PHASE CHANGE

• Is the transformation of matter from one state to another that involves the absorption or evolution
of heat.

TYPES OF PHASE CHANGE

• The change from solid to liquid is melting, liquid to gas is vaporization, and solid to gas is
sublimation. These changes take place when heat is absorbed (heat gained). They are
endothermic processes.

• The reverse change from gas to liquid is condensation, gas to solid is deposition, and liquid to
solid is freezing. These changes give off heat (heat lost) and are exothermic processes.

HEATING CURVE

Melting and Vaporization require the absorption of heat. The graph shows an increase in temperature as
the substance changes from solid to liquid and then to gas.

Starting with a solid, as heat is added, temperature also increases. At melting point, temperature
remains constant, and this is the temperature where the solid is being converted to liquid. When
all of the solid has been converted to the liquid state, temperature again rises as heat is
continuously added. When the liquid is being converted to its vapor, temperature again remains
constant this is called the boiling point. When all of the liquid has been converted to vapor,
temperature rises again.

COOLING CURVE
 It starts with a high temperature where the substance is present in the gas phase. As heat is
released temperature decreases until the point where the gas is being converted to liquid and the
temperature remains constant. When all of the gas has been converted to the liquid state,
temperature decrease again until a temperature is reached where the liquid is being converted. At
this point, temperature remains constant and both the solid and liquid coexist. This is called
freezing point. When all of the liquid has been converted to solid, the temperature decreases
again.

MELTING AND FREEZING: SOLID- LIQUID EQUILIBRIUM

During the transition, the average kinetic energy of the molecules does not change, so the
temperature stays constant. The melting point of a solid or the freezing point of a liquid is the
temperature at which solid and liquid phases coexist in equilibrium.

Melting points are distinct for each substance. It is dependent on the strength of attractive forces
that hold the particles in the solid. The stronger the attractive forces that hold the particles in the
solid, the higher is the melting point of the substance.

The melting (or freezing) point of a substance when the external pressure is 1 atm pressure is
called its normal melting (or freezing) point. For water, this is 0℃

At 0℃ and 1 atm, the dynamic equilibrium for water and ice is represented by:

ice ⇋ water

When heat is added to this system at equilibrium, ice will continue to melt until all have been transformed
to the liquid state. The amount of heat needed to convert the solid to the liquid state at the melting point is
called the heat of fusion of the substance.

Molar heat of fusion (ΔHfus) is the energy required to melt 1 mole of a solid.
• For water, the molar heat of fusion is 6.01 kJ / mol.
• The molar heat of fusion is equal to the amount of energy released when one mole or 18 grams of
liquid water at 0℃ freezes to ice, still at 0℃.

The heat change (q) for a given sample during freezing or melting may be calculated using the following
equation: is given by
q = m ΔHfus

BOILING AND CONDENSING: LIQUID-VAPOR EQUILIBRIUM

When a liquid is heated, its temperature increases as the kinetic energy of the molecules increases.
When the molecules have sufficient energy to escape from the surface, a phase change occurs.
Evaporation or vaporization is the process in which a liquid is transformed into a gas. The
temperature at which this occurs is the boiling point of the substance. While the liquid vaporizes,
the temperature remains constant.

The boiling point is a characteristic of each substance, and is dependent on the strength of
attractive forces that hold the particles or molecules in the liquid state. It is also dependent on the
external or atmospheric pressure. The boiling point of a liquid at 1 atm pressure is called its
normal boiling point. For water, this is at 100℃.

The reverse of vaporization or boiling is called condensation, the change from the gas phase to the
liquid phase. Condensation occurs because a molecule strikes the liquid surface and becomes
trapped by intermolecular forces in the liquid. This process occurs at the same temperature when
the liquid vaporizes into the gaseous state. The boiling point can thus be also called condensation
point (dew point), and occur at the same temperature.

At the boiling point, both liquid and gaseous states of the substance are present, and the
transformations of liquid to gas and gas to liquid happen at the same time.

At 100℃ and 1 atm, the dynamic equilibrium for water and steam is represented by
 water ⇋ steam

As heat is absorbed, some water will boil off but the temperature remains at 100℃ (373.15 K) until all the
liquid has vaporized. The amount of heat absorbed by the sample as the liquid transforms into gas is
called heat of vaporization.

Molar heat of vaporization (ΔHvap) is defined as the energy (usually in kilojoules) required to vaporize 1
mole of a liquid at a given temperature, usually, at the boiling point. The molar heat of vaporization of
water at 100℃ is 40.79 kJ/mol.

SOLID-VAPOR EQUILIBRIUM

Sublimation is the process in which molecules go directly from solid into vapor phase. The reverse
process is called deposition, where molecules make a transition directly from vapor to solid. The process
may be represented by the following equilibrium:

solid ⇋ vapor

MOLAR HEAT OF SUBLIMATION

Molar heat of sublimation (ΔHsub) of a substance is the amount of energy that must be added to a mole of
solid at constant pressure to turn it directly into a gas, without passing through the liquid phase.

This enthalpy change associated with sublimation is always greater than that of vaporization even
if both sublimation and evaporation involve changing a substance into its gaseous state because in
sublimation, the starting physical state of the substance is the solid state, which is lower in energy
than the liquid state where vaporization starts. , Sublimation requires that all the forces are broken
between the molecules (or other species, such as ions) in the solid as the solid is converted into a
gas.

