Chapter 4 Chemical bonding and Structure:

4.1 Ion bonding and structure:

Ions form when electrons are transferred:

- All atoms are electrically neutral, even though they contain charged particles known
as protons and electrons. This is because the number of protons (+) is equal to the
number of electrons (-), and so their charges cancel each other out.
- An ion is a charged particle. Ions form from atoms or from groups of atoms by loss
and gain of one or more electrons.

Ionic compounds form when oppositely charged ions attract:

Ions do not form in isolation. Rather the process of ionization- where electrons are
transferred between atoms- occurs when an atom that loses electrons passes them directly
to an atom that gains them. Typically, this means electrons are transferred from a metal
element to a non-metal element. For example, sodium (non-metal) passes an electron to
chlorine (non-metal) when they react together

The ionic bond is due to electrostatic attraction between oppositely charged ions.

Ionic compounds have a lattice structure:

The forces of electrostatic attraction between ions in a compound cause the ions to
surround themselves with ions of opposite charge. As a result, the ionic compound takes on
a predictable three-dimensional crystalline structure known as an ionic lattice.
The physical properties of ionic compounds reflect their lattice structure:
Physical properties are those that can be examined without chemically altering the
substance. Our knowledge of ionic bonds and lattice structure helps us to interpret and
explain some of these properties for ionic compounds.

Melting points and boiling points:

Ionic compounds tend to have high melting and points as the forces of electrostatic
attraction between the ions in the lattice are strong and so require large amounts of heat
energy to break.

Volatility: is a term used to describe the tendency of a substance to vaporize. IN summary,

ionic compounds can be described as having a low volatility or being non-volatile. Our
everyday encounter with them as crystalline solids with low odour is consistent with this.
- Ionic compounds have low volatility

Solubility:
Solubility refers to the case with which a solid (the state) becomes dispersed through a
liquid (the solvent) to form a solution.
- Ionic compounds are generally soluble in ionic or polar solvents but not soluble in
non-polar solvents.

Electrical conductivity:
The ability of a compound to conduct electricity depends on whether it contains ions that
can move and carry a charge. Ionic compounds are not able to conduct electricity in the
solid state as the ions are firmly held within the lattice and so cannot move. However, when
the ionic compound is either present in the liquid state (molten), or dissolved in water
(aqueous solution), the ions will be able to move.
- Ionic compounds do not conduct electricity in the solid state, but conduct when
molten or in aqueous solution.

Covalent Bonding 4.2:

Understandings:
- A covalent bond is formed by the electrostatic attraction between a shared pair of
electrons and the positively charged nuclei.
- Single, double, and triple covalent bonds involve one, two and three shared pair of
electrons respectively
- Bond length decreases and bond strength increases as the number of shared
electrons increases
- Bonds polarity results from the difference in electronegativity’s of the bonded atoms

A covalent bond forms by atoms sharing electrons:

When atoms of two non-metals react together each is seeking to gain electrons to achieve
the stable electron structure of a noble gas. BY sharing an electron pair, they are effectively
each able to receive this. The shared pair of electrons is concentrated in the region between
two nuclei and is attracted to them both. It therefore holds the atoms together by
electrostatic attraction and is known as a covalent bond. A group of atoms held together by
covalent bonds form a molecule.
- Molecules contain a fixed number of atoms. Those containing two atoms are
described as diatomic, those containing three atoms are triatomic.
- The octet rule states that when atoms react, they tend to achieve an outer shell with
eight electrons
- A covalent bond is the electrostatic attraction between a pair of electrons and
positively charged nuclei. A molecule is a group of atoms held together by covalent
bonds.

Short bonds are strong bonds:

Every covalent bond is characterized by two values:
1. Bond length: A measure of the distance between the two bonded nuclei
2. Bond strength: Usually described in terms of bond enthalpy, and is effectively a
measure of energy required to break the bond
As atomic radius increases as we go down a group we would expect the atoms to form
molecules with larger bonds.

In a covalent bond, the greater the difference in electronegativity values of the atoms, the
more polar the bond.

