Acid Base Note Chem1aa3

Additional Aspects of
Acid-Base Equilibria
©2008 – 2018 McMaster University

Chapter 17
Chem
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Ch 16 Review: Acids & Bases
• Brønsted-Lowry theory: Acid/base reactants & conjugate acid/base
products
• Strong acids: HCl, HBr, HI, HClO4, HNO3, H2SO4
• Strong bases: hydroxides (OH–), oxides (O2–), hydrides (H–) of group 1 and 2
• Weak/strong acids/bases: how do you identify them?
• Amphiprotic species (e.g. H2O) behave as an acid or a base

• Calculations with Ka, Kb, pKa, pKb, pH, pOH, Kw, pKw
• Approximations to avoid the quadratic formula
• % ionization
• Salt solutions: acidic, basic or neutral
Chem
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Overview of Acid-Base Equilibria

1. What’s going on?
2. What’s in the beaker?
Chem
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Ch 17: Acid-Base Reactions
• Strategy for solving acid-base problems:
A + B → ?
x mol y mol ? mol
• Part 1: What’s going on?
• Write the correct chemistry
• Determine which species acts as an acid/base

• Part 2: What’s in the beaker?
• Look for limiting reagent, excess reagent, and product(s)
• Identify what species are present after a reaction has
occurred that can contribute to the pH
Chem
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Worked Example #1
• A chemist mixes 0.85 moles of NaOH(aq) with 0.60 moles
of HBr(aq). Is the solution acidic, basic, or neutral?
• Strategy:

Chem
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Worked Example #1
• Strategy – part 1: what’s going on?

NaOH(aq) + HBr(aq) → NaBr(aq) + H2O(l)
_______ _______ _______ _______
Chem
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Worked Example #1
• Strategy – part 2: what’s in the beaker?

Stoichiometry table (moles, not molarity):
mol NaOH(aq) + HBr(aq) → NaBr(aq) + H2O(l)
Before 0.85 mol 0.60 mol 0 mol --
After _______ _______ _______ --
_______ _______ _______
Chem
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iClicker #1 (not for credit)
A. Acidic
B. Basic
C. Neutral

Chem
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Worked Example #2
• A chemist mixes 1.10 moles of KOH(aq) with 1.10 moles of
HNO2(aq) (Ka = 7.2 x 10-4). Is the solution acidic, basic, or
neutral?
KOH(aq) + HNO2(aq) → KNO2(aq) + H2O(l)
strong base weak acid _______ _______

Chem
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Solution
neutral?
• Stoichiometry table (moles, not molarity):

mol KOH(aq) + HNO2(aq) → KNO2(aq) + H2O(l)
Before 1.10 mol 1.10 mol 0 mol --
After 0 0 1.10 mol --
Limiting Limiting
(Both are consumed) basic salt
Chem
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neutral?
A. Acidic
B. Basic
C. Neutral

Chem
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Worked Example #3
• A 1.0 L solution contains 1.0 moles of CH3COOH(aq) (Ka =
1.8 x 10-5) and 0.60 moles of CH3COONa(aq). How can we
determine whether the solution is acidic, basic, or neutral?
• Strategy:

Chem
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Worked Example #3
These species
CH3COOH(aq) + CH3COONa(aq) → ?? form a
conjugate
acid base

acid/base pair.
CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + ?
Chem
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Worked Example #3
CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + ?

iClicker #3: In the balanced equation above, what is “?” ?
A. H3O+ C. H2O
D. Na +
B. OH –
Chem
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Worked Example #3
• A 1.0 L solution contains 1.0 moles of CH3COOH(aq) (Ka = 1.8 x
10-5) and 0.60 moles of CH3COONa(aq). How can we determine
whether the solution is acidic, basic, or neutral?
CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H3O+(aq)
iClicker #4: What happened to the Na+ from CH3COONa?

A. This is a net ionic equation. NOTE: In the same
B. Na+ is a spectator ion. way, counterions of
C. Na+ does not contribute to the pH. strong acids don’t
+
contribute to the pH
D. Na does not react with water. Cl- Br- I- NO3- ClO4-
E. All of the above.
Chem
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Worked Example #3
acid “base” base acid

Chem
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Worked Example #3
ICE table (with molarity, not moles):
mol/L CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H3O+(aq)
I 1.0 mol/L -- 0.60 mol/L 0

C –x -- +x +x
E 1.0 – x -- 0.60 + x x
acid base acid
(We will solve the rest of this question later in these notes)
Chem
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Congratulations!
• Without knowing much about buffers or titrations, you
just solved 80% of the problems in this unit!