HEAT CHANGE WITH CHANGE IN TEMPERATURE

• The amount of heat received or removed from the sample to effect a given change in temperature
can be calculated using the Specific heat of the substance . This is the amount of heat needed to
raise the temperature of 1 gram of a substance by 1 ℃. It is also equal to the amount of heat lost
by 1 gram of substance when its temperature drops by 1 ℃.
• The specific heat of a substance differs for the solid, liquid, and gaseous states. Water as an
example, has the following specific heat at different phases:
 𝐇𝟐 O (l) = 4.18 J / g ℃
𝐇𝟐 O (s) = 2.06 J / g ℃
𝐇𝟐 O (g) = 2.02 J / g ℃

The heat change (q)

q = m S ∆𝐓

where: m = mass of the sample in grams

S = specific heat of the sample in the appropriate physical state
T = change in temperature

Sample problem:
1. You found a piece of copper metal weighing 3.10 g imbedded in an ice block. How much heat is
absorbed by the piece of metal as it warms in your hand from the temperature of the ice block at
1.5 ℃ to your body temperature of 37 ℃? The specific heat of copper is 0.385 J / g −℃. Assume
that the metal is pure copper.

2. How much energy is required to change 2600 grams of ice at 0 ℃ into water at the same
temperature?

3. Calculate the amount of energy (in kJ) needed to heat 346 gram of liquid water from 0 ℃ to 182 ℃.

4. Calculate the heat released when 68.0 gram of steam at 124 ℃ is converted to water at 45 ℃.
 Intermolecular Forces of Liquids
and Solids; Phase Diagrams

What is a phase diagram?

A phase diagram is a graphical representation of the physical states of a substance under different
conditions of temperature and pressure. It gives the possible combinations of pressure and temperature at
which certain
physical state or states a substance would be observed.

What are the features of a phase diagram?

A. The Three Areas B. Three Lines (Curves)

1. The green line divides the solid and liquid phases, and represents melting (solid to liquid) and freezing
(liquid to solid) points.
Melting (or freezing) curve – the curve on a phase diagram which represents the transition
between liquid and solid states. It shows the effect of pressure on the melting point of the solid.
Anywhere on this line, there is equilibrium between the solid and the liquid.

2. The blue line divides the liquid and gas phases, and represents vaporization (liquid to gas) and
condensation (gas to liquid) points.
Vaporization (or condensation) curve – the curve on a phase diagram which represents the
transition between gaseous and liquid states. It shows the effect of pressure on the boiling point of
the liquid. Anywhere along this line, there will be equilibrium between the liquid and the vapor.

3. The red line divides the solid and gas phases, and represents sublimation (solid to gas) and deposition
(gas to solid) points.
Sublimation (or deposition) curve – the curve on a phase diagram which represents the
transition between gaseous and solid states. It represents the effect of increased temperature on a
solid at a very low constant pressure, lower than the triple point.

C. Two Important Points

The triple point

The triple point is the combination of pressure and temperature at which all three phases of matter are at
equilibrium. It is the point on a phase diagram at which the three states of matter coexist. The lines that
represent the conditions of solid-liquid, liquid-vapor, and solid-vapor equilibrium meet at the triple point

The critical point

The critical point terminates the liquid/gas phase line. It is the set of temperature and pressure on a
phase diagram where the liquid and gaseous phases of a substance merge together into a single phase.
Beyond the temperature of the critical point, the merged single phase is known as a supercritical fluid.
The temperature and pressure corresponding to this are known as the critical temperature and critical
pressure.

If the pressure on a gas (vapor) is increased at a temperature lower than the critical temperature, the
liquid-vapor equilibrium line will eventually be crossed and the vapor will condense to give a liquid.

How is the normal melting and boiling points determined in a phase diagram?

The normal melting and boiling points are those when the pressure is 1 atmosphere.

The Phase Diagram for Water

For water, the melting point gets lower at higher pressures. This is because solid ice is less dense than
liquid water. This phenomenon is caused by the crystal structure of the solid phase. In the solid forms of
water and some other substances, the molecules crystallize in a lattice with greater average space between
molecules, thus resulting in a solid occupying a larger volume and consequently with a lower density than
the liquid. When it melts, the liquid water formed occupies a smaller volume

ice ⇋ water

An increase in pressure will move the above equilibrium to the side with the smaller volume. Liquid water
is produced. To make the liquid water freeze again at this higher pressure, the temperature should be
reduced. Higher pressures mean lower melting (freezing) points.

The Phase Diagram for Water The Phase Diagram for Carbon Dioxide
Refer to the following phase diagram of a certain substance to answer the following questions.

1. In what phase is the substance at 50 °C and 1 atm pressure?

2. At what pressure and temperature conditions will all three phases of the substance be present?
3. What is the normal melting point of the substance?
4. What phase(s) will exist at 1 atm and 70 °C?
Solve and analyze the following problems.

1. What is the amount of heat required to convert 105 g of ice at – 15.2℃ to liquid water at 35.6℃.
2. Calculate the heat absorbed when 542 g of ice at – 15.0℃ melts and then the water is converted to
steam at 145℃
3. Calculate the heat release when 32.0 g of steam at 115℃ condenses and then the water s
converted to ice at – 15.0℃.

Refer to the following phase diagram of a certain substance to answer the following questions.

1. In what phase is the substance at 50 °C and 1 atm pressure?

2. At what pressure and temperature conditions will all three phases of the substance be present?
3. What is the normal melting point of the substance?
4. What phase(s) will exist at 1 atm and 70 °C?
Solve and analyze the following problems.

1. What is the amount of heat required to convert 105 g of ice at – 15.2℃ to liquid water at 35.6℃.
2. Calculate the heat absorbed when 542 g of ice at – 15.0℃ melts and then the water is converted to
steam at 145℃
3. Calculate the heat release when 32.0 g of steam at 115℃ condenses and then the water s
converted to ice at – 15.0℃.