CHM 101

STRUCTURE OF SOLIDS

There are many ways to classify solids, but the broadest categories are crystalline solids and

amorphous solids. Crystalline solids are those with a highly regular arrangement of their

components. When most liquids cool they form crystalline solids, solids in which the atoms, ions

and molecules are arranged in a definite repeating pattern. Metals and ionic compounds typically

form ordered crystalline solids. In a crystalline solid, the atoms, ions, or molecules are arranged

in a definite repeating pattern, but occasional defects may occur in the pattern. Several types of

defects are known one of which is vacancies. Vacancies are defects that occur when positions

that should contain atoms or ions are vacant.

Amorphous solids are those with considerable disorder in their structures. The particles of such

solids lack an orderly internal structure and are randomly arranged. Substances that consist of

large molecules, or a mixture of molecules whose movements are more restricted, often form

amorphous solids. For examples, candle waxes are amorphous solids composed of large

hydrocarbon molecules. Some substances, such as boron oxide can form either crystalline or

amorphous solids, depending on the conditions under which it is produced. Also, amorphous

solids may undergo a transition to the crystalline state under appropriate conditions.

Crystalline solids are generally classified according the nature of the forces that hold its particles

together. These forces are primarily responsible for the physical properties exhibited by the bulk

solids. The following are the major types of crystalline solids: ionic, molecular and atomic

(metallic, covalent network and Group 8A).

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It is convenient to classify solids according to what type of component occupies the lattice

points. This leads to the classifications:

Atomic solids - atoms at the lattice points

Molecular solids – discrete, relatively small molecules at the lattice points

Ionic solids - ions at the lattice points

There are many different types of crystalline solids. For example, although both sugar and salt

dissolve readily in water, the properties of the resulting solutions are quite different. The salt

solution readily conducts an electric current, whereas the sugar solution does not. This behavior

arises from the nature of the components in these two solids. Common salt (NaCl) is an ionic

solid; it contains Na+ and Cl- ions. When solid sodium chloride dissolves in the polar water,

sodium and chloride ions are distributed throughout the resulting solution and are free to conduct

electric current.

Table sugar (sucrose), on the other hand, is composed of neutral molecules that are dispersed

throughout the water when the solid dissolves. No ions are present, and the resulting solution

does not conduct electricity. These examples illustrate two important types of solids: ionic

solids, represented by sodium chloride, and molecular solids, represented by sucrose. Ionic

solids have ions at the points of the lattice that describes the structure of the solid. A molecular

solid, on the other hand, has discrete covalently bonded molecules at each of its lattice points. Ice

is a molecular solid that has an H2O molecule at each point.

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Elements such as carbon (which exists in the forms graphite, diamond, and the fullerenes),

boron, silicon, and all metals exist as atomic solids. These substances all have atoms at the lattice

points that describe the structure of the solid. In addition, atomic solids are placed into the

following subgroups based on the bonding that exists among the atoms in the solid: metallic

solids, network solids, and Group 8A solids. In metallic solids, a special type of delocalized non-

directional covalent bonding occurs. In network solids, the atoms bond to each other with strong

directional covalent bonds that lead to giant molecules, or networks, of atoms. In the Group 8A

solids, the noble gas elements are attracted to each other with London dispersion forces.

The markedly different bonding present in the various atomic solids leads to dramatically

different properties for the resulting solids. For example, although argon, copper and diamond all

are atomic solids, they have strikingly different properties. Argon (a Group 8A solid) has a very

low melting point -189°C whereas diamond (a network solid) and copper (a metallic solid) melt

at high temperatures (about 3500°C and 1083°C) respectively). Copper is an excellent conductor

of electricity, whereas argon and diamond are both insulators. Copper can be easily changed in

shape; it is both malleable (can be formed into thin sheets) and ductile (can be pulled into a

wire). Diamond, on the other hand, is the hardest natural substance known.

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Type of Solids Interaction Properties Examples

Ionic Ionic Hard, brittle, conducts NaCl, NaF, MgO and

electricity as a liquid and very Al2O3

high melting points.

