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GENII Engineering & Technology Training

UNIT 14 – Energy Changes, Sources and


Applications

Accreditation with

A credit towards

BTEC

National Certificate in Applied Science (Level 3)

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National Certificate in Applied Science

Each student will be provided with:

1. Unit Aims & Learning Outcomes Page 3


2. Delivery Method Page 3
3. Unit Contents Index Page 5
4. Unit Assessment & Accreditation Page 6
5. . Grade Descriptors Page 8
6. . Course Learning Materials Page 9

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Aim

This unit gives learners an understanding of the fundamental concepts of energy and how energy is
measured, with consideration of ‘useful’ energy and ‘wasted’ energy. Energy changes can cause a
rise or fall in temperature or changes of state: learners will study more about temperature and how it
relates to energy changes, as well as the relationship with volume and pressure. This unit allows
learners to develop an understanding of the need for portable energy sources in a laboratory
environment, and recognise the importance of tailoring the energy source to the application. They
will also learn about energy transfer mechanisms and how they are used in industrial applications.

Learning Outcomes

On completion of this course a learner should:

1. Know the fundamental concepts associated with energy and its measurement

2. Be able to demonstrate and relate changes of temperature or physical state to changes in


internal energy

3. Understand the differences between energy transfer mechanisms and the relationships
between them

4. Understand the properties of electrical energy sources.

Delivery Methods

This unit covers much of the foundation work relating to energy, energy changes and transfer
mechanisms to complement advanced scientific studies. The learners will have been introduced to
the concept of energy as part of Unit 1: Fundamentals of Science. This unit aims to develop the
quantitative aspects and qualitative understanding.

Practical investigation will form the backbone of the delivery strategy. Learners should carry out
measurements and see effects for themselves, rather than passive note-taking and bookwork.
Learners are not expected to carry out a series of standard practicals and should develop their own
investigations. For example, investigating the effectiveness of double glazing on reducing the rate at
which thermal energy is lost. It is important that all the work for this unit is related to industrial
applications of energy, highlighting differences in lab-based investigations compared with industry.
Consideration should be given to implications for industry, eg high pressure requires thickened
pipes.

During delivery of this unit, tutors should adopt the sequence in the content section. This sequence
starts by linking the concept of energy to physical work. Learners should recognise that energy is
the capacity to do work. All the common energy labels, such as electrical energy, chemical energy
and solar energy, are referring to kinetic or potential energies. These are energies due to the motion
or state of physical objects. Two concrete examples of potential energy are indicated in the unit
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content but tutors should make the learners aware of other forms of potential energy. It would be
valuable for learners to carry out a practical investigation of PE to KE conversion (or KE to PE, or
PE to PE, etc). This could be done on a simple level, by finding the height reached by a projectile
fired by a spring, for example.

It is important for learners to see that temperature is related to the internal energy of a substance. It
is not necessary for learners to do a detailed or quantitative study of distributions of quanta in a hot
solid. They should recognise that the kinetic energy of the atoms or molecules is related to the
temperature. Tutors should focus on how industrial processes make use of this concept. Learners
should carry out simple experiments to measure the specific heat or latent heat of a substance. The
aim is for learners to experience techniques used to measure physical quantities, rather than to learn
a standard experimental technique. Learners could, for example, use a data logger to record the
temperature, at regular intervals, of a container of crushed ice heated by an electric immersion
heater. This experiment allows the determination of values for specific heat capacity and latent heat
fusion of water. There is a very simple experiment for determining the latent heat of vaporisation of
water. Water is boiled with the kettle on a balance so that change in mass can be noted. The power
of the kettle is known, so the latent heat can be calculated from the electrical energy transferred
during the time it takes for a measured mass loss. The industrial applications and implications must
again be the focus here.

The treatment of thermal conductivity could be linked to insulation of buildings or the effectiveness
of double glazing. It is useful for the learners to see the heat flow equation as ‘push = flow x
resistance’. In this case the ‘push’ is indicated by the temperature difference, the flow is the energy
flow and the resistance is the inverse of the conductance (note: conductance = conductivity
area/length). Learners should comment on the effects of surface layers and the industrial
applications. This is a good time to draw out the parallels in different flow systems, ie flow of fluid,
flow of charge and flow of heat. This point need not be laboured, but it is useful for learners to draw
parallels across different systems, as it will help their understanding of science. Forced convection
produces a faster cooling rate than natural convection. Learners’ experience should tell them this.
At this level, learners should be aware of the five-fourths power law for cooling by natural
convection and the linear law for cooling in a steady draught. Quantitative questions requiring the
recall of those laws is not necessary. When dealing with thermal radiation, learners should
understand what is meant by a black body radiator, be able to complete calculations using Stefan’s
law and be able to explain the industrial applications and implications.

The treatment of energy sources is restricted to those used to power portable equipment. Learners
need to understand the basic principles, so they should study the simple cell, the leclanche dry cell
and the lead-acid cell. They should consult catalogues of cell suppliers and get to know the range of
cell types currently available. They should know how they differ from those studied in terms of
energy capacity, convenience, load performance, suitability for particular applications, etc. Fuel
cells are being developed as energy sources for vehicles and other devices. Learners should know
how fuel cells differ from conventional cells.

They should also investigate the energy per square metre delivered by sunlight, so they understand
the potential benefits and limitations of using solar panels to power remote instrumentation.

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Unit Contents Index

Section 1.

Know the fundamental concepts associated with energy and its measurement

Definitions: work as force x distance moved in direction of force (W=Fd); energy in terms
of work; kinetic energy (KE = ½ mv2); gravitational potential energy (PEg = mgh); elastic
potential energy (PEe = ½ kx2); power as the rate of transfer of energy

Concepts: principle of the conservation of energy; recognition of energy types as forms of


potential or kinetic energies; useful energy, wasted energy and efficiency

Quantities and units: energy (joule); power (watt, kilowatt)

Section 2

Be able to demonstrate and relate changes of temperature or physical state to changes in


internal energy

Temperature: degree of hotness; temperature scales (Kelvin, Celsius) and fixed points
(absolute zero); thermal expansion

Energy changes: transfer of energy can cause a rise or fall in temperature or changes of
state; calculations eg specific heat capacity (Q = mcΔt), specific latent heat (Q = mL);
fusion; vaporisation; condensation; applications

Gases: effect of changing temperature, pressure and volume of a gas; experimental evidence
for a gas law eg Charles’ law, Boyle’s law, pressure law; the ideal gas law; kinetic theory
dealt with qualitatively; applications

Section 3

Understand the differences between thermal energy transfer mechanisms and the
relationships between them

Energy transfer mechanisms: conduction (transfer of kinetic energy between atoms,


electrons or molecules); thermal conductivity of solids, liquids and gases; convection (bulk
motion of liquids); radiation (absorption, emission and relation to surface properties);
Stefan’s law of radiation (W = eσAT4 ); temperature gradient; applications

Relationships: eg differences between forced and natural convection

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Section 4

Understand the properties of electrical energy sources

Structure and operating principles of common primary and secondary cells: characteristics,
merits and limitations for particular applications; capacity and behaviour under load;
ampere-hours, milliampere-hours; disposal hazards; applications

Fuel cells: eg simple cell, the leclanche dry cell and the lead-acid cell, zinc-air fuel cells
(ZAFC), proton exchange membrane or solid polymer, direct methanol fuel cells, recent
developments, their prospects and limitations

Solar cells: recent developments; their prospects and limitations

Assessment & Accreditation

Successful completion of this course will provide the learner with a unit credit leading towards the
award of a BTEC National Certificate in Applied Science.

A BTEC certificate of achievement can be awarded for the completion of this single unit.

To gain the National Certificate additional units will be required:

• Fundamentals of Science
• Mathematics for Science Technicians
• Application of Numbers for Science Technicians
• Working in the Science Industry
• Industrial Applications of Chemical Reactions
• Electrical Circuits and their Industrial Applications
• Scientific Practical Techniques
• Applied Engineering Science (Electrical/Mechanical)

This unit will be assessed with written tests, along with practical observation and practical write
ups. These tests and observations will assess the unit outcomes.

All the pass grade criteria must be met in order for a learner to achieve this unit. This unit requires
learners to build up a portfolio of laboratory investigations, reports and calculations. The majority
of the pass criteria can be achieved through practical activity.

For P1, learners must describe the fundamental concepts of energy, in the context of industrial
applications. They must be able to define each term, and know the associated unit of measure, as
listed in the unit content.

For P2, learners must investigate a gas law. Experiments are available interactively on the web, but
learners should perform at least one in a real laboratory. The Charles’ law tube is a fairly

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inexpensive piece of equipment containing a small amount of mercury. A risk assessment must be
carried out.

For P3, learners must investigate conduction, convection and radiation. They could do this through
cooling experiments, and this would be a useful opportunity for learners to use data loggers.
Learners need to highlight and explain differences in their investigations compared with those used
in industry.

For P4, learners must describe the characteristics of primary cells and secondary cells and then
highlight the differences between these two types of cells including their uses.

