids
• There are multiple
equivalence points.
• Treat each step separately
with their corresponding
polyanions and K a .
• The halfway to each
equivalence point gives the
pK a
• The concentration of the
dianion is always equal to
Ka2.
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17.4 Solubility Equilibria
• Ionic compounds are strong electrolytes. They dissociate
completely to the extent that which they dissolve.
• When an equilibrium equation is written, the solid is the
reactant and the ions in solution are the products.
• The equilibrium constant expression is called the
solubility-product constant. It is represented as K sp .

Ba3 PO4 2 s  ƒ 3 Ba2 aq   2 PO 43 aq 

3 2
K sp   Ba2   PO 43 

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Solubility and K sp (1 of 2)
K sub s p

• K sp is not the same as solubility.

• Solubility is the quantity of a substance that dissolves to

form a saturated solution.
• Common units for solubility:

– Grams per liter g/L 

– Moles per liter mol/L 

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Solubility and K sp (2 of 2)
K sub s p

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Calculating Solubility from K sp (1 of 2) K Sub s p

• The K sp for CaF2 is 3.9 10  11 at 25 °C. What is its molar

solubility?
1) CaF2 s  ƒ Ca aq   2 F aq 
2 

2
2) K sp   Ca   F  3.9 10  11
2 

3) CaF2 (s ) ƒ Ca2 (aq )  2 F  (aq )

Initial concentration (M) Blank

0 0

Change (M) Blank

+x +2x

Equilibrium concentration (M) Blank

X 2x

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Calculating Solubility from K sp (2 of 2) K Sub s p

• Substitute the equilibrium concentration values from the

table into the solubility-product equation:

 x 2 x  4 x 3
 11 2
3.9 10
x 2.110  4 M

• If you require the answer in g/L, multiply by molar mass.

(This gives 0.016 g/L.)

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17.5 Factors That Affect Solubility
• The common-ion effect: If
one of the ions in a solution
equilibrium is already dissolved
in the solution, the solubility of
the salt will decrease.
– For CaF2 , if either calcium
ions or fluoride ions are
present, then calcium
fluoride will be less soluble.

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Calculating Solubility with a Common
Ion (1 of 2)
• What is the molar solubility CaF2 in 0.010 M Ca NO3 2 ?

1) CaF2 s  ƒ Ca2 aq   2 F aq 

2
2) K sp   Ca   F  3.9 10  11
2 

3) CaF2 (s ) ƒ Ca2 (aq )  2 F  (aq )

Initial concentration (M) Blank

0.010 0

Change (M) Blank

+x +2x

Equilibrium concentration (M) Blank

(0.010 + x) 2x

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Calculating Solubility with a Common
Ion (2 of 2)
4) Substitute the equilibrium concentration values from the
table into the solubility-product equation:

0.010  x 2 x 
 11 2
3.9 10

(We assume that x  0.010, so that 0.010  x 0.010!)

 0.010 2 x 
 11 2
3.9 10
x 3.110  5 M

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Solubility and pH
• When a salt has an anion that is the conjugate base of a
weak acid, it is more soluble in acidic solution, i.e., F .
• When a salt has an anion that is the conjugate base of a
strong acid, solubility is unchanged, i.e., Cl .

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Complex Ion Formation (1 of 4)
• Metal ions can act as Lewis acids and form complex
ions with Lewis bases in the solvent.
• The formation of these complex ions increases the
solubility of these salts.

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Complex Ion Formation (2 of 4)
• Silver chloride is insoluble. It has a K sp of 1.6 10  10 .
• In the presence NH3 , the solubility greatly increases because
of 
Ag will form a complex ion with NH3 .

K f 1.7 107

AgCl(s) Æ Ag (aq)  Cl (aq)

Ag (aq)  2NH3 (aq) Æ Ag NH3 2 (aq)


AgCl(s)  2NH3 (aq) Æ Ag NH3 2 (aq)  Cl (aq)




 Ag NH3 2 

K f Ag NH3 2

 
 Ag  NH3 
 2
1.7 10 7

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Complex Ion Formation (3 of 4)
Table 17.1 Formation Constants for Some Metal Complex Ions in Water at
25  C

Complex Ion Kf K sub f

Chemical Equation

Ag(NH3 )2 A g left parenthesis N H sub 3 right parenthesis sub 2 +

1.7 107
1.7 times 10 to the seventh power

Ag (aq )  2 NH3 (aq ) ƒ Ag(NH3 )2  (aq ) A g sup +, aqueous + 2 N H sub 3, aqueous gives A g left parenthesis N H sub 3 right parenthesis sub 2 +, aqueous.