Covalent Structures 4.3:

Understandings:
- The term ‘electron domain’ should be used in place of ‘negative charge centre’
- Electron pairs in a Lewis (electron dot) structure can be shown as dots, crosses, a
dash or any combination
- Coordinate covalent bonds be covered
- The ‘octet rule’ refers to the tendency of atoms to gain a valence shell with a total of
8 electrons.
- Some atoms, like Beryllium and Boron, might form stable compounds with
incomplete octets of electrons
- Shapes of species are determined by the repulsion of electron pairs per VSEPR
theory
- Carbon and silicon form giant covalent/network covalent/ macromolecular
structures
- Lewis (electron dot) structures show all the valence electrons in a covalently bonded
species

Lewis diagrams are used to show the arrangement of electrons in covalent molecules:
When describing the structure of covalent molecules, the most convenient method is
known as a Lewis structure. This used a simple notation of dots and crosses to represent the
outer energy level, or valence shell, electrons of all atoms in the molecule.
It can be derived as follows:
1. Calculate the total number of valence electrons in the molecule by multiplying the
number of valence electrons of each element by the number of atoms of the
element in the formula and totalling these.
2. Draw the skeletal structure of the molecule to show how the atoms are linked
3. Use a pair of crosses, a pair of dots, or a single line to show one electron pair and put
a pair in each bond between atoms
 4. Check that the number of electrons in your finished structure is equal to your
calculation in the first step.

When drawing the Lewis structure of ions, note that you must:
- Calculate valence electrons as above and then add one electron for each negative
charge and subtract one electron for each positive charge.
- Put the Lewis structure in a square bracket with the charge shown outside

In coordinate bonds both shared electrons come from one atom:

The examples so far involve covalent bonds where each bonded atom contributes one
electron to the shared pair. However, sometimes the bond forms by both the electrons in
the pair originating from the same atom. This means that the other atom accepts and gains
a share in a donated electron pair. Such bonds are called coordinate bonds, also known as
dative bonds. An arrow on the head of the bond is sometimes used to show a coordinate
bond, with the direction indicating the origin of the electrons.

The octet rule is not always followed:

There are few molecules that are exceptions to the octet rul. Small atoms such as Beryllium
(Be) and Boron (B) form stable molecules in which the central atom has fewer than eight
electrons in its valence shell. This is known as an incomplete octet.

Molecules with incomplete octets are said to be electron deficient, and tend to accept an
electron pair from a molecule with a lone pair, such as NH3 or H2O. This leads to the
formation of a coordinate compound in which the central atom has now gained an octet.

VSEPR theory- The shape of a molecule is determined by repulsion between electron

domains:
Predictions of molecular shape are bonded on the Valence Shell Repulsion (VSEPR) theory.
As its name suggests, this theory is based on the simple notion that because electron pairs
in the same valence shell carry the same charge they repel each other and so spread
themselves as far apart as possible.

Technically, VSEPR, should be called Valence Shell Electron Domain Repulsion. It can be
summarised as follows:
- The repulsion applies to electron domains, which can be single, double, triple
bonding pairs, or non-bonding pairs of electrons.
- The total number of electron domains around the central atom determines the
geometrical arrangement of the electron domains.
 - The shape of the molecule is determined by the angles between the bonded atoms
- Non-bonding pairs (lone pairs) have a higher concentration of change than a bonding
pair because they are not shared between two atoms, and so cause slightly more
repulsion than bonding pairs. The repulsion decreases in the following order.

Lone pair-lone pair > Lone pair-bonding pair > Bonding pair-bonding pair

Species with two electron domains:

Molecules with two electron domains will position them at 180 degrees to each other,
giving a linear shape to the molecule.

Species with three electron domains:

Molecules with three electron domains will position them at 120 degrees to each other,
giving a triangular planar shape to the electron domain geometry. If all three electron
domains are bonding, the shape of the molecule will also be triangular planar.
- The electron domain geometry is determined by the positions of all the electron
domains, but the molecular geometry depends only on the positions of the bonded
atoms.
However, if one of the electron domains is a lone pair, this will not be ‘seen’ in the overall
shape of the molecule, as it is part of the central atom. The molecular shape is determined
by the positions of the atoms fixed by the bonding pairs only. A further consideration is that,
as described above, lone pairs cause slightly more repulsion than bonding pairs, so in their
presence the angles are slightly altered.

