3.

0 BASIC CONCEPTS OF CHEMICAL BONDING

 Chemical bond: is a force that acts between two or more atoms to hold them together as a
stable molecule.
 There are three fundamental types of bonds;
(1) Ionic or Electrovalent bond
(2) Covalent bond
(3) Coordinate covalent bond
 A fourth type of bond found in metals, is the metallic bond
 Valence: is the number of bonds formed by an atom in a molecule.
 Electronic theory of valence: In chemical bond formation, atoms interact by losing,
gaining, or sharing of electrons so as to acquire a stable noble gas configuration.
 Octet theory of Valence. Stated as atoms interact by electron-transfer or electron-sharing,
so as to achieve the stable outer shell of eight electrons.

Lewis dot symbols

 When atoms interact to form a chemical bond, only their outer regions are in contact. Thus,
chemical bonding, is primarily concerned with the valence electrons of the atoms.
 To keep track of valence electrons in a chemical reaction, and to make sure that the total
number of electrons does not change, chemists use a system of dots devised by Lewis called
Lewis dot symbols.
 A Lewis dot symbol consists of the symbol of an element and one dot for each valence
electron in an atom of the element.

3.1 Ionic bonding

 Ionic or Electrovalent bond: The electrostatic attraction between the cation (+) and anion
(–) produced by electron-transfer. OR is the electrostatic force that holds ions together in
an ionic compound

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  Consider lithium fluoride:

For convenience, imagine that this reaction occurs in separate steps

Step 1: first the ionization of Li:

Step 2: acceptance of an electron by F:

Step 3: the two separate ions joining to form a LiF unit:

NB: that the sum of these three equations is

 The ionic bond in LiF is the electrostatic attraction between the positively charged lithium
ion and the negatively charged fluoride ion. The compound itself is electrically neutral.

3.1.1 Conditions for formation of ionic bond

 The conditions that favour ionic bond formation are:

(1) Number of valence electrons

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  Atoms that form cations should possess 1, 2 or 3 valence electrons, while the atom that
form anions should have 5, 6 or 7 valence electrons. The elements of group IA, IIA and
IIIA satisfy this conditions for forming cations and those of groups VA, VIA, and VIIA
satisfy this condition for forming anions.

(2) Net lowering of Energy

 A stable ionic compound is only formed when there a net lowering of the energy. Thus,
the process of forming an ionic compound must release as a result of the electron transfer
and formation of ionic compound. The steps involved in ionic compound formation are:
a) The removal of electron from atom A (A – e– → A+)
 This requires energy input i.e. ionization energy (IE). I.E should be low.
b) The addition of an electron to B (B + e– → B– )
This step releases energy, i.e. the electron affinity. The electron affinity should be high.
c) The electrostatic attraction between A+ and B– in the solid compound releases energy,
which is the electrical energy. This energy should also be high.
 If the energy released in steps (b) and (c) is greater than the energy consumed in step (a),
the overall process of electron transfer and formation of ionic compound results in a net
release of energy.
 Therefore, ionisation of A will occur and the ionic bond will be formed.

(3) Electronegativity difference of cation and anions

 The atoms/elements forming the ionic bond should have greatly different
electronegativities. The difference in their electronegativities should be 2 or more.

3.1.2 Factors governing the formation of ionic bond

(1) Ionisation Energy

 The metal should have low ionisation energy so that it forms the cations easily. The lower
the ionisation energy the greater the tendency of the metal atom to form its cation and hence
greater will be the ease of formation of ionic bond. Alkali metals and alkaline earth metals
form ionic bonds easily since they have low I.E.
(2) Electron Affinity

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The atom which accepts the electron and changes into anion should have high electron affinity.

 The higher the electron affinity the more is the energy released and consequently the more
stable will be the anion formed. The elements of group VI A and VII A have, in general,
higher electron affinity and have high tendency to form ionic bonds.
(3) Lattice Energy
 After the formation of cations and anions separately, they combine to form ionic
compound. In this process, energy, called Lattice Energy is released

 Lattice Energy is the amount of energy released when one mole of an ionic compound is
formed from its cations and anions. OR the energy required to completely separate one
mole of ionic compound into gaseous ions.

3.1.3 Lattice energy of ionic compounds

 Lattice energy is a measure of the stability of ionic compounds and its value be used to
explain the formula of ionic compounds. The greater the lattice energy, the greater the
strength of ionic bond.
 The value of lattice energy depends two factors:

(a) Size of the ions

 The force of attraction between the cations and anions is inversely proportional to the
square of the distance between them. The size of cations and anions should be as small as
possible in order to have greater force of attraction between.

(b) Charge on Ions

 Greater the charge on ions greater will be the force of attraction between them and,
therefore, greater will be the strength of the ionic bond.

Coulomb’s law

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  Lattice energy cannot be measured directly. However, if we know the structure and
composition of an ionic compound, we can calculate the compound’s lattice energy by
using Coulomb’s law
 Statement of the Coulomb’s law:
The potential energy (E) between two ions is directly proportional to the product of
their charges and inversely proportional to the distance of separation between them.

Consider LiF compound:

 For a single Li+ ion and a single F– ion separated by distance r, the potential energy of the
system is given by:

Where 𝑄𝐿𝑖 + and 𝑄𝐹− Q are the charges on the Li+ and F– ions and k is the proportionality
constant.
 Because 𝑄𝐿𝑖 + is positive and 𝑄𝐹− is negative, E is a negative quantity, and the formation
of an ionic bond from Li+ and F– is an exothermic process.
 Consequently, energy must be supplied to reverse the process (in other words, the lattice
energy of LiF is positive), and so a bonded pair of Li+ and F–ions is more stable than
separate Li+ and F–ions.

3.1.4 Characteristics of ionic compounds

 Ionic compounds have common properties because the (+) and (–) ions are held by
electrostatic forces in a crystal lattice. Each ion is surrounded by the opposite ions in
alternate positions in a definite order in all directions.

(1) Solids at Room Temperature

They have strong electrostatic forces between the opposite ions, these ions are locked in their
allotted positions in the crystal lattice. Since they lack the freedom of movement characteristic of
the liquid state, they are solids at room temperature.

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(2) High Melting Points

Since the (+) and (–) ions are tightly held in their positions in the lattice, only at high temperature
do the ions acquire sufficient kinetic energy to overcome their attractive forces and attain the
freedom of movement as in a liquid. Consequently, ionic compounds have high melting points (or
boiling points).

(3) Hard and brittle

The crystals of ionic substances are hard and brittle. Their hardness is due to the strong electrostatic
forces which hold each ion in its allotted position.

These crystals are made of layers of (+) and (–) ions in alternate positions so that the opposite ions
in the various parallel layers lie over each other. When external force is applied to a layer of ions
(Fig. 3.1), with respect to the next, even a slight shift brings the like ions in front of each other.
The (+) and (–) ions in the two layers thus repel each other and fall apart. The crystal cleaves at
that point.