Molecular Hydrogen Bonding, Variable hardness, variable H2O, CO2 and I2

Dipole-Dipole, London brittleness and low melting

Dispersion points

Metallic Metallic Bonding Shiny, malleable, ductile, Cu, Fe, Ti,

good conductor of heat and Pb and U

electricity,

Network Covalent High melting point Diamond and Quartz

Carbon and its Allotropes

Carbon is an essential element in our world. The unique properties of carbon atoms allow the

existence of carbon-based life forms such as us. Carbon forms a huge variety of substances that

we use on a daily basis. You may be familiar with diamond and graphite, the two most common

allotropes of carbon. Allotropes are different structural forms of the same element. Diamond is

one of the hardest-known substances, whereas graphite is soft enough to be used as pencil lead.

These very different properties stem from the different arrangements of the carbon atoms in the

different allotropes.

Diamond is extremely hard because of the strong bonding between carbon atoms in all

directions. Graphite (in pencil lead) rubs off onto paper due to the weak attractions between the

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carbon layers. An image of a graphite surface shows the distance between the centers of adjacent

carbon atoms.

You may be less familiar with a recently discovered form of carbon: graphene. Graphene was

first isolated in 2004 by using tape to peel off thinner and thinner layers from graphite. It is

essentially a single sheet (one atom thick) of graphite. Graphene is not only strong and

lightweight, but it is also an excellent conductor of electricity and heat. These properties may

prove very useful in a wide range of applications, such as vastly improved computer chips and

circuits, better batteries and solar cells, and stronger and lighter structural materials.

Self-study: find out the structures of diamond, graphite and graphene

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CHEMICAL BONDING AND INTERMOLECULAR FORCES

Valence Electrons

The electrons in the outer most shell, or valence shell, are known as valence electrons. These

valence electrons are responsible for the chemical properties of chemical elements. It is these

electrons which participate in chemical reactions with other elements. For example group I

elements: Li, Na, K, Rb, Cs and Fr have a single valence electron. These elements all have

similar chemical properties.

A bond is an attractive force between two ions or atoms. Without chemical bonds, the world

would have only free atoms or ions. We would not have the amazing variety of substances. There

would be no water and food. And, there would be no life! After all, all living things are made up

of millions of atoms and ions bound together, forming molecules. Molecules and materials are a

result of bonding of atoms in different ways. This results in molecules of various shapes and

formation of various substances.

To bind atoms we need glue, electrons present in atoms provide the magic glue. Do all the

electrons in an atom act as the glue? No. Only the valence electrons (electrons in the outermost

shell) are involved in the formation of chemical bonds. This makes carbon to have four valence

electrons while magnesium has just two valence electrons. What of hydrogen and oxygen?

The Octet rule: In explaining why atoms form bonds, G. N. Lewis proposed that an atom is most

stable if its outer shell is either filled or contains eight electrons. According to Lewis’s theory, an

atom will give up, accept, or share electrons in order to achieve a filled outer shell or an outer

shell that contains eight electrons. This theory has come to be called the octet rule.

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When chemical bonds are formed, the atoms involved in bond formation achieve the electronic

configuration of a noble gas. The noble gases, except helium, have eight electrons in their

outermost shells.

Ionic bond

The idea of the ionic bond was first proposed by Kossel in 1916. In an ionic bond:

- An electron is (or electrons are) transferred from one atom to another.

- The atom that transfers the electron (or electrons) attains a positive charge. The atom,

therefore, becomes a positive ion or a CATION.

- The atom that receives (or gains) the electron (or electrons) attains a negative charge. The

atom, therefore, becomes a negative ion or an ANION.

For example,

The lithium atom loses its valence electron, and becomes Li+ cation. This has the electronic

configuration of helium. The magnesium atom loses two electrons from the outermost shell

to form Mg2+cation. Note the magnesium atom has a bigger size than the magnesium ion.

Li → Li+

(2,1) (2)

Mg → Mg2+

(2,8,2) (2,8)

Remember, the atom that receives an electron (or electrons) gets a negative charge and

becomes an anion. The chlorine atom gains (accepts) an electron to become chloride (Cl-)

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anion. The oxide ion (anion) has a negative charge of two (O2-) because it accepts two

electrons.

Cl → Cl-

(2,8,7) (2,8,8)

Sodium has one valence electron. Chlorine has seven valence electrons. An electron is

transferred from the sodium atom to the chlorine atom.

Thus, an ionic bond is formed.

