Properties

Types of Properties
Thermodynamic properties are divided into two broad types: intensive properties and extensive
properties.
An extensive property is any property that depends on the size (or extent) of the system under consideration.
Volume is an example. If you double the length of all edges of a solid cube, the volume increases by a
factor of eight. Mass is another. The same cube will undergo an eight-fold increase in mass when the
length of the edges is doubled.
An intensive property is any property that can exist at a point in space. Temperature, pressure and density
are good examples. You could imagine moving a thermometer about a room or a pressure sensor about a
swimming pool so as to record the property at each location (point in space). You also know that the
density of the atmosphere is different from point to point, with air nearest the ground having the highest
density and air far above the earth's surface having the lowest.
On the other hand, it is silly to think of the volume of your swimming pool as being a property at a point.
It is a characteristic of the entire swimming pool and that makes it extensive.
A particularly important type of intensive property is the specific property, which is always given on a unit
mass basis. An example is specific volume, which has units of volume/mass, typically expressed as cubic
feet per pound or cubic meters per kilogram. Specific properties are intensive because they exist at a
point. For instance, specific volume is simply the reciprocal of density.
There is an important relationship between specific properties and extensive properties. Consider the case
where the intensive properties of a system are uniform, meaning they are the same at each point within the
system. The total volume V of the system (say in cubic feet) could be calculated from the mass M of the
system (in pounds) and the specific volume v of the material comprising the system (in cubic feet per
pound) by:
V = vM
This equation only works if the specific volume is constant throughout the system. Although this is not
always true, it is often sufficiently accurate to assume so. For instance, if you wanted to know the mass of
air in your bedroom, you could measure the volume of the room with a yardstick (to get V) and look up the
specific volume of air (v) at ambient conditions and calculate M from V/v. You would do this even though
the air near the ceiling has a slightly different density than the air near the floor.
Notice that we used an upper case V to represent the extensive property volume and a lower case v to
represent the intensive property specific volume. We will continue to follow this convention. Exceptions
are temperature and pressure which are generally represented by upper case letters T and P, even though

they are intensive properties.

You might wonder why we need to be concerned with both intensive and extensive properties. It is because
the expressions for the first and second laws of thermodynamics will be written in terms of extensive
properties and the charts we use to look up property values will contain intensive properties. So we will be
using V=vM (and the analogous equations for properties other than V) to convert the chart properties to
extensive variables for use in the equations.
Independence of Properties
There are a number of different intensive properties that are used to characterize material behavior. We
have already discussed temperature, pressure and density. A few other examples are heat capacity,
viscosity, thermal conductivity, and electrical conductivity. Of particular importance is the question of how
many of these properties can be regarded as independent variables. In other words, how many properties
can we specify before nature fixes the values of the rest of them? Can we, for instance, specify that we want
water that has a temperature of 50 oC, a pressure of 2 atm and a heat capacity of 1.0 cal/g oC?
It turns out that the magic number is 2 (observed experimentally and later verified theoretically). To put it
more formally:
For a pure substance existing in the form of a single phase (solid, liquid or gas), specifying the values of any
two intensive variables will fix the values of all of the others.
This result will have some importance in the following pages, where we will discuss the relationship
between pressure, specific volume and temperature for a pure substance. Before moving on, let us
summarize the important points about properties.

Important Points:

Extensive properties depend upon the size of the system. Intensive properties apply at a point.
Specific properties are intensive properties that are on a "per unit mass" basis.

If properties are uniform throughout a system, specific volume v may be related to total volume V
through V = Mv.

For a single phase of a pure substance, specifying values of any two variables fixes the remaining
ones.