Figure 3.1: (a) Two layers of (+) and (-) ions in a crystal. (b) When force is applied to one layer it
slips over the other so that similar ions come above one another and electrical repulsions between
them cause cleavage of the crystal.

(4) Soluble in water

When a crystal of an ionic substance is placed in water, the polar water molecules detach the (+)
and (–) ions from the crystal lattice by their electrostatic pull. These ions then get surrounded by
water molecules and can lead an independent existence and are thus dissolved in water. By the
same reason, non-polar solvents like benzene (C6H6) and hexane (C6H14) will not dissolve ionic
compounds.

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Figure 3.2: Solvation of NaCl in water.

(5) Conductors of electricity

Solid ionic compounds are poor conductors of electricity because the ions are fixed rigidly in their
positions. In the molten state and in water solutions, ions are rendered free to move about. Thus
molten ionic compounds or their aqueous solutions conduct a current when placed in an
electrolytic cell.

(6) Do not exhibit isomerism

The ionic bond involving electrostatic lines of force between opposite ions, is non-rigid and non-
directional. The ionic compounds, therefore, are incapable of exhibiting stereoisomerism.

(7) Ionic reactions are fast

Ionic compounds give reactions between ions and these are very fast.

3.2 Covalent bond

 A covalent bond is a bond that results from the sharing of electrons between atoms.
 Covalent bond, a bond in which two electrons are shared by two atoms.
 Covalent compounds are compounds that contain only covalent bonds

Formation of covalent bond

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 Consider the H–H bond in the H2 molecule as an example. As two hydrogen atoms come closer
together, electrostatic interactions begin to develop between them. The two positively charged
nuclei repel each other and the two negatively charged electrons repel each other, but each
nucleus attracts both electrons. If the attractive forces are stronger than the repulsive forces, a
covalent bond is formed, with the two atoms joined together and the two shared electrons
occupying the region between the nuclei.

Formation of a molecule by combination of two atoms (a) Atoms at a large distance, no

interaction.(b) Atoms coming closer, interaction begins (c)Bonded atoms.

The forces acting between two atoms when they come closer. NA and NB represent the nuclei
of the two atoms while eA and eB represent their electrons respectively.
In essence, the shared electrons act as a kind of “glue” to bind the two nuclei together into an
H2 molecule. Both nuclei are simultaneously attracted to the same electrons and are therefore
held together, much as tug-of-war teams pulling on the same rope are held together.
The magnitudes of the various attractive and repulsive forces between nuclei and electrons in
a covalent bond depend on how close the atoms are. If the hydrogen atoms are too far apart,
the attractive forces are small and no bond exists. If the hydrogen atoms are too close together,
the repulsive interaction between the nuclei becomes so strong that it pushes the atoms apart.

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 Thus, there is an optimum distance between nuclei called the bond length where net attractive
forces are maximized and the H–H molecule is most stable.

3.2.1 Conditions for formation of covalent bond

 The conditions favourable for the formation of covalent bonds are:

(1) Number of valence electrons

 Each of the atoms forming the molecule should have 5, 6 or 7 valence electrons so that
both achieve the stable octet by sharing 3, 2 or 1 electron-pair. H has one electron in the
valence shell and attains duplet. The non-metals of groups VA, VIA and VIIA respectively
satisfy this condition.

(2) Equal electronegativity

 The atoms should both have equal or nearly equal electronegativity so that no electron
transfer takes place, hence electron sharing occurs. This can be strictly possible only if both
the atoms are of the same element.

(3) Equal sharing of electrons

 The atoms should have equal (or nearly equal) electron affinity so that they attract the
bonding electron pair equally. Thus equal sharing of electrons will form a nonpolar
covalent bond. Of course, precisely equal sharing of electrons will not ordinarily occur
except when both atoms are atoms of the same element, for no two elements have exactly
the same electron affinity.

3.2.2 Characteristics of covalent compounds

 The atoms in a covalent molecule are firmly held by the shared electron pair, but the
individual molecules are attracted to each other by weak van der Waals forces (weak
intermolecular forces).
 The general properties of covalent compounds are;

(1) Gases, liquids or solids at room temperature

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  The covalent compounds are often gases, liquids or relatively soft solids under ordinary
conditions. This is so because of the weak intermolecular forces between the molecules.

(2) Low melting points and boiling points

 Covalent compounds have generally low melting points (or boiling points). The molecules
are held together in the solid crystal lattice by weak forces. On application of heat, the
molecules are readily pulled out and these then acquire kinetic energy for free movement
as in a liquid. For the same reason, the liquid molecules are easily obtained in the gaseous
form which explains low boiling points of covalent liquids.

(3) Neither hard nor brittle

 While the ionic compounds are hard and brittle, covalent compounds are neither hard nor
brittle.
 There are weak forces holding the molecules in the solid crystal lattice. A molecular layer
in the crystal easily slips relative to other adjacent layers and there are no ‘forces of
repulsion’ like those in ionic compounds. Thus the crystals are easily broken and there is
no sharp cleavage between the layers on application of external force.

(4) Soluble in organic solvents

 In general, covalent compounds dissolve readily in nonpolar organic solvents (benzene,

ether).
 The kinetic energy of the solvent molecules easily overcomes the weak intermolecular
forces.
 Covalent compounds are insoluble in water. Some of them (alcohols, amines) dissolve in
water due to hydrogen-bonding.

(5) Non-conductors of electricity

 Since there are no (+) or (–) ions in covalent molecules, the covalent compounds in the
molten or solution form are incapable of conducting electricity.

(6) Exhibit Isomerism

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  Covalent bonds are rigid and directional, the atoms being held together by shared electron
pair and not by electrical lines of force. This affords opportunity for various spatial
arrangements and covalent compounds exhibit stereoisomerism.

(7) Molecular reactions

 The covalent compounds give reactions where the molecule as a whole undergoes a
change.
 Since there are no strong electrical forces to speed up the reaction between molecules, these
reactions are slow.

3.3 Co-ordinate covalent bond

 Bond where the shared electron pair is supplied by one of the atom (a covalent bond in
which both electrons of the shared pair come from one of the two atoms (or ions). The
compounds containing a coordinate bond are called coordinate compounds.

3.5 Electronegativity
 In covalently bonded molecules having identical atoms e.g. H2, the electrons are equally
shared i.e., the electrons spend the same amount of time in the vicinity of each atom.
 However, in the covalently bonded molecules with different molecules e.g. HF molecule,
the H and F atoms do not share the bonding electrons equally because H and F are different
atoms:

 Experimental evidence indicates that in the HF molecule the electrons spend more time
near the F atom. Consequently the H—F is polar covalent bond or simply a polar bond
because the electrons spend more time in the vicinity of one atom than the other.
 Polar bonds can be thought of as being intermediate between a (nonpolar) covalent bond,
in which the sharing of electrons is exactly equal, and an ionic bond, in which the transfer
of the electron(s) is nearly complete.
 Electronegativity, is the ability of an atom to attract toward itself the electrons in a
chemical bond.
 Electronegativity is a relative, i.e. an element’s electronegativity can be measured only in
relation to the electronegativity of other elements.

