电化学专业英语

程新群 编

哈尔滨工业大学

2003 年 3 月
 前言

本教材是为我校化学工程与工艺（电化学）专业学生在学完大学基础英语后，
进一步学习专业英语知识而编写的。
本教材内容由浅入深，涉及化学基础、物理化学、电极过程、化学电源以及
电镀理论等方面的内容，与本专业的教学内容一致。学生在学习本书后，能掌握
相当数量的专业词条和知识，基本了解科技英语翻译的特点，为进一步阅读本专
业的英文书籍和文献、并将其译成通顺达意的汉语打下坚实的基础。熟练阅读本
书，掌握常用句式和词汇，可为英文摘要和文章写作创造条件。
本书参考了本专业王金玉老师编写的讲义，化学工程与工艺专业 99 级同学
在文字打印方面提供了很大帮助，在此一并表示感谢。
由于时间仓促，加之本人水平有限，错误在所难免，欢迎批评指正。

编者
2003 年 3 月
 1. Some Basic Conceptions

1.1 Matter
Everything on the earth is made of matter. Matter has weight and occupies space. Iron is a kind
of matter. It has weight and occupies space. Air is also a kind of matter. It has weight and occupies
space.
Matter exists in one of the three states: solid, liquid, or gaseous. Iron is a solid. It is not a liquid
or a gas. Water is a liquid. It is not a solid or a gas. Air is a gas. It is not a solid or a liquid.
Each state of matter has definite properties.
Solids are hard and have definite form. Solids also have volume. Liquids have not any definite
form. They take only the shape of their container. Like solids, liquids have definite volume. Gases
have neither definite shape nor definite volume. Molecules of gases move faster. Gases can be
easily compressed.
Matter can be changed from one state to another. This kind of change in the state of matter is
only a physical change. The physical change does not change the chemical composition of matter.
A chemical change is different from a physical change. In the chemical change a new substance is
formed at least.

1.2 What Is Matter?

What is matter? Everything on the earth is matter. Air is a kind of matter. Water and iron are
also different kinds of matter. The earth itself is matter. The world is made of matter. Matter is in
constant motion and in constant change.
Matter has many properties. Different kinds of matter have different properties. However, all
matter has weight and occupies space. Iron has weight and occupies space. It is heavy. Air also has
weight and occupies space, but it is very light. Most kinds of matter have the three states. Matter
changes from one state to another at different temperature and pressure. At ordinary pressure,
water changes into steam at the temperature of 100°C and changes into ice at the temperature of
0°C. Changes of matter in states are called physical changes. A change in the size or temperature
of matter does not change its chemical composition.

1.3 Chemical Changes

Different kinds of matter have different physical and chemical properties. The properties of a
substance are its characteristics. We know one substance from another by their physical and
chemical properties. In a physical change the composition of a substance is not changed. Ice can
be changed into water. This is a physical change because the composition of water is not changed.
In a chemical change the composition of a substance is changed. One or more new substances are
formed.
Iron rusts in moist air. When iron rusts, it unites with the oxygen from the air. A new substance
is formed. It is iron oxide. It has other different properties. Wood will burn if it is heated in air.
When wood burns, it reacts with the oxygen from the air. New substances are formed. They are

— 1 —
carbon dioxide and water. Carbon dioxide and water have different properties. Heat is given off if
the combustion of any fuel takes place.
The above two cases are chemical changes.

1.4 Molecules and Atoms

The world is made of matter. All forms of matter consist of a great many small particles－－
molecules, and these molecules are made of smaller particles－－atoms.
A molecule is the smallest particle of matter that can exist without any change in its properties.
If the molecule is broken down, we get atoms. An atom is a particle that cannot be broken down
into smaller particles by chemical means.
All atoms are made up of protons, neutrons, electrons, and so on. The protons and neutrons
form the nucleus of the atom. The electrons move round this nucleus.
A substance which consists only of atoms with the same properties is called an element, for
example, oxygen. If the molecule of a substance consists of atoms of different chemical properties,
the substance is called a compound, for example, water.
The molecule of water is written for H2O. This shows what kinds of atoms and how many are
found in the molecule. In water there are two atoms of hydrogen and one atom of oxygen.