Phase Diagrams of Pure Substances:

a Tutorial

Introduction
In thermodynamics, a system is a region of space of which we have some interest. Often the system will
consist of one or several pieces of equipment that we wish to use to accomplish a particular task. It may be
a boiler that we want to use to make steam, a pump to circulate water, or a gas turbine to produce power.
Most thermodynamics problems involve finding the heat and work flows that must be supplied to (or
removed from) the system to obtain the desired result.
In your study of thermodynamics, you will find that these heat and work flows depend on the properties of
the material inside or flowing through the system. For instance, if you want to change the temperature of
one pound of water by 10 degrees, the heat required will be different from that needed to change the
temperature of one pound of air by 10 degrees.
Thus, before you learn how to apply the laws of thermodynamics to solve for heat and work flows, you
must first understand a bit about properties of materials.
The purpose of this tutorial is to familiarize the reader with the relationship between three important
properties of pure substances: pressure, specific volume, and temperature. The relationship between these
properties generally is given in the form of a phase diagram, in which the different regions of phase state
(solid, liquid, and vapor and their combinations) are shown. An understanding of such diagrams is
essential to thermodynamics because there will be many occasions in which you will have to refer to a
phase diagram (or a tabular representation of one) in order to obtain needed property information.

Specifically, at the end of this tutorial the reader will

understand the different types of properties (intensive, extensive, specific) used to characterize pure
substances and know how many of them can be regarded as independent.

be able to identify the various parts of a three dimension Pressure-Volume-Temperature (PvT)

phase diagram including those regions where a single phase exists and those where two phases
coexist.

understand the various two-dimensional projections of the three-dimensional PvT surface.

know all of the basic nomenclature associated with phase diagrams of pure substances.

Later tutorials will focus on using phase diagrams to obtain property information, not only about
temperature, pressure and specific volume but for other properties as well.
This tutorial can be followed from one page to the next or you can jump to different topics using the
Contents. The latter is recommended only if you have already been through the tutorial once.
Before we jump into the relation between pressure, specific volume and temperature, we need to discuss a
few general points about thermodynamic properties. This is done on the next page.

Pressure-Volume-Temperature Relation
While there are a number of different properties that important in the field of
thermodynamics, the focus of this tutorial is on pressure, specific volume and
temperature of a pure substance. This is a good starting point because we can
imagine how each of these intensive properties could be measured. All we need is
a pressure gauge, a thermometer, a ruler (to measure volume) and a scale (to
measure mass so we can calculate specific volume). As you will see later, not all
thermodynamic properties are as easily obtained.
Another reason to focus on pressure, specific volume and temperature is that they
form the simplest set of variables from which a phase diagram can be constructed
- and gaining an understanding of phase diagrams is the point of this tutorial.
On the previous page, we discussed how, for a single phase, specifying two
intensive properties fixed the rest. Therefore, we can think of specific volume,
pressure and temperature as forming a relation (called the Pressure-VolumeTemperature or PvT relation) between two independent variables and a dependent
one. Which of these properties we consider to be the dependent one will depend

on the problem we are trying to solve.

The easiest way to understand the PvT relation is to generate it by a thought
experiment. Consider the piston-cylinder shown under letter A to the right.
Imagine that we have placed some liquid water in the cylinder and sealed it with
the piston ensuring that no air is present with the water. (You may want to
exercise your creative muscles and come up with an idea for how you might
practically accomplish this.) We will assume the piston to be freely floating (no
friction between the piston and the cylinder). Now we place the entire assembly in
a constant temperature bath at 100 degrees Fahrenheit and let the system
equilibrate. We will assume that the pressure of the water in the cylinder is
exactly one atmosphere (1 atm). You may be thinking that this is not possible
because the pressure of the water will equal the pressure of the external
atmosphere plus the additional pressure generated by the weight of the piston.
This is a thought experiment though so we can cook up some way to make the
pressure of the water equal to one atmosphere. For instance, we could imagine
that the entire assembly is in an evacuated chamber and the mass of the piston is
chosen so as to produce a pressure of exactly 1 atm on the water.
Now we add heat to the piston-cylinder assembly by increasing the bath
temperature. Let us suppose we increased the temperature to 200 degrees
Fahrenheit. What will happen to the temperature of the water in the cylinder?
We would observe that it would increase until it reached equilibration with the
bath temperature as shown in drawing B. What about the pressure of the water?
This might be a little tricky: It would remain constant because the piston is freely
floating. Take some time to convince yourself of this. Hint: Do a force balance at
the interface between the piston and the water. What are the forces acting
downward? Have any of these changed when we added heat to the water? If not,
will the upward force (caused by the pressure of the water) change?
We note also that the volume of the water increased (reflected by the rise of the
piston) as our system evolved from point A to B. Since the mass of water is
constant, this means that its specific volume must have increased. Why? Because
it is observed that liquids expand as temperature is increased at constant pressure.
Now suppose we change the bath temperature to 220 degrees. What will
happen? The pressure will remain constant and the temperature of the water will
begin to rise so as to equilibrate with the bath temperature. Therefore the volume
(and specific volume) of the water will increase as well. We make a curious
observation though. When the water temperature reaches 212 degrees (on its way
to 220) we observe a small bubble of water vapor form (Figure C).
In these drawings, dark blue represents liquid water and light blue represents
water vapor.
Now heat continues to flow into the water from the bath because the water is still
at a lower temperature. However, we observe that the temperature of the water in

