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Liquid Phase
Molecules move randomly with all three types of motion, but they are much closer
together and cannot travel very far between collisions.
Solid Phase
Atoms or molecules have all three types of motion, but they are very close together.
As a result, they cannot travel far at all before they collide.
Each molecule moves about within a small space and does not tend to wander.
Solid phase
Ch2, Lesson A, Page 4 - What Are Gas, Liquid and Solid Phases ?
Whats the difference between a gas, a liquid and a solid ?
The first things that come to mind usually have to do with measurable properties of each phase
such as density.
But at a molecular level, we could see some more fundamental differences.
In all phases, all the molecules or atoms are in motion. They can move in a variety of ways, but
the different types of motion are categorized as vibrational, rotational or translational motion.
Vibrational energies are related to changes in the length, and angle of the bonds within the
molecule. There can be many modes in which a molecule can be vibrating at the same time.
Rotational energy is the kinetic energy stored in a molecule because it is spinning.
Translational energy is the kinetic energy in a molecule because it has linear velocity.
The total energy stored in molecules in these forms is called the internal energy and we use the
symbol U for the total internal energy of a piece of mater.
The higher the temperature of a given pure substance, the higher its internal energy.
Well learn more about internal energy in the next chapter.
The first thing you might notice if you could view the 3 phases on a molecular scale is the
average distance between molecules.
In a gas phase the molecules are far apart, while in liquids and solids they are very close
together. As a result, gases are often called dispersed phases while liquids and solids are called
condensed phases.
Molecules in a gas phase have lots of vibrational, rotational and translational energy and
therefore have higher internal energies than when they are in the liquid or solid phases.
Similarly, molecules in the liquid phase tend to have higher internal energies than the same
molecules in the solid phase.
Its not as simple to compare internal energies of DIFFERENT molecules.
Now, solids have relatively rigid structure. But, the molecules or atoms in the lattice still vibrate,
rotate and translate. They just tend to stay within a small volume between the neighboring
molecules or atoms. They dont wander about too much.
OK, so what happens to molecules or atoms when a phase change such as boiling or melting
occurs ?
Well get to that in a minute, but first, can you think of any other phases besides the 3 principal
phases shown here ?
A system can have multiple liquid phases when the substances do not dissolve in each
other. Such substances are called immiscible.
For example, oil is not miscible in water. Thus, when oil and water are mixed, two
layers, or liquid phases, will exist.
When a system has multiple liquid components that completely dissolve in each
other,they are said to be miscible.
The resulting mixture can be considered apure substance if neither liquid participates in
a chemical reaction.
Phase Changes
Principle Phases: solid (ice), liquid (water), and gas (water vapor).
Phase Equilibrium
Consider a glass of ice water placed inside a sealed, perfectly insulated container.
Initially, the ice begins tomelt and the water begins to evaporate.
Eventually, the ice stops melting and the water stops evaporating.
The system has reached phase equilibrium.
Lesson Summary
Chapter 2, Lesson A - Introduction to Pure Substances
In this lesson we learned some fundamental ideas about the nature of matter and the
phases in which it can be found. First we studied the concept of a pure substance.
Then, we complicated matters by introducing the idea that a homogeneous mixture can
sometimes be considered a pseudo-component and treated like a pure substance. The
fact that multiple phases are present does not influence whether a substance is pure or
not.
This brought us to a general discussion of the nature of phases. We
discussed solids, liquids and gasesand the differences between them. This gave us a
chance to introduce the concepts of vibrational, rotationaland translational energies.
Before you studied this lesson you probably thought there were only three phases. Now,
you know that there can be many different solid phases, such as diamond and graphite,
as well as multiple immiscible liquid phases, such as oil and water.
Once we understood the nature of a phase, we introduced the concept of phase
equilibrium. We learned that gases and multiple liquid and solid phases can ALL be
in equilibrium with each other. We empasizedvapor-liquid equilirium (VLE) because
it is crucial to this course.
In the next lesson, we will study the relationship
between pressure, volume and temperature. This is really the heart of classical
thermodynamics. In Lesson 2E, we will learn much more about VLE.
= P* ).
Saturated Mixture :
A mixture of saturated liquid and saturated vapor in equilibrium. The temperature is the
saturation temperature, Tsat ,and the pressure is called the vapor pressure
P*= P
= P* ).
Superheated Vapor:.
A vapor at a temperature above its boiling point ( T
If you take a tiny bit of energy out of a satd vapor, keeping the pressure constant, some of the
vapor will condense and create a liquid phase. That liquid phase will be a satd liquid.
Do you see ? Satd vapor and liquid are phases that ARE or at least COULD be in equilibrium
with each other.
So what if we have liquid water at 1 atm and only 25oC ? Is this a satd liquid ? NO, because T
(25oC) is less than Tsat at 1 atm (100oC). Understand ? This is called a subcooled liquid because
it exists at a temperature BELOW the saturation temperature for that pressure.
Similarly, what if we have water vapor at 1atm and 125 oC ? This NOT a satd vapor because T >
Tsat. This is called a superheated vapor.
Quality x :In a mixture of saturated vapor and saturated liquid, the quality is the
fraction of the total mass that is in the vapor phase .
This is a very important quantity because vapor and liquid have dramatically different
thermodynamic properties.