1.5 Elements and Compounds

There are two kinds of substances, elements and compounds. Elements are pure substances
which cannot be decomposed by a chemical change. They are the simplest forms of matter.
Familiar examples are iron, carbon, sodium, oxygen, hydrogen, chlorine, silicon, and so on.
107 elements are known to us now. About twenty of the elements make up almost 99 per cent of
the earth’s crust. Oxygen and silicon make up about 75 per cent of the total quantity of the
elements in the world we know.
Compounds are substances which can be decomposed by chemical means, and they are
composed of two or more different elements. For example, white sugar is a compound. It consists
of the element carbon, which is a black solid when it is free, and the two elements hydrogen and
oxygen, which are colorless gases when they are uncombined. Water, a compound, can be
decomposed by an electric current into hydrogen and oxygen. Salt can be broken down by
electrolysis into sodium and chlorine.
Although there are only 107 known elements, there are a great many chemical compounds in
nature. Each of these compounds possesses definite chemical and physical properties by which we
can distinguish one compound from another.

1.6 Oxidation and Reduction

It is well known that a substance is oxidized when it unites with oxygen, an oxidizing agent.
The process which takes place is called oxidation. For example:

Cu + 12 O2 →CuO

The copper is oxidized by oxygen in the process. In a like manner, reduction is the removal of
oxygen from a compound by a reducing agent. It is clear that the compound loses the oxygen

— 2 —
when it is reduced. For example:
CuO + H2 →Cu + H2O
Hydrogen, a reducing agent, reduces copper oxide to copper in the process. It should be noted
that reduction is the reverse of oxidation and that each is accompanied by the other. This reveals
the fact that the reducing agent hydrogen has become oxidized because it has combined with
oxygen to form water, which process is oxidation.

1.7 Reversible Reaction

Many reactions are reversible. In order to carry out a reversible reaction efficiently, the
important conditions are that the reactants should be converted into products to the almost extent
and that this conversion should be brought about in the shortest possible time. For example,
consider the reaction:

N2 + 3H2 ⇌ 2NH3 + heat

In order to obtain a large yield of ammonia from a given quantity of nitrogen and hydrogen, the
left-to-right reaction must be as nearly complete as possible. It has been found by experiment that
a large yield of ammonia can be obtained under a high pressure, at a reasonable temperature and in
the presence of a catalyst.
Since the volume decreases in the left-to-right reaction, the amount of ammonia formed will
decrease with pressure decrease. Heat is given off in the reaction, hence the reaction will become
more nearly complete at comparatively low temperatures. Yet the trouble is that too low a
temperature will lower the reaction rate. Therefore, we must select a reasonable temperature. In
addition to it, we must use a catalyst to speed up the left-to-right reaction.

1.8 Pressure
In chemical work it is often necessary to know not only the temperature at which an experiment
is carried out, but also the pressure. For example, the industrial preparation of ammonia is carried
out at high pressure because the chemical reaction does not proceed satisfactorily at ordinary
pressure.
Pressure is force per unit area. Pressure may be measured in newtons per square meter, or in
pounds per square inch, or in other units. The atmosphere of the earth exerts a pressure on all
-2
objects at the surface of the earth, The pressure of the atmosphere is 101.325KN• m .
Another unit of pressure that is often used is the atmosphere. The pressure 1 atm. is the
average pressure at the surface of the earth (at sea level) that is due to the weight of the air.
Pressure is often expressed in the heights of the column of mercury necessary to balance it.
For example, the pressure 1 atm. is equal to 760 mm of mercury, or 760mm Hg.
The units that are used to measure pressure are summarized in the following equation:
1 atm = 760 mmHg = 101325 pa

1.9 Heat and Temperature

There have been some theories to explain the nature of heat. The history of these theories
reveals how science has developed theories as new experiments have provided new data. It was