For a merit grade, all the pass grade criteria and all the merit grade criteria must be met. All
calculations must be carried out correctly and the correct units must be used.

For M1, learners must do accurate calculations involving changes of state of substances used in
industrial process.

For M2, learners must perform calculations to determine the changes in pressure, volume and
temperature for gases used in industrial processes, as given by the tutor.

For M3, learners must calculate energy flow for given thermal conductivities and temperature
gradients, in an industrial application. They could involve the more practical applications of thermal
conductivity in the insulation of buildings, eg heat energy lost through single and double glazed
windows. The data for industrial calculations that use Stephan’s law will need to be provided
by the tutor.

For M4, learners must describe the characteristics of primary and secondary cells used for industrial
applications. They must also comment on the merits and limitations of the primary and secondary
cells, and the implications of these for their industrial applications.

For a distinction grade, all the pass, merit and distinction grade criteria must be met.

For D1 and D2, learners must apply the principles, in the unit content, to at least one industrial
system.

For D3, learners must explain the heat transfer mechanisms in solids, liquids, gases and
combinations of substances. In doing so, they must describe molecular motion, bulk motion and
surface properties, and highlight the differences of each in solids, liquids and gases. Learners must
use examples contextualised to industrial processes.

For D4, learners must evaluate the use of primary and secondary cells for mobile electronic units.
They could compare two portable devices which use primary and secondary cells, eg MP3 players,
torches.

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Grade descriptors

Grading Criteria
To achieve a pass grade the To achieve a merit grade the To achieve a distinction grade
evidence must show that the evidence must show that, in the evidence must show that, in
learner is able to: addition to the pass criteria, the addition to the pass and merit
learner is able to: criteria, the learner is able to:

D1 explain the behaviour and response of


P1 describe the fundamental concepts
M1 perform calculations involving industrial systems in terms of latent heat,
associated with energy using industrial
changes of state for industrial processes specific heat capacity, temperature changes
examples
and the gas laws

P2 report on the outcomes of an M2 calculate pressure, volume and


D2 explain gas pressure and how it affects
investigation of one gas law and relate temperature changes for gases in given
industrial processes
them to industrial processes industrial processes

D3 explain the differences between heat


M3 calculate energy flow using industrial transfer mechanisms in solids, liquids,
P3 investigate and describe the processes
examples for given thermal conductivities gases and combinations of substances, in
of conduction, convection and radiation
and temperature gradients, and also for terms of molecular motion, bulk motion
and their industrial applications
given emissivities and surface properties in industrial
processes

M4 give examples of primary and


P4 describe the difference between
secondary cells and describe their D4 evaluate the use of primary and
primary and secondary cells.
characteristics, merits and limitations, in secondary cells for portable applications.
industrial applications.

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Energy Changes, Sources and Applications

Accreditation with

BTEC

National Certificate in Applied Science (Level 3)

Chapter 1

Internal Energy

Unit 14 – Energy Changes, Sources and Application – Internal Energy 9


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Properties of gases
Particles in solids, liquids and gases:

Gases Liquids Solids


Diagram

They do not have a definite


Shape and

shape.
volume

They have a definite


volume.
Distance
particles
between

The particles are far apart


of particles
Movement

The particles can only move


by vibrating next to each
other
particles

There are tiny forces of


between
Forces

attraction between the


particles.

It is now accepted that matter consists of particles. The only difference between the ‘states’ is the
arrangement of these particles. The particles (which may be atoms, ions or molecules) are very
small (in the order of 0.07 nm  0.20 nm).

Solid: Particles are closely packed in a rigid structure. It allows no gross movement of particles –
they are locked in position. It only allows vibration. Solids are hard to compress and cannot
flow due to the rigid structure.

Liquid:Going from a solid to a liquid results in a small increase in volume (5  30 %) due to the
looser arrangement of the particles. Liquids allow a little more compression and free
movement of particles (they can flow and no longer have a fixed shape). The volume is
fixed due to the attractive forces (either hydrogen bonding as with HF, NH3, H2O, or dipole-
δ+ δ−
dipole as with H —Cl , or Van der Waals interactions with O2 or CS2) between the
particles.

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Gas: Going from a liquid to a gas there is a considerable increase in volume (over a 1000 times at
atmospheric pressure). Gases are readily compressed as the majority of a gas is empty space
between the particles. The forces between gas particles are negligible allowing free
movement of the gas with no fixed volume.

Questions:
1. A solid usually expands on melting because ______________________________________
__________________________________________________________________________
__________________________________________________________________________
2. A liquid has a fixed volume at a specified temperature because _______________________
__________________________________________________________________________
__________________________________________________________________________
3. A liquid does not have a fixed shape at a specified temperature because ________________
__________________________________________________________________________
__________________________________________________________________________
4. The volume of a gas gets a lot smaller when it changes to a liquid because ______________
__________________________________________________________________________
__________________________________________________________________________
5. Gases are easily compressed, but solids are not because _____________________________
__________________________________________________________________________
__________________________________________________________________________
6. What effect has increased pressure on the volume of a liquid and why? _________________
__________________________________________________________________________
__________________________________________________________________________
__________________________________________________________________________

Terms used when dealing with gases


Temperature:
This is a measure of how hot a substance is.
The common scale most of us use is the Celsius scale (also called the centigrade scale). This is
based on the changing states of water. The freezing point of water was taken to be 0 oC and the
boiling point of water was taken to be 100 oC. These two temperatures are known as fixed points.

The scale used in chemistry is known as the Kelvin or Absolute scale. Absolute zero is thought to
be the coldest temperature that can be obtained. It is the temperature at which a gas would have zero
volume. It is given the symbol 0 K. Note that there is no degree sign.

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Zero Kelvin is –273 oC (actually it is –273.15 oC but usually it is taken to be -273 oC). A Kelvin is
equal to a degree centigrade in size. So 0 K is –273 oC, 273 K is 0 oC, 373 K is 100 oC and 473 K is
200 oC.

Temperature in centigrade Temperature in Kelvin


0 oC
100 oC
100 K
298 K
30 oC
-15 oC

The Kelvin is the S.I. unit of temperature.

A temperature of 0 K has not yet been achieved. However, temperatures to within 0.001 K have
been. At this very low temperature the random movement of the particles almost vanishes. This
causes substances to have strange properties such as some metals losing their electrical resistance
and becoming superconductors.

Note that heat energy and temperature are two different things:
(i) A Bunsen burner was used to heat up a beaker of water and a bath of water.
(a) Which has been supplied with the most heat__________________________
(b) and which reaches the highest temperature? __________________________

(ii) A spark from a sparkler contains very little ____________ , but will have a very high
____________.

(iii) Bath water has a low ______________, but contains a lot of _______________ .

Pressure:
This is the force that a gas exerts, on the walls of the container which holds it, per unit area.
The S.I. unit for pressure is Newtons per metre squared, Nm-2. This is also called the Pascal, Pa.
Normal atmospheric pressure is 1 x 105 Nm-2, or 1 x 105 Pa.
(The old units of pressure were one atmosphere or 760 mm of mercury – the height the atmosphere
would hold a column of mercury. You may see this in some old textbooks).

Volume:
The volume of a gas is the same as the container that holds it (remember that gases fill up any
container). The S.I. unit of volume is the cubic metre, m3. This is too large a volume to use in most
cases so we generally use a volume of one litre (L); more commonly called a decimetre cubed, dm3.

Note: 1 cm3 = 0.001 dm3 = 0.000,001 m3.


1 dm3 = 1,000 cm3 = 0.001 m3.
1 m3 = 1,000 dm3 = 1,000,000 cm3.

Standard temperature and pressure – s.t.p.:

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When comparing volumes occupied by gases we always use a set temperature and pressure (so we
can compare like with like). This is known as s.t.p. or standard temperature and pressure. The
values used are
Standard temperature = 273 K (0 oC)
Standard pressure = 1 x 105 Pa (1 atm or 760 mmHg)

Gas laws and the Kinetic Theory of Gases


All gases are observed to have a range of similarities between their physical properties.

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Boyle’s Law:
Boyle, an Irish chemist, measured how the pressure exerted on a gas affected its volume. He
discovered that at a constant temperature there was a link between the volume and the pressure. He
proposed therefore that pressure was inversely proportional to volume.

Pressure α 1 / Volume
i.e. Pressure = 1 x constant
volume
Written as P = (1/V) x constant if the temperature is constant.

This means that as you increase the pressure by a set amount, there is a corresponding reduction in
the volume. i.e. You double the pressure and half the volume.

Boyles Law
At a constant temperature, the volume of a given mass of any gas is inversely
proportional to the pressure of the gas.

P=(1/V) x constant  PV = constant

Demo a syringe

We can plot the data as a graph:

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We can see that the data fit into a pattern called a hyperbola. If, however we plot pressure against
1/volume we get a linear (straight line) graph showing that the pressure is inversely (as it’s a graph
of 1/V) proportional (as it is a straight line) to the volume.

