DEPARTMENT OF CHEMISTRY

FACULTY OF SCIENCES

CHEMISTRY 221: Inorganic Chemistry (I)

Chapter 3
Acids, Bases
Solvents & Oxoanions
Dr. Adnan S. Abu-Surrah
Professor of Inorganic & Materials Chemistry
E-mail: asurrah@hu.edu.qa
 Acids and Bases: Basic Concepts
• Acids: react with bases, taste sour, turn blue litmus red, dissolve metals to
produce H2
• Bases: react with acids, taste bitter, turn red litmus blue, feel slippery.

Arrhenius Classification:
• Acids ionize to give H+(aq) also written as H3O+(aq)
• Bases ionize to give OH-(aq).
All are strong electrolytes and therefore strong acids.

Examples of Strong Acids and Bases

• Acids: HCl, HNO3, H2SO4, HClO4, etc
• Bases: NaOH, KOH, Ca(OH)2, etc.
– Metal Oxides + Water Produce Bases: BaO(s) + H2O(l) → Ba(OH)2(aq)
– Non-metal Oxides + Water Produce Acids: SO3(g) + H2O(l) → H2SO4(aq)
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 Bronsted Acids & Bases
 The Arrhenius Concept cannot explain why ammonia,
NH3, is a base since it is a weak electrolyte and has no
OH-
• A Bronsted acid is a proton donor and
a Bronsted base is a proton acceptor
Examples: Proton transfer between acids and bases

HCl + H2O ----> H3O+ + Cl-

conjugate acid conjugate base

NH3 + H2O - NH4+ + OH-

In the first reaction, water acts as a base. In the second water

acts as an acid. Thus it is amphiprotic (Amphiprotic describes
a substance that can both accept and donate a proton or H+). 3
 Conjugate acids and bases

When a species donates a proton, it becomes the

conjugate base; when a species gains a proton, it
becomes the conjugate acid. Conjugate acids and
bases are in equilibrium in solution.

Example

Bronsted Conjugate
acid base
• Water undergoes autoionization:

H2O + H2O  H3O+ + OH- and creates

conjugate acid-base pairs. 4
Acids vs Bases in our everyday life

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 The strengths of Brønsted acids
The strength of a Brønsted acid is measured by its
acidity constant, Ka .
The strength of a Brønsted base is measured by its
basicity constant, Kb.
The stronger the base, the weaker is its conjugate acid.

The strength of a Brønsted acid, such as HF, in aqueous solution is

expressed by its acidity constant (or ‘acid ionization constant’), Ka:

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 Acid and base strength
• For strong acids, Ka will be large because the acid nearly completely
dissociates and the denominator is small. For very weak acids it will be
small.

• Ka can also range for many orders of magnitude, so it is useful to define

a logarithmic measure of acid ionization strength. This is called the pKa
defined by

• which ranges typically from -11 for very strong acids to 14 for water.

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 Acid and base strength
Example:

• Consider the acid, HCN:

• The acid ionization constant is

• and the pKa is

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 Acid and base strength
• By analogy, there is a base ionization constant Kb.
• Example:

How do we calculate the value of Kb? Note that, since

the above expression becomes:

• Since the values of Ka are tabulated, we do not need

to tabulate Kb separately, as they are related by:
•

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 Acid and Base Strength
• Since Ka for NH4+ = 5.6 x 10-10 , the value of Kb is

• Very little ammonia protonated

• If Ka is large, corresponding to a strong acid, then the
conjugate base will be weak, since Kb will be small and
vice-versa.

