Acid –base equilibrium

Outline
• Definition of acids and bases;
• strong and weak acids and bases;
• Equilibrium constants;
• pH and pOH of acids and bases;
• Hydrolysis of salts of weak acids and
bases;
• Buffers;
• Indicators;
• Titration curves.
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 Acid/Base definitions
• Definition #1: Arrhenius (traditional)

Acids – produce H+ ions (or hydronium ions H3O+) in

water

Bases – produce OH- ions in water

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 Acids and Bases and Their Reactions
Definitions
1. Arrhenius Acids and Bases Acids are
• H+ donors
• Bases are OH- donors
2. Arrhenius Broadened Definition
Arrhenius
• Acids increase H+ concentration or 1903
[H+] increases Nobel Prize
• Bases increase OH- concentration or
[OH-] increases
(problem: some bases don’t have
hydroxide ions!)
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 Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

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 Acid/Base Definitions
• Definition #2: Brønsted – Lowry

Acids – proton donor

Bases – proton acceptor

A “proton” is really just a hydrogen atom

that has lost it’s electron!
 Bronsted Lowry Theory
Johannes Brønsted and Thomas Lowry revised
Arrhenius’s acid-base theory to include this behavior.
They defined acids and bases as follows:

Bronsted Lowry

“An acid is a hydrogen containing species that

donates a proton. A base is any substance that
accepts a proton”
HCl (aq) + H2O (l)  Cl- (aq) + H3O+ (aq)

In the above example what is the Brønsted acid? What is the Brønsted base?

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 Bronsted Lowry Theory
In reality, the reaction of HCl with H2O is an equilibrium
and occurs in both directions, although in this case the
equilibrium lies far to the right.
-
HCl (aq) + H2O (l)  Cl ( aq) + H3O+ (aq)

For the reverse reaction Cl - behaves as a Brønsted

base and H3O+ behaves as a Brønsted acid.

The Cl- is called the conjugate base of HCl. Brønsted

acids and bases always exist as conjugate acid-base
pairs.
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 CH3CO2H + H2O H3 O+ + CH3CO2-
Acetic Acid Acetate Ion

Pairs 1 2 2 1
acid base acid base

Point of View #1

CH3CO2H + H2O H3 O+ + CH3CO2-

acid base Conjugate acid Conjugate base of
of H2O CH3CO2H

Point of View #2

CH3CO2H + H 2O H3O+ + CH3CO2-

Conjugate acid Conjugate acid base
of CH3CO2- base of H3O+

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 A Brønsted-Lowry acid is a proton donor
A Brønsted-Lowry base is a proton acceptor
Conjugate Base - subtract an H+ from the acid
Conjugate Acid add H+ to the base

conjugate conjugate
base acid base
acid
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 Acids & Base Definitions
Definition #3 – Lewis
Lewis acid - a substance
that accepts an electron
pair

Lewis base - a substance

that donates an electron
pair
 Lewis Acids & Bases
• Lewis acid = electron
pair acceptor (BF3)
• Lewis base = electron
pair donor (NH3)

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 Lewis Acids & Bases
Formation of hydronium ion is also an excellent
example.
••••
O—H ••
+ H O—H
H
H
H
ACID BASE
•Electron pair of the new O-H bond
originates on the Lewis base.

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 Lewis Acid/Base Reaction

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 Lewis Acids & Bases
Other good examples involve metal ions.
•••
•O—H 2+ • ••
2+ Co • O—H
Co
H
H
ACID BASE

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 Lewis Acids & Bases
Other good examples involve metal ions.
• ••
••
••
•O—H
O—H 2+ • ••
••
2+ Co 2+
Co ••
•O—H
O—H
Co 2+
Co
H
H
H
H
ACID
ACID BASE
BASE
Such bonds as the H2O ---> Co bond are often called
COORDINATE COVALENT BONDS because both
electrons are supplied by one of the atoms of the
bond.

