States of Matter

By Cate Elsworth

We have considered the types of bonds that hold atoms, ions and molecules together. But how
do the type of bonds present influence the state we find the substance in a room temperature and
pressure? Why do we find water a liquid and nitrogen a gas and copper a solid?

The state of matter always depends on the temperature and pressure under which the observation
is made. For example, nitrogen a gas at room temperature, can be turned into liquid nitrogen by
increasing the pressure.

We can identify the state that a substance will occupy at a particular temperature and pressure
using a phase diagram. A phase diagram is graph showing the conditions of temperature and
pressure under which a substance exists in the solid, liquid, and gas phases. Below is a general
phase diagram. The lines represent the changes in states.

We can read the melting point and boiling point of a substance at any pressure using a phase
diagram. The normal melting point and normal boiling point is the temperature at the phase
changes at 1 atm (101 kPa). The phase diagram for H2O is shown below indicating the normal
melting and normal boiling points. There are two other points indicated on the graph (critical
point and triple point), an understanding of these points is not required in this course.
The Kinetic-Molecular Theory

The Kinetic Molecular Theory is a theory that explains the states of matter and is based on the
idea that matter is composed of tiny particles that are always in motion. The theory helps explain
observable properties and behaviors of solids, liquids, and gases.

Solids and liquids are similar in that both are condensed states of matter, with particles
that are closer together than those of a gas.
For most substances, the solid form is the densest of the three states of matter. This is not
true for ice.

The particles of most solids are packed tightly together in an orderly arrangement. The motion of
individual atoms, ions, or molecules in a solid is restricted, it is only vibrational motion. As a
solid is heated, the average kinetic energy of its particles increases, but due to their relatively
fixed positions, this results in stronger and more rapid vibrations. Eventually, the organisation of
the particles within the solid structure begins to break down and the solid starts to melt.

The melting point is the temperature at which a solid changes into a liquid. In the liquid state the
particles have enough energy to prevent the forces holding them in a fixed arrangement.

Then a change of state from the liquid to a gas occurs when there is sufficient energy overcome
the bonding between the particles. In gases, according to the Kinetic Molecular Theory there
is no force of attraction between gas particles. We will look at the other postulates of the Kinetic
Molecular Theory when we investigate gases.

Bonding and States of Matter

It is important to be able to identify the different bonds present in a substance (primary and
secondary) and use these bonds to understand why one substance has a particular state at room
temperature and why they may have different meting and boiling points.

Example

Compare the melting points of sodium chloride and water. Explain the differences in melting
point of the two substances, sodium chloride melts at 801C and the melting point of ice is 0C.

Sodium chloride (NaCl) is an ionic compound, so it consists of strong ionic bonds. It is the ionic
bonds in NaCl that are disrupted when NaCl melts.

Ice (solid H2O) is a molecular compound whose molecules are held together by hydrogen
bonds. It is the hydrogen bonds in ice that are disrupted when when ice melts not the covalent
bonds. Although hydrogen bonds are the strongest of the intermolecular forces, they are still
much weaker than ionic bonds.
Example

Explain the observation that at room temperature, chlorine is a gas, bromine a liquid and iodine a
solid.

Chlorine, bromine and iodine are all diatomic molecules. Chlorine, being a gas must have a
lower boiling point and melting point than bromine. Iodine is a solid at room
temperature and will have the highest melting point. The different melting points will be due to
the strengths of the intermolecular forces. The intermolecular forces are dispersion forces as the
molecules are all non-polar. Dispersion forces increase with increasing size of the molecules
(there is an increase in the number of electrons) and therefore there is in increase in the
polarisability of the molecules.

Iodine is the largest molecule and therefore will have the strongest dispersion forces leading to
the highest melting point. Chlorine is the smallest molecule and therefore will have the
weakest dispersion forces leading to the lowest melting point.

Liquids
By Cate Elsworth

The properties of liquids directly reflects the strength of the intermolecular force. That is the
evaporation, enthalpy of vaporisation, vapour pressure, boiling point and surface tension. We
will now investigate at each of these properties.

Evaporation

A liquid left undisturbed in an open container (image below) it eventually disappears. The liquid
molecules escape into the gas phase, becoming water vapour. Vaporisation is the process in
which a liquid is converted to a gas. Evaporation is the conversion of a liquid to its vapor below
the boiling temperature of the liquid.

