Chem1AA3 Lecture 1 PDF

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

Chapter 17
Chem
1 1AA3
Ch 16 Review: Acids & Bases
• Brønsted-Lowry theory: Acid/base reactants & conjugate
acids are donors
acid/base products bases are accptors
• Strong acids: HCl, HBr, HI, HClO4, HNO3, H2SO4

• Strong bases: hydroxides (OH–), oxides (O2–), hydrides (H–)
of group 1 and 2 oxygen more acidic check electronegative
no oxygen decreasing down period on the periodic table
more oxygen more acidic
• 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 product/reactant
• 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
4 1AA3
Worked Example
• A chemist mixes 0.85 moles of NaOH(aq) with 0.60 moles
of HBr(aq). Is the solution acidic, basic, or neutral?
• Strategy:

NaOH: strong base, weak acid
HBR: strong acid, weak base
HBR + NAOH --> NABR + H2O (l) --> neutral
Chem
5 1AA3
Worked Example
• Strategy – part 1: what’s going on?

NaOH(aq) + HBr(aq) → NaBr(aq) + H2O(l)
_______
base _______
acid _______
neutral _______
neutral
Chem
6 1AA3
Worked Example
• 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 _______
0.25 mol _______
0 mol _______
0.60 mol --
Excess Limiting
basic solution as excess of basic product
Chem
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iClicker (not for credit)
A. Acidic
B. Basic
C. Neutral

Chem
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Solution
• 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 _______
weak base _______
neutral

strong base so no Kb is needed ka is a hint that its a weak acid contributes to ph
since one is strong and weak you get in the reactant whatever is stronger
Chem
9 1AA3
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 weak base
both consumed
KNO2 + H2O --> HNO2 + HO-
This is a equilibrium, if you throw a weak base into water you set up a equilibrium
Chem
10 1AA3
neutral?
A. Acidic
B. Basic
C. Neutral

Chem
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Worked Example
weak acid
• A 1.0 L solution contains 1.0 moles of CH3COOH(aq) (Ka =

weak base
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
These species
CH3COOH(aq) + CH3COONa(aq) → ?? form a
conjugate
acid base

acid/base pair.
one weak acid and conjugate in the same flask
CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + ?
Chem
13 1AA3
Worked Example
CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + ?

iClicker: In the balanced equation above, what is “?” ?
A. H3O+
B. OH-
C. H2O
D. Na+
Chem
14 1AA3
Worked Example
CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H3O+(aq)

iClicker: What happened to the ___________________?
Na+ from CH3COONa
A. This is a net ionic equation.

B. Na+ is a spectator ion.
C. Na+ does not contribute to the pH.
D. Na+ does not react with water.
E. All of the above. (Choose E!)
NOTE: In the same way, counterions of strong acids don’t contribute to the pH
Chem
Cl- Br- I- NO3- ClO4- 15 1AA3
Worked Example
acid “base” base acid

Chem
16 1AA3
Worked Example
buffers are solutions with acid and conjucate acid all in one?
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 for the pH of the solution in a few slides.)
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.
strong base:
mL of _____
strong acid
1.50 M
CsOH(aq), 250. mL of _____
1 M HCI(aq), and 250. mL of
_____
1 M CH3COOH(aq). Ka (CH3COOH) = 1.8 ×10−5
.weak acid
• After mixing, which species has the dominant effect on the

pH of the solution that remains?
more strong base by multipling
A. HCl(aq) Follow-up iClicker:

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
Calculate the mols of everythin and see what is left and then find the total volume solution and then find the concentration and
then log it
Chem
19 1AA3
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)

usually a weak acid
“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)
alkali = strong base
Chem
20 1AA3
Worked Example
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?
You will need to calculate both moles and volumes of every substance
Chem
21 1AA3
Worked Example
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):
weak acid conjugate base
mol/L CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H3O+(aq)
I 1mol 0,6 0

C –x -- +x +x
0.6 +x
E 1-x
x
[CH3 COO− ][H3 O+ ] (0.6 + x) (x)

