CHEM 1820

INTRODUCTORY CHEMISTRY II ACIDS AND BASES

DR. JOYANN MARKS LECTURE 5
EMAIL: JOYANN.MARKS@UWIMONA.EDU.JM
Last time . . .
❖Acid base neutralization with weak acid and strong base
❖Buffer systems
Acids and bases and solvent systems
Solvents:
A solvent (from the Latin solvo-, "I loosen, untie, I solve") is a substance
that dissolves a solute (a chemically different liquid, solid or gas),
resulting in a solution. A solvent is usually a liquid but can be a solid or a
gas. The maximum quantity of solute that can dissolve in a specific
volume of solvent varies with temperature.
Although many inorganic reactions take place in aqueous solution, water
is not always the most suitable solvent; some reagents react violently or
decompose in water (e.g. the alkali metals) and non-polar molecules are
often insoluble in water.
 Acids and bases and solvent systems
Utility of a solvent depends on :
1. Its auto-dissociation properties
2. Its acidity or basicity auto-dissociation : electron or proton donor/acceptor properties
3. Its dielectric constant
4. Temperature over which it is a liquid

1. Auto-dissociation –A proton is transferred from one solvent molecule to the next,

generating the protonated cation of the solvent and the deprotonated anion of the solvent.
These solvents that contain ionizable protons and are called protic solvents
Examples:
2H2O(l) ⇌ H3O+(aq) + OH-(aq)
2HCl(l) ⇌ H2Cl+(sol) + Cl-(sol)
Class exercise:
Write the auto-dissociation equation for HF, H2SO4and NH3
Auto-dissociation of solvents

2H2SO4(l) ⇌ H3SO4+(sol) + HSO4-(sol)

3HF(l) ⇌ H2F+(sol) + HF2-(sol)

2NH3(l) ⇌ NH4+(sol) + NH2-(sol)

How would you explain the behaviour of HF?

Auto-dissociation and solvent systems
Solvents are defined as:
❑Protic – contains ionizable protons
Examples
H2O, HCl, HF and H2SO4
OR
❑Aprotic- no ionizable protons
1. Non-polar, non ionized: CCl4 and hydrocarbons
2. Polar, nonionized: DMF, DMSO, THF
3. Highly polar, autoionizing: BrF3, IF5
auto-dissociation of these are by F- transfer
e.g. 2BrF3 (l) ⇌ BrF4- (sol) + BrF2+ (sol)
 Molecular Autoionization
Applies to solvents that are both protic and aprotic
A reaction between two molecules of the same substance to produce ions
Protic Solvents Non-Protic Solvents
2H2O(l) ⇌ H3O+(aq) + OH-(aq) 2PF5(l) ⇌ PF4+(sol) + PF6-(sol)
2NH3(l) ⇌ NH4+(sol) + NH2-(sol) 2BrF3(l) ⇌ BrF2+(sol) + BrF4-(sol)
3HF(l) ⇌ H2F+(sol) + HF2-(sol)
Solvent system definition
▪Acid base properties are closely connected with the properties of
solvents
▪The solvent system definition applies in all cases where the solvent
is capable of autoionization whether protons are involved or not.
▪This model for acid-base reactivity was developed for solvents
that can dissociate into cations (acid) and anions (base)

2H2O(l) ⇌ H3O+(aq) + OH-(aq)

cation anion
acid base
 Solvent system definition
In this definition, an acid is a solute that produces +ve solvent ions (increases
the concentration of the solvent cation) and a base is a substance that
produces –vely charged solvent ions (increases the concentration of the
solvent anion
Example:
Recall the autoionization of ammonia 2NH3(l) ⇌ NH4+(sol) + NH2-(sol)
acid base

In liquid ammonia, a
substance that produces Treating CH3COOH as the solute and NH3 the solvent:
NH4+ ions is an acid and
a substance that NH3(l) + CH3COOH (l)⇌ CH3COO- (sol) + NH4+(sol)
produces amide ions, ACID
NH2- would be a base INCREASES NH4+ CONCENTRATION
Let’s look at another example . . .
The solvent BrF3 is an aprotic/non-protic solvent and
autoionizes via the equation:
2BrF3(l) ⇌ BrF2+(sol) + BrF4-(sol)

How would the salt BrF2AsF6 behave in BrF3 solvent?

How would the salt KBrF4 behave in BrF3 solvent?
 2BrF3(l) ⇌ BrF2+(sol) + BrF4-(sol)
In solution the salts will dissociate in the following way
BrF2AsF6 → BrF2+ + AsF6- Is the salt an acid or a base?

Is the salt an acid or a base?

KBrF4 → K++ BrF4-
Solvent system definition
Broadens the understanding of acid/base characteristics:
For some substances, acidic or basic character can only be
specified in relation to a particular solvent

Example:
CH3COOH(l) + H2O(l) ⇌ H3O+(aq) + CH3COO-(aq)
CH3COOH(l) + H2SO4(l) ⇌ CH3C(OH)OH+(sol) + HSO4-(sol)

How does acetic acid CH COOH (solute) behave in each solvent?