Chem
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• A solution is created by mixing 500. mL of 1.50 M
CsOH(aq), 250. mL of 1.00 M HCI(aq), and 250. mL of 1.00
M CH3COOH(aq). Ka (CH3COOH) = 1.8 ×10−5
• After mixing, which species has the dominant effect on the

pH of the solution that remains?
A. HCl(aq) Follow-up iClicker #6:

B. CH3COOH(aq) What is the pH of the solution?
C. CsOH(aq) A. 0.30
D. CsCl(aq) B. 0.60
E. CH3COOCs(aq) C. 13.40
D. 13.70
Chem
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Buffers
BUFFER: “a person or thing that prevents incompatible or
antagonistic people or things from coming into contact with or
harming each other.” (i.e. reducing the impact of something)

“a solution that resists changes in pH when acid or alkali
is added to it. Buffers typically involve a weak acid or
alkali together with one of its salts.” (i.e. reducing the
impact – change in pH – that would normally arise when a
strong base or strong acid is added to a solution)
Chem
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Worked Example #3
1.8 x 10-5) and 0.60 moles of CH3COONa(aq). What is the
pH of the solution?
• Strategy – Part 1: What’s going on?

• Strategy – Part 2: What’s in the beaker?
Chem
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Worked Example #3
• A 1.0 L solution contains 1.0 moles of CH3COOH(aq) (Ka = 1.8 x
10-5) and 0.60 moles of CH3COONa(aq). What is the pH of the
solution?
ICE table (with molarity, not moles):
mol/L CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H3O+(aq)
I 1.0 mol/L -- 0.60 mol/L 0
C –x -- +x +x

E 1.0 – x -- 0.60 + x x
[CH3 COO− ][H3 O+ ]
𝐾𝑎 = = = 1.8 × 10−5
[CH3 COOH]
(Use the “x is small” approximation!)
𝑥 = H3 O+ == ____________=>pH = _____
Chem
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Alternate calculation of pH: Henderson-
Hasselbalch equation
CH3 COO− H3 O+
• 𝐾a =
CH3 COOH
• Rearrange to get:
𝐾𝑎 CH5 COOH
• H3 O+ =
CH3 COO−

• Take –log of both sides:
CH3 COOH
• − log H3 O+ = − log 𝐾a − log
CH3 COO−
CH3 COO−
• pH = p𝐾a + log
CH3 COOH
Chem
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Henderson-Hasselbalch equation
• General form:
A−
• pH = p𝐾a + log 𝑒𝑞𝑛 17.7
HA
• Back to our example: the solution contains 1.0 mol/L
CH3COOH (Ka = 1.8 x 10-5) and 0.60 mol/L CH3COONa. The

pH will be:
0.60
• pH = −log(1.8 × 10−5 ) + log = 4.52
1.0
Chem
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Buffers
• Where do we see the importance of buffers?

• Biochemical assays
• Patients' blood pH (normal pH: 7.4 ± 0.05)
• Lakes and streams
• Ocean Acidification (pH 8.25 in 1750 → 8.14 currently)

• How do we control buffer pH?
• With addition of appropriate acid or base
Chem
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The chemistry of a buffer
• Buffer chemistry: equilibrium reaction of either weak species

with water (e.g. NH3/NH4+):
• NH3(aq) + H2O(l) ⇄ NH4+(aq) + OH–(aq)
AND
• NH4+(aq) + H2O(l) ⇄ NH3(aq) + H3O+(aq)

• Looks like weak base or weak acid ionization in water, but
now weak base and weak acid concentrations are both
significant.
Chem
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Buffers
• A buffer solution is:
• a solution of a weak acid-base conjugate pair
and
• both concentrations > 100 x Ka
• Buffer range and capacity:
• a buffer is in its effective range when:

weak base
0.1 < < 10 (17.8)
weak acid
• best capacity to resist pH changes from addition of acid or base
when [weak acid] & [weak base] are large and equal
Otherwise there isn’t enough buffer capacity to withstand much acid or base addition
Chem
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How can you tell it’s a buffer?
• Must have a weak conjugate acid-base pair in the beaker
• Substantial concentrations for both acid & base (> 100 x Ka)
• Ratio of [acid] : [conj base] (or [base] : [conj acid]) between
0.1 and 10