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 Lewis Acids & Bases
The combination of metal ions
(Lewis acids) with Lewis
bases such as H2O and NH3
------> COMPLEX
IONS
All metal ions form complex
ions with water —and are of
the type [M(H2O)x]n+ where x
= 4 and 6. [Cu(NH3)4]2+

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 OUTLINE
pH and pOH of acids and bases;
Hydrolysis of salts of weak acids and bases;
Buffers;
Autoionization of Water

 Although water is a molecular substance, very

low concentrations of hydronium ions and
hydroxides ions are formed by autoionization.

H O + H O H O -
+ H O+ H
H H H
Autoionization
Autoionization of Water
 Autoionization:
 the process in which water spontaneously forms
low concentrations of H+ and OH - ions by proton
transfer from one water molecule to another

2 H2O (l) H3O+ (aq) + OH- (aq)

 At any given time only a very small number of

water molecules are ionized.
• If every letter in our text represented a water
molecule, you would have to look through about 50
texts to find one H3O+!
Autoionization of Water
 An equilibrium constant expression can be
written for the autoionization of water:

2 H2O (l) H3O+ (aq) + OH - (aq)

Kw = [H3O+] [OH -] = [H+ ] [OH- ]

where Kw = ionization constant for water

= ion-product constant
= 1.00 x 10-14 at 25oC
 Autoionization of Water
 The value of Kw (and all other equilibrium constants) varies with
temperature:
 Kw = 1.14 x 10-15 at 0oC
 Kw = 1.00 x 10-14 at 25oC
 Kw = 9.61 x 10-14 at 60oC

 You should assume 25oC unless otherwise stated in a problem.

 Autoionization of Water
By definition:

 Neutral solution: [H+ ] = [OH- ]

 Acidic solution: [H+ ] > [OH- ]

 Basic solution: [H+ ] < [OH- ]

Autoionization of Water
Example: Calculate the [H+ ] and [OH- ] in a
neutral solution at 25oC.
Autoionization of Water
Example: What is the [H+ ] at 25oC for a
solution in which [OH- ] = 0.010 M.
Autoionization of Water
Example: What is the [OH- ] at 25oC in a
solution in which [H+ ] = 2.5 x 10-6 M.
 pH
 Since the [H+] is usually very small in aqueous solutions, we
normally express the [H+] in terms of pH.

pH = - log10 [H+]

 Sig Figs and logs: only the digits after the decimal point are
significant.
pH
Example: Calculate the pH of a solution with
[H+] = 2.52 x 10-5.
pH
Example: Calculate the pH of a solution with
[OH-] = 6.5 x 10-5.
 pH
 The negative log is also used to express the magnitude of other
small quantities:

 pOH = - log [OH- ]

 pH and pOH are related by the following equation that is

derived by taking the negative log of the expression for K w

pH + pOH = 14.00 at 25oC

pH
Example: Calculate the pOH of a solution with
[OH - ] = 2.5 x 10-3 M.
pH
Example: Calculate the pH of a solution with
[OH - ] = 2.5 x 10-3 M.

Approach 1:
pH
Approach # 2:
 pH
 Given the pH of a solution, you can also find the [H +] and the
[OH-].

 Since pH = - log [H+],

[H+] = 10 –pH

 Since pOH = - log [OH-],

[OH-] = 10 -pOH
pH
Example: What are the [H+] and [OH-] for a
solution with a pH of 2.50 at 25oC?
 Strong Acids
 Strong acid:
 Strong electrolyte
 Ionizes completely in aqueous solution

HNO3 (aq) H +
(aq) + NO3 – (aq)

 The only significant source of H+ ion in an aqueous solution of a

strong acid is usually the strong acid.
Strong Acids
 Consequently, the [H+] in a solution of a strong
monoprotic acid can be determined easily using
the concentration of the strong acid itself.