In order for a liquid molecule to escape into the gas state, the molecule must have enough kinetic
energy to overcome the intermolecular attractive forces in the liquid. A liquid sample will have
molecules with a wide range of kinetic energies. Liquid molecules that have this
minimum amount kinetic energy can escape the surface and become vapour.
As a result, the liquid molecules that remain now have a lower average kinetic energy. As
evaporation occurs, the temperature of the remaining liquid decreases. This is how evaporative
cooling works and how your body can cool itself through sweat.

The image below shows the kinetic energy distribution of liquid molecules at two temperatures.
The numbers of molecules that have the required kinetic energy to evaporate are shown in the
shaded area under the curve at the right. The higher temperature liquid (T2) has more molecules
that are capable of escaping into the vapor phase than the lower temperature liquid
(T1). Evaporation will occur faster at a higher temperature.

Enthalpy of Vaporisation

The enthalpy of vapourisation of a substance is the heat absorbed by one mole of that substance
as it is converted from a liquid to a gas. The following table shows the enthalpy of vaporisation
for selected compounds. The enthalpy of vaporisation is a reflection of the strength of the
intermolecular forces.

We will compare similar compounds:

HF and HBr: HF has a higher enthalpy of vaporisation due to hydrogen bonds in the
liquid, while HBr has weaker dipole-dipole bonds.
CH3CH2CH3 and CH3CH2CH2CH3 both have dispersion forces between the molecules in
the liquid state. CH3CH2CH2CH3 is a larger molecule and therefore is more
polarisable. There will be stronger dispersion forces between CH3CH2CH2CH3.
Vapour Pressure

If a liquid is instead kept in a closed container (Image below), the water vapour molecules do not
have a chance to escape into the surroundings and so the water level does not change. As some
water molecules become vapor, an equal number of water vapor molecules condense back into
the liquid state. This is an example of an equilibrium.

Vapor pressure is dependent on temperature. The greater number of vapor molecules hit the
container walls more frequently, resulting in an increase in pressure. Vapor pressure is also
dependant on the intermolecular forces present. Liquids with strong intermolecular forces have
lower vapor pressures than liquids with weaker intermolecular forces.

The table below shows vapor pressure (in kPa) of three liquids at various temperatures.

The structure of ethanol and diethyl ether are shown below. Ethanol has hydrogen bonding and
diethyl ether has dipole-dipole bonding and the stronger hydrogen bonds is reflected in the lower
vapor pressures.

Boiling Point

As a liquid is heated, the average kinetic energy of its particles increases. At a point bubbles
begin to form in the body of the liquid. When the vapor pressure inside the bubble is equal to the
atmospheric pressure, the bubbles rise to the surface of liquid and burst. The temperature at
which this process occurs is the boiling point of the liquid.

As atmospheric pressure can change based on location, the boiling point of a liquid changes with
the atmospheric pressure. The normal boiling point is a constant because it is defined relative to
the standard atmospheric pressure of 1 atm (760 mmHg or 101.3 kPa). The boiling point of
water is 100C at 1 atm and on top of Mount Everest is only about 70C. We can refer to the
phase diagram to see how boiling point varies with temperature for water. Click here to take you
to the page on phase diagrams.

Surface Tension

Molecules within a liquid are pulled equally in all directions by intermolecular forces. However,
molecules at the surface are pulled downwards and sideways by other liquid molecules, but not
upwards away from the surface. The overall effect is that the surface molecules are pulled into
the liquid, creating a surface that is curved as below. This reduces the surface area of the liquid

The surface tension of a liquid is the energy required to increase the surface area, to allow the
molecules in the interior of the liquid need to move to the surface. Liquids that have strong
intermolecular forces, like the hydrogen bonding in water, exhibit the greatest surface tension.

Viscosity

Viscosity is a liquids resistance to flow. Thicker liquids are more viscous than thinner liquids.
For example, the honey in image below is more viscous than water.

The viscosity is directly related to the strength of intermolecular forces.

Compare glycerol and 1-propanol (structures pictured below). Glycerol has a greater number of
-OH groups compared to 1-propanol for the same number of carbon atoms. Therefore glycerol
has a greater number of hydrogen bonds resulting in stronger intermolecular forces. Glycerol has
a greater viscosity (similar to honey) compared to 1-propanol (similar to water).
Types of Solids
By Cate Elsworth

There are two main categories of solidscrystalline solids and amorphous solids.

Crystalline solids are those in which the atoms, ions, or molecules that make up the solid exist in
a regular, well-defined arrangement.

Amorphous solids do not have much order in their structures. Although their molecules are close
together and have little freedom to move, they are not arranged in a regular order as are those in
crystalline solids. Common examples of this type of solid are glass and plastics.