Chem
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How to make a buffer – 3 ways
1. Mix together a weak acid & its conjugate base (or a weak
base & its conjugate acid)
e.g. 1 Mix HCOOH and HCOONa
e.g. 2 Mix NH4Cl and NH3
2. Mix an excess amount of weak acid with a limiting amount

of STRONG BASE (to produce the conjugate weak base,

with excess weak acid left over)
3. Mix an excess amount of weak base with a limiting

amount of STRONG ACID (to produce the conjugate weak
acid, with excess weak base left over)
Chem
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Worked Example #4: How to make a buffer
• A chemist mixes 25 mL of 1.0 M HBr with 50 mL of 1.0 M
CH3NH2 (Kb = 4.4 x 10-4).
• iClicker #7: Is the resultant solution a buffer? A = Yes; B = No
• Part 1: what’s going on?
HBr(aq) + CH3NH2(aq) → CH3NH3+(aq) + Br–(aq)
________ ________ ________ ________
Part 2: what’s in the beaker?

before 0.025 mol 0.050 mol 0 0
after ________ ________ ________ ________
________ ________
Chem
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Worked Example #5: How to make a buffer
• A chemist mixes 50 mL of 1.0 M HBr with 25 mL of 1.0 M
CH3NH2 (Kb = 4.4 x 10-4).
• iClicker #8: Is the resultant solution a buffer? A = Yes; B = No
• Part 1: what’s going on?
________ ________ ________ ________

• Part 2: what’s in the beaker?
before 0.050 mol 0.025 mol 0 0
after ________ ________ ________ ________
________ ________
Chem
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• If the pairs of solutions (1.0 mol/L each) are mixed
together, which will create a buffer?
1. 25 mL NH4Br + 50 mL NH3
2. 25 mL HBr + 50 mL NaOH
3. 25 mL NH4Br + 50 mL NaOH

Data: Kb (NH3) = 1.8 x 10-5
Chem
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Worked Example #6: Creating a buffer
• What mass of sodium acetate (CH3COONa, 82.0 g/mol)
would you add to a 1.00 L solution of 0.25 mol/L acetic acid
(CH3COOH, Ka = 1.8 x 10-5) to create a buffer with pH 5.00?
(Assume the volume of the solution remains 1.00 L.)
A. 25 g
B. 82 g

C. 51 g
D. 37 g
Chem
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Solution: Creating a buffer
• 1.00 L Buffer with pH _____
• _____ mol/L CH3COOH, Ka = 1.8 x 10-5
• Add CH3COONa, 82.0 g/mol
__________________________________________________
Let “y” grams represent the amount of CH3COONa to be
added.

Moles of CH3COONa = (y/82) mol
CH3COONa is a strong electrolyte and dissociates completely,
so in a 1.00 L solution:
[CH3COONa] = [CH3COO–] = (y/82) mol/L
Chem
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Solution: Creating a buffer
The acid dissociation equation for CH3COOH (Ka = 1.8 x 10-5) is:
At equilibrium:
[H3O+] = _______ mol/L
[CH3COOH] = _______ mol/L

[CH3COO–] = (y/82) mol/L
𝑦
[CH3COO–][H3O+] (82)( )
𝐾𝑎 = 1.8 × 10−5 = =
[CH3COOH]
Solve for y: 𝑦 = _______
Chem
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Alternate Solution: H-H Equation
• 1.00 L Buffer with pH _____
• _____ mol/L CH3COOH, Ka = 1.8 x 10-5
• Add CH3COONa, 82.0 g/mol
Let x mol/L represent [CH3COO–] in the buffer.
pH = pKa + log ([conj base]/[acid])

_____ = − log (1.8 x 10-5) + log (x/_____)
x = _____ mol/L
Mass of CH3COONa = (_____ mol/L)(1.00 L)(82.0 g/mol) = _____
Chem
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How to choose a buffer for desired pH
• Henderson-Hasselbalch equation:
CH3 COO−
CH3 COOH
• Choose a weak acid with pKa close

to the desired pH. “Coarse tuning”.

• Adjust ratio of weak acid: conjugate
base to achieve desired pH. “Fine
tuning”.
Chem
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iClicker #10
• What acid would be the best choice to make a buffer of pH
8.9?
A. HClO2 pKa = 1.96
B. CH3COOH pKa = 4.74
C. HOCl pKa = 7.54

D. NH4Cl pKa = 9.26
E. (C2H5)2NH2Cl pKa = 10.84
Chem
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iClicker #11
• To 1.0 L of pure water is added 1.0 mol NH4Cl (pKa = 9.26).
This solution is:
A. acidic
B. basic
C. neutral

D. a buffer
E. More than one option is correct
Chem
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iClicker #12
• To prepare a buffer with pH 8.9, we start with pure water
(1.0 L) and add 1.0 mol of NH4Cl (pKa = 9.26). Which
reagent(s) should be added to the solution to achieve the
desired pH?
A. NaOH
B. HCl

C. NH3
D. Either A or B
E. Either A or C
[See Example 17-5: Preparing a buffer solution of a desired pH]
Chem
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Effect of adding strong acid or base?
• xx