the cylinder does not change. Also, we notice that the volume continues to increase
but not because the temperature is changing. Rather it increases because the
liquid is vaporizing and the specific volume of vapor is larger than that of liquid.
This vaporization of water is illustrated by Figures C, D and E to the right.
Imagine now that Figure E represents the point at which the last small drop of
liquid vaporizes. What will happen at this point? Now the water is all vapor and
it will behave similarly to as it did when it was all liquid: The temperature of the
water vapor will begin to rise (at constant pressure) and will continue to rise until
it reaches 220 degrees (Figure F). The volume (and specific volume) will increase
because gases expand as temperature is increased at constant pressure.
Note that there were three distinct parts to this experiment: One in which the
water was entirely liquid, one in which it was entirely vapor, and one in which two
phases were present.
We can imagine plotting our results on a diagram of temperature T versus specific
volume v. Each point A through F would be plotted and then connected by a line.
For points in which two phases were present, we will simply divide the total
volume inside the piston-cylinder by the total mass of water (liquid+vapor). The
specific volume that we obtain in this manner would be an average value and
would be intermediate to the specific volumes of the individual vapor and liquid
phases.

Note that every point on the red line (which represents the continuum of states
that the water passed through) is at the same pressure of 1 atmosphere. We call
this line an isobar or line of constant pressure. Take a minute to convince yourself
that the line from A to C represents liquid water, from C to E represents two phase
behavior, and from E to F represents water vapor. We will call a diagram of this
type a Temperature-Volume or Tv diagram. Tv diagrams show the relation
between temperature and specific volume along lines of constant pressure
(isobars).

Now some nomenclature. Imagine that state C represents the point at which the
water is entirely liquid but the first very small bubble of vapor is just about to
form. The water in this state is called saturated liquid. Likewise, imagine that
state E represents the point at which the last drop of liquid has just disappeared
and the system is entirely vapor. The water vapor in this state is called saturated
vapor. In this context, saturated means that a single phase is right at the point of
becoming two phases. The specific volumes of the saturated liquid water in C and
the saturated water vapor in E are given the symbols vf and vg respectively.
Note that the horizontal portion of the isobar corresponds to the part of the
experiment in which two phases were present. We observed that the temperature
remained constant at 212 degrees. The temperature at which liquid and vapor
phases of a pure substance coexist at a given pressure is called the boiling
temperature Tb at that pressure. Thus the boiling temperature of water is 212
degrees Fahrenheit at a pressure of 1 atm.
This leads to an important point that we will return to several times: For those
states in which liquid and vapor were present at the same pressure, the
temperature was always the same value and is called the boiling temperature.
Thus, the boiling temperature of a pure substance depends only on the pressure
and not on the specific volume. To put it another way: When vapor and liquid
phases are present, there is a one to one relationship between temperature and
pressure. Specifying one fixes the other.
Note that this is different from what happens in a single phase where both
pressure and specific volume (two intensive variables) would have to be specified
in order to fix the temperature. We will find later that the same thing happens
when we have coexisting solid and liquid phases and coexisting solid and vapor
phases.
The specific volumes of the saturated liquid and saturated vapor, along with the
boiling temperature, are illustrated for our experiment in the next drawing:

Important Points:

The PvT relation provides the relationship between pressure, specific

volume, and temperature.

In a single phase, two of these properties must be specified in order to fix

the third.