−5
𝐾𝑎 = = (1-x)
= 1.8 × 10
[CH3 COOH]
(Use the “x is small” approximation!)
𝑥 = H3 O+ = ____________
3.0 x 10^-5 => pH = _____ 4.52
Chem
22 1AA3
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−
MEMORIZE THIS SHIZZ
CH3 COO−
• pH = p𝐾a + log
CH3 COOH
Pka= Constant look in some table
when ph=pka you know the ratio equals 1 so in this the concentration does not matter
Do this if the ratio of HA/A- is between 10-0.1, under these cicumstances it is a buffer so only works then
Chem
23 1AA3
Henderson-Hasselbalch equation
• General form:
pH= pKb + log (HA/A-) maybe this
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 1
= ________
4.52
Chem
24 1AA3
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)

IVF needs a certain ph
Stomach pH is 1.5, acetic acid

Small Intestine pH is 8
• How do we control buffer pH?
• With addition of appropriate acid or base
Chem
25 1AA3
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) kb
AND
• NH4+(aq) + H2O(l) ⇄ NH3(aq) + H3O+(aq) ka

• 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
Otherwise you have do a normal ICE table
• 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
27 1AA3
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
ph does not change drastically

Chem
28 1AA3
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 strong acid, weak base
strong base, weak acid
e.g. 2 Mix NH4Cl and NH3 weak has to be excess
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)
(See Petrucci, figure 17-5)
Chem
29 1AA3
Example 1: How to make a buffer
to finish
• A chemist mixes 25 mL of 1.0 M HBr with 50 mL of 1.0 M

CH3NH2 (Kb = 4.4 x 10-4). Is the resultant solution a buffer?
A = Yes; B = No
• Part 1: what’s going on?
strong acid weak base
HBr(aq) + CH3NH2(aq) → CH3NH3+(aq) + Br–(aq)

acid base acid neutral
________ ________ ________ ________

• Part 2: what’s in the beaker?
before 0.025 mol 0.050 mol 0 0
0 0.025 0.025 0.025
after ________ ________ ________ ________
LR ER
buffer b/c weak acid + conjugate base is present Chem
30 1AA3
Example 2: How to make a buffer
to finish
• A chemist mixes 50 mL of 1.0 M HBr with 25 mL of 1.0 M

CH3NH2 (Kb = 4.4 x 10-4). Is the resultant solution a buffer?
A = Yes; B = No
• Part 1: what’s going on?
base acid neutral
________
acid ________ ________ ________

• Part 2: what’s in the beaker?
before 0.050 mol 0.025 mol 0 0
0.025 0.025 0.025
after ________ ________
0 ________ ________
Not a buffer b/c weak is not in excess Chem

31 1AA3
• If the pairs of solutions (1.0 mol/L each) are mixed
together, will they create a buffer? A = Yes; B = No.
ratio of moles over conjugate base is 50/25, 2/1 in range so it is a buffer; yes; acid vs conjugate base
1. Y 25 mL NH4Br + 50 mL NH3
No because they both are strong acid and base so cant be a buffer; strong acid vs strong base
2. N 25 mL HBr + 50 mL NaOH
0.025 moles of the conjugate base (weak acid) and 0.5 mol NaOh meaning we are left with 0.025 mol NaOH theres too much strong
3. 25 mL NH4Br + 50 mL NaOH
so no buffer

Data: Kb (NH3) = 1.8 x 10-5 weak base / weak acid
when determining ratio to see if buffer
Chem
32 1AA3
Demo
H2CO3 + H2O ⇄ HCO3– + H3O+
HCO3– → CO2 + OH–
Fire’s burning, fire’s burning

Draw nearer, draw nearer

In the gloaming, in the gloaming
Come sing and be merry
Chem
33 1AA3
Sample problem: 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 (Assume the volume of the solution remains 1.00
L.)
Pka= 4.7
A. 25 g when ph=pka the ratio of conjucate base to weak acid is 1:1

Acetic acid is more excess at 5
B. 82 g Sodium acetate more excess at 9
lower ph more acetic acid