HNO3 (aq) H +
(aq) + NO3 – (aq)

 In a 0.05 M HNO3 (aq) solution,

[H+] = 0.05 mol HNO3 x 1 mol H+ = 0.05 M

L 1 mol HNO3
Strong Acids
Example: What is the pH of a 0.25 M HCl (aq)
solution?
 Strong Bases
 Strong Base
 strong electrolyte
 ionizes completely in aqueous solution

NaOH (aq) Na+ (aq) + OH- (aq)

 Common strong bases

 alkali metal hydroxides
 hydroxides of Ca, Sr, and Ba
Strong Bases
 The pH of an aqueous solution of a strong
base can be determined using the
concentration of the strong base

NaOH (aq) Na+ (aq) + OH- (aq)

 A 0.25 M solution of NaOH has an [OH -] of

0.25 M:

0.25 mol NaOH x 1 mol OH- = 0.25 M

L 1 mol NaOH
 Strong Bases
 The pH of the base solution can then be found in two ways:

 Calculate pOH
use pH + pOH = 14.00 to determine pH

 Calculate [H+]
use [H+] [OH-] = 1.00 x 10-14
Then calculate pH
Strong Bases
Example: Calculate the pH of a 0.25 M Ca(OH)2
(aq) solution.

Step 1: Determine [OH-]

 Strong Bases
Step 2: Calculate pOH

Step 3: Calculate pH
Strong Bases
Example: What is the pH of a solution prepared
by mixing 10.0 mL of 0.015 M Ba(OH)2 and 30.0
mL of 7.5 x 10-3 M NaOH?
Strong Bases
Step 1: Find the total [OH-]
 Strong Bases
Step 2: Find pOH

Step 3: Find pH
 Weak Acids
 Most acidic substances are weak acids:
 partially ionize in solution
 the solution contains an equilibrium mixture of acid molecules
and its component ions

CH3CO2H H+ (aq) + CH3CO2 - (aq)

 Weak Acids
 The extent to which a weak acid ionizes can be expressed using
an equilibrium constant known as the acid-dissociation constant
(Ka).

 For a general reaction:

HX (aq) H+ (aq) + X- (aq)

Ka = [H+][X-] Note: The rules for writing

an expression for Ka are the
[HX]
same as those for Kc, Kp and
Ksp.
 Weak Acids
 The magnitude of Ka indicates the tendency of the hydrogen ion
in an acid to ionize.

 The larger the value of Ka, the stronger the acid is.

 The pH of a weak acid solution can be calculated using the

initial concentration of the weak acid and its K a.
 Weak Acids
 To calculate the pH of a weak acid solution:
 Write the ionization equilibrium for the acid.
 Write the equilibrium constant expression and its numerical
value.

 Set up a table showing initial concentration, change,

equilibrium concentration.
 Substitute equilibrium concentrations into the equilibrium
constant expression.
 Weak Acids
 To calculate the pH of a weak acid solution (cont):
 Solve for the change in concentration.
Assume that the change in concentration is small (i.e. <
5%) compared to the initial concentration of the weak
acid.
 Check the validity of previous assumptions.
If x/initial concentration x 100% >5.0%, you must use the
quadratic equation to solve for x.
 Calculate the final concentrations and pH.
 Calculations With Ka
• How do you know when you can use
this simplifying assumption?
– It can be shown that if the acid concentration, Ca,
divided by the Ka exceeds 100, that is,
if [acid]  100
Ka
– then this simplifying assumption of ignoring the
subtracted x gives an acceptable error of less than 5%
otherwise must do quadratic formula. Another way
look at it factor of two - three difference in power of 10
is needed between Ka and conc of acid.
ex. Calculate the pH in a 1.00 M solution of nitrous acid, HNO2,
for which Ka = 6.0 x 10-4 at 25oC. acid, base, or salt? acid strong or weak? weak
HNO2 + H2O H3O+ + NO2-
[HNO2] [H3O+] [NO2-]
Initial, [ ]o 1.00 0 0
Change, D[ ] -x +x +x
Equilibrium, [ ]eq 1.00 - x x x

