Thermodynamics

Energy can be transferred to or from matter by working or by heating. This is illustrated

below:
Let other molecules hit them!
Hit the molecules yourself!

Molecules speeded up Piston pushed in

Work done
= force distance

Molecules speeded up Hot wall

Thermal transfer
= mc

In the left hand diagram, as the piston is pushed to the left molecules colliding with it bounce
off with more kinetic energy than they hit it with. The internal energy of the gas is increased
by an amount equal to the work, W, done by the piston. Rember that work = force
distance (moved in the direction of the force) if the force is constant or if an average value
for the force is used, or if force is not constant, the work done is equal to the area under a
force-distance graph.
In the right hand diagram the internal energy of the gas is increased by thermal transfer of
energy. The molecules in the right hand wall are at a higher temperature than the gas
molecules so their average kinetic energy is higher than for the gas molecules. In collisions
between the gas molecules and the wall, molecular kinetic energy will, on average, be
transferred from the wall molecules to the gas molecules. The thermal energy transfer is Q.
If work W is done on the gas and thermal energy transfer Q to the gas occurs, the change in
the internal energy of the gas, U will be:
U = W + Q
This expression is called the First Law of Thermodynamics and is a way of stating the
principle of conservation of energy.
Note that if the gas does work (i.e. expands) or transfers energy to its surroundings the
values of W and Q respectively will be negative. When a gas is heated it often expands,
giving a situation where W is negative and Q is positive.

Heat Engines
Engine processes are shown on a PV diagram. Besides constant pressure, volume and
temperature processes, a useful process is the adiabatic process where no heat enters or
leaves the system.

Isothermal Process
Since for an ideal gas the internal energy is proportional to temperature, it follows that there
is no change in the internal energy of the gas during an isothermal process. The first law of
thermodynamics then becomes.

U =0=QW , Q=W
All the heat in the system is used to do work. Practically, this change occurs when the work
is done slowly, and therefore any change in internal energy can be given off as heat (hence
Q is negative).
Adiabatic Process
An adiabatic process is one in which no heat is gained or lost by the system. The first law of
thermodynamics with Q=0 shows that all the change in internal energy is in the form of work
done.

Q=0, U =W
This change occurs when the work is done quickly and therefore there is not chance for the
heat to escape the system.
Constant Volume
The pressure is increased as a result of adding heat; no work is done because there is no
change in volume.

 U =Q

Constant Pressure
As the volume increases, work is done by the system. In order to accomplish this work,
energy must be added, and to calculate this energy, the temperatures must be determined.
They can be calculated from the pressure and volumes using the ideal gas law:

W =P V
Engine Cycles
For a constant mass of gas, the operation of a heat engine is a repeating cycle and its PV
diagram will be a closed figure. The idea of an engine cycle is illustrated below for one of the
simplest kinds of cycles. If the cycle is operated clockwise on the diagram, the engine uses
heat to do net work. If operated anti-clockwise, it uses work to transport heat and is therefore
acting as a refrigerator or a heat pump.

The Carnot Cycle

The most efficient heat engine cycle is the Carnot cycle, consisting of two isothermal
processes and two adiabatic processes. The Carnot cycle can be thought of as the most
efficient heat engine cycle allowed by physical laws

From A to B: the gas expands and does work on its surroundings while the engine absorbs
heat from a source (the hot reservoir). Along this isothermal, the internal energy and
temperature of the gas does not change.

W =Q

From B to C: the heat source is

removed but the internal energy of
the gas falls to allow the gas to
continue expanding while cooling
(lowering in temperature.) This
stage is called an adiabatic
expansion since no heat enters or
leaves the gas.

U=W
From C to D: the gas is
recompressed as heat is extracted and the gas volume decreases. The pressure increases.
The gas loses heat to the surroundings. This is an isothermal compression.
From D to A: the internal energy of the gas increases as the gas continues to be
compressed. Its temperature rises to its original state whist its volume decreases because
work is done on the gas. This is an adiabatic compression.

