Chapter 1:

Systems, Properties and State.

Thermodynamics is the study of the transformation of energy from one form to
another, particularly from heat into work.

In older times subjects of with content like this were called “Heat Engines”.

Sadi Carnot (1824) recognized that:

• Engines use a working substance. (Steam, air etc.)
o That substance can be solid liquid or vapour, but the vapour phase
presents more opportunities.
• The working substance executes a cycle. ie. The working substance is changed
by a sequence of operations that is repeated frequently and regularly.

Some definitions:

• A system. It is convenient to identify the matter to which physical laws (such

as conservation of mass, momentum and energy) are to be applied. That
collection of matter is called a system.
o It is important to recognize precisely the system to which you are
applying physical laws. For example, if you are investigating the
motion of two billiard balls, and apply conservation of energy to one
ball and conservation of momentum to the other, the variables in the
two equations may well look the same but they apply to two different
objects.
o A system is not necessarily a single item. Both billiard balls together
may be considered as one system. Systems may consist of a large
number of different components.
• System boundary.
o A system may be envisaged as being enclosed by an envelope called
the system boundary.
o Clearly no matter can pass through the system boundary. If it did, you
would no longer have the same system. The mass of a system cannot
change (conservation of mass).
o System boundaries may move along with the system they define.
• An Isolated system. Energy may cross a system boundary. For example heat
may be transferred into the system, or work may be performed by a system as
it moves its boundary against some resisting force. An isolated system is one
in which energy transfer across the system boundary is prevented.
• Properties and State of a System.
Associated with any system there are a number of variables that are connected
by the nature of the system.

Those variables that are related by the nature of the system are called
properties of the system.

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Example:
If the system is a tension spring, the force F and extension x are related by the nature
of the spring. If it were a rubber spring the relationship would be non-linear, but if the
spring were steel it would probably be linear. Whatever the relationship it could be
graphed and, from there on, knowing either property one could look at the graph and
find the other.

o If a sufficient number of properties are known then reference to a

graph, table, equation or similar would allow the determination of the
rest. In the example of a spring, knowing F allows x to be found, or
conversely knowing x allows F to be found. More complex systems
require more known properties, but the principle still applies.

o If sufficient properties are known to allow the rest to be determined

then the state1 of the system is known. In the spring example, either F
or x is sufficient to tell us how much the spring has been deformed.
The amount of deformation is the state of the system and it can be
measured by either of the properties.

Example:
Consider a system that consists of 1.0 kg of water at atmospheric pressure and 100 °C.
The statement “1.0 kg of water” defines the system. The pressure and temperature
define its state. ie. boiling water. From that information, provided someone has done
the experiment before and made the data available to you, you would expect to be
able to find: the density, the volume, the viscosity, the thermal energy content
(internal energy), the thermal expansion coefficient, the thermal conductivity and
electrical conductivity of the water. It would be expected that all samples of water
would give the same results for those variables at that temperature and pressure. All
of those variables are properties of the system. All are variables which would change
(in some cases only slightly) if the state of the system were changed (eg. If the
temperature were reduced to 50 °C).

o Not all of the variables involved in a problem are properties of the

system. Time is a good example. For the spring, the tension may well
be a function of time, but time has nothing to do with the relationship
between the tension and extension. The natural length of the spring
likewise has nothing to do with the relationship between tension and
extension. The mass of the spring is not even a variable. It cannot be
changed without redefining the system.2

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Do not confuse state with phase. Ice, water and steam are phases of an H2O system. (Solid, liquid and
gas are possible phases of most materials.) As you should know, from physics and materials science,
iron has numerous solid phases, as does sulphur. The state of a system is a more subtle and more
specific concept. To say that a system consists of 1.0 kg of H2O defines the system. To say that it is
water identifies its phase. To then add that the temperature is 45ºC and the pressure 200 kN/m2 defines
its state.
2
Many books on thermodynamics get this wrong. Many say explicitly that mass is a property of the
system. Many of those same books later treat Gibbs Phase Rule, which shows how many properties are
needed to identify the state of a system, and at that point it is clear that mass cannot be a property, but
they fail to notice.

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 • Extensive and intensive properties. Properties are divided into two groups,
extensive properties and intensive properties. If two systems in the same state
but of different mass are considered, some of the properties are proportional to
the mass and others are not.