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Demo Boyles’ Law apparatus

Volume
scale
Tube with volume
of air trapped by
oil
Bicycle
pump

Reservoir of oil
Valve

Pressure
gauge

The picture below shows a data-logging experiment for Boyle's Law.

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Explanation of Boyle’s Law:


Gases are in continuous motion. They exert a pressure when they collide with the sides of the
container. If the volume of the container is decreased, then the molecules are moving around in a
smaller space. This will result in more of the molecules crashing into the sides of the container per
second. The increased number of collisions will therefore cause an increase in the pressure.

See NASA web page

Charles’ Law:
The volume of a gas varies when the temperature is changed. Demo heating a test tube of air, bubbling into water.

Charles, a French scientist, discovered that equal volumes of different gases (at constant pressure)
all expanded by the same amount for a given rise in temperature. This can be written as:

V = T x constant
Where V = volume (in m3) and T = temperature (measured in Kelvins).

Charles’ Law
The volume of a fixed mass of any gas at constant pressure is directly
proportional to the temperature in Kelvins.

V = T x constant  V/T = constant

Charles investigated how the volume varied with temperature (under a constant pressure) using a
capillary tube blocked at one end by a bead of concentrated sulphuric acid. As he
cooled the apparatus, the air trapped in it reduced in volume. As he heated it, the
gas increased in volume (moving the bead of sulphuric acid). The expansion and
contraction was found to be the same for all gases. He plotted a graph of the
volume for a range of temperatures. He was unable to obtain very low
temperatures, so he extrapolated (continued the line with the same gradient
backwards)
until the
volume was
zero. This gave
a temperature
of –273 oC, or 0
K. From this he
stated the
above law.

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Whatever the gas we use, we find that the line always passes through the temperature axis at
-273.15 oC. This led to the concept of absolute zero, discovered by Lord Kelvin. If
we put the absolute zero point, 0 Kelvin, we get:

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Explanation of Charles’ Law:


If the temperature of the container of gas is raised, the particles of gas will have more energy and
therefore move faster. This means that they will make more collisions with the walls of the
container, resulting in a rise in pressure. Now, to keep the pressure constant the volume of
the container must be increased. (Think about what happens when a can of coke heats up
and is opened – the gas rushes out, as it wants to occupy a larger volume).

See NASA web page

The Pressure Law:


This law tells us that pressure is proportional to the Kelvin temperature, if the volume is fixed. The
traditional way to demonstrate this is with a large glass sphere immersed in water, connected to a
manometer, a way of detecting small differences in gas pressure.

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We can show this on a graph like this:

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So P ∝ T

Therefore P = kT and rearranging, P/T = constant

The combined gas law:


Boyle’s Law: V α 1/P at constant T. ⇒ PV = constant ⇒ P1V1 = P2V2
Charles’ Law:V α T at constant P. ⇒ V/T = constant ⇒ V1/T1 = V2/T2
Pressure Law:P α T at constant V ⇒ P/T = constant ⇒ P1/T1 = P2/T2

Combined Laws: PV α T under all conditions ⇒ PV = constant ⇒ P1V1 = P2V2


T T1 T2

Where P = pressure (Nm-2)


V = volume (m3)
T = temperature in Kelvin (K)

When using the Combined gas law you must use the temperature in Kelvin.

You may use whatever units you wish for volume and pressure, as long as you are consistent (use
the same on both sides of the equation).

Questions:
1. A sample of nitrogen has a volume of 75 cm3 at a temperature of 27 oC and a pressure of 95
kPa. Find the volume that the gas would occupy at s.t.p.

2. A sample of hydrogen of volume 100 cm3 at a pressure of 1 x 105 Pa is compressed to 55


cm3 at a constant temperature. What is the new pressure of this gas?

3. A chemical plant produced 2500 litres of ammonia at a pressure of 500 kPa and a
temperature of 100 oC. A chemical engineer wishes to store the ammonia at a pressure of
100 kPa and a temperature of 20oC. What volume would the gas occupy at this new
temperature and pressure?

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Gay-Lussac’s Law

Gay-Lussac, a French chemist, discovered that if you react 2 volumes of hydrogen with one of
oxygen then water is produced. All the reactants were used up in the reaction. He found that there
was always a simple whole number ratio between the volume of gases reacting and produced. He
came up with the following law:

Law of combining volumes


In reactions involving gases, the ratio of volumes reacting bear a simple ratio to
each other and to the product gas (assuming the temperature and pressure remain
constant).

Other examples are:


• (one) methane + (two) oxygen  (one) carbon dioxide + (two) water
• (two) carbon monoxide + (one) oxygen  (two) carbon dioxide

But Gay-Lussac could not explain this observation.

Avogadro’s Law
Avogadro was the one to explain Gay-Lussac’s Law of combining volumes.
Avogadro’s Law
Equal volumes of gases, under the same conditions of temperature and
pressure, contain equal numbers of molecules.

This means that 2 dm3 of oxygen gas at 300K and 100,000 Nm-2 has the same number of molecules
as 2 dm3 of nitrogen gas under the same conditions.

This helps to explain Gay-Lussac’s observations. He stated that 2 volumes of hydrogen react with
one volume of oxygen to make 2 volumes of water vapour.

Hydrogen + Oxygen  water vapour


2 volumes 1 volume  2 volumes

Assume there are N molecules of oxygen present, then, applying Avogadro’s Law which relates the
volume to the number of molecules present:

Hydrogen + Oxygen  water vapour


2N molecules 1N molecules  2N molecules

Then diving by N:

Hydrogen + Oxygen  water vapour

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2 molecules 1 molecule  2 molecules

Therefore the ratio of the volumes of gas is equal to the ratio of number of molecules involved in a
reaction. This is one way of deducing the equation for the reaction.

Hydrogen + Oxygen  water vapour


2H2 + O2  2H2O

Questions:
1. Sulphur dioxide reacts with hydrogen sulphide according to the equation:
2H2S (g) + SO2 (g)  3S (S) + 2H2O (g)
What volume of sulphur dioxide would be required to react completely with 140 cm3 of
hydrogen sulphide (all volumes being measured under the same conditions of temperature
and pressure)?
Answer: ____________

2. 140 cm3 of methane is found to react completely with oxygen according to the equation:

CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g)


Assume that all volumes are measured under the same conditions of temperature and
pressure.
a) What volume of oxygen is consumed in the reaction? ________________
b) What volume of carbon dioxide is formed in the reaction? ________________

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The Mole
It is impossible to weigh out one molecule of an element or compound because it is far too light.
But we can measure out volumes of gas accurately. We know that at the same temperature and
pressure, a set volume of all gases contain the same number of particles (Avogadro’s Law). So if we
want to produce hydrogen chloride gas from hydrogen and chlorine: ( H2 (g) + Cl2 (g)  2HCl (g) )
we need to react one volume of hydrogen and one volume of chlorine to form two volumes of
hydrogen chloride. This will leave us with no unreacted hydrogen or chlorine.

We can only do this for reactants which are gases. If they are solids or liquids we cannot measure
out the amount of molecules by volume (Gay-Lussac’s and Avogadro’s Laws do not apply). An
example of this is the reaction between sodium and hydrogen: H2 (g) + 2Na (s)  2NaH (s).

As we can’t always use volumes to ensure the right number of reacting particles, there was a need
to create a unit for the quantity of atoms, molecules and ions which is easily measurable. This unit
is known as the MOLE. As we cannot measure one molecule, it was decided to measure a much
larger number of particles and call this quantity the mole. In 12 grams of 12C there are 6.02 x 1023
particles. This number of particles makes up one mole of 12C, and is known as Avogadro’s
constant (L).

The definition of a mole is as follows:

A mole is the amount of substance which


contains as many particles as there are atoms of
12
C in 12 grams of 12C. This number of particles
(6.02 x 1023) is known as Avogadro’s Constant.

Now linking back to the reaction to produce water:

Hydrogen + Oxygen  water vapour


2 molecules 1 molecule  2 molecules

Multiplying by Avogadro’s number:

Hydrogen + Oxygen  water vapour


23
2 x 6.02 x 10 1 x 6.02 x 1023  2 x 6.02 x 1023
molecules molecules molecules
(two moles) (one mole) (two moles)

Molar volume of gases:

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According to Avogadro’s Law, equal volumes of all gases (at s.t.p.) contain the same number of
particles.

One mole of gas at s.t.p. occupies 22.4 dm3


(or 22,400 cm3).

e.g. one mole of CO2 occupies 22.4 dm3 (or 22,400 cm3) at s.t.p.
and one mole of H2 occupies 22.4 dm3 (or 22,400 cm3) at s.t.p.

22.4 dm3 is known as the molar volume (volume occupied by one mole of any gas).

Standard temperature and pressure – s.t.p.:


The volumes of gases are compared at a standard temperature and pressure as follows:
Pressure: 1 atmosphere = 760 mm of mercury = 1.0 x 105 Nm-2
Temperature: 273 K = 0oC.