Species with four electron domains:

Molecules with four electron domains will position them at 109.5 degrees to each other,
giving a tetrahedral shape to the electron domains. If all four electron domains are bonding,
the shape of the molecule will also be tetrahedral.
Molecules with polar bonds are not always polar:
The polarity of a molecule, depends on:
- The polar bonds that it contains
- The way in which such polar bonds are orientated with respect to each other, in
other words, on the shape of the molecule.

If the bonds are of equal polarity (i.e. involving the same elements) and are arranged
symmetrically with respect to each other, their charge separations will oppose each other
out.

However, if either the molecule contains both of different polarity, or its bonds are not
symmetrically arranged then the dipoles will not cancel out, and the molecule will be polar.
It has a net dipole moment, which refers to its turning force in an electric field. This is what
would happen in a game of tug-of-war if the players were not equally strong or were not
pulling in exactly opposite direction.

Electrons in multiple bonds can sometimes spread themselves between more than one
bonding position
A bond is a pair of electrons held in a specific position within a molecule. However, in some
molecules bonding electrons are less restricted than this. Instead of being confined to one
location they show a tendency to be shared between more than one bonding position and
are said to be delocalized. Free from the constraints of a single bonding position, delocalized
electrons spread themselves out, giving greater stability to the molecule or ion.

Delocalisation is a characteristic of electrons in multiple double bond within a molecule.

Resonance occurs when more than one valid Lewis structure can be drawn for a molecule.
The true structure is an average of these, known as a resonance hybrid.

Border order- is a measure of the number of electrons involved in bonds between two
atoms.

Resonance gives great stability to the benzeme molecule, making it chemically quite
unreactive. Resonance is an important concept that gives special properties where is occurs.

Some covalent substances form giant molecular crystalline solids:

Most covalent substances as discrete molecules with a finite number of atoms. However,
there are some that have a very different structure, a crystalline lattice in which the atoms
are linked together by covalent bonds. It is referred to as a giant molecular, network
covalent structure or macromolecular structure.

Allotropes of Carbon:
Allotropes are different forms of an element in the same physical state, such as oxygen (O 2)
and ozone (O3) which both exist as gases. Different bonding within these structures given
rise to distinct forms with different properties.

Graphene is a relatively new form of carbon. Given its hardness, strength, lightness,
flexibility, conductivity, and chemical inertness, it has enormous potential applications.
Some of the potential application and advantages of graphene are as follows:

- New conductive materials could be made by mixing graphene with plastics

- Transistors of graphene are predicted to be faster and smaller than silicon transistors
in electronics
- Touch screens of graphene printed on thin plastic instead of coatings layered onto
glass would be light, flexible, and almost unbreakable.
- Supercapacitors for storing charge could replace batteries and more effectively
power mobile devices and electric cars
- Solar panels in which photovoltaic cells that generate electricity form sunlight
contain graphene would be light and flexible, and so could be wrapped around any
surface such as clothing, furniture, or vehicles

Silicon and silicon dioxide:

Like carbon, silicon is a group 14 element so its atoms have four valence shell electrons. In
the elemental state, each silicon atom is covalently bonded to four others in a tetrahedral
arrangement. This results in a giant lattice structure much like diamond.

Silicon dioxide, SiO2, commonly known as silica or quartz also forms a giant covalent
structure based on a tetrahedral arrangement. But here the bonds are between silicon and
oxygen atoms. Where each Si atom is covalently bonded to form O atoms, and each O to
two Si atoms. You can think of the oxygen atoms as forming bridges between tetrahedral
bonded silicon atoms.
 Intermolecular forces:
Covalent bonds hold atoms together within molecules, but of course molecules do not exist
in isolation. So, what are the forces that exist between these molecules, the so-called
intermolecular forces? The answer depends on the polarity and size of the molecules
involved and so the intermolecular forces will vary from different molecules.

The strength of intermolecular forces determines the physical properties of a substance.