=
Does answer make sense?
Yes, acid pH
53
ex. Calculate the pH of 10.00 mL of 1.00 M solution of nitrous acid , HNO 2, diluted
to 100.0 mL with water for which Ka = 6.0 x 10-4 at 25oC. acid, base, or salt? acid
strong or weak?
HNO2 + H2O H3O + NO2
+ -
weak
[HNO2] [H3O+] [NO2-]
Initial, [ ]o 0.100 0 0
Change, D[ ] -x +x +x
Equilibrium, [ ]eq 0.100 - x x x

Does answer make sense?

Yes, acid pH
54
Weak Acids
Example: Calculate the pH of a 0.20 M
solution of HCN. Ka = 4.9 x 10-10

Step 1: Write the equation for the

ionization.

Step 2: Write the expression for Ka.

 Weak Acids
Step 3: Set up a table.
Weak Acids
Step 4: Substitute equilibrium concentrations
into the Ka expression.

Step 5: Assume that x << 0.20 M and solve

for x.
 Weak Acids
Step 6: Check the validity of our assumption.
 Weak Acids
 Step 7: Substitute value for x into the table to find the [H +].
 Weak Acids
Step 8: Calculate the pH using the [H +]
 Weak Bases
 Many substances behave as weak bases in water.

Weak base + H2O conjugate acid + OH-

 The extent to which a weak base reacts with water to form its
conjugate acid and OH- ion can be expressed using an
equilibrium constant known as the base-dissociation constant
(Kb).
Weak Bases

 Kb always refers to the equilibrium in

which a base reacts with water to form its
conjugate acid and OH- ion.

 For the reaction:

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

Kb = [NH4+] [OH-] Note: The rules for writing

[NH3] an expression for Kb are the
same as those for Kc, Kp and
Ksp.
 Weak Base
 To calculate the pH of a weak base solution:
 Write the ionization equilibrium for the base.
 Write the equilibrium constant expression and its numerical
value.
 Set up a table showing initial concentration, change,
equilibrium concentration.
 Substitute equilibrium concentrations into the equilibrium
constant expression.
 Weak Bases
 To calculate the pH of a weak base solution (cont):
 Solve for the change in concentration.
Assume that the change in concentration is small (i.e. <
5%) compared to the initial concentration of the weak
base.
 Check the validity of previous assumption.
 Calculate the [OH-] concentration and pOH
 Use pOH to calculate pH.
 A Problem To Consider
• What is the pH of a 0.20 M solution of
pyridine, C5H5N, in aqueous solution?
The Kb for pyridine is 1.4 x 10-9.
acid, base, or salt? base strong or weak? weak
– As before, we will follow the three steps in
solving an equilibrium.
1. Write the equation and make a table of
concentrations (ICE).
2. Set up the equilibrium constant expression.
3. Solve for x = [OH-].
 A Problem To Consider
C5 H 5 N(aq )  H 2O( l ) C5 H 5 NH  (aq )  OH  (aq )
[C5H5N] [C5H5NH+] [OH-]
Initial, [ ]o 0.20 0 0
Change, D[ ] - x +x +x
Equilibrium, [ ]eq 0.20 - x x x
 A Problem To Consider
C5 H 5 N(aq )  H 2O( l ) C5 H 5 NH  (aq )  OH  (aq )
[C5H5N] [C5H5NH+] [OH-]
Initial, [ ]o 0.20 0 0
Change, D[ ] - x +x +x
Equilibrium, [ ]eq 0.20 - x x x
 A Problem To Consider
– Note that