C. 51 g higher ph more sodium acetate
D. 37 g
conj/ acid base
Chem
34 1AA3
Solution: Creating a buffer
• 1.00 L Buffer with pH _____
5
• _____
0.25 mol/L CH3COOH, Ka = 1.8 x 10-5
• Add CH3COONa, 82.0 g/mol
5
pH = _____
5 means [H3O+] = 10-_____ 1 x10^-5
= _______ mol/L

Let y g 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
35 1AA3
Solution: Creating a buffer
The acid dissociation equation for CH3COOH (Ka = 1.8 x 10-5) is:
At equilibrium:
[H3O+] = _______
1 x 10^-5 mol/L
[CH3COOH] = _______
0.25 mol/L

[CH3COO–] = (y/82) mol/L
𝑦
[CH3COO–][H3O+] (82)(1 x 10^-5)
𝐾𝑎 = 1.8 × 10−5 = =
[CH3COOH] 0.25
Solve for y: 37g
Chem
36 1AA3
Alternate Solution: H-H Equation
5
• 1.00 L Buffer with pH _____
• _____
0.25
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])

5
_____ = -log (1.8 x 10-5) + log (x/_____)
0.25
x = ______
0.45 mol/L
Mass of CH3COONa = (_____
0.45 mol/L)(1.00 L)(82.0 g/mol) = 37g
Lemon Juice ph-2.6: sour soothers, citric acid, pka=2.79

Drain Cleaner: pH 13-14: NaOH
Type text here
Chem
37 1AA3
How to choose a buffer for desired pH
• Henderson-Hasselbalch equation:
CH3 COO−
CH3 COOH
base/acid
• 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
38 1AA3
iClicker
• What acid would be the best choice to make a buffer of pH
_____?
8.9
A. HClO2 pKa = 1.96 ph=pka when ratio is 1:1
chose pka close to ph

B. CH3COOH pKa = 4.74
C. HOCl pKa = 7.54

D. NH4Cl pKa = 9.26
E. (C2H5)2NH2Cl pKa = 10.84
Chem
39 1AA3
iClicker
• To 1.0 L of pure water is added 1.0 mol NH4Cl (pKa = 9.26).
weak acid
This solution is:
A. acidic weak acid + water --> Nh3 + H3O
generating some strong acid
B. basic
C. neutral

D. a buffer
E. More than one option is correct
Chem
40 1AA3
iClicker
• To prepare a buffer with pH 8.9, we start with pure water
(1.0 L) and add 1.0 mol of NH Cl (pKa = 9.26). Which
weak4acid
reagent(s) should be added to the solution to achieve the
desired pH?
A. NaOH base
B. HCl

C. NH3 base
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?
the solution will act as a buffer until all
conjugate acid base pair both weak
Buffer reduces change in acidity of it is concomed or the ratio passes 10
• 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 42 1AA3
Adding a strong acid to a buffer
benozic acid: pH stabilizer: weak acid
• A 250. mL buffer contains 0.100 M C6H5COOH(aq) and
0.0850 M C6H5COONa(aq). Ka for C6H5COOH = 6.3 x 10-5. pka=4.2
weak base
• What happens when we add 20.0 mL of 0.150 M HCl(aq)?

strong acid
• Strategy:

more acidic = lower pH

strong acid will not react with existing weak acid or strong acid
reacts w/ weak base and increases
Chem
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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: 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)
strong acid weak acid
Chem
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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?
strong acid weak base weak acid
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
3.00 x 10-3
After _______
0 _______
1.825 x 10^-2 _______
2.8 x 10 -2 _______

Limiting Excess
• iClicker: Is this a buffer?