Volatility, solubility, and conductivity can all be predicted and explained from knowledge of
the nature of the forces between molecules.

London (dispersion) forces:

Non-polar molecules such as chlorine, Cl2, have no permanent separation of change within
their bonds because the shared electrons are pulled equally by the two chlorine atoms.
They do not have a permanent dipole. Likewise, atoms of a noble gas such as Argon exist as
non-polar particles.

However, because electrons behave somewhat like mobile clouds of negative charge, the
density of this cloud may at any moment be greater over one region of a molecule or atom
than over another region of a molecule or atom than over another region. When this occurs,
a weak dipole known as a temporary or instantaneous dipole is formed. This will not last for
more than an instant as the electron density is constantly changing, but it may influence the
electron distribution in a neighbouring atom or molecule, causing an induced dipole.

London (dispersion) forces are the only forces that exist between non-polar molecules. Such
molecules generally have low melting and boiling points, because relatively little energy is
required to break the weak London (dispersion) forces and separate the molecules from
each other.

London (dispersion) forces are also components of the forces between polar molecules, but
often get somewhat overlooked because of the presence of stronger forces.

Dipole-dipole attraction:
- Polar molecules such as hydrogen chloride, HCl, have a permanent separation of
charge within their bonds as a result of the difference in electronegativity between
the bonded atoms. One end of the molecule is electron deficient with a partial
positive charge (S+), while the other end is electron rich with a partial negative
charge (S-). This is known as a permanent dipole. It results in opposite charges or
neighbouring molecules attracting each other, generating a force known as a dipole-
dipole attraction.

The strength of this intermolecular force will vary depending on the distance and relative
orientation of the dipoles. But dipole-dipole forces are generally stronger than London
(dispersion) forces, as we might expect from their origin in permanent rather than
instantaneous dipoles.

For two substances of similar molecular mass, the more polar substance will have the higher
boiling point.
Hydrogen bonding:
- When a molecule contains hydrogen covalently bonded to a very electronegative
atom (fluorine, nitrogen or oxygen), there molecules are attracted to each other by a
particularly strong type of intermolecular force called a hydrogen bond. The
hydrogen bond is a case of dipole-dipole attraction. The large electronegativity
difference between hydrogen and the bonded fluorine, oxygen, or nitrogen results in
the electron pair being pulled away from the hydrogen.

Hydrogen bonds are the strongest form of intermolecular attraction consequently; they
cause the boiling points of substances that contain them to be significantly higher than
would be predicted from their molar mass.

Note: Hydrogen bonding only occurs between molecules in which hydrogen is bonded
directly to fluorine, nitrogen, or oxygen.

The physical properties of covalent compounds are to largely a result of their

intermolecular forces:
- If we know the type of intermolecular force in a substance, we are in a good position
to predict its physical properties.

Melting and boiling points:

- Changing state by melting or boiling involves separating particles by overcoming the
forces between them. So, the stronger the intermolecular forces, the more energy
will be required to do this, and the higher will be the substances melting and boiling
points.

Covalent substances generally have lower melting and boiling points than ionic compounds.
The forces to be overcome to separate the molecules are the relatively weak intermolecular
forces, which are significantly easier to break than the electrostatic attractions in the ionic
lattice. This is why many covalent substances are liquids or gases at room temperature.

Solubility:
- Non-polar substances are generally able to dissolve in non-polar solvents by the
formation of London (dispersion) forces between solute and solvent. For example,
the halogens all of which are non-polar molecules, are readily soluble in the non-
polar solvent paraffin oil.

Likewise, polar covalent compounds are generally soluble in water, a highly polar solvent.

The solubility of polar compounds is, however, reduces in larger molecules where the polar
bond is only a small part of the total structure. The non-polar parts of the molecule, unable
to associate with water, reduce its solubility.

Polar substances have low solubility in the non-polar solvents as they will remain held to
each other by their dipole-dipole attractions and cannot interact well with the solvent.
Giant molecular substances are generally insoluble in all solvents, as too much energy would
be required to break the strong covalent bonds in their structure.