Example:
Consider two systems. One system is 2.0 kg of boiling water at 101.3 kN/m2 pressure.
The other is one is 1.0 kg of boiling water at 101.3 kN/m2 pressure. They are both in
the same state. The temperature, pressure, density, viscosity and thermal conductivity
will be the same for both systems; these are the intensive properties. On the other
hand the volume and stored energy of the first system will be precisely twice that of
the second because it has twice the quantity (mass) of water.

o Properties that are proportional to the mass of the system are called
Extensive Properties. The total volume of the system is an example of
an extensive property.
o Properties that are independent of the mass of the system are called
Intensive Properties. Pressure and temperature are examples of
intensive properties.
o For every extensive property there is a matching intensive property.3
V
For example Volume V and specific volume v = . Specific volume
m
and density ρ = 1 are both intensive properties.
v
o Some intensive properties have no extensive counterpart, eg.
Temperature T is an intensive property, but the counterpart extensive
property mT has no physical use and effectively does not exist.
Similarly density and pressure are intensive properties with no
extensive counterparts.
o It is convenient to use capital letters for extensive properties and lower
case letters for intensive ones. For example V and v. The exception to
this rule is T for temperature (an intensive property) and t for time
(which is not a property at all).

• Dependent and Independent Properties of a System. If the density ρ of a

system is a property then it follows that the specific volume is also a property
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since v = . However it is not particularly helpful to know both the density
ρ
and specific volume because the two are related by their definition. v and ρ are
called dependent properties. Likewise the kinetic energy and velocity are
related by definition, as are potential energy and height. The above are
examples of properties that are dependent because of their definitions.

Properties like volume and pressure are usually independent because

knowledge of one is not sufficient to find the other. However consider the
contents (both water and steam) of a boiling kettle as a system. If the pressure

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If the mass of a system were a property, would it be extensive or intensive?

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 is known then the temperature is the corresponding boiling temperature.
Similarly, if the temperature is known then the pressure is the corresponding
boiling pressure. On this occasion temperature and pressure are not
independent properties. Their dependence is not because of their definition but
because of the nature of the system.

Note too that the thermal energy content and the total volume, which are
independent properties, depend on how much of the system is water and how
much is steam.

• Constitutive Equations and Equations of State. For simple systems (like the
spring) it is often possible to express the relationship between properties by an
equation (F = k x, Hooke’s law). In thermodynamics such an equation is called
an Equation of State, but other disciplines often call it a Constitutive
Equation because it describes the constitution of the system. The perfect gas
equation is another example of an equation of state with which you are
probably familiar, as is Ohm’s law.

For many systems the relationship between properties is so complex that it

defies expression in an equation. That information must be expressed either
graphically or in tables.

• Equilibrium of a system. It is exceedingly difficult to provide a good

definition of equilibrium. It is easier to provide a test. Generally, if a system is
isolated and allowed to settle for a long time one expects that it will eventually
reach a steady state. Pressure, temperature etc. would be uniform throughout
the system and we say that the system is in equilibrium. In particular, no work
can be obtained by dividing the system into two halves (subsystems) and
allowing those halves to interact with each other but not the surroundings.

And so to our test: A system is in equilibrium if it can be isolated without any

consequent changes occurring inside the system.

This is not the same as saying that a system is in equilibrium if it is in a steady

state.

Example: Consider a metal bar conducting heat as shown below:

Cold
Hot
Q& Watts

System boundary

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To isolate the system the heat transfer in at the hot end and the heat transfer out at the
cold end would have to be stopped. Then the hot end would cool and the cold would
heat until the whole bar was at the same temperature. That change is a consequence of
the isolation, so the bar is not in equilibrium. After the bar had been left isolated for
some time it would reach equilibrium. Note that the bar with one end hot and the
other end cold is in a steady state.

• Properties and equilibrium. In the example above, what is the temperature

of the metal bar? Clearly, it varies from end to end and there is no one
temperature of the bar. This is typical of systems that are not in
equilibrium: one or more of the intensive properties cannot be identified
because it varies throughout the system.

Example: Take as an example an electric battery. If the battery were isolated then
there would be no current flowing. Measuring its terminal voltage at different states
of charge would produce a graph like the one shown below. This is an example of a
property diagram, where one property is shown plotted against one or more others.

o Recognize here that the terminal voltage V is an intensive property

whereas the stored energy E is an extensive property. The capacity
of the battery is proportional to the mass of active material in the
battery, so it may be necessary to exclude the casing from the
system for some analysis purposes. (It does not matter here.)
o If the battery were being charged or discharged then its terminal
voltage would be slightly different. Higher if it were being charged
and lower if it were being discharged.
o If there were a current flowing, then isolating the battery (turning
off the current) would result in some consequent internal changes.
Evidence of these changes is the change of terminal voltage toward
the value shown on the graph. Because some of the changes
involve diffusion of ions through the electrolyte it takes some time
for the terminal voltage to settle to a steady value.
o The system is clearly not in equilibrium if there is a current
flowing. The terminal voltage then does not simply depend on the
state of charge but also the current and the history of current
variations in the recent past.

