Part 3: Acid Base Solutions

Key Concepts

• Cations and anions in solution

• Acid-base titrations
• Buffers
Cations and Anions in Solution
• Species that turn solutions acidic or basic when dissolved in H2O are
not always obvious acids or bases
➢ i.e. you might not see protons or hydroxide in their formulae

• Individual anions (X-) and cations (X+) can form basic or acidic
solutions depending on their relationship to other acids or bases
Cations as Acids
In solution, cations that are conjugate acids of weak bases act as acids:
NH4+ + H2O ⇌ H3O+ + NH3
conjugate acid weak base
metal cation is
hydrated in aqueous
• Small highly charged metal cations are also acidic: solutions
pKa Fe3+(aq) = 2.5 (remember, small pKa = large Ka) H H
pKa Al3+(aq) = 4.9 = strong acid
O
H H
pKa Cr3+(aq) = 3.9 O Fe3+ O
H H
O
➢Due to electron withdrawing by metal cation: H H
Cations as Acids
The positive charge of the metal cation draws electron density away
from the O-H bond in water, making it weaker.

➢ H+ donated to neighbouring H2O, forming H3O+ ions in solution (i.e.

making the solution acidic)
• metal cations are not acids themselves but cause an acidic
solution:
Cations as Acids
➢The larger the charge / volume
ratio of the cation, the greater the
polarisation of surrounding water
molecules; the greater the acidity.

➢Large cations such as Na+, Li+, K+

(Ag+, Mg2+) have very little effect
on surrounding water molecules:
they are not acidic in water and do
not affect pH
Anions as Bases
• Anions can accept protons and therefore are potential bases

• In solution, anions that are conjugate bases of weak acids act as

proton acceptors (i.e. they act as bases)

PO43- + H2O ⇌ HPO42- + OH-

conjugate base weak acid

Anions as Bases
➢Conjugate bases of weak acids give basic solutions
• e.g. F-, CN-, OH-, PO43-

F-(aq) + H2O(l) ⇌ HF(aq) + OH-(aq)

➢Conjugate bases of strong acids give neutral solutions (i.e. no effect

on pH)
• e.g. Cl-, Br-, I-, NO3-

Cl-(aq) + H2O(l) ⇌ HCl(aq) + OH-(aq)

Activity 4.10
Quantifying Acidity and Basicity
Acid-base titrations allow us to
determine the acidity or basicity of an
unknown solution

➢By following the pH of acid-base

reactions we can quantify the acidity
or basicity of an unknown solution
when we react it with a solution of
known basicity or acidity
Titrations
The titrant (known) is quantitatively added to the analyte (unknown) to
find the equivalence point

➢The equivalence point (or end point) is reached when the number of
moles of H+ added is equivalent to the number of moles of OH–
originally present (or vice versa if the analyte is an acid)
i.e. n (H+) = n (OH–)

Note: equivalence point is also known as the stoichiometric point

Titrations of Strong Acid and Strong Base
Consider a titration between a strong acid and a strong base
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

At the end-point Titrant = known solution

➢sufficient titrant has been
added to react with all of the
analyte

Analyte = known volume but

unknown concentration
Titrations of Strong Acid and Strong Base
How do we know when the equivalence point has been reached?

• Follow the pH of the acid-base reaction

• Construct a titration curve of pH versus volume (titrant) added

• Find equivalence point from titration curve.

Or – observe a colour change using an indicator – will discuss further

later!
Titrations of Strong Acid and Strong Base
1. At the equivalence point, the number of moles (n) of titrant
added can be calculated:
n (titrant) = c (titrant)  V (titrant)

2. By considering the stoichiometry of the acid-base reaction, n

(analyte) can then be determined
n (titrant) : n (analyte) = x:y

3. Finally, the initial volume of analyte is known, so its initial

concentration can be calculated:
c (analyte) = n (analyte) / V (analyte)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l)
14
pH (NaOH)
0.42 M HCl - no titrant added

14
7

pH
Monitor pH with pH probe

25 mL NaOH
0
0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l)
14
A
0.42 M HCl

A ~7 mL titrant added:
13 7 n (OH-) still > n (H+)

pH
Monitor pH with pH probe basic pH reflects excess OH-

25 mL NaOH
0
+ ~7 mL 0.42 M HCl 0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l)
14
A
B
0.42 M HCl

12.8 B ~10 mL titrant added:

7 n (OH-) still > n (H+)

pH
Monitor pH with pH probe
basic pH reflects excess OH-

25 mL NaOH
0
+ ~10 mL 0.42 M HCl 0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l)
14
A S 15 mL titrant
B
0.42 M HCl added:
Equivalence Point
reached;
7.0 S n (NaOH) : n (HCl)
7
= 1:1

pH
Monitor pH with pH probe
pH change is
dramatic, from basic
to neutral

25 mL NaOH
0
+ 15 mL 0.42 M HCl 0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l) C 18 mL titrant added:
14
AEquivalence Point passed
Bn (H+) now > n (OH-)
0.42 M HCl
acidic pH reflects excess H+