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 In general, electronegativity increases from left to right across a period in the periodic table,
as the metallic character of the elements decreases.
 Within each group, electronegativity decreases with increasing atomic number, and
increasing metallic character.
o NB: that the transition metals do not follow these trends.
 The most electronegative elements—the halogens, oxygen, nitrogen, and sulfur—are found
in the upper right-hand corner of the periodic table, and the least electronegative elements
(the alkali and alkaline earth metals) are clustered near the lower left-hand corner.
 Atoms of elements with comparable electronegativities tend to form polar covalent bonds
with each other because the shift in electron density is usually small.
 An ionic bond forms when the electronegativity difference between the two bonding atoms
is 2.0 or more.
 This rule applies to most but not all ionic compounds. Sometimes chemists use the quantity
percent ionic character to describe the nature of a bond.
 A purely ionic bond would have 100 percent ionic character, although no such bond is
known, whereas a nonpolar or purely covalent bond has 0 percent ionic character.

Figure: Variation of electronegativity with atomic number. The halogens have the highest
electronegativities, and the alkali metals the lowest.

Electronegativity versus electron affinity

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  Electronegativity and electron affinity are related but different concepts. Both indicate the
tendency of an atom to attract electrons.
 However;
o Electron affinity refers to an isolated atom’s attraction for an additional electron,
whereas electronegativity signifies the ability of an atom in a chemical bond (with
another atom) to attract the shared electrons.
o Electron affinity is an experimentally measurable quantity, whereas
electronegativity is an estimated number that cannot be measured.

Exercise

Classify the following bonds as ionic, polar covalent, or covalent: (a) the bond in HCl, (b) the bond
in KF, and (c) the CC bond in H3CCH3.

Which of the following bonds is covalent, which is polar covalent, and which is ionic? (a) the bond
in CsCl, (b) the bond in H2S, (c) the NN bond in H2NNH2.

Strategy: follow the 2.0 rule of electronegativity difference and look up the values

3.4 Polar covalent bonds

 Consider a H2 or Cl2 molecule; the two electrons constituting the covalent bond are equally
shared by the two identical nuclei. Due to even distribution of (+) and (–) charge, the two
bonded atoms remain electrically neutral. Such a bond is called nonpolar covalent bond.
 However, when two different atoms are joined by a covalent bond as in HCl, the electron
pair is not shared equally.
 Polar covalent bond: A covalent bond in which electrons are shared unequally and the
bonded atoms acquire a partial positive and negative charge
 A molecule having partial positive and negative charge separated by a distance is
commonly referred to as a Dipole (two poles).
 The dipole of a bond is indicated by an arrow from positive to negative end with a crossed
tail as shown above in HF molecule.

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 The consequent charge separation can be represented as

Where the delta(δ) represents partial charge

 Since two atoms of different elements do not have exactly the same attraction for electrons
in a bond, all bonds between unlike atoms are polar to some extent. The amount of polarity
of a bond is determined by the difference of electronegativity (or tendency to attract
electrons) of the two bonded atoms. The greater the difference of electronegativity between
two atoms, greater the polarity.

Dipole Moments (μ)

 A quantitative measure of the polarity of a bond is its dipole moment (μ), which is the
product of the charge Q and the distance r between the charges:

 Q refers only to the magnitude of the charge and not to its sign, so μ is always positive.
 Dipole moments are usually expressed in debye units (D). The conversion factor is

Where C is coulomb and m is meter.

 Diatomic molecules containing atoms of different elements (for example, HCl, CO, and
NO) have dipole moments and are called polar molecules. Diatomic molecules containing
atoms of the same element (for example, H2, O2, and F2) are examples of nonpolar
molecules because they do not have dipole moments. For a molecule made up of three or
more atoms both the polarity of the bonds and the molecular geometry determine whether
there is a dipole moment. Even if polar bonds are present, the molecule will not necessarily
have a dipole moment. Carbon dioxide (CO2), for example, is a triatomic molecule, so its
geometry is either linear or bent:

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  The arrows show the shift of electron density from the less electronegative carbon
 atom to the more electronegative oxygen atom. In each case, the dipole moment of
 the entire molecule is made up of two bond moments, that is, individual dipole
 moments in the polar CPO bonds. The bond moment is a vector quantity, which
 means that it has both magnitude and direction. The measured dipole moment is equal
 to the vector sum of the bond moments. The two bond moments in CO2 are equal in
 magnitude. Because they point in opposite directions in a linear CO2 molecule, the
 sum or resultant dipole moment would be zero. On the other hand, if the CO2 molecule
 were bent, the two bond moments would partially reinforce each other, so that
 the molecule would have a dipole moment.
Consider the NH3 and NF3

Bond moments and resultant dipole moments in NH3 and NF3

Dipole moments can be used to distinguish between molecules that have the same formula but
different structures. For example, the following molecules both exist; they have the same
molecular formula (C2H2Cl2), the same number and type of bonds, but different molecular
structures:

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3.6 Hydrogen bonding (H-Bonding)
 Hydrogen bond: is the electrostatic attraction between an H atom covalently bonded to a
highly electronegative atom X and a lone pair of electrons of X in another molecule,
 When hydrogen (H) is covalently bonded to a highly electronegative atom X (O, N, F), the
shared electron pair is pulled so close to X that a strong dipole results.

 Since the shared pair is removed farthest from H atom, its nucleus (the proton) is practically
exposed. The H atom at the positive end of a polar bond nearly stripped of its surrounding
electrons, exerts a strong electrostatic attraction on the lone pair of electrons around X in a
nearby molecule.

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  Hydrogen bond is represented by a dashed or dotted line.

NB:

(1) Only O, N and F which have very high electronegativity and small atomic size, are capable
of forming hydrogen bonds.
(2) Hydrogen bond is longer and much weaker than a normal covalent bond. Hydrogen bond
energy is less than 10 kcal/mole, while that of covalent bond is about 120 kcal/mole.
(3) Hydrogen bonding results in long chains or clusters of a large number of ‘associated’
molecules like many tiny magnets.
(4) Like a covalent bond, hydrogen bond has a preferred bonding direction. This is attributed
to the fact that hydrogen bonding occurs through p orbitals which contain the lone pair of
electrons on X atom. This implies that the atoms X–H...X will be in a straight line.

3.6.1 Conditions for hydrogen bonding

 The necessary conditions for the formation of hydrogen bonding are

(1) High electronegativity of atom bonded to hydrogen

 The molecule must contain an atom of high electronegativity such as F, O or N bonded to

hydrogen atom by a covalent bond. The examples are HF, H2O and NH3.