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11
 Strong and Weak Acids and Bases
• When two bases compete for protons, the stronger base is
favored in equilibrium. This can be seen in the following
example:
• The equilibrium constant K for this reaction is

• The two bases competing for proton are F- and CN-. The
above reaction is actually the overall reaction produced from
the two acid dissociation reactions by subtraction of the
chemical equations, rather than by addition:

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 Strong and Weak Acids and Bases
• When two reactions are subtracted, the equilibrium
constants must be divided. The two acid ionization
constants are:

• and their ratio produces the equilibrium constant K

for the overall reaction
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 Strong and Weak Acids and Bases
• Then K can be computed from the ratio of the acid
ionization constants

• Since K is large, the products in the overall reaction

are favored, meaning that there will be a large
concentration of dissociated HF and not much
dissociated HCN
• So since CN- is the stronger base, it consumes most
of the protons donated by HF producing the acid
HCN and a high concentration of the weak base F- .
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 Strong and Weak Acids and Bases

• Strong acid: pKa <0:

• Fully deprotonated

• Weak acid: pKa > 0:

• Weakly deprotonated

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 Polyprotic Acids Apolyprotic acid is a
substance that can donate
H2S more than one proton.
H2S + H2O HS- + H3O+

pKa1 = 7.04

HS- + H2O S-2 + H3O+

pKa2 = 19

Second acidity constant (Ka) is almost always smaller than

first one
Reason: -- in second deprotonation the proton has to separate
from more negative charged species.
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17
 Acid-Base Equilibria:
Leveling Effect of Protonic Solvents
• An acid that is weak in water may appear strong in a solvent
that is a more effective proton acceptor, and vice versa.
• In any solution, the solvent is always the substance present in
the largest amount
• Protonic solvents (water, liquid ammonia, and glacial acetic
acid) will engage in acid-base reactions.
• When an acid which is stronger than the conjugate acid of
water, such as hydrochloric acid, is added to water the
stronger acid will react with water to give the weaker acid
which is the aquated proton or hydronium ion, H3O+:
HCl(g) + H2O --> H3O+(aq) + Cl-(aq).
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 Acid-Base Equilibria: Leveling Effect of Protonic Solvents
• All acids which are stronger than the hydronium ion will
react with water to quantitatively produce hydronium
ion, and so their strength will be leveled to that of the
hydronium ion -- levelling effect
• the strongest acid which can exist is the hydronium
ion. All others will be levelled to the hydronium ion
by reaction.
• In aqueous solution hydrochloric acid, sulfuric acid,
perchloric acid, and nitric acid are all equally strong.

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 Acid-Base Equilibria: Leveling Effect of Protonic Solvents
Glacial acetic acid: Glacial acetic acid can be used to
show that hydrogen chloride is a weak acid in glacial
acetic acid.

Methanol is also a protonic solvent in which some of

the acids which are strong (completely dissociated) in
water are found partially dissociated in methanol.

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 Solvent Leveling

The acid base discrimination windows of a variety of solvents. In each

case, the width of the window is proportional to the autoprotolysis
constant pK of the solvent
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Characteristics of Brønsted acids

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 Periodic Trends in Aqua Acid Strength

1. The strengths of aqua acids Increase with

increasing of +ive charge of the central atom ion
(high charge)
– More charge, more is the electric pull in H+ and H+
thus more willing to leave

2. Increase with decrease of ionic radius of central

metal ion (small radius)
– Less is size, more is effect on oxygen and more H+
possibility to leave 23
 Simple Oxoacids
• Mononuclear Oxoacids: One atom other than H & O
– Examples: H3PO4, H2SO4, H2CO3 etc
• Substituted Oxoacids: Substituted atoms may make
them weaker or stronger
• Examples: S(O)2(OH)F is stronger than S(O)2 (OH)2 as F is
more electronegative
• S(O)2(OH)(NH2) is weaker than S(O)2(OH)2
as NH2 can donate electrons (basicity)

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 Simple Oxoacids
• The strengths of a series of oxoacids containing a
specific central atom with a variable number of oxo and
hydroxyl groups are summarized by Pauling’s rules.