Key equations:
• Volume of gas at s.t.p. = No of moles x 22.4 dm3
• No of moles of gas = volume of gas
22.4

In all calculations, always convert masses and volumes into moles before you manipulate them
in equations. It makes life easier and always works.

1. What is the volume in (a) dm3 at s.t.p. of each of the following?

(i) 0.5 moles of oxygen (O2) gas ________ dm3

(ii) 0.025 moles of nitrogen (N2) gas ________ dm3

(iii) 3 moles of hydrogen sulfide (H2S) gas ________ dm3

(iv) 0.125 moles of methane (CH4) gas ________ dm3

(v) 7 moles of ammonia (NH3) gas ________ dm3

2. How many moles are there in each of the following (all volumes are measured at s.t.p.)

(i) 560 cm3 of oxygen gas _________ mol

(ii) 1120 cm3 of hydrogen gas _________ mol

(iii) 56 cm3 of methane gas _________ mol


(iv) 44.8 dm3 of carbon dioxide gas _________ mol

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(v) 1.12 dm3 of ammonia gas _________ mol

3. How many molecules are there at s.t.p. in

(i) 280 cm3 of nitrogen (N2) gas _________ molecules

(ii) 2.24 dm3 of oxygen (O2) gas _________ molecules

4. How many atoms are there at s.t.p. in

(i) 280 cm3 of nitrogen (N2) gas _________ atom

(ii) 2.24 dm3 of oxygen (O2) gas _________ atom

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Combined Laws: PV α T under all conditions ⇒ PV = constant ⇒ P1V1 = P2V2


T T1 T2

Where T = temperature in Kelvins (K)

1. Using the combined gas law, convert the following to volumes at s.t.p.:

(i) 37.5 cm3 of carbon dioxide at 300 K and 100,000 Pa

(ii) 82 cm3 of chlorine at 18 oC and 100,000 Pa

(iii) 224 dm3 of ammonia at 19 oC 1,000,000 Pa

(iv) 57 cm3 of nitrogen at 373 K and 90,000 Pa

2. Answer the following


(i) State Avogadro’s Law

(ii) How would you demonstrate experimentally that gases diffuse faster than
liquids?

(iii) What is Brownian motion? Explain how it arises.

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3. Answer the following


(i) How do the motion of particles differ in solids, liquids and gases?

(ii) How does the spacing between the particles differ in solids, liquids and gases?

(iii) What effect do you think a decrease in temperature would have on the rate of
diffusion of a gas? Why do you think this?

(iv) Explain why a gas exerts pressure on the walls of a closed vessel in which it is
contained. How is this pressure affected by increasing the temperature, and
why?

Extension question:

4. In a suitable apparatus at 423 K, 100 cm3 of hydrogen sulphide, measured at s.t.p., reacted
with 100 cm3 of sulphur dioxide, measured at s.t.p. The volume (when corrected to s.t.p.)
after the reaction was found to be150 cm3. When the water vapour was removed, a volume
(when corrected to s.t.p.) of 50 cm3 of gas remained. This gas was found to be sulphur
dioxide.

(i) What is the combining volume ratio of hydrogen sulphide and sulphur dioxide?
Explain how this data leads to this conclusion.

(ii) If the formulae for hydrogen sulphide gas and sulphur dioxide gas are H2S and
SO2 respectively, write a correct chemical equation for the reaction, given that
solid sulphur is the only other product formed.

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The Kinetic Theory


The above laws were explained by the Kinetic Theory of Gases. This theory came up with some
assumptions to account for these laws: They are:

1. Gases are made up of particles. The particles are in constant random motion.
2. There are no forces of attraction or repulsion between these particles.
3. The diameters of the particles are negligible in comparison to the distance between particles.
4. All collisions are perfectly elastic.
5. The average kinetic energy of particles is proportional to the Kelvin temperature.

The following Laws apply to an IDEAL GAS


An ideal gas is one which follows all the ideas behind the Kinetic Theory stated above.

Boyle’s Law: V α 1/P at constant T. ⇒ PV = constant ⇒ P1V1 = P2V2


Charles’ Law:V α T at constant V. ⇒ V/T = constant ⇒ V1/T1 =

V2/T2

Combined Laws: PV α T under all conditions ⇒ PV = constant ⇒ P1V1 = P2V2


T T1 T2

Avogadro’s Law: V α n at constant T and P

Where P = pressure (Nm-2)


V = volume (m3)
T = temperature in Kelvin (K)
n = number of moles (mol)

Combining Boyle’s, Charles’ and Avogadro’s Laws, V is proportional to 1/P x T x n


This can be re-written as V = R x 1/P x T x n

Where R is a constant, known as the gas constant.

This equation is known as the equation of state for an ideal gas, or the Ideal Gas Law. It is usually
written as:
PV = nRT The value for R = 8.31 JK-1 mol-1. Care with units

This equation is only obeyed by ideal gases, ones which follow the ideas behind the Kinetic Theory.
This is also true of all the other gas laws stated above.

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An ideal gas can be described as one which follows the ideal


gas law, PV = nRT, for all temperatures and pressures.

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Properties of gases
No moles = mass / Ar
No moles = mass / Mr
No moles = volume / 22.4 dm3
No moles = No of particles / 6.02 x 1023
PV = nRT (where R = 8.4 N m mol-1 K-1)
(P1V1) / T1 = (P2V2) / T2

a) State Boyles’s Law.

b) Define relative molecular mass (Mr).

c) What do you understand by an ideal gas?

d) What does n represent in the Ideal Gas Equation (PV = nRT)

e) 0.3 g of a gas occupies 169 cm3 at 300 K and a pressure of 1.0 x 105 Nm-2.
Calculate the relative molecular mass (Mr) of the gas. (R = 8.4 N m mol-1K-1).

f) A mass of 5.6 grams of a gaseous diatomic element (X2) occupies a volume of 4.98 x 10-3 m3
at 27oC and a pressure of 1.0 x 105 Nm-2. Find the relative molecular mass of the element
and give its name.

g) What is the volume at s.t.p. of one gram of nitrogen gas?

h) A gas occupies 500 cm3 at 273 K and 101 x 105 Nm-2 pressure. What volume will it
occupy at 819 K and 2.02 x 105 Nm-2 pressure?

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Effect of heat

1. Introduction
If we heat a solid material, it gets hotter and at the melting point it melts and
changes to a liquid. More heating will make the liquid hotter and when it
reaches the boiling point it evaporates to form a gas. Note that melting and
evaporating does not occur instantly. Energy is added to change the state of
the substance without raising the temperature.

2. Solids, liquids and gases

Bonding

In a solid material, the atoms or molecules are held together very strongly and
cannot wander about freely. As the temperature is raised the atoms vibrate
and so obtain kinetic energy. If the temperature is raised enough, this vibration
becomes so severe that the bonds break and the molecules are no longer able
to maintain a fixed structure so it melts and becomes a liquid.

A liquid has bonds strong enough to hold the particles together but also weak
enough that the substance will flow and can be poured into a vessel of any
shape. If the temperature of a liquid is raised the weak bonds get even weaker
and the particles move around with increased kinetic energy. The liquid
normally becomes more fluid – think of cold and hot custard.

At some point the particles will break free all together and unless constrained
in a vessel, they will fly off. This is evaporation. The substance has become a
gas.

3. Internal energy

The molecules of a substance possess kinetic energy. There may be elements


of other energy involved but basically it is the kinetic energy of the molecules
inside the substance that gives us the internal energy.
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If a substance changes temperature by ΔT and does not change state (melting


or evaporating), the
change in internal energy ΔU is directly proportional to the change in ΔT and
the mass m.

ΔU = m c ΔT

Note that a change in absolute temperature is the same as a change in


degrees Celsius. The units of temperature change may be stated in oC or K. The
constant of proportionality is c and this is called the specific heat capacity. This
is different for different materials. The units of c are J/kg K or kJ/kg K. The
symbol for internal energy is U kJ or u kJ/kg.

4. Heat transfer

Heat transfer occurs because one place is hotter than another. Heat will only
flow from a hot body to a cold body due to the temperature difference. There
are 3 mechanisms for this; conduction, convection and radiation.

A quantity of energy transferred as heat is given the symbol Q and its basic
unit is the Joule. The quantity transferred in one second is the heat transfer
rate and the unit is the Watt.

An example of this is when heat passes from the furnace of a steam boiler
through the walls separating the combustion chamber from the water and
steam. In this case, conduction, convection and radiation all occur together. In
many problems, the heat transfer is the same as the change in internal energy
so we often use the formula

Q = ΔU = m c ΔT

Calculate the energy needed to heat up 50 kg of aluminium from 20oC to


300oC. The specific heat capacity is 913 J/kg K.