(2) Small size of electronegative atom

 The electronegative atom attached to H-atom by a covalent bond should be quite small.
The smaller the size of the atom, the greater the attraction for the bonded electron pair.
 The polarity of the bond between H atom and electronegative atom should be high. This
results in the formation of stronger hydrogen bonding. For example, N and Cl both have
3.0 electronegativity. But hydrogen bonding is effective in NH3 in comparison to that in
HCl. It is due to smaller size of N atom than Cl atom.

3.6.2 Characteristics of hydrogen-bonded compounds

(1) Abnormally high boiling and melting points

(2) High solubilities of some covalent compounds

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 (3) Three dimensional crystal lattice
 Hydrogen bonds are directional and pretty strong to form three dimensional crystal lattice.
For example, in an ice crystal the water molecules (H2O) are held together in a tetrahedral
network and have the same crystal lattice as of diamond. This is so because the O atom in
water has two covalent bonds and can form two hydrogen bonds. These are distributed in
space like the four covalent bonds of carbon.
 Since there is enough empty space in its open lattice structure ice is lighter than water,
while most other solids are heavier than the liquid form.

3.7 Molecular geometry (VSEPR)

Molecular geometry is the three dimensional arrangement of atoms in a molecule
Molecular geometry affects a molecule physical and chemical properties e.g. mp, bp,
density and type of reactions it undergoes
In covalent bonds, the bonding electrons holds two atoms together
In polyatomic molecules, two or more bonds between the central atom and the surrounding
atoms, the repulsion between electrons in different bonding pairs causes them to remain as
far apart as possible. The geometry the molecule assumes (as defined by positions of all
atoms) minimizes the repulsion.
The approach to the study of molecular geometry (where there is minimum repulsion) is
called the Valence-Shell Electron Pair Repulsion (VSEPR) model/theory.
It accounts for geometric arrangement of electron pairs around a central atom in terms of
electrostatic repulsion between two electron pairs.

It states that: The electron pairs (both lone pairs and shared pairs, surrounding the central
atom will be arranged in space as far apart as possible to minimise the electrostatic
repulsion between them.

General rules that govern the use of VSEPR are;

(1) As far as electron repulsion is concerned, multiple bonds (double and triple bonds) can be
treated as a single electron-pair bond. They represent a single group of electrons.

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 (2) If a molecule has two or more resonance structures, we can apply VSEPR model to any of
them. Formal charges are usually not shown.
(3) Order of repulsions between lone pair and lone pair (lp-lp), lone pair and bonding pair (lp–
bp), and bonding pair and bonding pair (bp-bp) is; lp – lp > > lp – bp > bp – bp

When a molecule has lone pairs of electrons, the bonding electron pairs are pushed closer and thus
the bond angle is decreased

Rule 1 First find the number of bonding pairs of electrons in the molecule. The number of bonding
pairs of electrons in the molecule NH3 can be seen in the formula. There must be three
bonding pairs of electrons holding the three hydrogens onto the nitrogen.

Rule 2 Find the number of valence electrons (electrons in the outer energy level) on an atom of the
central atom (The one of which there is only one.) Nitrogen is in group V, so the nitrogen
has five electrons in the outer energy level.

Rule 3 Find the number of lone pairs on the central atom by subtracting the number of bonding
pairs (3) from the valence electrons (5) to find the number of electrons (2) that will make
up lone pairs of electrons. Divide this number by 2 to find the number of lone pairs, 2/2 =
1.

Rule 4 Distribute all the electron pairs around the central atom and learn the angles they will make
from molecules with no lone pairs.

Rule 5 Learn that the repulsion between lone pairs of electrons is greater than the repulsion
between bonding pairs, and subtract 2o from the bond angles for every lone pair.

Rule 6 Learn the names of the shapes. The shapes are named from the position of the atoms and
not the position of the orbitals.

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Rule for ions

If the molecule is an ion, e.g. ammonium [NH4]+, subtract 1 from the number of valence electrons
for every + charge on the ion and add 1 to the valence number for every - charge, then proceed as
before.

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Exercises: Determine the

1) Geometry of molecules in which the central atom has no lone pairs; ,AB2, e.g. BeCl2 AB3,
e.g BF3; AB4, e.g. CH4; AB5, PCl5; AB6, e.g. SF6.
2) Geometry of molecules in which the central atom has one or more lone pairs AB2E e.g.
SO2; AB3E, e.g. NH3; AB2E2 e.g. H2O; AB4E, e.g. SF4.
3) Geometry of molecules with more than one central atom e.g. methanol CH3OH.
 VSEPR is based on Lewis structures; provides simple and straightforward method for
predicting geometry of molecules. However, Lewis theory of chemical bonding has its own
limitation e.g. it explains bonding in H2 and F2 in same way but cannot explain why these have
very different bond energies and bond lengths.
Quantum mechanics provides more explanation on chemical bond formation and molecular
geometry. Two quantum mechanical theories are used to describe covalent bond formation
and the electronic structure of molecules:
Valence bond theory: assumes that electrons in a molecule occupy atomic orbitals of
individual atoms. It enables retain the picture of individual atoms taking part in chemical
bond formation.
Molecular orbital theory: assumes formation of molecular orbitals from
Neither of the theories perfectly explains all aspects of bonding but each contributes to the
current understanding of the observed molecular properties.

3.8 Resonance
Consider the Lewis structure for ozone (O3):

 The central atom satisfies the octet rule by placing a double bond between it and one of the
two end O atoms.
 The double bond can be placed at either end of the molecule, as shown by these two
equivalent Lewis structures:

 Each of these structures is called a resonance structure.

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  A resonance structure; is one of two or more Lewis structures for a single molecule that
cannot be represented accurately by only one Lewis structure.
 The double-headed arrow indicates that the structures shown are resonance structures.
 The term resonance itself means the use of two or more Lewis structures to represent a
particular molecule.
 Other examples:

Carbonate ion (𝐶𝑂3− )

Benzene

3.9 Exceptions to the Octet Rule

The Incomplete Octet
 In some compounds, the number of electrons surrounding the central atom in a stable
molecule is fewer than eight.

