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ACID-BASE EQUILIBRIA

Lecture 4

Mag.chem., researcher Lauma Buša


Contents of the lecture
• Various acid and base theories
• Conjugated acids and bases
• Autoionization of water
• Strength of acids and bases, constants Ka and Kb
• Strong acids and bases, weak acids and bases
• pH scale and calculation of pH
• Electrolytes and non-electrolytes
• Hydrolysis of salts

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Acetylsalicylic acid C9H8O4
Boric acid H3BO3 Sodium carbonate Na2CO3
Citric acid C6H8O7 Citric acid C6H8O7

Ascorbic acid
C6H8O6
Calcium carbonate CaCO3 Benzoic acid C7H6O2
Magnesium carbonate MgCO3

Acetic acid CH3COOH Sodium hydroxide NaOH Sodium hydrogen carbonate


NaHCO3

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Arrhenius acid-base theory
The Swedish scientist Svante Arrhenius in the end of 19th century developed his theory in
order to divide substances into acids and bases based on their chemical properties.

+
An Acid is a substance that, when dissolved in water, increases the concentration of H ions.

H2O + -
HCl (g) → H (aq) + Cl (aq)

-
A Base is a substance that, when dissolved in water, increases the concentration of OH ions.

+ -
NaOH (s) → Na (aq) + OH (aq)
H2O

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Limitations of Arrhenius theory
• There are known substances that demonstrate properties of a base, but
doesn’t contain OH- ions (e.g. NH3)

• Arrhenius theory functions only for aqueous solutions

• Bare proton H+, cannot exist for a long time in a water solution

• In theory any salt solution is neutral, in real life it is not so

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Brønsted- Lowry acid-base theory
In the beginning of 20th century scientists Brønsted and Lowry came up with a
theory that explains the properties of acid-base more widely.

Acid–base reactions involve the transfer of H+ ions (protons) from one substance to another

Acids: proton donors Bases: proton acceptors


Can free a proton (H+) Can add a proton (H+)

- + + -
HBr + H2O → Br + H3O NH3 + H2O → NH4 + OH

When acids dissolve in water, the When acids dissolve in water, the
concentration of hydronium (H3O+) ions concentration of hydroxide (OH-) ions
increases increases
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Conjugated acids and bases
- +
HBr + H2O → Br + H3O
ACID BASE

How are these


Any proton transfer process always includes acids and
both acid (proton donor) and base (proton acceptor). bases linked
to each other?

CONJUGATE
ACID
BASE
- +
HBr + H2O → Br + H3O
ACID CONJUGATE
BASE

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Relationship between conjugated acids and bases

• For each acid there is only one conjugate base.

• For each base there is only one conjugate acid.

• The acid that donates the proton, creates conjugate base.

• The base that accepts the proton, creates conjugate acid.

The pair formed from the acid and the conjugate base is called the conjugate acid–base
pair (each acid and base separately – a protolyte) and written as follows:
HCl/Cl-, NH4+/NH3, H2SO4/HSO4-, [Fe(H2O)n]3+/[Fe(H2O)n-1(OH)]2+ u.c.

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Acids and bases in aqueous solutions
Acids and bases in aqueous solutions can be:
• Molecules
• Negative ions
• Positive ions
ACIDS
Molecules: H2SO4 + H2O → HSO4- + H3O+
Negative ions: HS- + H2O → S2- + H3O+
Positive ions: [Al(H2O)6]3+ + H2O → [Al(H2O)5(OH)]2+ + H3O+

BASES
Molecules: NH3 + H2O → NH4+ + OH-
Negative ions: HS- + H2O → H2S + OH-
Positive ions: [Al(H2O)5(OH)]2+ + H2O → [Al(H2O)6]3+ + OH-

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Amphiprotic protolytes
Amphiprotic protolytes – substances that can both donate and accept protons, therefore
act both as an acid and as a base

- 2- +
HSO4 + H2O → SO4 + H3O
ACID BASE

- -
HSO4 + H2O → H2SO4 + OH
BASE ACID

Water is amphiprotic protolyte

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Lewis acid-base theory
In the 1920s, american scientist Lewis formulates acid-base theory based on
the ability of substances to add or give away electron pairs.

Acids: electron pair acceptors Bases: electron pair donors


Contains an empty orbital Has a lone electron pair

LEWIS LEWIS
BASE ACID

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All Brønsted-Lowry acids are Lewis acids

LEWIS LEWIS
BASE ACID

Not all Lewis acids will be also Brønsted-Lowry acids!