5. Change of state

When a solid is heated, a temperature is eventually reached when it cannot


absorb any more energy and it melts. Whilst it is melting, its temperature stays
constant. The energy absorbed by melting is called the latent energy of fusion.
The values of latent energy may be looked up in tables. The figures are always
given for 1 kg so it is called the specific latent energy of fusion. The change in

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specific internal energy is denoted as ui. If this is entirely due to a heat transfer
Q then :

Q = ΔU = m ui

Once a solid has melted, the addition of more energy will make the
temperature rise again. The specific heat capacity of the liquid is different to
that of the solid but the change in internal energy is again given by ΔU = m c
ΔT

There is also a maximum amount of energy that the liquid can absorb. When
this point is reached, it starts to evaporate and turns into vapour. The
temperature is more commonly called the boiling point. We all should know
that water boils at 100oC but we should also know that this is only true if the
pressure is standard atmospheric pressure. Liquids boil at higher temperatures
if it is at a higher pressure. (pressure cooker, gas lighters)

Q = ΔU = m c ΔT + m ui

80 kg of copper at 20oC is heated up to its melting point of 932oC and then just
exactly melted. Calculate the energy needed. The latent heat of fusion is 210
kJ/kg and the specific heat capacity is 385 J/kg K

Whilst liquid is evaporating, the temperature stays constant and energy is


absorbed. This energy is called the latent energy of evaporation. Because the
liquid changes volume as it turns into vapour, the energy transfer may be more
than the change in internal energy. The values of these latent energies must
be found in tables at the pressure and temperature required.

After the liquid has evaporated it becomes vapour. If this is heated, its
temperature rises again. A vapour does not accurately behave as a gas
because of the tendency to turn back into liquid if cooled. When it is heated
well above the boiling it becomes a gas and obeys gas laws. Steam and other
vapours are also called superheated vapours when heated above the boiling
point. The internal energy of vapours is found from charts and tables.

1. A boiler heats up 2.5 kg of water per second from 20oC to 100oC and then
evaporates it without raising the temperature. The specific heat capacity is
4.186 kJ/kg K and the latent heat ufg is
2090 kJ/kg. Calculate the change in internal energy. .

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2. Calculate the energy needed to heat up 2 kg of copper from 100oC to 250oC.


The specific heat capacity is 386 J/kg K.

3. Calculate the change in internal energy when 30 kg of water is heated from


20oC to 80oC. Take c = 4186 J/kg K.

4. 5 kg of lead at 20oC is heated up to its melting point of 600oC and then just
exactly melted. Calculate the energy needed. The specific heat capacity of
solid lead is 126 J/kg K and the latent energy of fusion ui is 26 kJ/kg.

5. A boiler heats high pressure water from 80oC to 152oC and then evaporates
it without raising the temperature. The specific heat capacity is 4.86 kJ/kg K
and the latent heat ufg is 1923 kJ/kg. Calculate the change in internal energy of
1 kg.

5. Thermal expansion

When solids and liquids are heated, the molecules vibrate more and take up
more space so the material expands. Consider first the expansion in one
direction. If a bar of material of length Lo has its temperature increased by T
degrees, the increase in length is ΔL.

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This is directly proportional to the original length L and to the temperature


change ΔT. It follows
that :-

ΔL = constant x Lo ΔT

The constant of proportionality is called the coefficient of linear expansion (α).

ΔL = α Lo ΔT

A thin steel band 850 mm diameter must be expanded to fit around a disc 851
mm diameter. Calculate the temperature change needed. The coefficient of
linear expansion is 15 x 10-6 per oC.

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Superficial expansion

This is about the change in area of a flat shape. Consider a flat plate of metal with area Ao. The
change in area is ΔA and this is directly proportional to the temperature change so:-

ΔA = constant x Ao ΔT

The constant is the coefficient of superficial expansion β

ΔA = β Ao ΔT

A steel sheet has an area of 500 cm2 at 20oC. Calculate the area when it is heated to 300 oC. The
coefficient of superficial expansion is 30 x 10-6 per oC.

Cubical expansion

Since a material expands in all directions, the volume changes. The change in volume is . ΔV. This
is directly proportional to the original volume Vo and to the temperature change ΔT. It follows that

ΔV = constant x Vo ΔT

The constant of proportionality is called the coefficient of cubical expansion (γ).

ΔV = γ L ΔT

1. Calculate the change in volume of 1 m3 of water when it is heated from 10 oC to 80 oC. The
coefficient of cubical expansion is 210 x 10-6 per oC

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2. A brass bar is 600 mm long and 100 mm diameter. It is heated from 20 oC to 95 oC.
Calculate the change in length. α is 18 x 10-6 per oC.

3. A steel ring is 50 mm diameter and 2 mm thick. It must be fitted onto a shaft 50.1 mm
diameter. Calculate the temperature to which it must be heated in order to fit on the shaft.
The initial temperature is 20 oC and the coefficient of linear expansion is 15 x 10-6 per oC.

4. A stub shaft 85.2 mm diameter must be shrunk to 85 mm diameter in order to insert it into a
housing. By how much must the temperature be reduced? Take the coefficient of linear
expansion is 12 x 10-6 per oC.

5. A tank contains 40 m3 of oil at 10oC. Calculate the volume at 40oC given γ = 700 x 10-6 per
o
C.

6. Copper sheet covers a wall and has an area of 20 m2 at 15oC. What is the change in area
when it is heated to 80oC? β = 34 x 10-6 per oC.

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Energy Changes, Sources and Applications

Accreditation with

BTEC

National Certificate in Applied Science (Level 3)

Chapter 2

Electrical Energy Sources

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Electric Batteries and Cells

A cell is a device that produces electricity from a chemical reaction. It consists of a negative
electrode, an electrolyte which conducts ions and a positive electrode. So, basically, there are two
electrodes separated by an electrolyte. The name of the cell usually includes reference to the
materials used in the construction and the voltage of each cell depends on the chemicals used, eg an
Alkaline Manganese AA 1.5 V, or a Lead-acid cell of about 2 V.

A battery is a collection of two or more cells, but the term is commonly used for a single cell.
Examples include the PP3 9V (6 cells in series) or the Lead-acid car battery (typically 12 V, also 6
cells). Although the voltages are quoted usually as if they were accurate, mostly they are not.
Voltages vary according to many factors including the temperature and state of charge.

Symbol for a cell

Symbol for a battery

Battery History

• 1748 - Benjamin Franklin first coined the term "battery" to describe an array of charged
glass plates.
• 1780 to 1786 - Luigi Galvani demonstrated what we now understand to be the electrical
basis of nerve impulses and provided the cornerstone of research for later inventors like
Volta. He got frogs legs to kick when passing electric current through them.
• 1800 - Alessandro Volta invented the voltaic pile and discovered the first practical method
of generating electricity. Constructed of alternating discs of zinc and copper with pieces of
cardboard soaked in brine between the metals, the voltic pile produced electrical current.
Alessandro Volta's voltaic pile was the first "wet cell battery" that produced a reliable,
steady current of electricity.
• 1836 - John F. Daniel invented the Daniel Cell that used two electrolytes: copper sulphate
and zinc sulphate. The Daniel Cell was somewhat safer and less corrosive then the Volta
cell.
• 1839 - William Robert Grove developed the first fuel cell, which produced electricity by
combining hydrogen and oxygen.
• 1859 - Gaston Plante developed the first practical storage lead-acid battery that could be
recharged (secondary battery). This type of battery is mainly used in cars.

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• 1866 - Georges Leclanche patented the carbon-zinc wet cell battery called the Leclanche
cell. George Leclanche's original cell was assembled in a porous pot. The positive electrode
consisted of crushed manganese dioxide with a little carbon mixed in. The negative pole was
a zinc rod. The cathode was packed into the pot, and a carbon rod was inserted to act as a
currency collector. The anode or zinc rod and the pot were then immersed in an ammonium
chloride solution. The liquid acted as the electrolyte, readily seeping through the porous cup
and making contact with the cathode material.
• 1881 - J.A. Thiebaut patented the first battery with both the negative electrode and porous
pot placed in a zinc cup.
• 1881 - Carl Gassner invented the first commercially successful dry cell battery (zinc-carbon
cell).
• 1899 - Waldmar Jungner invented the first nickel-cadmium rechargeable battery.
• 1901 - Thomas Alva Edison invented the alkaline storage battery.
• 1949 - Lew Urry invented the small alkaline battery.
• 1954 - Gerald Pearson, Calvin Fuller and Daryl Chapin invented the first solar battery.

These Baghdad batteries from 2000 years ago are thought to have been used to electroplate artifacts
and also as a medicine to relieve pain. They consist of a vase made of clay. Inside this vase was a
cylinder made of copper.

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The above is a replica. The assembly can generate a weak electric current. Close to the vases pieces
of thinner iron and copper rods were found which might have been used as conductive wires.

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Cell types:

There are two fundamental types of cells, Primary and Secondary.

Primary cells are meant to be used once only, through to the discharged state.

Secondary cells are designed to be recharged over and over again, typically several hundreds of
times.

Primary Cells:
A primary cell is any kind of electrochemical cell in which the electrochemical reaction is
irreversible. So these batteries can only be used once and are disposed of when they run down.