Examples:

 Beryllium hydride (BeH2): The electron configuration of beryllium is 1s22s2; it has two
valence electrons in the 2s orbital. In the gas phase,) exists as discrete molecules. The Lewis
structure of BeH2 is

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  Only four electrons surround the Be atom, and there is no way to satisfy the octet rule for
beryllium in this molecule.
 In BX3 compounds (B = boron, X= halogen) B is 1s22s22p1
 In boron trifluoride there are only six electrons around the boron atom

 The following resonance structures all contain a double bond between B and F and satisfy
the octet rule for boron even though in each case the negative formal charge is placed on
the B atom and the positive formal charge on the more electronegative F atom:

Odd-Electron Molecules
 Some molecules contain an odd number of electrons. example:
 nitric oxide (NO) and nitrogen dioxide (NO2):

The Expanded Octet

 Atoms of the second-period elements cannot have more than eight valence electrons around
the central atom, but atoms of elements in and beyond the third period of the periodic table
form some compounds in which more than eight electrons surround the central atom. In
addition to the 3s and 3p orbitals, elements in the third period also have 3d orbitals that can
be used in bonding. These orbitals enable an atom to form an expanded octet.
 Example; sulfur hexafluoride, a very stable compound has an expanded octet.
 The electron configuration of sulfur is [Ne]3s23p4.
 In SF6, each of sulfur’s six valence electrons forms a covalent bond with a fluorine atom,
so there are 12 electrons around the central sulfur atom:

23
3.10 Intermolecular Forces
 Intermolecular forces are attractive forces between molecules.
 The different types of intermolecular forces in condensed matter are:
1 Van der Waals forces; forces contributing to the van der Waal forces are
(i) Dipole-dipole,
(ii) Dipole-induced dipole,
(iii) Dispersion forces
NB: these three make up the van der Waal forces.
2 Ion-dipole forces: electrostatic forces between Ions and dipoles, (these are not
categorised as van der Waals forces).
3 Hydrogen bonding is a particularly strong type of dipole-dipole interaction (treated
as a separate category – seen earlier.).
Dipole-Dipole Forces
 Dipole-dipole forces are attractive forces between polar molecules, that is, between
molecules that possess dipole moments.
 Their origin is electrostatic, and they can be understood in terms of Coulomb’s law. The
larger the dipole moment, the greater the force. Figure 11.1 shows the orientation of polar
molecules in a solid.

Figure: Molecules that have a permanent dipole moment tend to align with opposite
polarities in the solid phase for maximum attractive interaction.
 In liquids, polar molecules are not held as rigidly as in a solid, but they tend to align in a
way that, on average, maximizes the attractive interaction.
Ion-Dipole Forces

24
 ion-dipole forces: forces that attract an ion (either a cation or an anion) and a polar
molecule to each other (Figure 11.2).

Figure 11.2 Two types of ion dipole interaction.

 The strength of this interaction depends on the charge and size of the ion and on the
magnitude of the dipole moment and size of the molecule.
 The charges on cations are generally more concentrated, because cations are usually
smaller than anions. Therefore, a cation interacts more strongly with dipoles than does an
anion having a charge of the same magnitude.
 Example of ion-dipole interaction - Hydration. Heat of hydration is the result of the
favourable interaction between the cations and anions of an ionic compound with water.
Figure 11.3 shows the ion-dipole interaction between the Na+ and Mg2+ ions with a water
molecule, which has a large dipole moment (1.87 D). Because the Mg2+ ion has a higher
charge and a smaller ionic radius (78 pm) than that of the Na1 ion (98 pm), it interacts more
strongly with water molecules. (In reality, each ion is surrounded by a number of water
molecules in solution.) Consequently, the heats of hydration for the Na+ and Mg2+ ions are
2405 kJ/mol and 21926 kJ/mol, respectively. Similar differences exist for anions of
different charges and sizes.

25
  Figure 11.3: (a) Interaction of a water molecule with a Na+ ion and a Mg2+ ion. (b) In
aqueous solutions, metal ions are usually surrounded by six water olecules in an octahedral
arrangement.
Dispersion Forces
What attractive interaction occurs in nonpolar substances? To learn the answer to this question,
consider the arrangement shown in Figure 11.4.

26
Figure 11.4 (a) Spherical charge distribution in a helium atom. (b) Distortion caused by the
approach of a cation. (c) Distortion caused by the approach of a dipole.

If we place an ion or a polar molecule near an atom (or a nonpolar molecule), the electron
distribution of the atom (or molecule) is distorted by the force exerted by the ion or the polar
molecule, resulting in a kind of dipole. The dipole in the atom (or nonpolar molecule) is said to be
an induced dipole because the separation of positive and negative charges in the atom (or
nonpolar molecule) is due to the proximity of an ion or a polar molecule. The attractive interaction
between an ion and the induced dipole is called ion-induced dipole interaction, and the attractive
interaction between a polar molecule and the induced dipole is called dipole-induced dipole
interaction.
The likelihood of a dipole moment being induced depends not only on the charge on the ion or the
strength of the dipole but also on the polarizability of the atom or molecule—that is, the ease with
which the electron distribution in the atom (or molecule) can be distorted. Generally, the larger the
number of electrons and the more diffuse the electron cloud in the atom or molecule, the greater
its polarizability. By diffuse cloud we mean an electron cloud that is spread over an appreciable
volume, so that the electrons are not held tightly by the nucleus.
Polarizability allows gases containing atoms or nonpolar molecules (for example, He and N2) to
condense. In a helium atom the electrons are moving at some distance from the nucleus. At any
instant it is likely that the atom has a dipole moment created by the specifi c positions of the
electrons. This dipole moment is called an instantaneous dipole because it lasts for just a tiny
fraction of a second. In the next instant the electrons are in different locations and the atom has a
new instantaneous dipole, and so on. Averaged over time (that is, the time it takes to make a dipole
moment measurement), however, the atom has no dipole moment because the instantaneous
dipoles all cancel one another. In a collection of He atoms, an instantaneous dipole of one He atom
can induce a dipole in each of its nearest neighbours (Figure 11.5). At the next moment, a different
instantaneous dipole can create temporary dipoles in the surrounding He atoms. The important
point is that this kind of interaction produces dispersion forces, attractive forces that arise as a
result of temporary dipoles induced in atoms or molecules. At very low temperatures (and reduced
atomic speeds), dispersion forces are strong enough to hold He atoms together, causing the gas to
condense.

27
Figure 11.5 Induced dipoles interacting with each other. Such patterns exist only momentarily;
new arrangements are formed in the
next instant. This type of interaction is responsible for the condensation of nonpolar gases.
The attraction between nonpolar molecules can be explained similarly.
A quantum mechanical interpretation of temporary dipoles was provided by Fritz London† in
1930. London showed that the magnitude of this attractive interaction is directly proportional to
the polarizability of the atom or molecule. As we might expect, dispersion forces may be quite
weak. This is certainly true for helium, which has a boiling point of only 4.2 K, or 2269°C. (Note
that helium has only two electrons, which are tightly held in the 1s orbital. Therefore, the helium
atom has a low polarizability.)
Dispersion forces, which are also called London forces, usually increase with molar mass because
molecules with larger molar mass tend to have more electrons, and dispersion forces increase in
strength with the number of electrons. Furthermore, larger molar mass often means a bigger atom
whose electron distribution is more easily disturbed because the outer electrons are less tightly
held by the nuclei. Table 11.2 compares the melting points of similar substances that consist of
nonpolar molecules.
As expected, the melting point increases as the number of electrons in the molecule increases.
Because these are all nonpolar molecules, the only attractive intermolecular forces present are the
dispersion forces.
In many cases, dispersion forces are comparable to or even greater than the dipole-dipole forces
between polar molecules. For a dramatic illustration, let us compare the boiling points of CH3F
(278.4°C) and CCl4 (76.5°C). Although CH3F has a dipole moment of 1.8 D, it boils at a much
lower temperature than CCl4, a nonpolar molecule. CCl4 boils at a higher temperature simply
because it contains more electrons.