+ +
Ag (aq) + 2 NH3(aq) ↔ [Ag(NH3)2] (aq)
LEWIS LEWIS
ACID BASE

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Autoionization of water

In autoprotolysis a proton is
+ - -14
transferred between two Kw = [H3O ][OH ] = 1,0·10 (25 °C)
identical molecules, one of
which acts as a Brønsted acid,
releasing a proton which is
accepted by the other molecule
acting as a Brønsted base pH + pOH = 14

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pH scale

+ - + - + -
[H3O ] > [OH ] [H3O ] = [OH ] [H3O ] < [OH ]
Acidic Neutral Alkaline
pH < 7 pH = 7 pH > 7

pH – the negative decimal logarithm of the molar concentration of hydrogen ions


pH = -log10[H3O+]
pH = -lg [H3O+]
[H3O+] = 10-pH
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ALKALINE

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Measuring the pH

• Using indicators

Universalindicator paper Indicator phenolphtalein Indicator bromthymolblue

• With pH meter

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Acid constant Ka
Ionization of an acid in aqueous solution: HA (aq) + H2O (l) ↔ A- (aq) + H3O+

𝑨− [𝑯𝟑 𝑶+ ]
Equilibrium constant: 𝑲𝒂 = 𝒑𝑲𝒂 = −𝒍𝒈𝑲𝒂
[𝑯𝑨]

Ka – acid constant (acid ionization constant, acid dissociation constant)

The bigger the acid constant Ka and the smaller the pKa – the stronger the acid.

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Polyprotic acids
Acids which are capable of donating several protons are called polyprotic acids.

H2SO3 + H2O → HSO3- + H3O+

𝑯𝑺𝑶− +
𝟑 [𝑯𝟑 𝑶 ]
1. equilibrium constant: 𝑲𝒂𝟏 =
[𝑯𝟐 𝑺𝑶𝟑 ]

HSO3- + H2O → SO32- + H3O+

𝑺𝑶𝟐−
𝟑 [𝑯𝟑 𝑶 +]
2. equilibrium constant: 𝑲𝒂𝟐 =
[𝑯𝑺𝑶−
𝟑]

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Base constant Kb
+ -
Proton addition to the base in aqueous solution: B (aq) + H2O (l) ↔ HB (aq) + OH

𝑯𝑩+ [𝑶𝑯− ]
Equilibrium constant: 𝑲𝒃 = 𝒑𝑲𝒃 = −𝒍𝒈𝑲𝒃
[𝑩]

Kb – base constant

The bigger the base constant Kb and the smaller the pKb – the stronger the base.

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Relationship between Ka and Kb

𝐾𝑎 ∙ 𝐾𝑏 = 𝐾𝑤 = 1,0 ∙ 10−14

−𝑙𝑔𝐾𝑎 − 𝑙𝑔𝐾𝑏 = −𝑙𝑔𝐾𝑤

𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 𝑝𝐾𝑤

! This relationship can be applied within only one conjugate acid-base pair (acid-conjugate base;
base-conjugate acid).

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Relative acid and base strength
Some acids are better proton donors than others, while some bases are better proton acceptors than others.

• Strong acid completely dissociates into ions (the


conjugate base shows negligible basicity).

• Weak acid only partially dissociates into ions (the


conjugate base is a weak base).

• A substance with negligible acidity contains


hydrogen but does not demonstrate any acidic
behavior (the conjugate base is a strong base).

In every acid–base reaction, equilibrium


favors transfer of the proton from the stronger acid to the
stronger base to form the weaker
acid and the weaker base

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pKA SkābeA
Acid A Bāze Bbase B
Conjugate pKB

~ -9 HClO4 ClO4- ~ 23
~ -7 HCl Cl - ~ 21
~ -3 H2SO4 HSO4- ~ 17
-1,4 HNO3 NO3- 15,4
0,0 H3O+ H2 O 14,0
2,1 H3PO4 H2PO4- 11,9
3,8 HCOOH HCOO- 10,2
4,8 CH3COOH CH3COO- 9,2
6,4 H2CO3 HCO3- 7,6
7,0 H2S HS- 7,0
7,2 H2PO4- HPO42- 6,8
9,1 H3BO3 H2BO3- 4,9
9,2 NH4+ NH3 4,8
10,3 HCO3- CO32- 3,7
12,4 HPO42- PO43- 1,6
13,8 HS - S2- 0,2
14,0 H2O OH- 0,0
23 NH3 NH2- -9
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Strong acids and bases