Crystalline Solids

Crystalline substances can also be described by the types of particles in them (what is
represented by the spheres) and the types of chemical bonding that take place between the
particles. There are four types of crystals: (1) ionic, (2) metallic, (3) covalent network, and (4)
molecular. The table below shows the melting points and boilings of the different types at 1
atm. The melting point will tell us at what temperature the substance will exist as a solid.
Properties of Ionic Solids

The ionic solids consists of alternating positively-charged cations and negatively-charged anions.
The ions may either be monatomic or polyatomic. Generally, ionic crystals form from a
combination of Group 1 or 2 metals and Group 16 or 17 nonmetals or nonmetallic polyatomic
ions. The properties of ionic solids include:

High melting points due to the strong ionic bond.

Do not conduct electricity as solids as the ions are fixed in place, but do conduct when molten or
in aqueous solution where the ions are free to move.
Ionic crystals are hard and brittle.

Properties of Metallic Solids

Metallic solids consist of metal cations surrounded by a sea of electrons. These electrons, also
referred to as delocalised electrons, do not belong to any one atom, but are capable of moving
through the entire crystal.

Good conductors of electricity.

Melting points display a wide range as seen in the table above.
Have a relatively high density as the atoms pack in a very efficient manner.
The more valence electrons the metal has the stronger the bonding. Melting point and hardness
depend upon the number of valence electrons, compare Na to Mg melting point in the table
above.
The majority of metals are ductile and malleable as the layers of cations can slide past each
other. Ductile means they can be pulled into long, thin shapes, like the aluminium wires pictured
below. Malleable means that they can be formed into thin sheets without breaking, for example
aluminium foil, also pictured below.

Properties of Covalent Network Solids

A covalent network solid consists of atoms at the lattice points of the crystal, with each atom
being covalently bonded to its nearest neighbor atoms (see Figure below). The covalently bonded
network is 3D and contains a very large number of atoms. Network solids include diamond,
quartz, many metalloids, and oxides of transition metals and metalloids.

Network solids are hard and brittle.

Have extremely high melting and boiling points
They do not conduct electricity in any state as they are composed of atoms rather than ions

Examples of covalent network solids include silicon dioxide (SiO2) and diamond. Diamond is
one of the allotropes of carbon, we will investigate these in the next module. There are also
different forms of SiO2, pictured below is one of these forms.

Properties of Molecular Solids

Molecular solids typically consist of molecules held together by relatively weak intermolecular
forces. The intermolecular forces may be dispersion forces in the case of non-polar molecules, or
dipole-dipole forces in the case of polar molecules or hydrogen bonds.

In all cases, the intermolecular forces holding the particles together are far weaker than either
ionic or covalent bonds. The properties of molecular solids are:

The melting and boiling points of molecular solids are low due to the weak intermolecular
forces.
Molecular solids are poor electrical conductors as they lack free ions or electrons.

Iodine is a molecular solid. As iodine is non-polar the bonds holding the molecules together are
dispersion forces.

Iodine is the only halogen that is solid at room temperature, we can see that the melting point and
the boiling points of the halogens vary with the size of the molecules and the increased
polarisability leading to increased dispersion forces.

Noble Gases

Noble gases if cooled down to the liquid or solid state would only have dispersion forces
between the atoms. The larger the atom the stronger the dispersion forces. Note the melting and
boiling points are measured in K below.
Metal and Alloys
By Cate Elsworth

Packing of Metal Atoms

Metals atoms arrange themselves in a regular way. It is easy to describe the structure of metals
as the atoms that form these metals can be thought of as spheres. We can think about the way
these spheres pack. Different metals pack in different ways. Lets look at the possible ways the
spheres can pack in one layer. The second option is more efficient, that is there is less space
between the spheres.

Then the layers can be placed on top of each other and this can form the 3D structure (lattice).
We need to have ways to describe these different packing arrangements. A unit cell is the
smallest portion of a lattice that shows the 3D pattern of the entire crystal. A crystal can be
thought of as the same unit cell repeated over and over in three dimensions. The diagram below
illustrates the unit cell for packing option 1. The red and yellow spheres represent atoms in
different layers, in this case these are the same metal atoms.
Packing option 2 is quite complex and there are different ways the layers can be placed on top of
each other, this gives rise to different unit cells. Unit cells are used to describe the packing in
other crystal structures such as ionic, covalent molecular and covalent network.

Alloys

An alloy is a mixture of a metal with one or more other elements. The other elements may be
metals, nonmetals, or both. An alloy is formed by melting a metal and dissolving the other
elements in it. The molten solution is then allowed to cool and harden. Alloys generally have
more useful properties than pure metals. They can have higher melting points and greater
conductivity than the pure metal.