1.5 7
S

pH
Monitor pH with pH probe

25 mL NaOH
0
+ ~18 mL 0.42 M HCl 0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l) D 26 mL titrant added:
14
A Titration complete
B
0.42 M HCl acidic pH reflects excess H+

1.0 7
S

pH
Monitor pH with pH probe

C
D
25 mL NaOH
0
+ ~26 mL 0.42 M HCl 0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l)
14
A
B
0.42 M HCl
Stoichiometric
point
1.0 7
S

pH
Monitor pH with pH probe

C
D
25 mL NaOH
0
+ ~26 mL 0.42 M HCl 0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Strong Base
1. At equivalence point (steepest point on curve):
15 mL of 0.42 M HCl was added
𝑛 = 𝑐𝑉 = 0.42 𝑀 × 0.015 𝐿 = 0.0063 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐶𝑙

2. Stoichiometric ratio 𝑛 𝑁𝑎𝑂𝐻 : 𝑛 𝐻𝐶𝑙 = 1: 1

Therefore, 0.0063 moles of NaOH in 25 mL

𝑛 0.0063 𝑚𝑜𝑙
3. 𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝑵𝒂𝑶𝑯 = = = 0.25 𝑀
𝑉 0.025 𝐿

At equivalence point:
25 mL NaOH NaOH(aq) + HCl(aq) →NaCl(aq) + H2O(l)
+ 15 mL 0.42 M HCl
Titrations of Strong Acid and Strong Base
➢For strong acid / strong base 14
A
titrations the equivalence point is B

reached at pH = 7
Stoichiometric
point
➢Strong acids and bases undergo
S
7
complete H+ transfer

pH
➢Solution contains salt + H2O
i.e. products do not contribute to C
D
the pH
0
0 10 20 30
Vol. HCl added (mL)
Titrations of Strong Acid and Weak Base
NH3(aq) + HCl(aq) → NH4+(aq) + Cl-(aq)

NH4+ is conjugate acid of a weak base = acidic

➢Therefore, excess of H3O+ exists in solution
because:
NH4+ + H2O ⇌ H3O+ + NH3
➢Stoichiometric point occurs on acidic side of
pH 7
 Blackman Ch 11.7

Titrations of Weak Acid and Strong Base

NaOH(aq) + CH3COOH(aq) → CH3COO-(aq) + Na+(aq) + H2O(l)

CH3COO- is conjugate base of a weak acid = basic

➢excess of OH- exists in solution because:
CH3COO- + H2O ⇌ CH3COOH + OH-
➢Stoichiometric point occurs on basic side of pH 7
Acid-Base Indicators
14
A
B
What if we do not have a pH
meter, or automatic titration unit?
Stoichiometric
point
S
➢We can still find the end point 7

pH
by using an acid-base indicator.

C
D
0
0 10 20 30
Vol. HCl added (mL)
Acid-Base Indicators
Indicators are molecules that change colour at the end point.
e.g. Phenolphthalein is a weak acid:

-
HO O
OH O

C C
O
CO CO2-

H-In In-

Acid form → colourless Conjugate base → pink

Acid-Base Indicators
Indicators are molecules that change colour at the end point.
e.g. bromothymol blue is a weak acid:

H-In In-
Acid form → colourless Conjugate base → blue
Acid-Base Indicators
Indicators are molecules that change colour at the end point.

Colour changes when pH of solution = pKa of the indicator

= when 50% of molecules are coloured
= 9.4 for phenolphthalein
= 7.1 for bromothymol blue
Acid-Base Indicators
Acid-Base Indicators
• Some plants and vegetables
are acid-base indicators

Chart source: http://chemistry.about.com/od/acidsbase1/ss/Edible-Ph-Indicators-Color-Chart.htm

Acid-Base Indicators
Ideal: Choose indicator with end point 14
A
+/- 1 pH from equivalence point B

Colour changes when pH = pKa Stoichiometric

= 7.1 for bromothymol blue point
S
7

pH
C
D
0
0 10 20 30
Vol. HCl added (mL)
Acid-Base Indicators
Acid-Base Indicators
Indicator colour is due to absorption of light

-
O
incident white light O
many wavelengths complementary colour
light detected
C

CO2-

In-

selected wavelengths
absorbed
UV-Vis Spectroscopy
Spectroscopy is the study of interaction between matter and energy (light)

Many molecules absorb light in the UV and visible wavelength range

UV-Vis Spectroscopy
The absorbance of light can be used to measure the concentration of
molecules according to the Beer-Lambert Law:
A = εcl

A = absorbance
ε = molar extinction coefficient
(constant for a given molecule)
(describes how strongly light is absorbed) ε, c
c = concentration of absorbing molecule
l = path length (measured in cm)
(i.e. distance over which molecule &
light interact) light out (I1) vs light in (I0)
Activity 4.11
Buffer Solutions
Buffer solutions are systems that have the ability to resist a change in
pH upon addition of small amounts of acid or base