— 3 —
not until the 17th century that men began to think about heat in terms of molecular motion.
As many experiments were made and studied, it became clear that heat is a form of motion.
Many scientists did a lot of work to put the molecular theory of heat on a firm foundation. They
considered that, if an object is hot on account of motion, the motion must be carried on by
particles of the objects too small to be seen. These small particles are molecules. Although the
speed of a molecule is very great, the molecules of solid objects more only through a very short
distance. In this case we must take into account the facts that not all molecules have the same
speed, that there are many collisions between them, and that the velocities of millions of
molecules are always changing in amount and in direction.
If two objects are at the same temperature, the average energy of motion of their molecules is
the same. In mechanics the energy of motion is called kinetic energy. Thus, the temperature of an
object depends on the average kinetic energy of its molecules. When an object is heated, the
average speed of its molecules is increased, their average kinetic energy becomes greater, or in
other words, the object is at a higher temperature. The amount of heat in an object, however,
depends also on the number of molecules each of which has a certain average kinetic energy.
In the case of a cup and a kettle of boiling water, the average speed of the molecules is the
same in both, and the temperature is the same for both. But the kettle has much more molecules of
water than the cup so that the total energy of all its molecules is many times greater. Its heat
content is therefore many times greater. It may be seen from this that heat is different from
temperature.

1.10 The Three Gas Laws

Consider the apparatus illustrated by Figure 1. The cylinder shown in the figure is fitted with
a piston of negligible friction so that the pressure of the contained gas is always the same whether
3
it expands or contracts. Suppose (that) we start with 2730 cm of gas at 0℃. If we increase the
1 3
temperature of the gas to 1℃, its volume increases by 273
or 10 cm , the new volume being 2740

3
cm . If we decrease the temperature to –1℃, the volume decreases by 1
273 , becoming 2720 cm3.

by experiment we find that the volume of a gas at constant pressure varies with the temperature at
constant volume.
These two relations may be expressed below:

V1 T1 P T
= , and 1 = 1 ,
V2 T2 P2 T2
where V1 and V2 represent volumes, P1 and P2 (represent) pressures, and T1 and T2 (represent) the
corresponding absolute temperatures.
Boyle's law states that the pressure of a gas varies inversely with its volume if its temperature
is constant. The relation can be expressed below:

P1 V2
=
P2 V1
Combining these three relations into one general gas law, we obtain:

— 4 —
 P1V1 P2V2
=
T1 T2
The three gas laws and the general gas law presented here are known as the ideal gas laws.

weight

thermometer

V1

P1 V2 P 2

(a) (b)

Fig. 1-1 V-T relation P=const Fig. 1-2 P-V relation T=const

1.11 Boyle's Law

Whenever a gas is confined in a closed container, it exerts pressure. Consider a container
such as that shown in Fig. 2, one wall of which is a movable piston. In its initial position (a) there
is a pressure P1 when the volume is V1. If, however, the piston is pressed down until it is in the
new position shown in (b), the volume has been decreased to V2 while the pressure has been
increased to P2. If this change takes place so slowly that there is no change in temperature, the
volume occupied by the confined gas is inversely proportional to the pressure:
1
V ∝
P
In other words, the product of pressure and volume is always the same, that is:
P1 V1 = P2 V2
This relation is expressed in Boyle' law, which may be written as follows: the volume of a
given amount of gas varies inversely as the pressure, the temperature remaining constant. In
symbols:
PV = constant
Boyle's law is approximately true over considerable ranges of temperature and pressure.
There are, however, conditions under which it cannot be applied. If the temperature is near that at
which the gas will liquefy, there will be large deviations from the law. The change in volume is
greater than that predicted by the law. Also if the pressure becomes very great, the deviation from
Boyle's law is large, in this case the change in volume being less than that predicted by the law.

— 5 —
1.12 Expressing Concentrations
Because mixtures vary in composition, there must be a way of telling how much solute is
present in a solution. The amount of solute in a solution is called the concentration.
One common way of expressing the concentration of solutions is in per cent. A 10 per cent
solution is one that has 10 parts by weight of solute to 90 parts by weight of solvent in 100 parts
by weight of solution. A 10 per cent solution that weighs 100 grams will have 10 grams of solute
and 90 grams of solvent.
In chemical laboratories the concentration of solutions is often expressed in terms of the
molecular weight or moles of the solute in 1 liter of solution. A gram molecular weight of a solute
is the same number of grams as the sum of the atomic weights of the atoms represented in the
formula of the compound. One gram molecular weight of ammonia: NH3 is 17 grams (N—14, H
－1). The weight of a compound that is equal to the sum of the atoms represented in its formula is
called 1 mole of the substance.
A 1-mole solution contains 1 liter of solution, not in 1 liter of solvent. For this reason, in
forming a solution, you first add the solute to less than 1 liter of solvent. After it is dissolved, you
add enough solvent to make 1 liter.