Alloys can be one of two general types. In one type, called a substitutional alloy, the various
atoms simply replace each other in the crystal structure. In another type, called an interstitial
alloy, the smaller atoms such as carbon fit in between the larger atoms in the crystal packing
arrangement. The spaces between the atoms are called interstitial sites.

The relative size of each element plays a role in determining which type of alloy will form.

When the atoms are relatively similar in size, a substitutional alloy can form. Examples of
substitutional alloys include bronze and brass, in which some of the copper atoms are
substituted with either tin or zinc atoms.
In interstitial alloys, one atom is usually much smaller than the other. The smaller atoms
become trapped in the spaces . Steel is an example of an interstitial alloy, because the very small
carbon atoms fit into spaces between the iron atoms.
Sometimes an alloy can be both and substitutional and interstitial alloy. Stainless steel is an
example, because the carbon atoms fit into the interstices, but some of the iron atoms are
replaced with nickel and chromium atoms.

Shape Memory Alloys

Shape memory alloys (SMAs) are metals that remember their original shapes. They can
change shape in response to external factors such as temperature, this is called a phase
change. It is not a phase change in that is is changing into a liquid, but a phase change from one
solid packing structure to another. This is a solid-solid phase change where there
is rearrangement of the position of the atoms in the solid state and the unit cells change.

Nickel-titanium (Nitinol) alloys have been found to be the most useful of all SMAs, the diverse
applications for these metals have made them increasingly important to the world. If you have
braces you may have a SMA in your mouth. The following diagram show the phase changes that
can occur. The two phases, which occur in Nitinol, are called martensite and austenite. When
you cool the sample you change the phase from the austenite to the martensite form. The
martensite phase is very easy to bend and can be deformed. When this is heated it returns to the
austenite form and the original shape is formed.

Allotropes of Carbon
By Cate Elsworth

Diamond is one form of crystalline carbon. Carbon also exists in an amorphous form in
substances such as coal and charcoal. Different forms of the same element are called
allotropes. There are a number of other allotropes of crystalline carbon and these include
graphite and fullerenes. The arrangement of atoms in the crystal differs for each form of carbon
and explains why the different forms have different properties.
Diamond (left) and graphite (right). Image source: Itubderivative work of Materialscientist
Wikimedia commons

Diamond

Diamond is a form of carbon in which each carbon atom is covalently bonded to four other
carbon atoms. This forms a strong, rigid, three-dimensional structure as pictured in the diagram
above. Diamond is the hardest natural substance, and no other natural substance can scratch it.
This property makes diamonds useful for cutting and grinding tools as well as for rings and other
jewellery.

Diamond has a very high melting point (almost 4000C). Very strong carbon-carbon
covalent bonds need to be broken before melting occurs.
Diamond is very hard, due to the very strong covalent bonds that need to be broken.
Diamond does not conduct electricity. All the electrons are held tightly between the
atoms, and are not free to move.
Diamond is insoluble in water.

Graphite
Graphite is a form of crystalline carbon in which each carbon atom is covalently bonded to three
other carbon atoms. The carbon atoms are arranged in layers, with strong bonds within each
layer but only weak bonds between layers which are dispersion forces. The electrons in graphite
are delocalised across the sheets, this makes them easily polarisable. The layers can be seen in
the diagram above.

The weak bonds between layers allow the layers to slide over one another, so graphite is
relatively soft and slippery. This makes it useful as a lubricant.
The delocalisation of electrons within graphite allows it to act as an electrical conductor.

Fullerenes

Fullerene are allotropes of carbon the are different shapes, they can be tubes and hollow spheres.
C60 is a spherical fullerene where each sphere contains 60 carbon atoms, and each carbon atom is
bonded to three others by single covalent bonds and are arranges in rings of hexagons and
pentagons. Electrons are delocalised across the sphere. However there is little movement of
electrons between the molecules.

Cylindrical fullerenes are known as nanotubes. Their unique molecular structure results in
extraordinary macroscopic properties, including strength and high electrical conductivity.

Graphene

Graphene is a super-substance! Related to diamond and graphite, graphene is a better conductor

of electricity than silver, a better conductor of heat than diamond, and stronger than steel. The
future of electronics may rest on its extremely thin surface.

Graphene is graphite that makes up one sheet. Graphene is just one layer of atoms thick. There
are many possible uses for graphene, but research is needed to more easily and cheaply be able to
create a sheet of graphene.