Some battery uses require long dormancy periods so charge retention is important. In these
circumstances, certain rechargeable battery technologies may not be appropriate as many have a
high self-discharge rate compared to equivalent non-rechargeable batteries. For example, a
flashlight used for emergency purposes must work when needed, even if it has sat on a shelf for an
extended period of time.

The following are some examples of Primary Cells in use today.

Zinc Carbon: nominal 1.5 V, an old type, cheap and voltage varies considerably during use. These
have mainly been replaced by Alkaline Manganese cells, commonly known as alkaline batteries.

Alkaline Manganese: nominal 1.5V, the main replacement for zinc-carbon, higher energy more
expensive.

Mercury: phased out in many applications because mercury is very poisonous, was/is used in small
applications, eg cameras, hearing aids.

Lithium: a wide ranging group with voltages varying from 1.5 V to 3.6 V, high energy density,
voltage almost constant and very long shelf life. Lithium is a very reactive element which can lead
to explosions (there were some laptops which were withdrawn due to the batteries being unstable
with a possibility of explosions). They are also very expensive.

Zinc Air: nominal 1.4V, as its name suggests must be exposed to the air (a seal is usually removed
when first used), high self-discharge rate.

Silver Oxide: nominal 1.55V. Often sold as button cells, for use in calculators, cameras, watches etc
where its stable discharge characteristics are valuable.

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Electrochemical Cells

A primary cell is an electrochemical cell.

A simple electrochemical cell can be made from copper and zinc metals with solutions of their
sulphates. In the process of the reaction, electrons are transferred from the zinc to the copper
through an electrically conducting path as an electric current.

An electrochemical cell can be created by placing metallic electrodes into an electrolyte where a
chemical reaction generates an electric current. Electrochemical cells which generate an electric
current are called voltaic cells or galvanic cells.

In an electrochemical cell hydrogen ions are converted into hydrogen atoms and bubbles of
hydrogen gas appear at the positive plate. These bubbles interfere with the chemical action of the
cell, causing the voltage and thus current to be reduced, and becoming severely polarized as the
bubbles cover the entire plate. A depolarizer prevents this from happening.

Voltaic Cells

An electrochemical cell which causes external electric current flow can be created using any two
different metals since metals differ in their tendency to lose electrons. Zinc more readily loses
electrons than copper, so placing zinc and copper metal in solutions of their salts can cause
electrons to flow through an external wire which leads from the zinc to the copper.

English chemist John Frederick Daniell developed a voltaic cell in 1836 which used zinc and
copper and solutions of their ions.

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As a zinc atom provides the electrons, it becomes a positive ion and goes into aqueous solution,
decreasing the mass of the zinc electrode. On the copper side, the two electrons received allow it to
convert a copper ion from solution into an uncharged copper atom which deposits on the copper
electrode, increasing its mass. The two reactions are typically written

Zn(s)  Zn2+(aq) + 2e-

Cu2+(aq) + 2e-  Cu(s)

The zinc "half-reaction" is classified as oxidation since it loses electrons. The terminal at which
oxidation occurs is called the "anode". For a battery, this is the negative terminal.

The copper "half-reaction" is classified as reduction since it gains electrons. The terminal at which
reduction occurs is called the "cathode". For a battery, this is the positive terminal.

In order for the voltaic cell to continue to produce an external electric current, there must be a
movement of the sulfate ions in solution from the right to the left to balance the electron flow in the
external circuit. The metal ions themselves must be prevented from moving between the electrodes,
so some kind of porous membrane or other mechanism must provide for the selective movement of
the negative ions in the electrolyte from the right to the left.

Energy is required to force the electrons to move from the zinc to the copper electrode, and the
amount of energy per unit charge available from the voltaic cell is called the electromotive force
(emf) of the cell. Energy per unit charge is expressed in volts (1 volt = 1 joule/coulomb).

To get energy from the cell, you must get more energy released from the oxidation of the zinc than
it takes to reduce the copper.

The cell can yield a finite amount of energy from this process, the process being limited by the
amount of material available either in the electrolyte or in the metal electrodes. This is why cells
and batteries run down. The supply of chemicals has been used up. Larger cells of the same type
last longer as they have a greater supply of chemicals.

If there was one mole of copper sulphate on the copper side, then the process is limited to
transferring two moles of electrons through the external circuit. Once this has occurred all the
copper ions have been used up.

The amount of electric charge contained in a mole of electrons is called the Faraday constant, and is
equal to Avogadro's number times the charge on an electron:

Faraday constant = F = 6.022 x 1023 x 1.602 x 10-19 = 96,485 Coulombs/mole

The energy yield from a voltaic cell is given by the cell voltage Ecell times the number of moles of
electrons transferred, n, times the Faraday constant.

Electrical energy output = nFEcell

The cell emf Ecell may be predicted from the standard electrode potentials for the two metals. For the
zinc/copper cell under the standard conditions, the calculated cell potential is 1.1 volts.

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Leclanché Cell

Georges Leclanché invented and patented in 1866 his


battery, the Leclanché cell. It contained a conducting
solution (electrolyte) of ammonium chloride, a cathode
(negative terminal) of carbon, a depolarizer of manganese
dioxide, and an anode (positive terminal) of zinc.

The original form of the cell used a porous pot. The


depolarizer, which consisted of crushed manganese dioxide,
was packed into a porous pot, and a carbon rod was inserted
to act as the cathode. The anode, which was a zinc rod, was
then immersed along with the pot in a solution of ammonium
chloride. The liquid solution acted as the electrolyte,
permeating through the porous pot to make contact with the
cathode.

Zinc atoms on the surface of the anode oxidize, ie they give up both their electrons to become
positively-charged ions. As the zinc ions move away from the anode, leaving their electrons on its
surface, the anode becomes more negatively charged than the cathode. When the cell is connected
in an external electrical circuit, the excess electrons on the zinc anode flow through the circuit to the
carbon rod, the movement of electrons forming an electrical current.

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When the electrons enter the rod, they combine with molecules of manganese dioxide and
molecules of water, which react with each other to produce manganese oxide and negatively
charged hydroxide ions. This is accompanied by a secondary reaction in which the negative
hydroxide ions react with positive ammonium ions in the ammonium chloride electrolyte to produce
molecules of ammonia and water.

The Leclanché battery (or wet cell as it was referred to) was the forerunner of the modern dry cell
zinc-carbon battery.

Zinc Carbon Cells

A Zinc-carbon dry cell or battery is packaged in a zinc can that serves as both a container and
anode. It was developed from the wet Leclanché cell – doesn’t spill so more convenient to use in
appliances. The cathode is a mixture of manganese dioxide and carbon powder. The electrolyte is a
paste of zinc chloride and ammonium chloride dissolved in water. Carbon-zinc batteries are the
least expensive primary batteries and thus a popular choice by manufacturers when devices are sold
with batteries included. They can be used in remote controls, flashlights, toys, or transistor radios,
where the power drain is not too heavy.

The container of the zinc-carbon dry cell is a zinc can. This contains a layer of NH4Cl paste
separated by a paper layer from a mixture of powdered carbon & manganese (IV) oxide (MnO2)
which is packed around a carbon rod.

In a dry cell, the outer zinc container is the anode (-). The zinc is oxidised according to the
following half-equation.

Zn(s) → Zn2+(aq) + 2 e-

A graphite rod surrounded by a powder containing manganese(IV) oxide is the cathode(+). The
manganese dioxide is mixed with carbon powder to increase the conductivity of the cathode
mixture. The cathode reaction is as follows:

2MnO2(s) + 2 H+(aq) + 2 e- → Mn2O3(s) + H2O(l)

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The H+ comes from the NH4+(aq):

NH4+(aq) + H2O(l) → H+(aq) + NH3(aq)

and the NH3 combines with the Zn2+.

In this half-reaction, the manganese is reduced from an oxidation state of (+4) to (+3).

There are other possible side-reactions, but the overall reaction in a zinc-carbon cell can be
represented as:

Zn(s) + 2 MnO2(s) + 2 NH4+(aq) → Mn2O3(s) + Zn(NH3)22+(aq)

The battery has an e.m.f. of about 1.5 V.

When the dry cell has been used for a certain time, the zinc container becomes thinner because zinc
metal is oxidised to zinc ions. Therefore Zinc Chloride Solution leaks out the battery. The old dry
cell is not leak proof. It becomes very sticky as the paste leaks through the holes in the zinc case.
The service life of the battery is short, with a shelf life of around 1.5 years. Also, the zinc casing in
the dry cell gets thinner slowly, even when the cell is not being used. It is because the ammonium
chloride inside the battery is acidic, reacting with the zinc.

Cell capacity

The number of different battery types, properties and applications is enormous, quite apart from the
fact that each type comes in a variety of sizes, usually dictated by voltage and capacity. Capacity is
measured in ampere-hours (Ah) or thousandths of ampere hours (mAh).

An ampere-hour (abbreviated as Ah or A-h) is a unit of electric charge. One ampere-hour is equal to


3600 coulombs, and is the amount of electric charge transferred by a steady current of one ampere
for one hour.