3
 Solvent system definition
For some substances, acidic or basic character can only be
specified in relation to a particular solvent

Example:
CH3COOH(l) + H2O(l) ⇌ H3O+(aq) + CH3COO-(aq)
CH3COOH(l) + H2SO4(l) ⇌ CH3C(OH)OH+(sol) + HSO4-(sol)
How does acetic acid CH COOH behave in each solvent?
3
It is an acid in water (increases the concentration of the solvent cation)
It is a base in sulfuric acid! (increases the concentration of the solvent anion)
How else can we explain the relative behaviour of acetic acid in each?
Recap
❑First consider the Auto-dissociation or auto-ionization of solvent:
oFor protic solvents: transfer of a proton one solvent molecule to the next,
generating the protonated cation of the solvent and the deprotonated anion
of the solvent.
oFor aprotic solvents: transfer of an atom (e.g. F- in BrF3) to generate cations
and anions of the solvent

❑The principle of the solvent system definition:

An acid is a solute that produces +ve solvent ions (increases the
concentration of the solvent cation) and a base is a substance that
produces –vely charged solvent ions (increases the concentration of the
solvent anion)
 Lux Flood Definition
An acid is an oxide ion (O2-) acceptor
A base is an oxide ion donor.

This acid-base theory was a revival of the oxygen theory of acids and
bases, proposed by German chemist Hermann Lux in 1939 and further
improved by Håkon Flood circa 1947.

Take a look at this video as a preview to this lecture: https://www.youtube.com/watch?v=Nf8cuvl62Vc&t=1s

Consider ways that human practices impact the environment. What are some ways that we can remedy or reduce
these effects?
Acidic or basic oxides
How would you classify these oxides based on the Lux
Flood definition?

Na2O (s) + H2O(l) → 2 Na+(aq) + 2 OH- (aq)

SO2 (g) + H2O(l) → H2SO3(aq)
Acidic and basic oxides
❑Oxides are not obvious proton donors or acceptors
❑Their acidic and basic behaviour relate to their reaction
with water, which can generate H3O+(aq) or OH-(aq).
E.g.
❖Sodium oxide (Na2O) is a basic oxide - it reacts with
water to form an alkaline solution of NaOH
❖Sulfur dioxide (SO2) is an acidic oxide – it reacts with
water to form an oxoacid
Acidic and basic oxides
❑Na2O (s) + H2O(l) → 2 Na+(aq) + 2 OH- (aq)

❑SO2 (g) + H2O(l) → H2SO3(aq)

H2SO3(aq) + H2O(l) ⇌ HSO3-(aq) + H3O+(aq)
Reactions of basic and acidic oxides
Basic oxides react with acids
O2- donor
❑Na2O (s) + 2HCl (aq) → 2NaCl(aq) + H2O (l)

Acidic oxides react with bases

❑SO2 (g) + OH- (aq) → HSO3-(aq) O2- acceptor
Lux-Flood Definition

The nature of basic and

acidic oxides changes as
you move from left to right
across the periodic table

Look at the trend in the table.

What are some general comments
that you can make about elements
that form basic and acidic oxides?
Acidic and Basic Oxides
Oxides of metallic elements
are generally basic oxides,
and oxides of nonmetallic
elements acidic oxides.
❑ CaO + H2O → Ca(OH)2
CaO is called a basic anhydride
Is MgO a basic anhydride?
❑ CO2 +H2O → H2CO3
CO2 is called an acid anhydride

Acid-base reaction between a basic oxide and an acidic oxide

❑ CaO + CO2 → CaCO3

Identify the acid and base using Lux-Flood definition
Acidic and Basic Oxides
Oxides of metallic elements
are generally basic oxides,
and oxides of nonmetallic
elements acidic oxides.
❑ CaO + H2O → Ca(OH)2
CaO is called a basic anhydride
Is MgO a basic anhydride?
❑ CO2 +H2O → H2CO3
CO2 is called an acid anhydride

Acid-base reaction between a basic oxide and an acidic oxide

❑ CaO + CO2 → CaCO3
The base (CaO) donates O2- to the acid (CO2) to form CO32-
https://people.wou.edu/~courtna/ch412/oxides.html
 Amphoteric oxides
❑Some oxides can react with both acids and bases
❑Aluminium oxide is an amphoteric oxide

❑Al2O3 (s) + 6HCl (aq) → 2AlCl3 (aq) + 3H2O (l)

❑Al2O3 (s) + 2NaOH (aq) + 3H2O → 2Na[Al(OH)4] (aq)
❑Many metals (such as copper, zinc, tin, lead, aluminium, and
beryllium) form amphoteric oxides or hydroxides. Amphoterism
depends on the oxidation state of the oxide.
❑Amphoteric oxides,
are located along the
diagonal line between
the two extremes.
❑The word has Greek
origins, amphoteroi (ά
μφότεροι) meaning
"both".
Trends in the behaviour of oxides

❑Basicity of the oxides increase with

increasing atomic number down a
group:
BeO < MgO < CaO < SrO < BaO
❑Acidity increases with increasing
oxidation state of the element:
MnO < Mn2O3 < MnO2 < Mn2O7
in keeping with the increase in
covalent character.
Let’s practice
1. How does Lux-Flood define:
a) An acid
b) A base
2. Identify the reactants as acid or base and provide some indication of the
expected product
a) MgO (?) + CO2 (?) ⇌ ?

b) CaO (?) + SiO2 (?) ⇌ ?

Bonus: NO3- (?) + S2O72- (?) ⇌ NO2+ + 2 SO42- (identify the acid and base)