TYPES OF SOLID

Solid-state is nothing but one of the states of matter. In our early days of schooling, we
have learnt that matter exists in three states – solid, liquid and gas. However, as we
progress from lower to higher classes the concepts get more advanced and there are
more things to learn. In this lesson, we will be dealing with the concept of solid-state in
a broader aspect and understand all the underlying terms including the properties as
well as the types of solids.
Solids generally exhibit certain characteristics that set them apart from liquids and
gases. For example, they have the ability to resist any force that is applied to its
surface. However, the solid-state of compounds largely depends on the properties of
atoms such as their arrangement and the forces acting between them.

Table of Content
 Physical and Chemical Properties of Solids
 Solid State Chemistry
 Types of Solid States
 Crystalline Solid State
 Amorphous Solid State

Physical and Chemical Properties of Solids

 Solids are incompressible, meaning the constituent particle is arranged close to
each other and because of that, there is negligible space between the
constituent particle.
 Solids are rigid. This is due to lack of space between the constituent particles
which make it rigid or fixed.
 Solids have definite mass, volume and shape due to which it has a compact
arrangement of constituent particles.
 The intermolecular distance between molecules is short. Due to this, the force
between the constituent particles (atoms, molecules or ions) is very strong.
 The constituents particles can only oscillate about their mean positions.
Also Read: Defects in Solids

Solid State Chemistry

Solid-state in Chemistry is the study of the structure, properties and the synthesis of
solid materials. It is also sometimes called as materials chemistry. More significantly, in
solid-state chemistry, we study the concept of a compound in a more deeper level. It
basically helps us understand the compound from a molecular level to the crystal
structure level.
In solid-state chemistry, nonstoichiometric compounds are categorized as exclusive
solid-state compounds due to their structure and thermodynamic characteristics.
Types of Solid States
Based on the arrangement of constituent particles, solids are classified into two-state
types:

1. Crystalline Solids
2. Amorphous Solids

Crystalline Solid State

Crystalline solids are those that have a typical geometry. In such type of solids, there
are definite arrangements of particles (atoms, molecules or ions ) throughout the 3-
dimensional network of a crystal in a long-range order. Examples include Sodium
Chloride, Quartz, Diamond, etc.
Properties of Crystalline Solids

 Crystalline solids have a sharp melting point and start melting when it reaches a
particular temperature.
 The shape of crystalline solids are definite and having typical arrangements of
particles.
 They show cleavage property i.e. when they are cut with the edge of a sharp tool
they split into two pieces and the newly generated surfaces are smooth and
plain.
 They have definite heat of fusion (amount of energy needed to melt a given mass
of solid at its melting point).
 Crystalline solids are anisotropic which means their physical properties like
electrical resistance or refractive index show different values when they are
measured along with different directions in the same crystal.
 Crystalline solids are true solids.
Types of Crystalline Solids
On the basis of the nature of intermolecular forces or chemical bonding, crystalline
solids are further classified into four categories. They are,

 Molecular Solids
 Ionic solids
 Metallic solids
 Covalent solids

Molecular solids
In molecular solids the constituent particles are molecules. They are further divided into
three categories:
1. Non-Polar Molecular Solids
These solids are formed from molecules or atoms that share a non-polar covalent
bond. The atoms or molecules are held by weak dispersion force or by London forces.

 The physical nature of non-polar solids are soft.

 They don’t conduct electricity so they are insulators.
 They have a very low melting point.
 Examples: H2, Cl2, I2 etc.
2. Polar Molecular Solids

 These solids are held together by polar covalent bonds and the atoms/molecules
are bonded by relatively stronger dipole-dipole interactions.
 The physical nature is soft and most of these are gases or liquids at room
temperature.
 They do not conduct electricity and they have a higher melting point than the
non -polar molecular solids.
 Examples: HCl, SO2, NH3 etc.
3. Hydrogen-Bonded Molecular Solids
The solids contain polar covalent bonds with Hydrogen, Fluorine, Oxygen and Nitrogen
atoms. In these solids, molecules are held together via strong hydrogen bonding.

 The physical nature of such solids are hard.