Cb
 0.20 9  1.4  10 8
Kb 1.4  10
which is much greater than 100 (also factor of 8
difference between the powers of 10 of Kb [2.0 x 10-1]
and concentration of base [1.4 x 10-9]), so we may use
the simplifying assumption that (0.20-x)  (0.20).
 A Problem To Consider
C5 H 5 N(aq )  H 2O( l ) C5 H 5 NH  (aq )  OH  (aq )
[C5H5N] [C5H5NH+] [OH-]
Initial, [ ]o 0.20 0 0
Change, D[ ] - x +x +x
Equilibrium, [ ]eq 0.20 - x x x
 A Problem To Consider
– Solving for pOH
 5
pOH   log[OH ]   log(1.7  10 )  4.77
– Since pH + pOH = 14.00
pH  14.00  pOH  14.00  4.77  9.23
Does answer make sense? Yes, base pH

or combine equations into one:

Weak Bases
Example: Calculate the pH of a 0.20 M solution
of methylamine, CH3NH2. Kb = 3.6 x 10-4.

Step 1: Write the equation for the ionization.

Step 2: Write the expression for Kb.

 Weak Bases
Step 3: Set up a table.
Weak Bases
Step 4: Substitute equilibrium concentrations
into the Kb expression.

Step 5: Assume that x << 0.20 M and solve

for x.
 Weak Bases
Step 6: Check the validity of our assumption.
 Weak Bases
 Step 7: Substitute value for x into the table to find the
[OH-].
 Weak Acids
Step 8: Calculate the pOH

Step 9: Calculate the pH

 Point to note
 Both Ka and Kb show the extent of ionization.
 The smaller the value of Ka or Kb the smaller the extent of
ionization and the equilibrium lies more to the left
 For an acid and its conjugate base, their respective acid and
base dissociation constants have the following relation:
 Buffers

 Allow pH to be maintained over

small additions of acid or base
 Made up of a weak acid and its Ka 
A H O 

3


conjugate base, e.g. HA

HA + H2O  A- + H3O+  HA 
acid conjugate base  

H 3O  K a   
 
 The equilibrium will shift to the  A 
 HA 
right on addition of a small
amount to base and shifts to  

 log H 3O  logK a  log   
 
 A 
the left on addition of small
amounts of acid
pH  pK a  log
A  
 Henderson-Hasselbalch HA
equation allows determination
of pH in buffer systems:

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Question
Calculate the pH of a solution containing 0.25 M CH3COOH and
0.35 M CH3COONa?

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 Question
A buffer solution is made by adding 0.3 mol of acetic acid and 0.3 mol of
sodium acetate to enough water to make 1L of solution. Determine the
pH of the buffer solution. The Ka for acetic acid is 1.8 × 10-5

pH = pKa + log [A-] / [HA] A- = sodium acetate

HA = acetic acid
pH = -log (1.8 × 10-5) + log (0.3) / (0.3)
pH = 4.74

Calculate the pH of the buffer solution after 0.02 moles of sodium

hydroxide is added

1 litre of buffer contains 0.3 moles of sodium acetate and 0.3 moles of
acetic acid. Sodium hydroxide is a strong base. The acetic acid will
react with the base added to try to maintain the pH. What the acid
loses in concentration, the salt (sodium acetate) will gain.
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 CH3COOH + OH-  CH3COO- + H2O

CH3COOH OH- CH3COO-

Initial conc 0.3 0 0.3
Change 0.3 – 0.02 0.02 0.3 + 0.02
Equil. Conc. 0.28 0.02 0.32

pH = pKa + log [A-] / [HA]

pH = - log (1.8 × 10-5) + log (0.32) / (0.28)
pH = 4.74 + 0.058
pH = 4.8

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 Dissociation of Polyprotic Acids
 Polyprotic acids are those that contain more than one atom of hydrogen
that can be lost upon dissociation. Examples of these types of acids are
H2SO4 and H2S with two ionisable hydrogens and H 3PO4 with three
ionisable hydrogens.

For the dissociation of sulphuric acid we can write the following

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For

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