Strong acid is converted to Strong base is converted to
weak acid: weak base:
pH decreases pH increases
Chem
Fig. 17-4 How a buffer works 41 1AA3
Effect of adding strong acid or base at a molecular level

the total number of moles of buffer do not change in response
to adding strong acid or base to the buffer
Fig. 16-3 Buffering Action, Chemistry – A Molecular Approach, 3rd Ed. 42

Chem
1AA3
Adding a strong acid to a buffer
• A 250. mL buffer contains 0.100 M C6H5COOH(aq) and
0.0850 M C6H5COONa(aq). Ka for C6H5COOH = 6.3 x 10-5.
• What happens when we add 20.0 mL of 0.150 M HCl(aq)?
• Strategy:

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• A 250. mL buffer contains 0.100 M C6H5COOH(aq) and
0.0850 M C6H5COONa(aq). Ka for C6H5COOH = 6.3 x 10-5.
• What happens when we add 20.0 mL of 0.150 M HCl(aq)?
• What’s going on? iClicker #13: Which chemical equation
represents the reaction of HCl with the buffer?
A. HCl(aq) + C6H5COO–(aq) → C6H5COOH(aq) + H3O+(aq)

B. HCl(aq) + C6H5COOH(aq) → C6H5COO–(aq) + H3O+(aq) + Cl–(aq)
C. HCl(aq) + C6H5COOH(aq) + C6H5COO–(aq) → H2O(l) + Cl–(aq)
D. HCl(aq) + C6H5COOH(aq) → C6H5COO–(aq) + H2O(l) + Cl–(aq)
E. HCl(aq) + C6H5COO–(aq) → C6H5COOH(aq) + Cl–(aq)
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• 250. mL buffer, 0.100 M C6H5COOH(aq), 0.0850 M
C6H5COONa(aq). Add 20.0 mL of 0.150 M HCl(aq).
What’s in the beaker?
mol HCl(aq) + C6H5COO–(aq) → C6H5COOH(aq) + Cl–(aq)
Before 3.00 x 10-3 2.125 x 10-2 2.50 x 10-2 0
After _______ _______ _______ _______

_______ _______
iClicker #14: Is this a buffer? • weak acid and conjugate base
• Concentrations > 100 x Ka
A. Yes weak base
• 0.1 < < 10
B. No weak acid
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Before 3.00 x 10-3 2.125 x 10-2 2.50 x 10-2 0
After _______ _______ _______ _______
_______ _______
• iClicker #15: Hey! What about the Cl–?
A. Cl– does not react with water.

B. Cl– does not contribute to the pH.
C. Cl– is a spectator ion.
D. All of the above.
Chem
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Before 3.00 x 10-3 2.125 x 10-2 2.50 x 10-2 0
After _______ _______ _______ _______
_______ _______
• The total volume has increased from 250. mL to 270. mL.
• New concentrations:

2.80×10−2 𝑚𝑜𝑙 𝑚𝑜𝑙
• C6 H5 COOH = = 0.104
0.270 𝐿 𝐿
− 1.825 ×10−2 𝑚𝑜𝑙 𝑚𝑜𝑙
• C6 H5 COO = = 0.0676
0.270 𝐿 𝐿
• Left half of class: solve for pH using ICE table and Ka expression.
• Right half of class: solve for pH using Henderson-Hasselbalch eqn.
Chem
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Data:
• [C6H5COOH] = 0.104 M; [C6H5COO–] = 0.0676 M
• Ka for C6H5COOH = 6.3 x 10-5
Using ICE table & Ka expression:
C6H5COOH(aq) + H2O(l) ⇄ C6H5COO–(aq) + H3O+(aq)
I

C
E
x = _________ => pH = _______
Chem
48 1AA3
Data:
• [C6H5COOH] = 0.104 M; [C6H5COO–] = 0.0676 M
• Ka for C6H5COOH = 6.3 x 10-5
Using Henderson-Hasselbalch equation:
pKa =
pH =
You can also use moles (instead of molarity) in H&H:

−2
−
1.82 5 × 10 𝑚𝑜𝑙
C6 H5 COO 0.270 𝐿
=
C6 H5 COOH 2.80 × 10−2 𝑚𝑜𝑙
0.270 𝐿
1.825 × 10−2 𝑚𝑜𝑙 C6 H5 COO− 𝑚𝑜𝑙 C6 H5 COO−
= =
2.80 × 10−2 𝑚𝑜𝑙 C6 H5 COOH 𝑚𝑜𝑙 C6 H5 COOH
Chem
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A note about pH calculations in buffers
• The “x is small” approximation will always work for a buffer.
• In fact, the “x is small” approximation is built into the
Henderson-Hasselbalch equation.
• In buffer calculations, you can use initial concentrations of
conjugate acid-base pair rather than equilibrium
concentrations.

