Chemistry

The Molecular Nature of Matter and Change Eighth

Edition

Martin S. Silberberg and Patricia G. Amateis

©McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom.  No reproduction or further distribution permitted without the prior written consent of McGraw-Hill Education.
• Ionic Equilibria in Aqueous Systems
• 19.1 Equilibria of Acid-Base Buffers
• 19.2 Acid-Base Titration Curves

©McGraw-Hill Education.
• Acid-Base Buffers
• An acid-base buffer is a solution that lessens the impact of pH
from the addition of strong acid or strong base.
• An acid-base buffer usually consists of a conjugate acid-base
pair where both species are present in appreciable quantities
in solution.
• An acid-base buffer is therefore a solution of a weak acid and
its conjugate base, or a weak base and its conjugate acid.

©McGraw-Hill Education.
• The Effect of Adding Strong Acid or
Strong Base to an Unbuffered Solution
• A 100-mL sample of dilute HCl is adjusted to pH 5.00 (left)
• Adding 1 mL of strong acid or of strong base changes the pH
by several units.

Figure 19.1

©McGraw-Hill Education. © McGraw-Hill Education/Stephen Frisch, photographer

• The Effect of Adding Strong Acid or
Strong Base to a Buffered Solution
• A 100-mL sample of an acetate buffer is adjusted to pH 5.00.
• The addition of 1 mL of strong acid (left) or strong base (right)
changes the pH very little.

Figure 19.2

©McGraw-Hill Education.  McGraw-Hill Education/Stephen Frisch, photographer

• Buffers and the Common-ion Effect
•  A buffer works through the common-ion effect.
• Acetic acid in water dissociates slightly to produce some
acetate ion:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
• If NaCH3COO is added, it provides a source of CH3COO– ion,
and the equilibrium shifts to the left. CH3COO– is the common-
ion to both solutions.
• The addition of CH3COO– reduces the % dissociation of the
acid.

©McGraw-Hill Education.
• Relative Concentrations of Buffer
Components
•   CH COOH(aq) + H O(l) CH COO (aq) + H O (aq)
3 2 3
–
3
+

• and
• Since Ka is constant, the [H3O+] of the solution depends on the
ratio of buffer component concentrations.
• If the ratio increases, [H3O+] increases.
• If the ratio decreases, [H3O+] decreases.

©McGraw-Hill Education.
• Buffers and Equilibrium
• The
  buffer components (HA and A-) are able to consume small
amounts of added OH- or H3O+ by a shift in equilibrium
position.
CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq)
• Added OH– reacts with CH3COOH, causing a shift to the right.
• Added H3O+ reacts with CH3COO–, causing a shift to the left.
• The shift in equilibrium position absorbs the change in [H3O+]
or [OH–], and the pH changes only slightly.

©McGraw-Hill Education.
• The Henderson-Hasselbalch Equation
•   HA(aq) + H2O(l) A-(aq) + H3O+(aq)
and

OR

©McGraw-Hill Education.
• Sample Problem 19.1 – Problem and Plan
Calculating the Effect of Added H3O+ or OH- on Buffer pH

• PROBLEM: Calculate the pH: (a) of a buffer solution consisting

of 0.50 M HClO (Ka = 2.9×10−8) and 0.60 M NaClO;

(b) after adding 0.020 mol of solid NaOH to 1.0 L of the buffer solution in

part (a); [assume that the addition of NaOH causes negligible volume
change]
(c) after adding 0.020 mol of HCl to 1.0 L of the buffer solution in part
(a). [assume that the addition of HCl causes negligible volume change]

©McGraw-Hill Education.
• Sample Problem 19.1 – Solution (a)
•• SOLUTION:
  (a)

• Using Henderson-Hasselbalch Equation,

= 7.62

©McGraw-Hill Education.
• Sample Problem 19.1 – Solution (b)
•• (b)
 

Concentration (M)    HClO(aq) +      OH−(aq)     ClO−(aq) + H2O(l)

Initial 0.50    0.020 0.60 —
Change
Change –0.020
–0.020 –0.020
–0.020 +0.020
+0.020 —
—
Final 0.48 0      0.62 —
Final 0.48 0      0.62 —
• Using Henderson-Hasselbalch Equation,