Strong acid in water Strong base in water


completely dissociates into ions completely dissociates into ions

H2SO4 – sulfuric acid NaOH – sodium hydroxide


HNO3 – nitric acid KOH – potassium hydroxide
HCl – hydrochloric acid Ba(OH)2 – barium hydroxide
HClO4 – perchloric acid Ca(OH)2 – calcium hydroxide
Sr(OH)2 – strontium hydroxide

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Calculation of pH
• Solution of a strong acid • Solution of a weak acid

𝑝𝐻 = −𝑙𝑔𝒄𝒂 𝑝𝐻 = 0,5 ∙ 𝑝𝐾𝑎 − 0,5 ∙ 𝑙𝑔𝒄𝒂

• Solution of a strong base • Solution of a weak base

𝑝𝐻 = 14 − 𝑝𝑂𝐻 = 14 + 𝑙𝑔𝒄𝒃 𝑝𝐻 = 7 + 0,5 ∙ 𝑝𝐾𝑎 + 0,5 ∙ 𝑙𝑔𝒄𝒃


𝑝𝐻 = 14 − 0,5 ∙ 𝑝𝐾𝑏 + 0,5 ∙ 𝑙𝑔𝒄𝒃

• Solution of amphiprotic protolyte


𝑝𝐻 = 0,5 ∙ 𝑝𝐾𝑎1 + 0,5 ∙ 𝑝𝐾𝑎2

ca – acid concentration, mol/L


cb – base concentration, mol/L

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Electrolytes and non-electrolytes
Electrolytes – substances that dissociate into ions when dissolved in water and which
solutions conduct electricity

Electrolytes are divided:


• Strong electrolytes – almost completely dissociated into ions in
aqueous solutions (strong acids and bases, salts) (b)
• Weak electrolytes – only a small fraction is dissociated into ions
in aqueous solutions (weak acids and bases) (c)

Non-electrolytes – substances that in aqueous


solutions are in molecular form (a)

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Hydrolysis of salts
Because nearly all salts are strong electrolytes, we can assume that any salt dissolved in water is
completely dissociated. Consequently, the acid–base properties of salt solutions are due to the behavior
of the cations and anions. Many ions react with water to generate H+ (aq) or OH- (aq) ions. This type of
reaction is called hydrolysis.

• The cation of the salt can react with water, forming the conjugate base and hydronium ion

• The anion of the salt can react with water, forming the conjugate acid and hydroxide ion

A salt can be made of:


Strong acid Weak acid
Strong base
Weak base

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Cation from a strong base Anion from a strong acid
+ + 2+ 2- - -
(Na , K , Ca u.c.) (SO4 , Cl , NO3 u.c.)

Cation has negligible acidity, Anion has negligible basicity,


doesn’t react with water doesn’t react with water
SALT

Hydrolysis doesn’t take place

pH of the aqueous solution is neutral


pH = 7

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Cation from a weak base Anion from a strong acid
3+ + 2+ 2- - -
(Fe , NH4 , Cu u.c.) (SO4 , Cl , NO3 u.c.)

Cation is a weak acid, Anion has negligible basicity,


hydronium ion is formed in doesn’t react with water
the reaction with water SALT

Hydrolysis takes place


[Al(H2O)n]3+ + H2O →
→ [Al(H2O)n-1(OH)]2+ + H3O+

pH of the aqueous solution is acidic


The solution pH is
calculated as for a pH < 7
weak acid!
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Cation from a strong base Anion from a weak acid
+ + 2+ 2- - -
(Na , K , Ca u.c.) (SO3 , I , NO2 u.c.)

Cation has negligible acidity, Anion is a weak base,


doesn’t react with water hydroxide ion is formed in the
SALT reaction with water

2-
SO3 + H2O →
Hydrolysis takes place -
→ HSO3 + OH
-

The solution pH is
pH of the aqueous solution is alkaline
calculated as for a
pH > 7 weak base!

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Cation from a weak base Anion from a weak acid
3+ + 2+ 2- - -
(Fe , NH4 , Cu u.c.) (SO3 , I , NO2 u.c.)

Cation is a weak acid, Anion is a weak base,


hydronium ion is formed in hydroxide ion is formed in the
the reaction with water SALT reaction with water
3+
[Al(H2O)n] + H2O → SO32- + H2O →
→ [Al(H2O)n-1(OH)]2+ + H3O+ Hydrolysis is complete → HSO3- + OH-

The pH of the solution depends on the relative strengths of cations and anions forming the salt!

If Ka > Kb, the solution is acidic and pH < 7


If Ka = Kb, the solution is neutral and pH = 7
If Ka < Kb, the solution is alkaline and pH > 7

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