• In the Henderson-Hasselbalch equation, you can use moles
rather than molarity.
Chem
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iClicker #16
• Our buffer contains 0.100 M C6H5COOH and 0.0850 M
C6H5COONa. What is the most likely outcome when:
1. A small amount of C6H5COOH is added to the buffer?
2. A small amount of NaOH is added to the buffer?
3. A large amount of water is added to the buffer?
4. A large amount of NaOH is added to the buffer?

A. The pH increases slightly.
B. The pH decreases slightly.
C. The buffer is destroyed (buffer capacity is exceeded).
D. There is no change.
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Trauma, Critical Care & pH Monitoring
• Blood pH (7.4) is a highly regulated parameter of
physiology
• Blood pH is regulated primarily by volatile CO2 & non-
volatile acids, such as bicarbonate, phosphate, lactate,
protein, etc.
• Acidosis (pH < 7.35) can be triggered by acute infection

(sepsis), cardiac arrest or pulmonary dysfunction (hypoxia)
• Alkalosis (pH > 7.45) can be triggered by hyperventilation
• Blood pH < 6.8 or > 7.8 is fatal.
Chem
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Blood pH
Two equilibria control dissolution/desorption & ionization of CO2:
CO2(g) + H2O(l) ⇄ H2CO3(aq) K = 3.4 x 10-2
H2CO3(aq) + H2O(l) ⇄ HCO3–(aq) + H3O+(aq) Ka1 = 4.5 x 10-7
CO2(g) + 2 H2O(l) ⇄ HCO3–(aq) + H3O+(aq) (K)(Ka1) = 1.5 x 10-8
• Mild Acidosis during exercise generates CO2 (pH drops). Body
counteracts this by faster ventilation (removes CO2).

• Mild Alkalosis from hyperventilation was treated by breathing
into a bag to reduce CO2 loss.
• Persistent Acidosis may be treated symptomatically by injecting
NaHCO3, to prevent acute organ failure and buy the physician
time to address the underlying causes.
Chem
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Buffers: Key Concepts
• Buffers resist changes in pH upon addition of a small
amount of strong acid or strong base. The buffer contains
components that can neutralize small amounts of strong
acids or bases.
• Three ways to prepare a buffer:

• Directly mix conjugate weak acid-base pair together
• React weak acid with limiting amount of strong base
• React weak base with limiting amount of strong acid
Chem
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Buffers: Key Concepts
• A buffer solution contains a weak conjugate acid-base pair
with both concentrations > 100 x Ka.
weak base
• Buffer capacity is in the range 0.1 < < 10;
weak acid
alternately, pH = pKa ± 1.
• Buffers are most effective when [weak acid] = [conjugate
base] (or [weak base] = [conjugate acid]).

Alternately, pH = pKa.
• To solve for pH, you can use an ICE table with Ka expression
(the “x is small approximation” will always work!) or the
A−
Henderson-Hasselbalch equation: pH = p𝐾a + log .
HA
Chem
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Acid-Base Titrations

Why are we doing this? It’s analytical – how much acid/base is in solution?
(i.e., there really is a reason!)
Chem
56 1AA3
Titration “Nomenclature”
The “Titrant”

containing “Analyte”
Or beaker
Chem
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Acid-Base Titrations
• Consider 3 options:
1. STRONG BASE + STRONG ACID

2. STRONG BASE + weak acid
3. weak base + STRONG ACID

(We will not consider weak base + weak acid in this course)
Chem
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17.4 Acid-Base Titrations
• Limiting reactant questions: either acid or base is always in excess,
except at the equivalence point*
*(mol acid = mol base for 1:1 acid:base titration)
• In these titrations different species are formed as pH changes:
Strong Acid + Strong Base

strong acid → neutral salt → strong base

Weak Acid + Strong Base
weak acid → buffer → basic salt → strong base
Weak Base + Strong Acid
weak base → buffer → acidic salt → strong acid
Chem
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Strong Acid-Strong Base Titration (Lab 1, 6)
Strong base in excess

12.0
pH
7.0
Equivalence point, pH = 7

Strong acid
NaCl(aq) – neutral salt
1.0
in excess
Volume of strong base (mL)
Titrate 25.0 mL 0.100 M HCl(aq) with 0.100 M NaOH(aq)
Chem
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Practice Calculations: Strong Acid – Strong Base
Titrate 25.0 mL 0.100 M HCl(aq) with 0.100 M NaOH(aq)
• Calculate pH at 4 points:
0 mL NaOH
12.5 mL NaOH
25.0 mL NaOH
37.5 mL NaOH