= 7.66

©McGraw-Hill Education.
• Sample Problem 19.1 – Solution (c)
• (c)
Concentration (M)    ClO−(aq) +      H+(aq)     HClO(aq)
Initial
Initial 0.60
0.60     0.020
 0.020 0.50
0.50
Change
Change −0.020
−0.020 −0.020
−0.020 +0.020
+0.020
Final 0.58 0      0.52
Final 0.58 0      0.52

• Using Henderson-Hasselbalch Equation,

 

= 7.59

©McGraw-Hill Education.
• Buffer Capacity
• The buffer capacity is a measure of the “strength” of the
buffer, its ability to maintain the pH following addition of
strong acid or base.
• The greater the concentrations of the buffer components, the
greater its capacity to resist pH changes.
• The closer the component concentrations are to each other,
the greater the buffer capacity.

©McGraw-Hill Education.
• Acid-Base Titrations
• In an acid-base titration, the concentration of an acid (or a
base) is determined by neutralizing the acid (or base) with a
solution of base (or acid) of known concentration.
• The equivalence point of the reaction occurs when the
number of moles of OH– added equals the number of moles of
H3O+ originally present, or vice versa.
• The end point occurs when the indicator changes color.
– The indicator should be selected so that its color change occurs
at a pH close to that of the equivalence point.

©McGraw-Hill Education.
• Strong Acid–Strong Base Titration

Figure 19.6

©McGraw-Hill Education.
• Calculating the pH During a Strong Acid–Strong
Base Titration
•  Initial pH:
– [H3O+] = [HA]init, pH = -log [H3O+]

• pH before equivalence point:

– initial mol H3O+ = Vacid x Macid
– mol OH- added = Vbase x Mbase
– mol H3O+ remaining = (mol H3O+init) – (mol OH-added)
– pH = -log[H3O+]

• pH at the equivalence point

– pH = 7.00 for a strong acid-strong base titration

©McGraw-Hill Education.
• Calculating the pH During a Strong Acid–Strong
Base Titration, Cont’d
•  pH beyond the equivalence point:
– initial mol H3O+ = Vacid x Macid
– mol OH- added = Vbase x Mbase
– mol OH- excess = (mol OH-added) – (mol H3O+init)
– [OH-] =
– pOH = -log[OH-] and pH = 14.00 – pOH

©McGraw-Hill Education.
• Strong Acid-Strong Base Example
•  40.00 mL of 0.1000 M HCl is titrated with 0.1000 M NaOH.
• The initial pH is simply the pH of the HCl solution:
– [H3O+] = [HCl]init = 0.1000 M and pH = –log(0.1000) = 1.00

• To calculate the pH after 20.00 mL of NaOH solution has

been added:

The OH– ions react with an equal amount of H3O+ ions, so

H3O+ remaining = 4.000x10–3 – 2.000x10–3 = 2.000x10–3 mol H3O+

©McGraw-Hill Education.
• Strong Acid-Strong Base Example, Cont’d
•  
pH = –log(0.03333) = 1.48
• To calculate pH at equivalence point
 The equivalence point occurs when mol of OH– added = initial mol of HCl,
so when 40.00 mL of NaOH has been added.
 Only salt contain in the solution. The salt dissociates in water to form
weak conjugate acid, Na+ and weak conjugate base, Cl-. Both ions do not
react with water. So, pH of solution will be based on pH of water which is
7.00. Solution is neutral.

©McGraw-Hill Education.
 •• To
  calculate the pH after 50.00 mL of NaOH solution has been added:

OH– in excess = 5.000x10–3 – 4.000x10–3 = 1.000x10–3 mol OH–

• pOH = –log(0.01111) = 1.95 pH = 14.00 – 1.95 = 12.05

©McGraw-Hill Education.
• Weak Acid–Strong Base Titration

Figure 19.7

©McGraw-Hill Education.
• Calculating the pH During a Weak Acid–
Strong Base Titration
•  Initial pH:
– and [H3O+]=
– pH = -log [H3O+]

• pH before equivalence point:

– or

©McGraw-Hill Education.
• Calculating the pH During a Weak Acid–
Strong Base Titration, Cont’d
•  pH at the equivalence point:
– A–(aq) + H2O(l) ↔ HA(aq) + OH–(aq)

– where and
– and pH = -log[H3O+]

• pH beyond the equivalence point:

–
– pH = -log[H3O+]