A. Yes • weak acid and conjugate base
• Concentrations > 100 x Ka
B. No weak base
• 0.1 < < 10
weak acid
Chem
45 1AA3
Before 3.00 x 10-3 2.125 x 10-2 2.50 x 10-2 0
0 1.825 x 10^-2
After _______ _______ _______
2.8 x 10 -2 _______
3.00 x 10-3
Limiting Exess
• iClicker: 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
46 1AA3
Before 3.00 x 10-3 2.125 x 10-2 2.50 x 10-2 0
0 1.825 x 10^-2 3.00 x 10-3
After _______ _______ _______
2.8 x 10 -2 _______
Limiting Excess
• 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
47 1AA3
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)
0.676
0

0.104
I
x
-x x
C
E 0.104 -x
0.676 +x x
6.3x 10^-5= (0.676 +x)x / (0.104-x)
x= (H3O+)
Chem
48 1AA3
Data:
• [C6H5COOH] = 0.104 M; [C6H5COO–] = 0.0676 M
• Ka for C6H5COOH = 6.3 x 10-5
Using Henderson-Hasselbalch equation:
-log(6.3x 10^-5) = 4.2
pKa =
pH = 4.2 + log (0.0676/0.104) = 4.01

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
=
2.80 × 10 𝑚𝑜𝑙 C6 H5 COOH 𝑚𝑜𝑙 C6 H5 COOH
Chem
49 1AA3
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. YOU DO NOT NEED TO KNOW VOLUMES
Chem
50 1AA3
iClicker
• 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?
weak acid
2. A small amount of _______ is added to the buffer?
NaOH
strong base
3. A large amount of _______
water is added to the buffer?
4. A large amount of _______
NaOH is added to the buffer?
strong base

A. The pH increases slightly. 2 because adding a strong base
B. The pH decreases slightly. 1 because adding a weak acid 4 because added a strong base
ate up the acid
C. The buffer is destroyed (buffer capacity is exceeded).
D. There is no change. 3 because volumes do not matter but at some points theres nothing left to any
buffering --> need to know how much water is acc added
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
52 1AA3
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)
pH goes down
• Alkalosis (pH > 7.45) can be triggered by hyperventilation

how does this work; pH goes up
• Blood pH < 6.8 or > 7.8 is fatal.

acidity of CO2 affects carbonic acid in drinks
Chem
53 1AA3
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
54 1AA3
Biomineralization

• Microbes produce CaCO3 as part of their basic metabolic
activities.
• Biomineralization depends on equilibrium, pH, and Ksp.
putting in more acid drives the equilibrium the wrong way and some are too acidic to even form hard shells
--> bad for earth and sustainability
https://doi.org/10.3389/fmicb.2013.00314 55
Chem
1AA3
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
56 1AA3
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
57 1AA3
Titration “Nomenclature”
The “Titrant”

containing “Analyte”
Or beaker
Chem
58 1AA3
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
59 1AA3
An example: Urinalysis
• Part of evaluating renal functions in maintaining the acid-base balance, involves
independent determinations pH, titratable acid (TA), NH4+ and HCO3- of urine, with much
trouble (these data are also related to ‘urinary’ stone factors).

Titrations of urine show unexpected
differences between expected and
measured values
Related to complex equilibria
And presence of uric acid (ouch)
Chem
60 1AA3
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
• Not covered: weak acid + weak base. 61 1AA3
Strong Acid-Strong Base Titration (Lab 1, 6)
Type text here

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)
Easiest to understand, but dead boring! Chem

62 1AA3
Practice Calculations: Strong Acid – Strong Base
• 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
63 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 =
𝑡𝑜𝑡𝑎𝑙 L
Chem
64 1AA3
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
65 1AA3
iClicker: 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.
B.

C.
D.
Chem
66 1AA3
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 =
𝑡𝑜𝑡𝑎𝑙 L
pH =
Chem
67 1AA3
Strong Acid – Strong Base Titration
• 4 points calculated:
12.301
Strong base in excess
12.0
mols of strong acid=strong base
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

Equivalence Point is the point where moles of base added
are equal to the moles of acid originally present. Chem
68 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 buffer regime is the linear part WA - SB
4 SA - SB
2
0
0 5 10 15 20 25 30
volume of strong base (mL)
Purple Curve: has higher pH than 7 at equivilance point , the initial pH (higher more basic pH)
Chem
69 1AA3
Weak Acid – Strong Base Titration
if pKa= 4.7 starting pH should be
14
12
10

4
0
0 5 10 15 20 25 30 35 40
weak acid strong base
Titrate 25.0 mL 0.100 M CH3COOH(aq) with 0.100 M NaOH(aq)
Chem
70 1AA3
iClicker: 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. 1.40
Chem
71 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)
0
Initial 0.100 0
x
Change
x x
Eqm 0.100-x

x= (H3O+) --> -log
Chem
72 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 --
1.25 x 10^-3 0
After ________ ________ ________
1.25 x 10^-3 --

Excess Limiting
consumed
Some CH3COOH remains and some CH3COONa is formed.