0 mL NaOH = only strong acid present
• HCl is a strong acid, so [H3O+] = [HCl]
pH = −log[H3O+] = −log(0.100) = 1.000
Chem
61 1AA3
12.5 mL NaOH = ½-equivalence point
• ½ of HCl consumed.
• Stoichiometry (mole) table:
mol HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
Before 2.50 x 10-3 1.25 x 10-3 0 --
After ________ ________ ________ --
________ ________

Some HCl remains, but in a new total (larger) volume. The
solution that remains is STRONGLY ACIDIC.
mol
pH = − log H3 O+ = − log =
0.0375 L
Chem
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25.0 mL NaOH = equivalence point
• All HCl consumed.
Before 2.50 x 10-3 2.50 x 10-3 0 --
After ________ ________ ________ --

NaCl is a neutral salt and does not affect the pH. The solution
that remains is neutral (pH = 7.000).
Chem
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iClicker #17: Strong Acid – Strong Base
Titrate 25.0 mL 0.100 M HCl(aq) with 0.100 M NaOH(aq).
Calculate the pH of the solution when 37.5 mL NaOH has
been added.
A. 13.150
B. 12.301

C. 12.010
D. 11.509
Chem
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Solution: Strong Acid – Strong Base
37.5 mL NaOH = only strong base present
Before 2.50 x 10-3 3.75 x 10-3 0 --
After ________ ________ ________ --

Some NaOH remains, but in a new total (larger) volume. The
solution that remains is STRONGLY BASIC.
mol
pOH = − log OH − = − log =
0.0625 L
pH = =
Chem
65 1AA3
Strong Acid – Strong Base Titration
• 4 points calculated:
12.301
Strong base in excess
12.0
7.000 Equivalence point, pH = 7
pH NaCl(aq) – neutral salt

7.0 ½ Eq. Point

Very little base is needed to go from pH 4
1.477
1.000 to pH 10 (a fraction of a drop).
Strong acid
1.0
Chem
66 1AA3
SA – SB vs WA – SB Titration
Titration curves for weak acid-strong base &
strong acid-strong base, 0.1 M each
14
12
10
8
pH
6 WA - SB

4 SA - SB
2
0
0 5 10 15 20 25 30
volume of strong base (mL)
Chem
67 1AA3
Weak Acid – Strong Base Titration
14
12
10
8
pH
6

2
0
0 10 20 30 40
Titrate 25.0 mL 0.100 M CH3COOH(aq) with 0.100 M NaOH(aq)
Chem
68 1AA3
iClicker #18: Weak Acid – Strong Base Titration
Titrate 25.0 mL 0.100 M CH3COOH(aq) with 0.100 M
NaOH(aq). Calculate the pH when no NaOH has been added.
(Data: Ka for CH3COOH is 1.8 x 10-5).
A. 9.26
B. 4.74

C. 2.87
D. 1.50
Chem
69 1AA3
Solution: Weak Acid – Strong Base Titration
0 mL NaOH = only weak acid present
Solve pH of weak acid; use Ka
Ka
CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq)
Initial
Change

Eqm
CH3 COO− H3 O+
𝐾𝑎 = =
CH3 COOH
𝑥 = H3 O+ =
pH = =
Chem
70 1AA3
Practice Calculations: Weak Acid – Strong Base
12.5 mL NaOH = ½-equivalence point
• ½ of CH3COOH consumed.
mol CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l)
Before 2.50 x 10-3 1.25 x 10-3 0 --
After ________ ________ ________ --

Some CH3COOH remains and some CH3COONa is formed.
This is a buffer!
Note that the total volume has changed.
Chem
71 1AA3
• Solve for pH of a buffer with use of an ICE table or the
Henderson-Hasselbalch equation (below)… more to come!
CH3 COO−
CH3 COOH
• = 4.74 + log _____________________________
• =

pH = pKa at ½ equivalence point of a weak-strong titration
Chem
72 1AA3
• All of CH3COOH consumed.
Before 2.50 x 10-3 2.50 x 10-3 0 --
After _________ _________ _________ --

iClicker #19: Titrate 25.0 mL 0.100 M CH3COOH(aq) with 0.100
M NaOH(aq). At the equivalence point, the solution is:
A. Acidic B. Basic C. Neutral
Chem
73 1AA3
Before 2.50 x 10-3 2.50 x 10-3 0 --
After 0 0 2.50 x 10-3 --
iClicker #20: Titrate 25.0 mL 0.100 M CH3COOH(aq) with 0.100 M