Na + Cl → NaCl

(2,8,1) (2,8,7)

Another example is the reaction between magnesium and oxygen. The magnesium atom

transfers its two valence electrons to oxygen (which needs two electrons to obey the octet

rule).

Mg + O → MgO

(2,8,2) (2,6)

Ionic bonds are generally formed between metallic elements of groups 1 and 2 and non-

metallic elements of groups 16 and 17. The metallic elements transfer electrons and become

cations. The non-metallic elements receive electrons and become anions.

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Covalent Bonds

What would happen if all the chemical bonds were ionic? There would be no oxygen, water,

sugar and carbon dioxide. Oxygen, carbon dioxide, nitrogen, proteins and such molecules

make life possible on earth. All these compounds in nature have COVALENT BONDS

formed by the sharing of electrons.

The number of bonds varies with the number of shared electrons. In oxygen, two electrons of

each atom are shared. The bond between two oxygen atoms, therefore, involves four

electrons. Chlorine atoms form sodium chloride (NaCl) and chlorine (Cl2) molecules.

Chlorine reacts with sodium to form sodium chloride. Here, chlorine receives an electron

from sodium and becomes chloride ion (anion). In a chlorine molecule, the two chlorine

atoms share a pair of electrons with each other.

The shared electrons between atoms can be from two atoms of the same element as in: Cl 2

and Br2. It can also be from two atoms of different elements like in HBr and HCl.

Electrons in the valence shell of an atom are represented by dots and crosses. This way of

representing bonds is known as the Lewis representation, after G. N. Lewis who first

proposed the method. The idea of covalent bond was mooted by Lewis in 1916. In a covalent

bond, two atoms share as many pairs of electrons as are required to attain the stable

electronic configuration.

A covalent bond is generally expressed as a line ―-‖ and each line represents a bond. The

number of lines signifies the number of bonds. In H2, there are two electrons forming the

covalent bond. So, one pair of electrons is shared by two hydrogen atoms (single bond). In

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O2, two pairs of electrons are shared by two oxygen atoms (double bond). In N2, three pairs

of electrons are shared by two nitrogen atoms (triple bond).

Note: one covalent bond is formed by a pair of electrons. Therefore, to form a double bond,

there is need for 4 electrons and to form a triple bond, there is need for 6 electrons.

Intermolecular Forces

Intermolecular forces are attractive forces between molecules and are primarily responsible

for the bulk properties of matter (for example, melting point and boiling point). If it takes

more energy to separate molecules of substance A than of substance B; then molecules of A

are held together by stronger intermolecular force. So, the boiling point of A will be higher

than that of B. The same principle applies also to the melting points of the substances. In

general, the melting points of substances increase with the strength of the intermolecular

forces.

Dipole-Dipole Force

Polar molecules can attract one another through dipole–dipole forces. The dipole–dipole

force is an attractive intermolecular force resulting from the tendency of polar molecules to

align in such that the positive end of one molecule is near the negative end of another. For

example, hydrogen chloride, HCl, is a polar molecule because of the difference in

electronegativities of the H and Cl atoms.

H-Cl----H-Cl------H-Cl

+- + - + -

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London (Dispersion) Forces

In nonpolar molecules, there can be no dipole–dipole force. In 1930 Fritz London found he

could account for a weak attraction between any two molecules. London forces (also called

dispersion forces) are the weak attractive forces between molecules resulting from the small,

instantaneous dipoles that occur because of the varying positions of the electrons during their

motion about nuclei.

Hydrogen Bonding

Hydrogen bonding is a weak to moderate attractive force that exists between a hydrogen

atom covalently bonded to a very electronegative atom, X (F, N or O).

H-X—

Class work

What kinds of intermolecular forces are expected in the following substances?

a. Methane

b. Trichloromethane

c. Butanol (butyl alcohol)

Solution

a. Methane is a nonpolar molecule. Hence, the only intermolecular attractions are London

forces.

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b. Trichloromethane is an unsymmetrical molecule with polar bonds. Thus, we expect

dipole–dipole forces, in addition to London forces.

c. Butanol has a hydrogen atom attached to an oxygen atom. Therefore, you expect hydrogen

bonding. Because the molecule is polar (from the O-H bond), you also expect dipole–dipole

forces. London forces exist too, because such forces exist between all molecules.

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