This is a buffer!
Note that the total volume has changed.
Chem
73 1AA3
• Solve for pH of a buffer with use of an ICE table or the
Henderson-Hasselbalch equation.
CH3 COO−
CH3 COOH
1.25×10−3 mol/0 .0375 L
• = 4.74 + log
1.25×10−3 mol/0 .0375 L

• = 4.74
Chem
74 1AA3
• All of CH3COOH consumed.
Before 2.50 x 10-3 2.50 x 10-3 0 --
2.5x 10-3
After ________
0 ________
0 ________ --

iClicker: 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
75 1AA3
Before 2.50 x 10-3 2.50 x 10-3 0 --
After 0 0 2.50 x 10-3 --

iClicker: Titrate 25.0 mL 0.100 M CH3COOH(aq) with 0.100 M
NaOH(aq). At the equivalence point, [CH3COO–] is:
A. 2.5 x 10^-3
B. 5.00 x 10^-3
C. 5.00 x 10^-2
D. 0.100
Chem
76 1AA3
Before 2.50 x 10-3 2.50 x 10-3 0 --
After 0 0 2.50 x 10-3 --

iClicker: 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
77 1AA3
25 mL NaOH = main species present is CH3COO–
Solve pH of weak base; use Kb
Kb
CH3COO–(aq) + H2O(l) CH3COOH(aq) + OH– (aq)
Initial
Change
Eqm

Chem
78 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 0 1.25 x 10-3 2.50 x 10-3 --

Limiting Excess
(consumed) STRONG BASE weakly basic salt
Excess strong base & weak base: strong base determines pH.
Chem
79 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
Buffer region
½ equivalence point, pH = pKa
Equivalence point pH > 7
Chem
80 1AA3
iClicker: 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
81 1AA3
Solution: Weak Base – Strong Acid
• Label the key features on the weak base-strong acid
titration curve.
Weak base
12
½ equivalence: pH = pKa of conjugate acid
10

8
Buffer region:
pH = pKa ± 1 Equivalence point:
pH
6
acidic salt, pH < 7
4
Excess strong acid
2
0
0 10 20 30 40
volume acid (mL)
Chem
82 1AA3
Sample problem
• A chemist wishes to prepare a 100. mL solution with pH
10.00. They find the following solutions: 0.10 M CH3NH3Cl,
0.10 M NaOH, and 0.10 M HCl. What volume (in mL) of
each solution should be mixed together to get the desired
pH?
• Data: Kb(CH3NH2) = 4.2 × 10−4

CH3NH3Cl NaOH HCl
A.
B.
C.
D.
Chem
83 1AA3
Solution
• Identify whether each species acts as an acid or a base.
• CH3NH3Cl
• NaOH
• HCl
• What choice(s) can be discarded?
• Calculate numbers or plug in MC choices?

Chem
84 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
85 1AA3
HCl / NaOH 1M / 1 M

1M HCl
Chem
86 1AA3
HCl / NaOH 0.1M / 0.1 M

0.1M HCl
1M HCl
Chem
87 1AA3
HCl / NaOH 0.01M / 0.01 M

0.01M HCl
Chem
88 1AA3
HCl / NaOH 0.001M / 0.001 M

0.001M HCl
Chem
89 1AA3
HCl / NaOH 0.0001M / 0.0001 M

0.0001M HCl
Chem
90 1AA3
HCl / NaOH 0.00001M / 0.00001 M
Equivalence point pH stays at 7.0