©McGraw-Hill Education.
• Sample Problem 19.4 – Problem and Plan
Finding the pH During a Weak Acid–Strong Base Titration
• PROBLEM: Calculate the pH during the titration of 40.00 mL
of 0.1000 M propanoic acid (HPr; Ka = 1.3x10–5) after adding
the following volumes of 0.1000 M NaOH:
(a) 0.00 mL (b) 30.00 mL (c) 40.00 mL (d) 50.00 mL

• PLAN: The initial pH must be calculated using the Ka value for

the weak acid. We then calculate the number of moles of HPr
present initially and the number of moles of OH– added. Once
we know the volume of base required to reach the
equivalence point we can calculate the pH based on the
species present in solution.

©McGraw-Hill Education.
• Sample Problem 19.4 – Solution (a) and (b)
•• SOLUTION:
  (a)
pH = –log(1.1x10–3) = 2.96
(b) 30.00 mL of 0.1000 M NaOH has been added.
Initial amount of HPr = 0.04000 L x 0.1000 M = 4.000x10–3 mol HPr
Amount of NaOH added = 0.03000 L x 0.1000 M = 3.000x10–3 mol OH–
Each mol of OH– reacts to form 1 mol of Pr–, so

Amount (mol) HPr(aq) + OH−(aq) Pr−(aq) + H2O(l)

Initial 0.004000     0.003000   0   —

Change
Change ‒0.003000
‒0.003000    ‒0.003000
‒0.003000    +0.003000 
+0.003000  —
—

Final 0.001000 0   0.003000 —

Final 0.001000 0   0.003000 —

©McGraw-Hill Education.
• Sample Problem 19.4 – Solution (b) and (c)
• Calculating pK
  a: pKa = −log Ka = −log (1.3×10 ) = 4.89
−5

Solving for pH using the Henderson-Hasselbalch equation:

(c): Calculating the initial amounts of HPr and OH−:

Initial amount (mol) HPr = 0.04000 L x 0.1000 M = 0.004000 mol HPr
Amount (mol) of NaOH added = 0.04000 L x 0.1000 M = 0.004000 mol OH-

Amount (mol) HPr(aq) + OH−(aq) Pr−(aq) + H2O(l)

Initial 0.004000     0.004000      0                —
Change
Change 0.004000
0.004000    –0.004000
–0.004000    +0.004000
+0.004000    —
—
Final 0           0                  0.004000   —
Final 0           0                  0.004000   —

©McGraw-Hill Education.
• Sample Problem 19.4 – Solution (c)
• Calculating [Pr
  ‒
] after all HPr has reacted:

Pr− is a weak base, so we calculate

pH = –log(1.6x10-9) = 8.80

©McGraw-Hill Education.
• Sample Problem 19.4 – Solution (d)
•• (d)
  Calculating the initial amounts of HPr and OH−:
Amount of OH– added = 0.05000 L x 0.1000 M = 0.005000 mol
Excess OH– = OH–added – HAinit = 0.005000 – 0.004000 = 0.001000 mol
Amount (mol)   HPr(aq) +   OH–(aq)    Pr–(aq) + H2O(l)
Initial   0.004000   0.005000    0  —
Change
Change –0.004000
–0.004000 –0.004000
–0.004000 +0.004000
+0.004000    —
—
Final  0   0.001000    0.004000  —
Final  0   0.001000    0.004000  —

pH = –log(9.0x10–13) = 12.05

©McGraw-Hill Education.
• Weak Base–Strong Acid Titration

Figure 19.8

©McGraw-Hill Education.
• Acid-Base Indicators
• An acid-base indicator is a weak organic acid (HIn) whose
color differs from that of its conjugate base (In–).
• The ratio [HIn]/[In–] is governed by the [H3O+] of the solution.
Indicators can therefore be used to monitor the pH change
during an acid-base reaction.
• The color of an indicator changes over a specific, narrow pH
range, a range of about 2 pH units.

©McGraw-Hill Education.
• Colors and Approximate pH Range of Some
Common Acid-Base Indicators

Figure 19.9

©McGraw-Hill Education.
• The Color Change of Bromothymol Blue

Figure 19.10

©McGraw-Hill Education. © McGraw-Hill Education/Stephen Frisch, photographer

• Acid-Base Indicator Selection for Different
Acid-Base Titrations

Figure 19.11

©McGraw-Hill Education.