It is VERY important to note that regardless of the quality of the 2-phase mixture, you can always
determine the molar volume of the satd liquid at a given pressure by reading the molar volume
from the satd liquid curve at that pressure.
The same is true for the satd vapor.
Consider the fact that as the quality increases the total volume of the system also increases.
However, the molar volume of the satd liquid at a given pressure and the molar volume of the
satd vapor remains constant. Remember that molar volume has units of volume per mole.
The point is that the properties of satd liquids and vapors DO NOT depend on the quality !
The range of temperature and molar volume shown on this phase diagram is most important to
this course.
Now, lets consider a P-V Phase Diagram.
Roll the mouse over number 3 to see the sats vapor curve. The 2-phase envelope may be
shaped a bit differently in a P-V diagram, but its meaning doesnt change. All of the ideas and
equations associated with quality apply to P-V diagrams in the same way they did for T-V
diagrams.. X = 0 for sats liquids and X = 1 for satd vapors.
The critical point, number 4, is still located where the satd liquid and satd vapor curves meet.
Roll the mouse over number 5. The isotherm that passes through the critical point is called the
critical isotherm and we represent this temperature with the symbol Tcr. Roll-over the number 6.
Now, we didnt mention this when we discussed the T-V Diagram, but what happens when the
temperature is greater than Tc ?
This is called a super-critical fluid and the isotherm labeled number 6 is a super-critical isotherm.
We will discuss super-critical fluids in more detail when we discuss P-T diagrams in the following
pages..
In our P-V diagram, we also expanded the range of pressures and volumes to include regions
where solids exist. These regions exist in T-V diagrams as well, but we wanted to break you into
all of these ideas slowly.
This P-V diagram represents a substance in which the solid has a smaller molar volume than the
liquid. This means the solid is more dense than the liquid. Some substances do not follow this
trend. Water is the most common example of a fluid in which the solid is less dense than the
liquid. Basically, ice floats. The concept of solid-vapor equilibrium is probably new to you. Click
to the next page and Ill tell you a little more about it.
Critical Point:The point at which the saturated liquid curve and the saturated vapor
curve meet.At the critical point, the saturated liquid and saturated vapor phases are
the same.
Triple Point:The point at which solid, liquid and vapor phases can all exist
in equilibrium. All three of the processes listed above can occur. At equlibrium the
forward rateequals the reverse rate for each process.
Ch2, Lesson B, Page 7 - Key Terms to Describe the P-T Phase Diagram
Here are a few more definitions that will help us understand P-T Phase Diagrams.
Vaporization should be a pretty familiar concept to you. It is commonly called boiling when the
fluid under consideration is a pure substance.
Condensation is the same process going in the opposite direction. A vapor condenses to enter
the liquid phase.
Melting is probably also pretty familiar to you. Freezing or fusion is the process by which a pure
liquid is converted into the solid phase.
The phase change that is probably new to you is called sublimation.
Sublimation and de-sublimation relate to solid-vapor equilibrium in the same way that
vaporization and condensation relate to VLE.
The most common example of sublimation occurs in the ice-cube tray of the freezer in your
kitchen.
If you leave the ice cubes in the freezer too long, they shrink ! The cubes no longer fill the slots in
the tray.
You see, over a period of time, the ice sublimates and the water molecules move from the solid
phase directly into the vapor phase without ever forming a liquid.
The conclusion that we draw is that solids, just like liquids, exert a vapor pressure ! More about
this when we look at the P-T Diagram on the next page.
I hope you remember what the critical point means, but the triple point may be new to you.
Recall that in the 2-phase envelope satd liquid and satd vapor both existed at equilibrium.
Well, at the triple point, satd liquid and vapor exist in equilibrium with the solid phase !
Since all 3 phases are in equilibrium, all 3 of the processes I just mentioned are occurring
simultaneously.
Equilibrium means that the three reverse processes are also occurring and that the rates of the
three forward processes are exactly equal to the rates of the three reverse processes.
Evaporation and condensation are occurring at the same rate.
Melting and freezing are occurring at the same rate.
And sublimation and de-sublimation are occurring at the same rate.
Now, lets see how all these ideas translate into a phase diagram.
Lesson Summary
Chapter 2, Lesson B - P-V-T : Phases and Phase Diagrams
In this lesson, we began by introducing the two important intensive variables and .
We used to help us define two of the three key phase diagrams for a pure substance:
the T-V Diagram, the P-V Diagram and the P-T Diagram.
We used these three types of diagrams to help explain the nature
of subcooled and saturated liquids and saturated and superheated vapors. This led into
an explanation of saturation temperature and vapor pressure. We will consider these
topics in more detail in lesson 2D. We also learned that the saturated liquid curve and
the saturated vapor curve meet at the critical point to form the two-phase envelope on
both the T-V Diagram and the P-V Diagram. We took this opportunity to define
a supercritical fluid. Next, we briefly discussed solid-liquid equilibriumand solid- vapor
equilibrium and how they are represented on a P-V Diagram.
The P-T Diagram looks quite different from the other two phase diagrams. Here we
introduced the ideas of sublimation-desublimation, melting-fusion, vaporizationcondensation and the dynamic nature of phase equilibrium. We also described the triple
point and contrasted substances that contract upon fusion with those
that expand upon fusion. Water is the most notable example of a substance
that expands when it freezes.
In the next lesson, we will consider how to obtain P-V-T data from tables.