• In general, for any series of oxoacids, the one with the

most O atoms is the strongest.
•
• For example, the acid strengths of the oxoacids of
chlorine decrease in the order HOCl4 (O3Cl(OH) > HClO3
> HClO2 > HClO. Similarly, H2SO4 (O2S(OH)2) is stronger
than H2SO3 (OS(OH)2) and HNO3 is stronger than HNO2.
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Pauling’s Rule: Observed strengths of mononuclear
oxoacids can be systematized by using two rules:

1. For the oxoacid the OpE(OH)q, pKa = ~8-5p,

p = number of unprotonated oxygen atoms
HO-Cl, p = 0, so predicted pKa = ~8, actual = 7.2
Rule 1 predicts that neutral hydroxoacids with p= 0 have pKa ≈ 8, acids
with one oxo group have pKa ≈ 3, and acids with two oxo groups have
pKa ≈ –2. For example, sulfuric acid, O2S(OH)2, has p=2 and q= 2, and
pKa1 ≈ –2 (signifying a strong acid). Similarly, pKa2 is predicted to be
+3, although comparison with the experimental value of 1.9 reminds us
that these rules are only approximations.

2. The successive pKa values of polyprotic acids increase

by 5 units for each successive proton transfer
H3PO4 = pKa1 = 2.1, pKa2 = 2.1 + 5 = 7.1;
actual 7.4
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Table 4.3

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Nonmetallic Oxides

Metallic Oxides

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29
 3The solvent system definition of acids & bases
• The solvent system definition of acids and bases extends the
Brønsted – Lowry definition to include species that do not
participate in proton transfer.

• The General Solvent System Definition is an extension to any

autoionizing solvent:
– An acid is defined as a substance increasing the concentration of
the characteristic cation of the solvent.
– One that increases the concentration of the characteristic anion
(or decreases the concentration of the cation) is a base.

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Here acids are solute that increases the concentration of cation &
bases are solute that increases the concentration of anion .

The salt BrF2SbF6 is soluble in BF3. Is it an acid or base in this solvent?

From the autoinizaion, BrF2 cation is produced. As the salt increases the
concentration of the cations of the solvent, it is defined as an acid in the solvent
system.

Self-test: Is the salt KBrF6 an acid or base in BrF3?

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 4Hard and Soft acids and bases
• Hard acids include transition metals and main group
elements that are small and highly charged e.g. Li+, Mg+2,
Al+3, Fe+3
• Soft acids include transition metals and main group
elements that are large and not as highly charged e.g. Tl+,
Ag+, Pb+3
• Hard bases generally contain main group elements that are
small and very electronegative e.g. F-, R-O-, NH3, Cl-
• Soft bases generally contain main group elements that are
large and weakly electronegative e.g. I-, SR2, AsR3, R-NC
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Hard and Soft Ions

• In general, hard acids tend to form compounds with

hard bases and soft acids tend to bind to soft bases.

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Hard and Soft Ions

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 5Lewis Acids & Bases

• acid => electron pair acceptor

• base => electron pair donor

• Broadest of the common acid-base theories

– In kinetic terminology, a Lewis acid is an electrophile and a
Lewis base is a nucleophile.

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 Lewis Acids & Bases

• All Lewis acids are also Bronsted or Arrhenius acids:

the lone pair on water acts as a proton acceptor and
creates H3O+(aq).

• General types of Lewis acid-base reactions:

– Adduct formation (combination): I2 + I- ---> I3-

– Single replacement: SO2•DMSO + NH3 ---> SO2•NH3 + DMSO

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We meet many examples of Lewis acids later, but we should be alert to
the following possibilities:

Amolecule with an incomplete octet of valence electrons can complete its

octet by accepting an electron pair.A prime example is B(CH3)3, which
can accept the lone pair of NH3 and other donors:

Hence, B(CH3)3 is a Lewis acid.