1.13 Solubility
The amount of solute that will saturate 100 grams of solvent at a certain temperature is called
the solubility of the substance. The solubility of table salt, NaCl, is the weight that has been used
to saturate 100 grams of water.
How much of a substance will go into solution is determined by four factors: (1) the nature of a
solute, (2) the nature of a solvent, (3) temperature, and (4) pressure.
The effect of the nature of the solute is clearly shown by the fact that 100 ml of water at room
temperature will dissolve very different amounts of chlorides of different metals. For example:
ZnCl2 362 grams
CaCl2 74 grams
NaCl 36 grams
AgCl only 0.00015 gram
It is clear that every substance has its own characteristic solubility.
Also solvents act differently. Oil dissolves in carbon tetrachloride but not in water. In addition to
it, solubility depends on the nature of the solvent used.
Increasing the temperature usually increases the amount of solute which can be held in solution.
In a few instances (for example, NaCl) temperature has little effect on the solubility, while a very
few solid substances (for example, Ca(OH)2) are more soluble in cold water than in hot. All gases,
however, decrease in solubility as the temperature is increased and come out of solution, therefore,
on warming.
Pressure affects only solutions of gases, in liquids. We may use increasing the pressure to
increase the solubility of gases. Gases are more soluble in liquids under pressure.
It must be noted that, in general, boiling and freezing points of solutions are different from those
of solvents used.

— 6 —
1.14 Chemical Action and Electricity
The fact that chemical action can produce a direct current of electricity was discovered in 1785.
The simplest chemical cell consists of a strip of copper and a strip of zinc immersed in a solution
of sulfuric acid and water. We call this solution an electrolyte.
The chemical action of the acid on the
zinc causes the flow of electrical
charges. The current produced is the
result of chemical energy being changed
to electrical energy. When the copper
and the zinc plate are connected with a
wire, the electrons flow to the copper.
The zinc is the negative plate. The
copper is positive with respect to the
zinc. This is because the copper has a
lower electric potential than the zinc.
Let us consider what happens to cause Fig. 1-3 A Chemil Cell
the zinc to have so many electrons. The
―
sulfuric acid is in the form of H+ and SO42 . Notice that these are ions. When the zinc is
undergoing chemical action, it forms zinc ions, Zn2+, and two electrons. We can write this process
as an equation:
―
Zn → Zn2+ + 2e
In the change from zinc two electrons are given off. The zinc ions surround the zinc plate, and
the electrons collect on the plate or flow through the external circuit.
Hydrogen ions, H+, are also present in the solution. These have the same electrical charge as the
zinc, so the two repel each other. The excess zinc ions, Zn2+, repel the hydrogen ions, H+. The
hydrogen ions are driven to the copper strip where they collect electrons and become hydrogen
atoms.
―
2H+ + 2e → H2 ↑
The zinc ions and the sulfate ions are remaining in the solution. Gradually the zinc will be used
up. The removal of electrons from the copper plate by the hydrogen ions, H+, makes the flow of
electrons in the external circuit possible. Electrical charges will flow until the zinc has all
dissolved.

1.15 A Chemical Cell

A chemical cell where chemical energy is converted into electrical energy is made up of two
electrodes immersed in an electrolyte. In the simplest chemical cell the electrolyte is a solution of
sulfuric acid in water.
When zinc dissolves, part of zinc atoms leave the zinc plate and mix with the water. Each zinc
atom, as it enters the water, leaves behind two electrons. We call such a zinc atom an ion with a
double positive charge, Zn2+. The zinc plate becomes more and more negatively charged with
electrons, as more atoms of zinc dissolve.
When a copper plate is put into the sulfuric acid electrolyte, very few of its atoms dissolve. The