28
As a result, the dispersion forces between CCl4 molecules are stronger than the dispersion forces
plus the dipole-dipole forces between CH3F molecules. (Keep in mind that dispersion forces exist
among species of all types, whether they are neutral or bear a net charge and whether they are polar
or nonpolar.)
Example 11.1 shows that if we know the kind of species present, we can readily determine the
types of intermolecular forces that exist between the species.

Exercise
What type(s) of intermolecular forces exist between the following pairs: (a) HBr and
H2S, (b) Cl2 and CBr4, (c) I2 and 𝑁𝑂3− (d) NH3 and C6H6?
Strategy Classify the species into three categories: ionic, polar (possessing a dipole moment), and
nonpolar. Keep in mind that dispersion forces exist between all species.

29
Molecules (or basic units) in each of the following species: (a) LiF, (b) CH4, (c) SO2.

30
Lewis dot structures of molecules and ions, Structures and shapes of simple molecules, polar and
non-polar molecules, intermolecular forces, electronegativity, bond character, simple ionic
compounds, structure of ionic solids. Resonance, Exceptions to octet rule, bond energy;

Reactions in aqueous solutions: acid-base reactions, redox reactions, precipitation reactions, Mole
concept, limiting and excess reagents, concentration and dilution of solutions.

31
4.0 REACTIONS IN AQUEOUS SOLUTIONS

 A solution is a homogeneous mixture of two or more substances.

 The solute is the substance present in a smaller amount, and the solvent is the substance
present in a larger amount.
 A solution may be gaseous (such as air), solid (such as an alloy), or liquid (seawater, for
example).
 Solutions prepared by dissolving substances in water, called aqueous solutions.
 Three major categories of reactions that occur in aqueous solutions: precipitation reactions,
acid-base reactions, and redox reactions

4.1 General Properties of Aqueous Solutions

Electrolytic Properties

 All solutes that dissolve in water fit into one of two categories: electrolytes and
nonelectrolytes.
 An electrolyte is a substance that, when dissolved in water, results in a solution that can
conduct electricity. A nonelectrolyte does not conduct electricity when dissolved in water
 Electrolyte are further categorised into two: strong and weak electrolytes.
 Strong electrolytes; solute is assumed to be 100 percent dissociated into ions in solution.
(Dissociation - the breaking up of the compound into cations and anions.)
 For instance, we can represent sodium chloride dissolving in water as

32
Figure 4.1: An arrangement for distinguishing between electrolytes and nonelectrolytes. A
solution’s ability to conduct electricity depends on the number of ions it contains. (a) A
nonelectrolyte solution does not contain ions, and the light bulb is not lit. (b) A weak electrolyte
solution contains a small number of ions, and the light bulb is dimly lit. (c) A strong electrolyte
solution contains a large number of ions, and the light bulb is brightly lit. The molar amounts of
the dissolved solutes are equal in all three cases.
 When an ionic compound such as sodium chloride dissolves in water, the three-
dimensional network of ions in the solid is destroyed. The Na+ and Cl– ions are separated
from each other and undergo hydration, the process in which an ion is surrounded by water
molecules arranged in a specifi c manner.

4.2 Precipitation Reactions

 Precipitation reaction, which results in the formation of an insoluble product - a precipitate.
 Precipitate: an insoluble solid that separates from the solution.
 Precipitation reactions usually involve ionic compounds
 Example, when an aqueous solution of lead(II) nitrate [Pb(NO3)2] is added to an aqueous
solution of potassium iodide (KI), a yellow precipitate of lead(II) iodide (PbI2) is formed:

33
  This reaction is an example of a metathesis reaction (also called a double-displacement
reaction), a reaction that involves the exchange of parts between the two compounds.
 (In this case, the cations in the two compounds exchange anions, so Pb2+ ends up with I– as
PbI2 and K+ ends up with NO3– as KNO3.

Solubility:

 It depends on the solubility of the solute, which is defined as the maximum amount of
solute that will dissolve in a given quantity of solvent at a specific temperature.
 Substances are categorised as soluble, slightly soluble, or insoluble in a qualitative sense

NB: all ionic compounds containing alkali metal cations; the ammonium ion; and the nitrate,
bicarbonate, and chlorate ions are soluble. For other compounds, to refer to Table 4.2

Molecular Equations, Ionic Equations, and Net Ionic Equations

 A molecular equation: equation where the formulas of the compounds are written as
though all species existed as molecules or whole units. It helps identifies the reagents.
 Ionic equation, which shows dissolved species as free ions

34
 To be more realistic, the equations should show the dissociation of dissolved ionic
compounds into ions. For instance, the reaction between potassium iodide and lead(II)
nitrate;

 To see whether a precipitate might form from this solution, we first combine the cation and
anion from different compounds; that is, PbI2 and KNO3. Referring to Table 4.2, we see
that PbI2 is an insoluble compound and KNO3 is soluble.
 Therefore, the dissolved KNO3 remains in solution as separate K+ and NO3– ions, which
are called spectator ions,
Spectator ions: ions that are not involved in the overall reaction.
 Because spectator ions appear on both sides of an equation, they can be eliminated from
the ionic equation

 Finally, we end up with the net ionic equation, which shows only the species that actually
take part in the reaction:

 Consider reaction of BaCl2 and Na2SO4

 The steps for writing ionic and net ionic equations:

35
1. Write a balanced molecular equation for the reaction, using the correct formulas for the reactant
and product ionic compounds. Refer to Table 4.2 to decide which of the products is insoluble and
therefore will appear as a precipitate.

2. Write the ionic equation for the reaction. The compound that does not appear as the precipitate
should be shown as free ions.

3. Identify and cancel the spectator ions on both sides of the equation. Write the net ionic equation
for the reaction.

4. Check that the charges and number of atoms balance in the net ionic equation.

Exercise

Predict what happens when a potassium phosphate (K3PO4) solution is mixed with a calcium
nitrate [Ca(NO3)2] solution. Write a net ionic equation for the reaction.

Predict the precipitate produced by mixing an Al(NO3)3 solution with a NaOH solution. Write the
net ionic equation for the reaction.