NaOH(aq). At the equivalence point, [CH3COO–] is:
A. 2.50 x 10-3 M
B. 5.00 x 10-3 M −
mol
CH3 COO = =
C. 5.00 x 10-2 M L
D. 0.100 M
Chem
74 1AA3
Before 2.50 x 10-3 2.50 x 10-3 0 --
After 0 0 2.50 x 10-3 --
iClicker #21: At the equivalence point, which chemical equation

shows how CH3COO– behaves as a base in water?
A. CH3COO–(aq) + H3O+(aq) ⇄ CH3COOH(aq) + OH–(aq)
B. CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H3O+(aq)
C. CH3COOH(aq) + OH–(aq) ⇄ CH3COOH(aq) + H2O(l)
D. CH3COO–(aq) + H2O(l) ⇄ CH3COOH(aq) + OH–(aq)
Chem
75 1AA3
25 mL NaOH = main species present is CH3COO–
Solve pH of weak base; use Kb
Kb
CH3 COO–(aq) + H2O(l) CH3COOH(aq) + OH– (aq)
Initial
Change
Eqm
CH3 COOH OH −
𝐾𝑏 = =

CH3 COO −
𝑥 = OH − =
pOH = =
pH = =
Chem
76 1AA3
37.5 mL NaOH = only strong base present
• All CH3COOH consumed; excess NaOH
Before 2.50 x 10-3 3.75 x 10-3 0 --
After _________ _________ _________ --

Excess strong base & weak base: strong base determines pH.
Chem
77 1AA3
Weak Acid – Strong Base Titration
14 12.301 Strong base in excess
12 ½-equivalence
10 pH = pKa Equivalence point
8
8.72
4.74 pH > 7
pH
2.87
6
CH3COONa(aq)
4 basic salt
2
Buffer region: pH = pKa ± 1

0
0 10 20 30 40
Volume of base (mL)
Features different from strong acid-strong base:

● Start at higher pH ●½ equivalence point, pH = pKa
● Buffer region ●Equivalence point pH > 7
Chem
78 1AA3
iClicker #22: Weak Base – Strong Acid
• At which point on this titration curve is pH = pKa?
A
12
C
10
8
B
D
pH

4
E
2
0
0 10 20 30 40
volume acid (mL)
Chem
79 1AA3
Solution: Weak Base – Strong Acid
• Label the key features on the weak base-strong acid
titration curve.
12
10

pH
0
0 10 20 30 40
volume acid (mL)
Chem
80 1AA3
Compare HCl / NaOH (strong / strong) with
CH3COOH / NaOH (weak / strong) Titrations
We will look at titrations with [HA] = [NaOH] from 1 M to 0.00001 M.
Look for effects of [HA] and [B] on the shape of the titration curve:
▪ starting pH,

▪ pH at ½ equivalence point,
▪ pH at equivalence point,
▪ vertical part of curve
▪ pH at end of titration
▪ buffer properties as function of [HA], [B]
Chem
81 1AA3
HCl / NaOH 1M / 1 M

1M HCl
Chem
82 1AA3
HCl / NaOH 0.1M / 0.1 M

0.1M HCl
1M HCl
Chem
83 1AA3
HCl / NaOH 0.01M / 0.01 M

0.01M HCl
Chem
84 1AA3
HCl / NaOH 0.001M / 0.001 M

0.001M HCl
Chem
85 1AA3
HCl / NaOH 0.0001M / 0.0001 M

0.0001M HCl
Chem
86 1AA3
HCl / NaOH 0.00001M / 0.00001 M
Equivalence point pH stays at 7.0

0.00001M HCl

Chem
87 1AA3
CH3COOH / NaOH 1M / 1M
Equivalence Point pH
9.1

1 M AcOH
Chem
88 1AA3
CH3COOH / NaOH 0.1M / 0.1M
9.1
8.7

0.1 M AcOH
Chem
89 1AA3
9.1
8.7
8.2

0.01 M AcOH
Chem
90 1AA3
9.1
8.7
8.2
7.7
0.001 M AcOH

Recall: mixture of weak acid with conjugate weak base is only a buffer
if both [HA] and [B] > 100 x Ka= 1.8 x 10-3 = 0.0018. Not a buffer!
Chem
91 1AA3
CH3COOH / NaOH 0.0001M / 0.0001M
9.1
8.7
8.2
7.7
7.3
0.0001 M AcOH

if both [HA] and [B] > 100 x Ka= 1.8 x 10-3 = 0.0018. Not a buffer!
Chem
92 1AA3
CH3COOH / NaOH 0.00001M / 0.00001M
9.1
8.7
8.2
7.7
7.3
0.00001 M AcOH 7.1