U =W
The Otto cycle
the German engineer Nicolaus Otto was the first to develop a functioning four-stroke engine,
which is why the four-stroke principle today is commonly known as the Otto cycle and fourstroke engines using spark plugs often are called Otto engines. The Otto Cycle consists of
adiabatic compression, heat addition at constant volume, adiabatic expansion and rejection
of heat at constant volume. (See the next page for the schematic)

Questions: Thermodynamics
Figure 1 shows a pV graph that you are to use to illustrate the process of a gas
undergoing two changes.
3
In its initial state, the gas has a pressure of 50 kPa and a volume of 1.5 m ; this is plotted
on the graph.
3
First, the gas undergoes an isothermal change from an initial volume of 1.5 m to 0.85
3
3
m followed by a compression at constant pressure to a volume of 0.35 m .

100
p re s s u re /k P a
80

60

40

20

0 .1

0 .2

0 .3

0 .4

0 .5

0 .6

0 .7

0 .8 0 .9
v o lu m e /m

1 .0
3

Figure 1

(a)

Show that the final pressure of the gas is about 90 kPa.

1 .1

1 .2

1 .3

1 .4

1 .5

(b)

Complete the graph in Figure 1 to show both changes.

(c)

(i)

Use your graph to estimate the work done during the whole process.

(ii)

State and explain whether the work in part (c)(i) is done on or by the gas.

Answers: Thermodynamics
(a)
(b)

pV = constant seen
p = 88 kPa
completes correct shape curve to (0.85,88 000 or 90000),
3
then horizontal to 0.35 m

(c)

attempts to measure area [graph evidence or words]

correct use of graph scale
answer in range (80 91) Kj

(d)

done on gas because it is compressed

Second Law of
Thermodynamics
The second law of thermodynamics is a general principle which places constraints
upon the direction of heat transfer and the attainable efficiencies of heat engines. In
so doing, it goes beyond the limitations imposed by the first law of thermodynamics.
It's implications may be visualized in terms of the waterfall analogy.

The maximum efficiency which can be achieved is given by:

Efficency =

W QiQ0 T H T c
=
=
Qi
Qi
Tc

Questions: Calculating efficiency

1.

What is the theoretical maximum efficiency of a heat engine which

(a)

has a furnace at 2000 K and the surroundings at 300 K?

(b)

runs on the 15 K difference between surface ocean water at about 288 K and deep water at
nearly 273 K? Suggest why such an engine may be a good idea.

2. (a)

The Birdsville geothermal power station starts with water at 98 C and has a temperature of
30 C at the condensers. What is the theoretical maximum efficiency?

(b)

The electrical output of 80 kW is in fact 6% of the heat input. What was the heat input?

(c)

It is suggested that pumping more cold water to the hot rocks below would improve the
output. Comment on this suggestion.

3. (a)

A power station starts with steam at 543 C and an output temperature of 100 C
Calculate the maximum theoretical efficiency.

(b)

The same site has a more modern system where the input steam temperature is 565 C. By
how much is the theoretical efficiency improved at the more modern site?

Answers: Calculating efficiency

1. (a)
(b)

Maximum efficiency = (THOT TCOLD)/THOT = (2000 -300) / 2000 = 0.85 = 85%

Maximum efficiency = (THOT TCOLD)/THOT = (288-273) / 288 = 0.052 = 5.2%
The temperature difference is maintained by the world climate, and affects large masses of
water, so that a substantial amount of renewable energy might be extracted, provided that
doing so did not materially affect the temperature gradient. Such a power station is called
Ocean Thermal Energy Conversion (OTEC).

2. (a)

Maximum efficiency = (THOT TCOLD)/THOT = ([98+273] [30 + 273]) / [98 + 273]

= (371 303) / 371 = 0.183 =18.3%

(b)

Efficiency = useful power out / total power in

so power in = power out / efficiency = 80 / 6% = 1333 kW

(c)

3. (a)

The energy keeps on coming, as long as we don't pump too much cold water down and cool
the rocks too much.
Maximum efficiency = (THOT TCOLD)/THOT = ([543+273] [100 + 273]) / [543 + 273]
= (816 373) / 816 = 0.54 = 54%

(b)

Maximum efficiency = (THOT TCOLD)/THOT = ([565+273] [273+100]) / [565 + 273]

= (838 373) / 838 = 0.67 = 67%
So efficiency is improved by 67% - 54% = 13%