When both liquid and vapor phases are present, there is a one-to-one
relationship between temperature and pressure. The temperature when
two phases are present is called the boiling temperature.

Saturated liquid refers to a liquid that is at the point of forming a vapor

phase. Saturated vapor is vapor that is at the point of forming a liquid
phase.

An isobar is a line of constant pressure.

a Temperature-Volume (Tv) diagram shows the relation between

temperature and specific volume along isobars.

One of the advantages of Web-based tutorials is that they allow for animation.
The static description of the thought experiment given here may be easier to
visualize in an animated form. The animated version of the experiment is given on
the next page. Spend a few minutes with it to fix the ideas presented on this page.

Generating the Tv Diagram

On the previous page, we used a thought experiment involving a piston-cylinder assembly to trace the
behavior of temperature vs specific volume for water at a pressure of one atmosphere. Now we will
examine what happens at other pressures.
Suppose that we were to throw some weights on the piston so as to make the pressure of the water equal to
10 atmospheres. Then we repeat the experiment. What do you think would happen? Ask yourself first
what would happen to the boiling temperature: would it increase or decrease? It turns out it would
increase. In other words, boiling temperature increases with increasing pressure and decreases with
decreasing pressure. Any of you that have tried to cook food in boiling water while camping in the

mountains (lower atmospheric pressure) have probably observed that the water boils at a lower
temperature.
So if pressure is increased from 1 atm to 10 atm, the boiling temperature of the water would increase and
our isobar for the new experiment might be expected to look like this:

Notice that in addition to an increase in boiling temperature there is also a change in the specific volumes of
the saturated liquid and vapor.
The fact that the boiling temperature of a substance depends on pressure may seem counter-intuitive to
those of you that are used to hearing that the boiling temperature of water is 212 degrees Fahrenheit. This
is a result of sloppy semantics. The boiling temperature of a pure substance at a pressure of 1 atm is called
the normal boiling temperature. So the correct usage is that the boiling temperature of water depends on
the pressure but the normal boiling temperature of water is 212 degrees Fahrenheit.
We are on a run now so let's add more weight to the piston and do the experiment again. In fact, let's
assume that we have added weight to the piston such that the pressure of the water is 218 atmospheres. We
would observe a curious result: At no point would we ever observe two phases inside the cylinder. The
isobar of the process is shown by the 218 atm line in the next drawing and it would have the characteristic
that it becomes flat at only one single point - a horizontal inflection point:

If were to add even more weight, say enough to generate a pressure of 280 atmospheres on the water, we
would obtain an isobar that was not flat at even a single point:

Whats going on here? It turns out for water that 218 atm is the highest pressure for which a liquid and a
vapor can coexist (and there only at the single point in which the isobar is flat) . For any higher pressure,
water will always be in a single phase - no matter what the temperature or specific volume are.
Recall that the flat regions of the isobars correspond to states for which vapor and liquid coexist. Also, we
know that the ends of these flat regions correspond to saturated liquid and saturated vapor states. We can
connect the locus of all saturated liquid states and saturated vapor states to show the region where two
phases are present:

Note that for any state inside the green dome, vapor and liquid are both present. Anywhere outside the
dome, only a single phase is present. Note also that the isobar that became flat at a single point coincides
with the highest point of the two-phase dome.
We know that the region to the left of the dome is liquid and the region to the right is vapor but what
happens above the dome? And if we were to follow the highest isobar in the drawing above from its lowest
temperature to its highest, would that not suggest that we have moved from liquid to vapor without moving
through a two phase region?
We will examine these questions on the next page. Before doing so, let's review the important ideas from
this page.

Important Points:

The boiling temperature of a pure substance increases with pressure. The specific volumes vf and vg

of the saturated liquid and vapor also change with pressure.

The normal boiling temperature of a pure substance is the temperature at which it boils under a
pressure of exactly 1 atm.

A series of isobars can plotted on a Tv diagram. If the locus of all saturated liquid and vapor states
are connected, a dome enclosing the region of two phases (liquid+vapor) results.

Each pure substance has one isobar that becomes horizontal (flat) at only one point. This point
coincides with the top of the two-phase dome.