The ampere-hour is a unit frequently used in measurements associated with electrochemical


processes such as electroplating and electrical batteries. Although it is not a direct measure of the
energy in a battery (like the joule (J) or watt-hour (Wh)), it is a common rating of how long a
battery will last (or in the case of a rechargeable battery, how long it will last when fully charged).
The commonly seen milliampere-hour (mAh) is equal to 3.6 coulombs

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Secondary Cells:
A secondary cell is one which is rechargeable. These cells can be restored to full charge by the
application of electrical energy. In other words, they are electrochemical cells in which the
electrochemical reaction that releases energy is readily reversible.

Rechargeable batteries can offer an economic benefit when used instead of one-time-use disposable
batteries. Most rechargeable battery technology has been adapted into the standard “AA,” “AAA,”
“C,” “sub-C,” “D,” and “9-volt” configurations that consumers are familiar with. While the
rechargeable versions of these types of cells have a higher up-front cost than disposable batteries,
rechargeable batteries can be discharged and recharged many times. Some manufacturers of NiMH
type rechargeable batteries claim a lifespan up to 3000 charge cycles for their batteries.

The following are some examples of Secondary Cells in use today.

Lead-acid: nominal 2 V per cell, as used in cars, well known to be rechargeable, large capacities but
lead is very poisonous. Can be either wet or dry. Probably the easiest to recycle because the large
amount of lead in each battery has a value in the scrap metal industry. Lead-acid and Sealed Lead-
acid (SLA) are used where relatively large energy ratings are called for but weight is not a major
problem.

Nickel-Cadmium (Ni-Cd): 1.2 V per cell. Used extensively in rechargeable situations and because it
exhibits a memory effect is either continuously trickle-charged or recharged after complete
discharge (ie not partially discharged and then charged). Ni-Cd can be recharged a large number of
times (say, more than a thousand), which may be the reason why they are so popular. Cadmium is
very poisonous.

Nickel Metal Hydride (NiMH): 1.2V per cell. They are a new generation which can replace Ni-Cd
and have higher energy density and longer life cycle, and don't exhibit memory effect, are usually
charged with constant-current source. They do not contain the the most dangerous heavy metals so
are more environmentally friendly than Ni-Cd. The disadvantage is that they cannot be recharged so
many times as Ni-Cd (maybe less than a thousand).

Nickel-zinc: 7 cells for 12V, is claimed to provide the lowest impact to the environment of any
standard rechargeable battery technology mainly because of the absence of contamination from the
dangerous heavy metals. They have lower cost than NiMH, are lighter and better performers than
lead acid, have a high capacity per cycle and high cycle life and they also have low maintenance
requirement. Size may be less than Lead-acid and about the same as Ni-Cd.

Lithium Ion (Li-Ion): used, as well as NiMH, in special applications eg laptop computers, are
expensive to produce and cost a lot. They have the advantage that they have about twice the energy
density of Ni-Cd and around 50% more than NiMH and therefore can be much lighter and smaller
for the same capacity. They can be recharged for up to 1000 times approximately.

Lithium Polymer (LI-Polymer): apparently could become the battery of the future. They are reputed
to have similar characteristics to Li-Ion but should be much cheaper to produce.

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Usage and application

Unlike primary cells, secondary cells must be charged before use (attempting to recharge non-
rechargeable batteries may cause an explosion).

Rechargeable batteries currently are used for lower power applications such as portable consumer
devices, tools, and uninterruptible power supplies. Emerging applications in hybrid vehicles and
electric vehicles are driving the technology to improve cost, reduce weight, and increase lifetime.

Charging

During charging, the positive active material is oxidized, producing electrons, and the negative
material is reduced, consuming electrons. These electrons constitute the current flow in the external
circuit. The electrolyte may serve as a simple buffer for ion flow between the electrodes, as in
lithium-ion and nickel-cadmium cells, or it may be an active participant in the electrochemical
reaction, as in lead-acid cells.

The energy used to charge rechargeable batteries mostly comes from mains electricity using an
adapter unit. Most battery chargers can take several hours to charge a battery.

General Comments:

There have been significant advances in battery technology over the past few years. The battery
market is a lucrative one. Some batteries contain metals which are very dangerous to humans and
animals which is why proper disposal rather than disposing of in standard waste is important. This
allows the expensive and dangerous metals to be recycled

Three heavy metals present in batteries, namely lead, cadmium and mercury, pose serious health
hazards. The effects of these elements on animals (including humans) are terrible, leading to
debilitating pain with fatal consequences. There are some minor recycling schemes, including
experimental council schemes.

Lead-acid car batteries are relatively well catered for because they have an obvious scrap value (a
substantial amount of lead) and you could possibly collect money by taking them to the scrap metal
dealer. Local councils will usually take them for recycling.

Ni-Cd rechargeable batteries contain Cadmium and are increasingly popular. In any piece of
equipment they should be easily removable. As long as they're being used they are not dangerous
but if they are dumped into landfill they are. Some firms will take them back in part exchange.

Mercury is used in miniature primary cells (hearing aids, some cameras). Certain hospitals and
jewellers may take these for safe disposal.

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Fuel Cells
A fuel cell is an electrochemical energy conversion device. It produces electricity from external
supplies of fuel (on the anode side) and oxidant (on the cathode side). These react in the presence of
an electrolyte. Generally, the reactants flow in and reaction products flow out while the electrolyte
remains in the cell. Fuel cells can operate virtually continuously as long as the necessary flows are
maintained.

Fuel cells are different from batteries in that they consume reactant which must be replenished,
while batteries store electrical energy chemically in a closed system. Additionally, while the
electrodes within a battery react and change as a battery is charged or discharged, a fuel cell's
electrodes are catalytic.

Many combinations of fuel and oxidant are possible. A hydrogen cell uses hydrogen as fuel and
oxygen as oxidant. Other fuels include hydrocarbons and alcohols. Other oxidants include air,
chlorine and chlorine dioxide.

Fuel cell design

A fuel cell works by catalysis, separating the electrons and protons of the reactant fuel, and forcing
the electrons to travel through a circuit, converting them to electrical power. Another catalytic
process takes the electrons back in, combining them with the protons and the oxidant to form waste
products (typically simple compounds like water and carbon dioxide).

Zinc-air battery

Zinc-air batteries, also called “zinc-air fuel cells,“ are non-rechargeable electro-chemical batteries
powered by the oxidation of zinc with oxygen from the air. These batteries have high energy
densities and are relatively inexpensive to produce. They are used in hearing aids and in
experimental electric vehicles.

Particles of zinc are mixed with an electrolyte (usually potassium hydroxide solution); water and
oxygen from the air react at the cathode and form hydroxidel ions which migrate into the zinc paste
and form zincate (Zn(OH)42-), at which point electrons are released and travel to the cathode. The
zincate decays into zinc oxide and water is released back into the system. The water and hydroxide
ions from the anode are recycled at the cathode, so the water serves only as a catalyst. The reactions
produce a maximum voltage level of 1.65 volts, but this is reduced to 1.4–1.35 V by reducing air
flow into the cell; this is usually done for hearing aid batteries to reduce the rate of water drying out.

The term zinc-air fuel cell usually refers to a zinc-air battery in which zinc fuel is replenished and
zinc oxide waste is removed continuously. This is accomplished by pushing zinc electrolyte paste or
pellets into an anode chamber. Waste zinc oxide is pumped into a waste tank or bladder inside the
fuel tank, and fresh zinc paste or pellets are taken from the fuel tank. The zinc oxide waste is
pumped out at a refuelling station and sent to a recycling plant.

Zinc-air batteries have properties of fuel cells as well as batteries: the zinc is the fuel, the rate of the
reaction can be controlled by controlling the air flow, and used zinc/electrolyte paste can be

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removed from the cell and replaced with fresh paste. Research is being conducted in powering
electric vehicles with zinc-air batteries.

Proton exchange membrane fuel cell

Proton exchange membrane fuel cells, also known as polymer electrolyte membrane fuel cells
(PEMFC), are a type of fuel cell being developed for transport applications as well as for stationary
and portable applications. Their distinguishing features include lower temperature/pressure ranges
and a special polymer electrolyte membrane.

A proton exchange membrane fuel cell transforms the chemical energy liberated during the
electrochemical reaction of hydrogen and oxygen to electrical energy, as opposed to the direct
combustion of hydrogen and oxygen gases to produce thermal energy.

A stream of hydrogen is delivered to the anode side of the membrane-electrode assembly (MEA).

At the anode side it is catalytically split into protons and electrons. This oxidation half-cell reaction
is represented by:

Eo = 0 V

The newly formed protons permeate through the polymer electrolyte membrane to the cathode side.
The electrons travel along an external load circuit to the cathode side of the MEA, thus creating the
current output of the fuel cell.