 They do not conduct electricity.
 The physical state of these solids are volatile liquids or soft solids under room
temperature.
 They have a low melting point.
 Examples: H2O (Ice ).
Metallic Solids
 Positive metal ions in a sea of delocalized electrons. These electrons are evenly
spread out throughout the crystal.
 Due to the presence of free and mobile electrons, they are responsible for high
electrical and thermal conductivity.
 They are conductors in both solid and molten state.
 The physical nature of these solids are hard but they are malleable and ductile.
 They have high melting point than ionic solids.
 Examples: Fe, Cu, Ag, Mg, etc.

Covalent or Network Solids

A wide range of crystalline solids of non-metal form covalent bond between adjacent
atoms throughout the crystal and form a giant molecule or large molecules.
  These solids are hard like diamond and soft like graphite which are isotopes of
carbon.
 They are insulators as in the case of a diamond but in case of graphite due to
free electrons, they conduct electricity and act as a conductor.

Amorphous Solid State

Amorphous solid-state comprises of those solids which have the property of rigidity and
incompressibility but to a certain extent. They do not have a definite geometrical form
or long range of order. Examples include glass, rubber, plastic, etc.
Properties of Amorphous Solids

 Amorphous solids are gradually softened over a range of temperature and they
can be moulded into different shapes on heating.
 Amorphous solids are pseudo solids or super cooled liquids which means they
have a tendency to flow very slowly. If you observe that the glass pans which is
fixed to windows of old buildings they are found to be slightly thicker from the
bottom than at the top.
 Amorphous solids have irregular shape i.e. their constituent particles do not have
definite geometry of arrangements.
 When amorphous solids are cut with a sharp edge tool they form pieces with
irregular surfaces.
 Amorphous solids do not have definite heat of fusion due to its irregular
arrangement of the particles.
 Amorphous solids are isotropic in nature which means the value of any physical
property would be same along any direction because of the irregular
arrangement of particles.

Crystalline solids fall into one of four categories. All four categories involve
packing discrete molecules or atoms into a lattice or repeating array, though
network solids are a special case. The categories are distinguished by the nature
of the interactions holding the discrete molecules or atoms together. Based on
the nature of the forces that hold the component atoms, molecules, or ions
together, solids may be formally classified as ionic, molecular, covalent
(network), or metallic. The variation in the relative strengths of these four types
of interactions correlates nicely with their wide variation in properties
In ionic and molecular solids, there are no chemical bonds between the
molecules, atoms, or ions. The solid consists of discrete chemical species
held together by intermolecular forces that
are electrostatic or Coulombic in nature. This behavior is most obvious for

an ionic solid such asNaClNaCl, where the positively charged Na ions +

are attracted to the negatively charged Cl−Cl− ions. Even in the absence
of ions, however, electrostatic forces are operational. For polar molecules
such as CH Cl 2 2CH2Cl2, the positively charged region of one molecule
is attracted to the negatively charged region of another molecule (dipole-

dipole interactions). For a nonpolar molecule such as CO

2CO2, which has
no permanent dipole moment, the random motion of electrons gives rise to
temporary polarity (a temporary dipole moment). Electrostatic attractions
between two temporarily polarized molecules are called London Dispersion
Forces.

Hydrogen bonding is a term describing an attractive interaction between a

hydrogen atom from a molecule or a molecular fragment X–H in which X is
more electronegative than H, and an atom or a group of atoms in the same
or a different molecule, in which there is evidence of bond formation. (See
the IUPAC Provisional Recommendation on the definition of a hydrogen
bond.) Dots are employed to indicate the presence of a hydrogen bond: X–
H•••Y. The attractive interaction in a hydrogen bond typically has a strong
electrostatic contribution, but dispersion forces and weak covalent bonding
are also present.

In metallic solids and network solids, however, chemical bonds hold the
individual chemical subunits together. The crystal is essential a single,
macroscopic molecule with continuous chemical bonding throughout the
entire structure. In metallic solids, the valence electrons are no longer
exclusively associated with a single atom. Instead these electrons exist in
molecular orbitals that are delocalized over many atoms, producing an
electronic band structure. The metallic crystal essentially consists of a set of
metal cations in a sea of electrons. This type of chemical bonding is called
metallic bonding.