4.3 Acid-Base Reactions

 These are proton-transfer processes

General Properties of Acids and Bases

Acids

• Acids have a sour taste; for example, vinegar owes its sourness to acetic acid, and lemons and
other citrus fruits contain citric acid.

• Acids cause colour changes in plant dyes; for example, they change the colour of litmus from
blue to red.

• Acids react with certain metals, such as zinc, magnesium, and iron, to produce hydrogen gas. A
typical reaction is that between hydrochloric acid and magnesium:

• Acids react with carbonates and bicarbonates, such as Na2CO3, CaCO3 and NaHCO3, to produce
carbon dioxide gas. For example,
36
• Aqueous acid solutions conduct electricity.

Bases

• Bases have a bitter taste.

• Bases feel slippery; for example, soaps, which contain bases, exhibit this property.

• Bases cause colour changes in plant dyes; for example, they change the colour of litmus from red
to blue.

• Aqueous base solutions conduct electricity.

Acid-Base Neutralization
 A neutralization reaction is a reaction between an acid and a base.
 Generally, aqueous acid-base reactions produce water and a salt, which is an ionic
compound made up of a cation other than H+ and an anion other than OH– or O2– :

 Consider the reaction:

 Because both the acid and the base are strong electrolytes, they are completely ionized in
solution. The ionic equation is;

 Therefore, the reaction can be represented by the net ionic equation

 Both Na+ and Cl– are spectator ions

 Consider a reaction between a weak acid such as hydrocyanic acid (HCN) and a strong
base NaOH:

37
  Because HCN is a weak acid, it does not ionize appreciably in solution. Thus, the ionic
equation is written as

 The net ionic equation is

 Other examples of acid-base neutralization reactions given as molecular equations,

Acid-Base Reactions Leading to Gas Formation

 Certain salts like carbonates (containing the CO322 ion), bicarbonates (containing the
HCO3 2 ion), sulfites (containing the SO322 ion), and sulfides (containing the S22 ion)
react with acids to form gaseous products.

 Carbonic acid is unstable and if present in solution in sufficient concentrations decomposes

as follows:

 Similar reactions involving other mentioned salts are

4.4 Oxidation-Reduction Reactions

 Oxidation-reduction, or redox, reactions are electron transfer reactions.

Consider the formation of magnesium oxide (MgO) from magnesium and oxygen:

38
  Magnesium oxide (MgO) is an ionic compound made up of Mg2+ and O2– ions.
 Take that te reaction occurs in two separate steps, one involving the loss of four electrons
by the two Mg atoms and the other being the gain of four electrons by an O 2 molecule

 Each of these steps is called a half-reaction, which explicitly shows the electrons involved
in a redox reaction. The sum of the half-reactions gives the overall reaction:

or, if we cancel the electrons that appear on both sides of the equation,

Finally, the Mg2+ and O2– ions combine to form MgO:

The term oxidation reaction refers to the half-reaction that involves loss of electrons.

Chemists originally used “oxidation” to denote the combination of elements with oxygen.
However, it now has a broader meaning that includes reactions not involving oxygen. A reduction
reaction is a half-reaction that involves gain of electrons.

In the formation of magnesium oxide, magnesium is oxidized. It is said to act as a reducing agent
because it donates electrons to oxygen and causes oxygen to be reduced. Oxygen is reduced and
acts as an oxidizing agent because it accepts electrons from magnesium, causing magnesium to be
oxidized. Note that the extent of oxidation in a redox reaction must be equal to the extent of
reduction; that is, the number of electrons lost by a reducing agent must be equal to the number of
electrons gained by an oxidizing agent.

The occurrence of electron transfer is more apparent in some redox reactions than others. When
metallic zinc is added to a solution containing copper(II) sulfate (CuSO4), zinc reduces Cu 21 by
donating two electrons to it:

39
In the process, the solution loses the blue colour that characterizes the presence of hydrated Cu2+
ions (Figure 4.10):

The oxidation and reduction half-reactions are

Similarly, metallic copper reduces silver ions in a solution of silver nitrate (AgNO3):

40
Figure 4.10 Metal displacement reactions in solution. (a) First beaker: A zinc strip is placed in a
blue CuSO4 solution. Immediately Cu2+ ions are reduced to metallic Cu in the form of a dark layer.
Second beaker: In time, most of the Cu2+ ions are reduced and the solution becomes colourless.
(b) First beaker: A piece of Cu wire is placed in a colourless AgNO3 solution. Ag 1 ions are reduced
to metallic Ag. Second beaker: As time progresses, most of the Ag+ ions are reduced and the
solution acquires the characteristic blue color due to the presence of hydrated Cu2+ ions.

Oxidation Number

 An atom’s oxidation number, also called oxidation state, signifies the number of charges
the atom would have in a molecule (or an ionic compound) if electrons were transferred
completely.
 Example:

For the product molecules, however, it is assumed that complete electron transfer has taken
place and that atoms have gained or lost electrons.
The oxidation numbers reflect the number of electrons “transferred.”
Oxidation numbers enable us to identify elements that are oxidized and reduced at a glance.
The elements that show an increase in oxidation number—hydrogen and sulfur in the
preceding examples—are oxidized. Chlorine and oxygen are reduced, so their oxidation
numbers show a decrease from their initial values.
The sum of the oxidation numbers of H and Cl in HCl (+1 and –1) is zero. Likewise, if we
add the charges on S (+4) and two atoms of O [2 × (–2)], the total is zero. The reason is
that the HCl and SO2 molecules are neutral, so the charges must cancel.
 We use the following rules to assign oxidation numbers:
1. In free elements (that is, in the uncombined state), each atom has an oxidation number of
zero. Thus, each atom in H2, Br2, Na, Be, K, O2 , and P4 has the same oxidation number:
zero.
2. For ions composed of only one atom (that is, monatomic ions), the oxidation number is
equal to the charge on the ion. Thus, Li+ ion has an oxidation number of +1; Ba2+ ion, +2;

41
 Fe3+ ion, +3; I– ion, –1; O2– ion, –2; and so on. All alkali metals have an oxidation number
of +1 and all alkaline earth metals have an oxidation number of +2 in their compounds.
Aluminium has an oxidation number of 13 in all its compounds.
3. The oxidation number of oxygen in most compounds (for example, MgO and H2O) is –2,
but in hydrogen peroxide (H2O2) and peroxide ion (O22–), it is –1.
4. The oxidation number of hydrogen is 11, except when it is bonded to metals in binary
compounds. In these cases (for example, LiH, NaH, CaH2), its oxidation number is –1.
5. Fluorine has an oxidation number of –1 in all its compounds. Other halogens (Cl, Br, and
I) have negative oxidation numbers when they occur as halide ions in their compounds.
When combined with oxygen—for example in oxoacids and oxoanions—they have
positive oxidation numbers.
6. In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero. In a
polyatomic ion, the sum of oxidation numbers of all the elements in the ion must be equal
to the net charge of the ion. For example, in the ammonium ion, NH4+, the oxidation
number of N is –3 and that of H is +1. Thus the sum of the oxidation numbers is –3 + 4(+1)
= +1, which is equal to the net charge of the ion.
7. Oxidation numbers do not have to be integers. For example, the oxidation number of O in
the superoxide ion, O2–, is –½ .