Ag(CN)2 A g left parenthesis C N right parenthesis sub 2 negative

11021
1 times 10 to the twenty-first power

Ag (aq )  2 CN (aq ) ƒ Ag(CN)2  (aq )

A g sup +, aqueous + 2 C N sup negative, aqueous gives A g left parenthesis C N 2 right parenthesis sub 2 negative, aqueous

Ag(S2O3 )23 
A g left parenthesis S sub 2 O sub 3 right parenthesis sub 2, sup 3 negative

2.9 10
2.9 times 10 to the thirteenth power
13 Ag (aq )  2 S2O3 2 (aq ) ƒ Ag(S2O3 )23  (aq )
A g sup +, aqueous + 2 S sub 3 O sub 3, sup 2 negative aqueous gives A g left parenthesis S sub 2 O sub 3 right parenthesis sub 2, sup 3 negative, aqueous

Ag(OH)4  A g left parenthesis O H right parenthesis sub 4 negative

1.11033
1.1 times 10 to the thirty-third power

AI3  (aq )  2 OH (aq ) ƒ AI(OH)4  (aq )

A g sup 3 +, aqueous + 2 O H sup negative, aqueous gives A l left parenthesis O H right parenthesis sub 4 negative, aqueous

CdBr42 C d B r sub 4, sup 2 negative

5 103 5 times 10 to the third power

Cd2 (aq )  4 Br  (aq ) ƒ CdBr42 (aq ) C d sup 2 +, aqueous + 4 B r sup negative, aqueous gives C d B r sub 4, sup 2 negative, aqueous

Cr(OH)4  C r left parenthesis O H right parenthesis sub 4 negative

8 1029
8 times 10 to the twenty-ninth power

Cr 3  (aq )  4 OH (aq ) ƒ Cr(OH)4  (aq )

C r sup 3 +, aqueous + O H sup negative, aqueous gives C r left parenthesis O H right parenthesis sub 4 negative, aqueous

Co(SCN)42
C o left parenthesis S C N right parenthesis sub 4, sup 2 negative

110 3
1 times 10 to the third power

Co2 (aq )  4 SCN (aq ) ƒ Co(SCN)4 2 (aq )

C o sup 2 +, aqueous + 4 S C N sup negative, aqueous gives C o left parenthesis S C N right parenthesis sub 4, sup 2 negative, aqueous

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Complex Ion Formation (4 of 4)
Table 17.1 [continued]

Complex Ion Kf K sub f

Chemical Equation

Cu(NH3 )42C u left parenthesis N H sub 3 right parenthesis sub 4, sup 2 +

5 1012
5 times 10 to the twelfth power

Cu2 (aq )  4 NH3 (aq ) ƒ Cu(NH3 )42 (aq )

C u sup 2 +, aqueous + 4 N H sub 3, aqueous gives C u left parenthesis N H 3 right parenthesis sub 4, sup 2 +, aqueous

Cu(CN)42 C u left parenthesis C N right parenthesis sub 4, sup 2 negative

11025
1 times 10 to the twenty-fifth power

Cu2 (aq )  4 CN (aq ) ƒ Cu(CN)42 (aq )

C u sup 2 +, aqueous + 4 C N sup negative, aqueous gives C u left parenthesis C N right parenthesis sub 4, sup 2 charge, aqueous

Ni(NH3 )62 N i left parenthesis N H sub 3 right parenthesis sub 6, sup 2 +

1.2 109
1.2 times 10 to the ninth power

Ni2 (aq )  6 NH3 (aq ) ƒ Ni(NH3 )62 (aq )

N I sup 2 +, aqueous + 6 N H sub 3, aqueous gives N i left parenthesis N H sub 3 right parenthesis sub 6, sup 2 +, aqueous

Fe(CN)6 4 F e left parenthesis C N right parenthesis sub 6, sup 4 negative

11035
1 times 10 to the thirty-fifth power

Fe2 (aq )  6 CN (aq ) ƒ Fe(CN)6 4  (aq )

F e sup 2 +, aqueous + 6 C N sup negative, aqueous gives F e left parenthesis C N right parenthesis sub 6, sup 4 negative, aqueous

Fe(CN)63 
F e left parenthesis C N sup negative right parenthesis sub 6, sup 3 negative

11042
1 times 10 to the forty-second power

Fe3  (aq )  6 CN (aq ) ƒ Fe(CN)63  (aq )

F e sup 2 +, aqueous + 6 C N sup negative, aqueous gives F e left parenthesis C N right parenthesis sub 6, sup 3 negative, aqueous

Zn(OH)42 Z n left parenthesis O H right parenthesis sub 4, sup 2 negative

4.6 1017
4.6 times 10 to the seventeenth power

Zn2 (aq )  4 OH (aq ) ƒ Zn(OH)42 (aq )

Z n sup 2 +, aqueous + 4 O H sup negative, aqueous gives Z n left parenthesis O H right parenthesis sub 4, sup 2 negative, aqueous

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Amphoterism
• Amphoteric oxides and hydroxides are soluble in
strong acids or base, because they can act either as
acids or bases.
• Metals with this behavior: Al3 , Cr 3 , Zn2 , and Sn2.

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17.6 Precipitation and Ion Separation
• To decide if precipitation will occur, calculate the
reaction quotient, Q, and compare it to K sp .
• Q uses the given conditions and has the same form as
the K expression.
– If Q K sp , the system is at equilibrium and the
solution is saturated.
– If Q  K sp , more solid can dissolve, no precipitate
forms.
– If Q  K sp , a precipitate will form.

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Selective Precipitation of Ions
• Ions can be separated from solution based on their solubilities
in the presence of different ions.

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17.7 Qualitative Analysis of Ions
One can use differences in
solubilities of salts to
separate ions in a mixture.
This has been used for
qualitative analysis of the
presence of ions in a
solution. A new application
is recovery of metal ions
from batteries used in
electric vehicles.

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Copyright

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