Molecular Solids

Molecular solids consist of atoms or molecules held to each other by dipole–

dipole interactions, London dispersion forces, or hydrogen bonds, or any
combination of tThe structure of solid benzene. In solid benzene, the molecules are not
arranged with their planes parallel to one another but at 90° angles. (CC BY-NC-SA;
Anonymous by request).
Because the intermolecular interactions in a molecular solid are relatively
weak compared with ionic and covalent bonds, molecular solids tend to be
soft, low melting and easily vaporized

ΔH
( fusΔHfus and ΔH vapΔHvap are low). For similar substances, the
strength of the London dispersion forces increases smoothly with increasing
molecular mass. For example, the melting points of benzene (C 6H6),
naphthalene (C10H8), and anthracene (C14H10), with one, two, and three fused
aromatic rings, are 5.5°C, 80.2°C, and 215°C, respectively. The enthalpies of
fusion also increase smoothly within the series: benzene (9.95 kJ/mol) <
naphthalene (19.1 kJ/mol) < anthracene (28.8 kJ/mol). If the molecules have
shapes that cannot pack together efficiently in the crystal, however, then the
melting points and the enthalpies of fusion tend to be unexpectedly low
because the molecules are unable to arrange themselves to optimize
intermolecular interactions. Thus toluene (C6H5CH3) and m-xylene [m-
C6H4(CH3)2] have melting points of −95°C and −48°C, respectively, which are
significantly lower than the melting point of the lighter but more symmetrical
analog, benzene.

Self-healing rubber is an example of a molecular solid with the potential for

significant commercial applications. The material can stretch, but when
snapped into pieces it can bond back together again through
reestablishment of its hydrogen-bonding network without showing any sign
of weakness. Among other applications, it is being studied for its use in
adhesives and bicycle tires that will self-heal.
The major types of solids are ionic, molecular, covalent, and metallic. Ionic
solids consist of positively and negatively charged ions held together by
electrostatic forces; the strength of the bonding is reflected in the lattice
energy. Ionic solids tend to have high melting points and are rather hard.
Molecular solids are held together by relatively weak forces, such as dipole–
dipole interactions, hydrogen bonds, and London dispersion forces. As a
result, they tend to be rather soft and have low melting points, which depend
on their molecular structure. Covalent solids consist of two- or three-
dimensional networks of atoms held together by covalent bonds; they tend
to be very hard and have high melting points. Metallic solids have unusual
properties: in addition to having high thermal and electrical conductivity and
being malleable and ductile, they exhibit luster, a shiny surface that reflects
light. An alloy is a mixture of metals that has bulk metallic properties
different from those of its constituent elements. Alloys can be formed by
substituting one metal atom for another of similar size in the lattice
(substitutional alloys), by inserting smaller atoms into holes in the metal
lattice (interstitial alloys), or by a combination of both. Although the
elemental composition of most alloys can vary over wide ranges, certain
metals combine in only fixed proportions to form intermetallic compounds
with unique properties

Diamonds
The structure of diamond is shown at the right in a "ball-and-stick" format.
The balls represent the carbon atoms and the sticks represent a covalent
bond. Be aware that in the "ball-and-stick" representation the size of the
balls do not accurately represent the size of carbon atoms. In addition, a
single stick is drawn to represent a covalent bond irrespective of whether the
bond is a single, double, or triple bond or requires resonance structures to
represent. In the diamond structure, all bonds are single covalent bonds

σ
( σ bonds). The "space-filling" format is an alternate representation that
displays atoms as spheres with a radius equal to the van der Waals radius,
thus providing a better sense of the size of the atoms.

Summary

The major types of solids are ionic, molecular, covalent, and metallic. Ionic
solids consist of positively and negatively charged ions held together by
electrostatic forces; the strength of the bonding is reflected in the lattice
energy. Ionic solids tend to have high melting points and are rather hard.
Molecular solids are held together by relatively weak forces, such as dipole–
dipole interactions, hydrogen bonds, and London dispersion forces. As a
result, they tend to be rather soft and have low melting points, which depend
on their molecular structure. Covalent solids consist of two- or three-
dimensional networks of atoms held together by covalent bonds; they tend
to be very hard and have high melting points. Metallic solids have unusual
properties: in addition to having high thermal and electrical conductivity and
being malleable and ductile, they exhibit luster, a shiny surface that reflects
light. An alloy is a mixture of metals that has bulk metallic properties
different from those of its constituent elements. Alloys can be formed by
substituting one metal atom for another of similar size in the lattice
(substitutional alloys), by inserting smaller atoms into holes in the metal
lattice (interstitial alloys), or by a combination of both. Although the
elemental composition of most alloys can vary over wide ranges, certain
metals combine in only fixed proportions to form intermetallic compounds
with unique properties