Example

Assign oxidation numbers to all the elements in the following compounds and ion:

(a) Li2O, (b) HNO3 , (c) Cr2O72.

Strategy In general, we follow the rules just listed for assigning oxidation numbers.

Remember that all alkali metals have an oxidation number of +1, and in most cases hydrogen has
an oxidation number of +1 and oxygen has an oxidation number of –2 in their compounds.

42
Figure 4.11 shows the known oxidation numbers of the familiar elements, arranged according to
their positions in the periodic table. We can summarize the content of this figure as follows:

43
Figure 4.11 The oxidation numbers of elements in their compounds. The more common
oxidation numbers are in colour.

• Metallic elements have only positive oxidation numbers, whereas non-metallic elements may
have either positive or negative oxidation numbers.
• The highest oxidation number an element in Groups 1A–7A can have is its group number. For
example, the halogens are in Group 7A, so their highest possible oxidation number is 17.
• The transition metals (Groups 1B, 3B–8B) usually have several possible oxidation numbers.

44
4.4.1 Types of Redox Reactions
 The most common oxidation-reduction reactions are: combination, decomposition,
combustion, displacement reactions, and disproportionation reactions.
Combination Reactions
 A combination reaction is a reaction in which two or more substances combine to form a
single product. Figure 4.12 shows some combination reactions. For example,

Decomposition Reactions
 Decomposition reactions are the opposite of combination reactions. Specifically, a
decomposition reaction is the breakdown of a compound into two or more components
(Figure 4.13). For example:

Combustion Reactions
 A combustion reaction is a reaction in which a substance reacts with oxygen, usually with
the release of heat and light to produce a flame. The reactions between magnesium and
sulfur with oxygen described earlier are combustion reactions. Another example is the
burning of propane (C3H8), a component of natural gas that is used for domestic heating
and cooking:

 Assigning an oxidation number to C atoms in organic compounds is more involved. Here,

we focus only on the oxidation number of O atoms, which changes from 0 to 22.

Displacement Reactions

45
  In a displacement reaction, an ion (or atom) in a compound is replaced by an ion (or atom)
of another element: Most displacement reactions fi t into one of three subcategories:
hydrogen displacement, metal displacement, or halogen displacement.

1. Hydrogen Displacement. All alkali metals and some alkaline earth metals (Ca,

Sr, and Ba), which are the most reactive of the metallic elements, will displace hydrogen
from cold water ( Figure 4.14 ):

Many metals, including those that do not react with water, are capable of displacing
hydrogen from acids. For example, zinc (Zn) and magnesium (Mg) do not react with cold water
but do react with hydrochloric acid, as follows:

Figure 4.15 shows the reactions between hydrochloric acid (HCl) and iron (Fe), zinc
(Zn), and magnesium (Mg). These reactions are used to prepare hydrogen gas in the laboratory.
2. Metal Displacement. A metal in a compound can be displaced by another metal in the elemental
state. We have already seen examples of zinc replacing copper ions and copper replacing silver
ions (see p. 137). Reversing the roles of the metals would result in no reaction. Thus, copper metal
will not displace zinc ions from zinc sulfate, and silver metal will not displace copper ions from
copper nitrate.
An easy way to predict whether a metal or hydrogen displacement reaction will actually occur is
to refer to an activity series (sometimes called the electrochemical series), shown in Figure 4.16 .
Basically, an activity series is a convenient summary of the results of many possible displacement
reactions similar to the ones already discussed. According to this series, any metal above hydrogen
will displace it from water or from an acid, but metals below hydrogen will not react with either
water or

46
an acid. In fact, any metal listed in the series will react with any metal (in a compound)
below it. For example, Zn is above Cu, so zinc metal will displace copper
ions from copper sulfate.
(a) (b) (c)
Figure 4.15 Reactions of (a) iron (Fe), (b) zinc (Zn), and (c) magnesium (Mg) with hydrochloric
acid to form hydrogen gas and the
metal chlorides (FeCl 2 , ZnCl 2 , MgCl 2 ). The reactivity of these metals is refl ected in the rate
of hydrogen gas evolution, which is slowest
for the least reactive metal, Fe, and fastest for the most reactive metal, Mg.
Metal displacement reactions fi nd many applications in metallurgical processes,

the goal of which is to separate pure metals from their ores. For example, vanadium

is obtained by treating vanadium(V) oxide with metallic calcium:

Similarly, titanium is obtained from titanium(IV) chloride according to the

reaction

In each case, the metal that acts as the reducing agent lies above the metal that is
reduced (that is, Ca is above V and Mg is above Ti) in the activity series. We will
see more examples of this type of reaction in Chapter 19.
3. Halogen Displacement. Another activity series summarizes the halogens’ behavior
in halogen displacement reactions:

The power of these elements as oxidizing agents decreases as we move down Group
7A from fl uorine to iodine, so molecular fl uorine can replace chloride, bromide, and
iodide ions in solution. In fact, molecular fl uorine is so reactive that it also attacks
water; thus these reactions cannot be carried out in aqueous solutions. On the other
hand, molecular chlorine can displace bromide and iodide ions in aqueous solution.

47
The displacement equations are

Disproportionation Reaction

A special type of redox reaction is the disproportionation reaction. In a disproportionation

reaction, an element in one oxidation state is simultaneously oxidized and reduced.

One reactant in a disproportionation reaction always contains an element that can have at least
three oxidation states. The element itself is in an intermediate oxidation state; that is, both higher
and lower oxidation states exist for that element in the products. The decomposition of hydrogen
peroxide is an example of a disproportionation reaction:

Here the oxidation number of oxygen in the reactant (-1) both increases to zero in

O2 and decreases to -2 in H2O. Another example is the reaction between molecular chlorine
and NaOH solution:

48
 This reaction describes the formation of household bleaching agents, for it is the
hypochlorite ion (ClO2) that oxidizes the color-bearing substances in stains, converting them to
colorless compounds.

Finally, it is interesting to compare redox reactions and acid-base reactions. They are
analogous in that acid-base reactions involve the transfer of protons while redox reactions involve
the transfer of electrons. However, while acid-base reactions are quite easy to recognize (because
they always involve an acid and a base), there is no simple procedure for identifying a redox
process. The only sure way is to compare the oxidation numbers of all the elements in the reactants
and products. Any change in oxidation number guarantees that the reaction is redox in nature.

The classification of different types of redox reactions is illustrated in Example below.

Example

Classify the following redox reactions and indicate changes in the oxidation numbers of
the elements:

49
50