0.00001M HCl

Chem
91 1AA3
CH3COOH / NaOH 1M / 1M
Equivalence Point pH
9.1

1 M AcOH
Chem
92 1AA3
CH3COOH / NaOH 0.1M / 0.1M
9.1
8.7

0.1 M AcOH
Chem
93 1AA3
9.1
8.7
8.2

0.01 M AcOH
Chem
94 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
95 1AA3
CH3COOH / NaOH 0.0001M / 0.0001M
9.1
8.7
8.2
7.7
7.3
0.0001 M AcOH

Chem
96 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
Chem
97 1AA3
Titrations – Key Concepts
• Equivalence point: mol acid = mol base (if 1:1 reaction)
• Strong acid – strong base titration

• pH = 7 at equivalence point
• Sharp pH change at equivalence

• Weak acid – strong base / 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
98 1AA3
Titrations – Key Concepts
• Equivalence point: mol acid = mol base (if 1:1 reaction)
Strong acid – strong base titration Weak acid – strong base AND
Strong acid – weak base titrations

NO buffer zone Buffer region, pH = pKa ± 1
Chem
99 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
100 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
101 1AA3
• Chart of many indicators

Bromthymol blue:
Blue (base colour), pH = pKa + 1
‘Green’ (colour change mid-point), pH = pKa
Yellow (acid colour), pH = pKa − 1
Chem
102 1AA3
Demo
103

Chem
1AA3
Acid-Base Indicators
• We see:
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
104 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
pH = pKa of acid in titration
Weak acid – strong base titration 105

Chem
1AA3
iClicker
• 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

(B) Bromocresol green
(C) Phenol red
(D) Thymol Blue
Chem
106 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
107 1AA3
Antimicrobial Surfaces
• Ammonium ions (R4N+ R = H, alkyl, aryl) are frequently associated with
antibacterial efficacy.

• A researcher made surfaces using both the amino acid lysine (pKa 2.18 and
10.53) and dialkylphenylamine (pKa 5.2). It was necessary to titrate the surface
to establish the surface charge at physiological pH (~7.4). At certain pHs, the
materials lose efficacy – where and why?
• At what pH would the pure lysine surface of become neutral (and not
efficacious)? Pure dialkylphenylamine?
Chem
108 1AA3
Maybe
antibacterial
109

Chem
1AA3
Titrations for Biobased Nanomaterials –
Chitin Nanofibers (ChNF)

Chem
110 1AA3

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Additional Aspects of

©2008 – 2018 McMaster University

• Strong acids: HCl, HBr, HI, HClO4, HNO3, H2SO4

©2008 – 2018 McMaster University

• Salt solutions: acidic, basic or neutral

©2008 – 2018 McMaster University

• Strategy for solving acid-base problems:

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

HBR + NAOH --> NABR + H2O (l) --> neutral

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

basic solution as excess of basic product

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

KNO2 + H2O --> HNO2 + HO-

©2008 – 2018 McMaster University

• A 1.0 L solution contains 1.0 moles of CH3COOH(aq) (Ka =

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

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

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

A. This is a net ionic equation.

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

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

A. HCl(aq) Follow-up iClicker:

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

[CH3 COO− ][H3 O+ ] (0.6 + x) (x)

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

• Where do we see the importance of buffers?

©2008 – 2018 McMaster University

Stomach pH is 1.5, acetic acid

• Buffer chemistry: equilibrium reaction of either weak species

©2008 – 2018 McMaster University

• A buffer solution is:

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

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

©2008 – 2018 McMaster University

(See Petrucci, figure 17-5)

• A chemist mixes 25 mL of 1.0 M HBr with 50 mL of 1.0 M

HBr(aq) + CH3NH2(aq) → CH3NH3+(aq) + Br–(aq)

©2008 – 2018 McMaster University

• A chemist mixes 50 mL of 1.0 M HBr with 25 mL of 1.0 M

©2008 – 2018 McMaster University

Not a buffer b/c weak is not in excess Chem

©2008 – 2018 McMaster University

HCO3– → CO2 + OH–

Fire’s burning, fire’s burning

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

lower ph more acetic acid

©2008 – 2018 McMaster University

©2008 – 2018 McMaster University

Solve for y: 37g