Meanwhile, a stream of oxygen is delivered to the cathode side of the MEA. At the cathode side
oxygen molecules react with the protons permeating through the polymer electrolyte membrane and
the electrons arriving through the external circuit to form water molecules. This reduction half-cell
reaction is represented by:

Eo = 1.229V

To function, the membrane must conduct hydrogen ions (protons) but not electrons as this would in
effect "short circuit" the fuel cell. The membrane must also not allow either gas to pass to the other

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side of the cell, a problem known as gas crossover. Finally, the membrane must be resistant to the
reducing environment at the cathode as well as the harsh oxidative environment at the anode.

Unfortunately, while the splitting of the hydrogen molecule is relatively easy by using a platinum
catalyst, splitting the stronger oxygen molecule is more difficult, and this causes significant electric
losses. An appropriate catalyst material for this process has not been discovered, and platinum is the
best option. Another significant source of losses is the resistance of the membrane to proton flow,
which is minimized by making it as thin as possible, on the order of 50 μm.

Despite their success in space programs, fuel cell systems were limited to space missions and other
special applications, where high cost could be tolerated. It was not until the late 1980s and early
1990s that fuel cells became a real option for wider application base. Several pivotal innovations,
e.g. low platinum catalyst loading and thin film electrodes drove the cost of fuel cells down, making
development of PEMFC systems more or less realistic. However, there is significant debate as to
whether hydrogen fuel cells will be a realistic technology for use in automobiles or other vehicles
for many decades.

Direct methanol fuel cell

Direct-methanol fuel cells or DMFCs are a subcategory of proton-exchange fuel cells where, the
fuel, methanol (CH3OH), is not reformed, but fed directly to the fuel cell. Because methanol is fed
directly into the fuel cell, complicated catalytic reforming is unneeded. Storage of methanol is much
easier than that of hydrogen because it does not need to be done at high pressures or low
temperatures, as methanol is a liquid from -97.0 °C to 64.7 °C (-142.6 °F to 148.5 °F). The energy
density of methanol, the amount of energy contained in a given volume of methanol, is an order of
magnitude greater than even highly compressed hydrogen.

However, the efficiency of direct-methanol fuel cells is low due to the high permeation of methanol
through the membrane, which is known as methanol crossover. Other problems include the
management of carbon dioxide created at the anode. Current DMFCs are limited in the power they
can produce, but can still store a high energy content in a small space. This means they can produce
a small amount of power over a long period of time. This makes them ill-suited for powering
vehicles, but ideal for consumer goods such as mobile phones, digital cameras or laptops.

The DMFC relies upon the oxidation of methanol on a catalyst layer to form carbon dioxide. Water
is consumed at the anode and is produced at the cathode. Positive ions (H+) are transported across
the proton exchange membrane (often Nafion) to the cathode where they react with oxygen to
produce water. Electrons are transported via an external circuit from anode to cathode providing
power to external devices.

The half-reactions are:

Anode: CH3OH + H2O → CO2 + 6H+ + 6e-

The methanol is adsorbed on a catalyst, usually Pt, and deprotonized, until a CO species is left.
Another catalyst, usually Ru is used to oxidize water, producing an OH species which reacts with
the CO to form carbon dioxide.

Cathode: 1.5 O2 + 6H+ + 6e- → 3H2O

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Net reaction: CH3OH + 1.5 O2 → CO2 + 2H2O

Because water is consumed at the anode in the reaction, pure methanol cannot be used without
provision of water via either passive transport such as back diffusion (osmosis), or active transport
such as pumping. The need for water limits the energy density of the fuel.

Currently, platinum is used as a catalyst for both half-reactions. This contibutes to the loss of cell
voltage potential, as any methanol that is present in the cathode chamber will oxidize. If another
catalyst could be found for the reduction of oxygen, the problem of methanol crossover would
likely be significantly lessened. Furthermore, platinum is very expensive and contributes to the high
cost per kilowatt of the fuel cell.

In one of the steps of the methanol oxidation reaction, CO is produced, which adsorbs strongly on
the platinum catalyst reducing the surface area for the catalyst reaction. The addition of other
catalysts such as Ruthenium or Gold tends to reduce this problem because these catalysts oxidize
water. The oxygen atom from the oxidized water molecule combines with the CO to produce CO2
which can then be released as a gas.

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Solar Cells
A solar cell or photovoltaic cell is a device that converts light energy into electrical energy.

Sometimes the term solar cell is reserved for devices intended specifically to capture energy from
sunlight, while the term photovoltaic cell is used when the light source is unspecified.

The device needs to fulfil two functions:


• photogeneration of charge carriers (electrons and holes) in a light-absorbing material
• separation of the charge carriers to a conductive contact that will transmit the electricity
(simply put, carrying electrons off through a metal contact into a wire or other circuit).

This conversion is called the photovoltaic effect.

Solar cells have many applications. They have long been used in situations where electrical power
from the grid is unavailable, such as in remote area power systems, Earth-orbiting satellites and
space probes, consumer systems, e.g. handheld calculators, remote radiotelephones and water
pumping applications. More recently, solar cells are starting to be used in assemblies of solar
modules (photovoltaic arrays) connected to the electricity grid through an inverter, often in
combination with a net metering arrangement.

History of solar cells

The first generation photovoltaic, consists of a large-area, single layer p-n junction diode, which is
capable of generating usable electrical energy from light sources with the wavelengths of sunlight.
These cells are typically made using a silicon wafer. First generation photovoltaic cells (also known
as silicon wafer-based solar cells) are the dominant technology in the commercial production of
solar cells, accounting for more than 86% of the solar cell market.

The second generation of photovoltaic materials is based on the use of thin-film deposits of
semiconductors. These devices were initially designed to be high-efficiency, multiple junction
photovoltaic cells. Later, the advantage of using a thin-film of material was noted, reducing the
mass of material required for cell design. This contributed to a prediction of greatly reduced costs
for thin film solar cells. Typically, the efficiencies of thin-film solar cells are lower compared with
silicon (wafer-based) solar cells, but manufacturing costs are also lower, so that a lower cost per
watt can be achieved. Another advantage of the reduced mass is that less support is needed when
placing panels on rooftops and it allows fitting panels on light or flexible materials, even textiles.

Third generation photovoltaics are very different from the previous semiconductor devices as they
do not rely on a traditional p-n junction to separate photogenerated charge carriers. These new
devices include photoelectrochemical cells, polymer solar cells, and nanocrystal solar cells. Dye-
sensitized solar cells are now in production.

Fourth generation Composite photovoltaic technology with the use of polymers with nano particles
can be mixed together to make a single multispectrum layer. Then the thin multi spectrum layers
can be stacked to make multispectrum solar cells more efficient and cheaper based on polymer solar
cell and multi junction technology used by NASA on Mars missions. The layer that converts
different types of light is first, then another layer for the light that passes and last is an infra-red
spectrum layer for the cell - thus converting some of the heat for an overall solar cell composite.

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What happens:

1. Photons in sunlight hit the solar panel and are absorbed by semiconducting materials, such
as silicon.

2. Electrons are knocked loose from their atoms, allowing them to flow through the material to
produce electricity. The complementary positive charges that are also created are called
holes and flow in the direction opposite of the electrons in a silicon solar panel.

3. An array of solar panels converts solar energy into a usable amount of direct current (DC)
electricity.

4. The DC current enters an inverter. The inverter turns DC electricity into 120 or 240-volt AC
(alternating current) electricity needed for home appliances. The AC power enters the
utility panel in the house.

5. The electricity is then distributed to appliances or lights in the house. The electricity that is
not used will be re-routed and used in other facilities.

Comparison of energy conversion efficiencies

Solar cell efficiencies vary from 6% for amorphous silicon-based solar cells to 42.8% with
multiple-junction research lab cells. Solar cell energy conversion efficiencies for commercially
available multicrystalline Si solar cells are around 14-16%. The highest efficiency cells have not
always been the most economical.

To make practical use of the solar-generated energy, the electricity is most often fed into the
electricity grid using inverters (grid-connected PV systems); in stand alone systems, batteries are
used to store the energy that is not needed immediately.

A common method used to express economic costs of electricity-generating systems is to calculate


a price per delivered kilowatt-hour (kWh). Using the commercially available solar cells (as of 2006)
and system technology leads to system efficiencies between 5 and 19%. As of 2005, photovoltaic
electricity generation costs ranged from ~0.60 US$/kWh down to ~0.30 US$/kWh in regions of
high solar irradiation. This electricity is generally fed into the electrical grid on the customer's side
of the meter. The cost can be compared to prevailing retail electric pricing (as of 2005), which
varied from between 0.04 and 0.50 US$/kWh worldwide. (Note: in addition to solar irradiance
profiles, these costs/kwh calculations will vary depending on assumptions for years of useful life of
a system.

Solar cells and energy payback

In the 1990s, when silicon cells were twice as thick, efficiencies 30% lower than today and lifetimes
shorter, it may well have cost more energy to make a cell than it could generate in a lifetime. The
energy payback time of a modern photovoltaic module is anywhere from 1 to 20 years (usually
under five) depending on the type and where it is used (see net energy gain). This means solar cells
can be net energy producers, meaning they generate more energy over their lifetime than the energy
expended in producing them.

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