Electrical conductivity:
- Covalent compounds do not contain ions, and so are not able to conduct electricity
in the solid or liquid state. Some polar covalent molecules, however, in conditions,
where they can ionize will conduct electricity. For example, HCl dissolved in water
(hydrochloric acid) is an electrical conductor as it dissociated into H+(aq) + Cl- (aq).

Metallic bonding 4.5:

Understandings:
- A metallic bond is the electrostatic attraction between a lattice of positive ions and
delocalized electrons.
- The strength of a metallic bond depends on the charge of the ions and the radius of
the metal ion.
- Alloys usually contain more than one metal and have enhanced properties

Applications and skills:

- Explanation of electrical conductivity and malleability in metals
- Explanation of trends in melting points in metals
- Explanation of the properties of alloys in terms of non-directional bonding

Metals are found on the left of the periodic table and have a small number of electrons in
their outer shell. These atoms with low ionization energies, and typically react with other
elements by losing their valence electrons and forming positive ions. So, these elements are
characterized by having a loose control over their outer shell electrons.

In the element state, when there is no other element present to accept the electrons and
form an ionic compound, the outer electrons are held only loosely by the metal atoms
nucleus and so tend to ‘wander off’ or, more correctly become delocalized. Delocalized
electrons are not fixed in one position. This means that in metals they are no longer
associated closely with any one metal nucleus but instead can spread themselves through
the metal structure. The metal atoms without these electrons have become positively
charged ions and form a regular lattice structure through which these electrons can move
freely.

In metals, there is a force of electrostatic attraction between the lattice of cations and the
delocalized electrons, and this is known as metallic bonding.

The strength of a metallic bond is determined by:

- The number of delocalized electrons
- The charge on the cation
- The radius of the cation

The greater the number of delocalized electrons and the smaller the cation the greater
binding force between them.
The strength of metallic bonding tends to decrease down a group as the size of the cation
increases, reducing the attraction between the delocalized electrons and the positive
charge.

The transition elements tend to have very strong metallic bonds due to the large number of
electrons that can become delocalized.

Metallic bonds are the strong forces of attraction between delocalized electrons and
positive ions.

The sigma bond:

When two atomic orbitals overlap along the bond axis- an imaginary line between the two
nuclei- the bond is described as a sigma bond. This type of bond forms by the overlap of S
orbitals, P orbitals, and hybrid orbitals in different combinations. It is always the bond that
forms in a single covalent bond.
- All single covalent bonds are sigma bonds. Sigma bonds form by overlap of orbitals
along the bond axis.

In sigma bonds the electron density is concentrated between the nuclei of the bonded
atoms.

The Pi bond:
When two ‘P’ orbitals overlap sideways, the electron density of the molecular orbital is
concentrated in two regions, above and below the plane of the bond axis. This is known as a
Pi bond. This type of bond only forms by the overlap of ‘P’ orbitals alongside the formation
of a sigma bond. In other words, Pi bonds on forms within a double bond or a triple bond.

Pi bonds are weaker than sigma bonds as their electron density is further from the positive
charge of the nucleus, and so they break ever more easily during chemical reactions.

14.2 Hybridization

- A hybrid orbital results from the mixing of different types of atomic orbitals on the
same atom.

Hybridization is the process where atomic orbitals within an atom mix to produce hybrid
orbitals of intermediate energy. The atom can form stronger covalent bonds using these
hybrid orbitals.
- Hybrid orbitals have different energies, shapes, and orientation in space from their
parent orbitals and can form stronger bonds by allowing for greater overlap.

Hybridization can involve different numbers and types of orbital, leading to the formation of
distinct hybrid orbitals.

Sp3 hybridization:
When carbon forms four single bonds, it undergoes sp 3 hybridization, producing four equal
orbitals.

These orbitals orientate themselves at 109.5, forming a tetrahedron. Each hybrid orbital
overlaps with the atomic orbital of another forming four sigma bonds.

Sp2 hybridization:
When carbon forms a double bond, it undergoes sp2 hybridization, producing three qual
orbitals.

These orbitals orientate themselves at 120 degrees, forming a triangular planar shape. Each
hybrid orbital overlaps with a neighbouring atomic orbital, forming three sigma bonds.