— 7 —
copper plate does not become negatively charged. If a wire is connected from the zinc plate to the
copper plate, the crowded electrons on the zinc flow along the wire to the copper plate. At the
copper plate the electrons join part of the hydrogen ions (H+) in the solution. The hydrogen ions
thereby become neutral hydrogen atoms, and collect around the copper plate in the form of
hydrogen gas bubbles. Part of this gas is given off. But part clings to the copper plate.
The flow of electrons from the zinc plate to the copper plate represents electrical energy. This
energy comes from the zinc that has been dissolved in the electrolyte. When electrons move
through a wire, electrical energy is available. Moving electrons can do work. They can produce
heat and light and can make motors run.
Before electrons were discovered, it was assumed that the invisible fluid of electricity flowed
from the positive to the negative object. Now we still speak of an electric current as going from
the positive to the negative. When you speak of electrons, however, you will have to describe
them as moving from the negative to the positive.

1.16 Insulators
In an insulator it is impossible to free more than a very few electrons from the atoms.
Suppose that the insulating material were a sheet of glass about 3/8 inch thick. Depending on
the kind of glass, no appreciable current would flow through it until you had raised the pressure to
somewhere between 300,000and 1,500,000 volts. At that terrific pressure the glass would puncture,
the electric pressure would force a hole right through the glass. Then current would flow through
the air in the hole because it takes an electromotive force of only about 10,000 volts to force
electricity through 3/8 inch of air. If instead of the sheet of glass you were to use a small cube of
glass measuring 3/8 inch on one side, the resistance of that piece of glass to flow of current
through it would be a thousand million, million, million times as great as the resistance of a piece
of copper of the same size. The rate of current flow through the glass would be correspondingly
smaller than through the copper, and could be called infinitesimal.
The insulating material has millions and millions of times the resistance to flow of current
that is offered by any of metals. Were it not for this fortunate fact we would have no more success
in keeping electricity within the paths which we wish it to follow.

— 8 —
 2. Some Basic Facts

2.1 Conduction
Most simple systems which conduct electricity obey Ohm's Law, though electrolytes with
direct current may need a ‘minimum decomposition potential’ of up to 2 volts before significant
current passes. Ohm's Law states that the current I is proportional to the potential difference E
across any conductor, so:
E = IR or I = EG
where the constants of proportionality are called the resistance R and the conductance G. If E is
measured in volts and I in amperes, R will have the unit volts per ampere, named the ohm and
―1
given the symbolΩ.Since conductance is the reciprocal of resistance, G will have the unitΩ , at
one time called the mho. Electricians, but not often chemists, refer to the reciprocal ohm as the
siemens.
The resistance of a particular body is usually proportional to the length l of the path of the
current, and inversely proportional to the cross-sectional area a. Therefore in order to eliminate the
geometry of the particular sample, and to obtain the resistivity of the substance, the resistance is
multiplied by (area/length). The common unit of resistivity is Ωcm.
Similarly, conductivity κ (kappa) is obtained by the relationship:
1 a
κ= G or I=κE
a l
Conductivities of various substances may be compared, roughly, by means of a circuit
consisting of a 6 V supply, an ammeter, a pair of copper plates, and a variable resistor (rheostat) of
about 20Ω, adjusted to give full-scale deflection on the meter when the copper plates are in
contact. The ‘ohm's’ range of any multi-range meter will serve the same purpose. For solids,
similarly sized sample are pressed between the plates; and for liquids, the plates are immersed to
some standard depth. More careful methods of measurement will be discussed in Chapter 3.
In the case of metallic (electronic) conductors and semiconductors, no chemical change
results from the passage of the electric current, but when a current passes through an electrolyte
there is invariably chemical reaction at the electrodes. The electrodes are the points of contact
where the current enters or leaves the electrolyte, that is, where there is a change from electronic
to electrolytic conduction.
An interesting difference between metallic and electrolytic conductors is the effect of
temperature on conductance. The conductance of metals decreases with rise in temperature,
though the effect is not very pronounced; but the conductance of electrolytes increases markedly
with increasing temperature—it may increase by a factor of five from 10℃ to 80℃. (Graphite is
anomalous in that it is an electronic conductor which increases its conductance on heating; carbon
filament lamps exploit this property.)
The explanation of this difference is that since the conduction in electrolytes is due to the
movement of ions (electrically charged atoms of molecules), there is considerable friction of
viscosity within the electrolyte: so an increase in temperature, and freer movement of the particles,
reduces this friction. In metals, however, conduction is due to the movement of electrons, which
may be pictured as small and fast-moving compared to atoms: a rise in temperature causes an

— 9 —
increase in the space between the atoms, which hinders the electron flow.