• Basis of homeostasis: a self-regulating process to maintain stability

and also remain responsive to environment

• pH buffers
➢pH (blood) = 7.35-7.45
➢pH (gastric juices) = 1.5
➢pH (world’s oceans) = 8.1
Buffer Solutions
Acid buffer (pH < 7)
• mixture of weak acid and its conjugate base
e.g. CH3COOH and CH3COO-

Base buffer (pH > 7):

• mixture of weak base and its conjugate acid
e.g. NH3 and NH4+
Buffer Solutions – How buffers work
Example: solution of CH3COOH and CH3COONa

CH3COOH(aq) + H2O(l) ⇋ CH3COO-(aq) + H3O+(aq)

weak acid conjugate base

Add strong base:

OH– + CH3COOH ⇋ CH3COO-(aq) + H2O(l)

neutralisation
Add strong acid:
H+ + CH3COO- ⇋ CH3COOH(aq) + H2O(l)
Buffer Solutions – How buffers work
Buffer Solutions – How buffers work
➢As long as amount of added acid/base is relatively small, solution acts
to neutralise addition so pH change is small

• Best buffering conditions:

[conjugate base (A-)] = [acid (HA)]
and
concentration of added acid or base << [conjugate base] and [acid]
Activity 4.12
pH of Buffer Solutions
The pH of a buffer solution can be calculated from the Henderson-
Hasselbalch equation:

(Note: sometimes [salt], [conjugate base] or [A-] is used

instead of [base], and [HA] instead of [acid])
pH of Buffer Solutions
Example 1 – Calculate the pH of a buffer solution containing 0.05 M acetic
acid (CH3COOH) and 0.05 M sodium acetate (CH3COONa). The pKa of
acetic acid is 4.75.
[𝑏𝑎𝑠𝑒]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
Acid – CH3COOH [𝑎𝑐𝑖𝑑]
Base – CH3COONa
0.05
𝑝𝐻 = 4.75 + 𝑙𝑜𝑔
0.05
𝑝𝐻 = 4.75 + log 1

𝒑𝑯 = 𝟒. 𝟕𝟓
pH of Buffer Solutions
Example 2 - Calculate the change in pH of the previous buffer when
0.03 mol of NaOH is added to 1 litre of the buffer solution

NaOH is a strong base so all of it (0.03 mol) will react with the acid to
form more of the conjugate base:
CH3COOH(aq) + OH–(aq) ⇋ CH3COO–(aq) + H2O(l)
-0.03 -0.03 +0.03 +0.03

Put the new concentrations back

so [CH3COOH]final = 0.05 – 0.03 = 0.02 M into the Henderson-Hasselbalch
and [CH3COO-]final = 0.05 + 0.03 = 0.08 M equation and calculate the new
concentration.
pH of Buffer Solutions
Example 2 - Calculate the change in pH of the previous buffer when
0.03 mol of NaOH is added to 1 litre of the buffer solution

CH3COOH(aq) + OH–(aq) ⇋ CH3COO–(aq) + H2O(l)

0.08
𝑝𝐻 = 4.75 + 𝑙𝑜𝑔
0.02
𝑝𝐻 = 4.75 + log 4
pH increased from 4.75 to 5.35
𝒑𝑯 = 𝟓. 𝟑𝟓
when 0.03 mol of NaOH was added
The Power of Buffers
Compare the change in pH that would have occurred if we added
0.03 mol NaOH to water without the buffer present.
𝑂𝐻− ≈ 0.03 𝑀

𝑝𝑂𝐻 = − log 𝑂𝐻 − = − log 0.03 = 1.5

𝑝𝐻 = 14 − 1.5

𝒑𝑯 = 𝟏𝟐. 𝟓
The presence of a buffer has
resisted a change in pH
Buffer Capacity
Buffer capacity: measure of amount of acid (or base) that can be
added without substantial pH change

➢Buffers with high concentrations have higher capacity.

➢Dilution of a buffer decreases buffer capacity.

Buffer exhaustion: occurs when most of weak acid (or weak base) is
converted to base (or acid)
Buffer Capacity
Buffers are generally effective within the range pH = pKa ± 1
➢Remember a change of 1 pH unit is equal to a 10-fold change in
concentration
➢Hence the ideal ratio of acid : base in a buffer should not exceed 10 : 1
or 1: 10
[𝑏𝑎𝑠𝑒] 10 1
= 𝑜𝑟
[𝑎𝑐𝑖𝑑] 1 10

𝑖𝑓 𝑏𝑎𝑠𝑒 = 10 × [𝑎𝑐𝑖𝑑] 𝑖𝑓 𝑎𝑐𝑖𝑑 = 10 × [𝑏𝑎𝑠𝑒]

𝑡ℎ𝑒𝑛 𝑝𝐻 = 𝑝𝐾𝑎 + log 10 𝑡ℎ𝑒𝑛 𝑝𝐻 = 𝑝𝐾𝑎 + log 0.1

𝑝𝐻 = 𝑝𝐾𝑎 + 1 𝑝𝐻 = 𝑝𝐾𝑎 − 1
 Thank you everyone!
Good luck and see you in semester 2!

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