Equivalence point is still, though barely, alkaline
Initial pH for [AcOH] = 10-5 = ~ 5 → reflects high degree of ionization
if both [HA] and [B] > 100 x Ka= 1.8 x 10-3 = 0.0018. Not a buffer! 93 Chem
1AA3
Titrations – Key Concepts
• Equivalence point is when mole acid = mole base (if 1:1 reaction)
• Strong acid – strong base titration
• pH = 7 at equivalence point
• Sharp pH change at equivalence
• Weak acid – strong base or strong acid – weak base titrations
• Buffer region, pH = pKa ± 1

• pH = pKa at ½ equivalence
• pH ≠ 7 at equivalence (pH depends on the salt present –
acidic or basic)
Chem
94 1AA3
Strong acid – strong base titration Weak acid – strong base AND
Strong acid – weak base titrations
NO buffer zone Buffer region, pH = pKa ± 1

Features in weak acid – strong base and strong acid – weak base
titrations that are different from strong acid – strong base titration:
• Start at higher pH
• Buffer region
• ½ equivalence point, pH = pKa
• Equivalence point pH ≠ 7
Chem
95 1AA3
17.3 Acid-Base Indicators
• Equivalence point: theoretical point where mol acid = mol
base (1:1 titration)
• With an indicator, we observe the endpoint (colour change)
Acetic Acid / NaOH titrations at 1, 0.1, 10-2, Titrations of acids with different pKa values
10-3, 10-4 and 10-5 M each, will have will lead to different equivalence point pH’s
different starting and equivalence point pH and hence require different pH indicators
Weak acids pKa

Phenol 9.98
4-Nitrophenol 7.15
Acetic Acid 4.78

Lactic Acid 3.86
HCl -7
We use TEENY TINY amounts of a colored weak acid or weak base to follow the
main titration (HUGE CHANGES IN pH OCCUR NEAR THE EQUIVALENCE POINT). Chem
96 1AA3
Acid-Base Indicators
• Colour depends on pH
• Indicators are weak acids/bases (HIn, In−):
HIn(aq) + H2O(l) H3O+(aq) + In−(aq)

acid colour base colour
In− H3 O+

• 𝐾HIn =
HIn
In−
• pH = p𝐾HIn + log 17.9
HIn
Eq. 17.9 relates solution pH to pKa of indicator
Chem
97 1AA3
• Chart of many indicators
In−
pH = p𝐾HIn + log eqn 17.9
HIn

Bromthymol blue:
Blue (base colour), pH = pKa + 1
‘Green’ (colour change mid-point), pH = pKa
Yellow (acid colour), pH = pKa − 1
Chem
98 1AA3
Acid-Base Indicators
In−
pH = p𝐾HIn + log eqn 17.9
• We see: HIn
acid colour when pH < (pKHIn – 1 ) (10-fold excess of HIn)

base colour when pH > (pKHIn + 1) (10-fold excess of In−)
• Colour change over ~ 2 pH units
• Want the colour change to be at or close to* the equivalence
point of the major reaction (SA/SB, WA/SB, WB/SA) we want to

observe.
Chem
99 1AA3
Choosing an Indicator
• Indicator should change colour close to the equivalence point
of the major reaction (SA/SB, WA/SB, WB/SA).
• pKa of indicator (also called pKHIn) ≈ pH at equivalence
• pKa of indicator ≠ pKa of weak acid in the titration.
pH ≈ pKHIn of indicator Weak acid –

strong base
titration
pH = pKa of acid in titration
Chem
100 1AA3
iClicker #23
• From the following list of indicators, select the most
suitable indicator for the titration of
(1) HBr(aq) + KOH(aq)
(2) HI(aq) + NH3(aq)
Indicator Colour change range (pH)
(A) Methyl violet 0.1 – 1.7

(B) Bromocresol green 4.0 – 5.8
(C) Phenol red 6.3 – 8.0
(D) Thymol Blue 8.0 – 10.0
Chem
101 1AA3
Indicators - Key concepts
• Indicators are weak acids/bases
• Colour changes from acid form to base form
• Colour change occurs over ~2 pH units

• Choose indicator with pKa close to pH of titration equivalence
point
Chem
102 1AA3

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CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + ?

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iClicker #4: What happened to the Na+ from CH3COONa?

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• After mixing, which species has the dominant effect on the

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• Where do we see the importance of buffers?

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• Buffer chemistry: equilibrium reaction of either weak species

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2. Mix an excess amount of weak acid with a limiting amount

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3. Mix an excess amount of weak base with a limiting

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• Choose a weak acid with pKa close

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Fig. 16-3 Buffering Action, Chemistry – A Molecular Approach, 3rd Ed. 42

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