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In general, if a system is not in equilibrium its state cannot be determined
because some of its intensive properties have no single identifiable value.

It is curious that the extensive properties of a system that is not in equilibrium can be
found. In the metal bar example the specific volume (or density) would vary from end
to end because of the temperature gradient and thermal expansion, but the total
volume could be found. The thermal energy density likewise would vary from end to
end, but the total stored thermal energy could be found. In the battery example, the
quantity of energy in store at any time could be determined whether the battery is
being charged, discharged or is isolated.
• A Process. The state of a system can be changed, usually by either
transferring energy of some kind across the system boundary or by a
chemical reaction inside the system. Changing the state of a system is
called a process. For example, heating water in a kettle raises its
temperature while keeping the pressure constant. The water undergoes an
isobaric process. (Isobaric = constant pressure.) If the system passes
through a series of equilibrium states then the process path can be drawn
on an appropriate property diagram. (More on property diagrams shortly.)
• A Cycle. A process or series of processes which return the system to its
initial state is called a cycle.

• Identifying State. It is important to know how many properties are needed

to identify the state of the system. Unfortunately no simple answer can be
given to this question at this stage. However, the systems under
consideration in this course mostly require knowledge of two properties to
identify their state. This is sometimes called the Two Property Rule, but it
is important to remember that it is only a ‘rule of thumb’ and has no
physical basis. Some systems require a very large number of properties
whereas others, like the spring example, require only one.

The Work Done by and Expanding System.

The sketch shows a system trapped within

a cylinder by a piston. The force on the
F piston F = p A where A is the piston area
and p the pressure.

dx The small amount of work done as the

piston moves a distance dx is :

System boundary δW = pA dx = p dV where V is the

volume of the system. If the system
expands from state 1 to state 2 then
W = ∫ p dV , w = ∫ p dv
2 2

1 1

This important result shows that: the work done by a system as it expands is given
by the area under the process path on a p-v or p-V diagram.

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 1
p

v
w = ∫ p dv
2

The p-v diagram is an example of a property diagram.

Some Notes on Pressure.

o Absolute pressure:
A vacuum has zero absolute pressure.
Steam tables invariably use absolute pressure.
Unless stated otherwise pressure is absolute.
A barometer measures the absolute pressure of the atmosphere. Called
atmospheric or barometric pressure, it varies with the weather and with
altitude. The internationally accepted standard for average atmospheric
pressure at sea level 1.0 atm = 101.325 kN/m2.
o Some people like to measure pressure in bar. 1.0 bar = 100.0 kN/m2. This is
tolerated but not recommended within the SI system of units.
o s.t.p. is a commonly used abbreviation for standard temperature and pressure.
The standard was changed in 1982 and s.t.p now refers to 100.0 kN/m2 and 0.0
ºC. (Previously the pressure was 101.325 kN/m2.)
o n.t.p is a commonly used abbreviation for normal temperature and pressure.
Usually this means 1.0 atm and 20.0 ºC but there is no standard and the term
seems to be going out of use.
o Gauge pressure.
Pressure gauges measure pressure differences. The pressure in your car
tyre, as shown on the gauge, is the pressure difference between the
atmosphere outside and the air inside the tyre.
Absolute pressure = gauge pressure + atmospheric pressure.

Specific heats

The specific heat of a substance is the amount of energy required to raise the
temperature of 1 kg of the substance by 1 °C. For gases and vapours, which expand
when heated, the specific heat depends on how the substance is heated.

The specific heat at constant volume cv is found by keeping the volume of the system
constant during heating. ie. An isochoric process.

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The specific heat at constant pressure cp is found by keeping the pressure of the
system constant during heating. ie. An isobaric process.

Generally cp and cv are variables which depend upon the state of the system. ie. cp and
cv are intensive properties. (The corresponding extensive properties are often called
the heat capacity.) However for some systems, particularly perfect gases, they are
constant or nearly constant, which makes them particularly useful for those systems.