A molecule or ion may be able to expand its valence shell (or simply be
large enough) to accept another electron pair. An example is the
formation of the complex [SiF6]2– when two F– ions (the Lewis bases)
bond to SiF4 (the acid).
SiF4 + 2 F-  [SiF6]2-

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 Reactions and properties of Lewis acids and bases
1

2
Catalyst:
Lewis acid

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Friedel-Craft Alkylation and acylation Reactions

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 Solvents
Solvent Properties
Their usefulness is a function of:
1. Liquid temperature range
2. Dielectric constant
3. Its Lewis acid/base properties
4. Its Brønsted/Lowry acid base properties
5. Autodissociations properties

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 Solvents as acids and bases
Solvent Properties
1. Liquid temperature range
• The most useful are liquid at room temperature but we
often need solvents to go up to high or low temperatures.
• The range is large for DMF and propane-1,2-diol
carbonate.
• Ammonia is a good solvent for many reactions but it
boils at about -33oC.
• Hydrogen fluoride, which boils at about 20 oC is also
useful, but very corrosive.
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Dielectric Constant
This factor is important if the solvent is to dissolve
ionic compounds. Water happens to have a very high
dielectric constant (82) and is probably the best all-round
solvent for ionic compounds that we have.
The key formula here is:
F = q+q-/4πɛr2 (ɛr) called DIELECTRIC CONSTANT, q+ and q- are
two point charges placed at a distance of r from each other,
electrostatic force between them is F

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Lewis Acid/Base Properties
• The extent to which the solvent can act as a ligand determines
how good a solvent will be.
• In the crystal lattice with simple ions, the anions effectively
complex the cations and vice versa. The solvent will have to do a
better job.
• The effective complexation of the cations by solvent is crucial, so it
is the Lewis basicity of the solvent that is more important. For
common solvents the basicity is:

(CH3)2SO > H(CO)N(CH3)2= H2O > (CH3)2CO >

(CH3CHCH2)O2CO > (CH3)2SO2 > CH3NO2 > C6H5NO2 »
CH2Cl2 43
Protic Solvents:
• These solvents contain protons which can be ionized, in
other words the solvent is a Brønsted acid.
• Examples are H2O, HF, H2SO4, HCN and even NH3.
• Autodissociation also known as autoionization.
• Examples in protic solvents are:

2H2O = H3O+ + OH-

3HF = H2F+ + HF2-
2H2SO4 = H3SO4+ + HSO4-
2H3N = H4N+ + NH2-
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Aprotic Solvents
Such solvents fall into three broad classes:
1. Non-polar, or weakly polar solvents which do not
dissociate and are not strongly coordinating.
Examples:
• Hydrocarbons and CCl4.
• They are poor solvents for everything
except like substances, i.e. other nonpolar
molecules.
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Aprotic Solvents:
2. Strongly solvating (usually polar) solvents which do not
dissociate.
Examples:
• acetonitrile ( CH3CN)
• N,N-dimethyformamide (DMF, H(CO)N(CH3)2),
• dimethyl sulphoxide (DMSO (CH3)2SO),
• tetrahydrofuran (THF C4H8O)
• liquid sulphur dioxide (SO2).

 They are similar in being very strongly coordinating towards cations

although SO2 forms an adduct with acetonitrile.
 The dielectric constants can vary quite a bit (DMSO = 45, THF = 7.6)
which will govern their ability to dissolve ionic materials. 46
3. Highly polar and autoionizing solvents. Examples are:
2BrF3 = BrF2+ + BrF4-
2NO2 = NO+ + NO3-
2Cl3PO = Cl2PO+ + Cl4PO-
Molten Salts
These are the extreme case of autoionizing solvents.
Generally they will be very high temperature systems but
lower temperatures can be attained by the right eutectic
mixtures (example on next slide)

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Examples:
LiNO3/NaNO2/KNO3 mixtures can reach as low as 130oC
(C2H5)2NH2Cl melts at 215oC ; [N,N-RR'N2C3H3]+Cl- with
AlCl3 can be liquid at room temperature.

A eutectic mixture is defined as a mixture of two

or more components which usually do not interact
to form a new chemical compound but, which at
certain ratios, inhibit the crystallization process of
one another resulting in a system having a lower
melting point than either of the components

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Chemistry of some anions
“Coordination behavior”

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Simple Anions

K2[Ni(CN)4]:The distance from the nickel

atom to the carbon is 1.87 Å, and the
carbon-nitrogen distance is 1.16 Å

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Discrete Oxo Anions

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Discrete Oxo Anions

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Polymeric Oxo Anions

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Complex Anions

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