Table 2.1 Results of Conductivity Tests

☆
(i) Very good conductors All metals (solid or molten) Fe, Pb, Na, Hg
(ii) Good conductors Some compounds (electrolytes) when NaOH, PbBr2
molten, but not solid
Some aqueous solutions of salts, acids NaOH, H2SO4, CuCl2
and bases (electrolytic solutions)
Graphite C (gr)
(iii) Poor conductors A few solid compounds (solid AgCl
electrolytes)
Solutions of weak (slightly dissociated) CH3COOH(aq), NH 3 (aq)
electrolytes
※
(iv)Very poor conductors A few pure liquids (slightly ionized) pure H 2SO4, H2O
(v) Non-conductors Non-metal elements (solid or liquid) S, Br 2, C (diamond)
Molecular compounds CCl4, C6H6, PCl5
(non-electrolytes)
Some aqueous solutions C12H22O11, CO(NH2)2
(non-electrolytes)
Gases conduct only at low pressures and with high potential differences
☆ Powdered metals may appear to conduct badly because of poor contact between particles.
※ These very weak electrolytes show a misleadingly high conductivity unless specially purified.

2.2 Ionic theory

X-ray crystallography shows that solids consist off regular crystal lattices, but while some
solids have the same unit (the molecule) at all lattice points, others (the 'ionic' solids) have two (or
more) different types of unit. In the ionic crystal, any one ion is surrounded by several (often 6)
oppositely-charged ions, all equally distant. No ion is connected to any other particular ion, there
are no ion-pairs such as Na-Cl or Ca-SO 4 in the solid (though they are predominant in the vapour).
Molecular solids melt and boil at relatively low temperatures, showing that although the
bonds within molecules are strong, the forces between molecules are weak. In contrast, ionic
solids melt at high temperatures, showing the strong forces between the particles－forces which
are interpreted as attractions between oppositely-charged ions.
The modern theory of electrolyte solutions is due to Arrhenius, who announced it in 1883
although it was not generally accepted until 20 years later. The theory is that all solutions of
'strong' electrolytes consist entirely of ions, now known to be 'hydrated' by association with a
number of solvent molecules♦. Thus aqueous sodium chloride solution is Na+ (aq) +Cl (aq), with
―

♦
The manner and extent of hydration of aqueous ions are not properly understood, and only recently have
techniques such as the effect of high pressure on conductivity begun to provide answers. There is little doubt,
though, that the hydration arises from electrostatic attraction between the ion and either the partly negative O or
the positive H atoms of appropriately oriented H2O molecules. The energy of hydration (and hence the number of
molecules held) is a function of the charge density on the ion (which increases with smaller size and higher
charge).

— 10 —
 ― ―
no NaCl molecules; and aqueous H2SO4 is almost entirely H+ (aq), HSO4 (aq) and SO42 (aq).
Chemists in 1890 found this hard to accept because they did not understand the important
difference between ions and atoms. Since sodium and chlorine combine so vigorously to form
sodium chloride, it was difficult to believe that merely dissolving the salt in water could separate
the sodium and chlorine. They were happier with an earlier theory of dynamic equilibrium
between dissolved molecules and a small proportion of ions, since this would not require so much
‘energy of ionization’.
Fortunately van't Hoff had provided evidence of a non-electrochemical kind: his vapour
pressure measurements on aqueous solutions only made sense if the electrolyte solutions
contained a number of particles twice of three times as great as that of these supposed 'molecules'
of the electrolytes. The depression of the vapour pressure of 1 dm3 of water by 1 mole of CaCl2
approached a value three times as great as that caused by 1 mole of the non-electrolyte urea; that is,
the van't Hoff factor i was approximately 3.
However, conductivity and vapour pressure measurements on solutions of some acids and
bases showed that they existed largely as molecules with only a small proportion of 'dissociation'
▲
into ions. These were the 'weak electrolytes' , for example ethanoic (acetic) acid, hydrocyanic
(prussic) acid, or ammonia solution.
The ionic theory for strong electrolytes gained further support from the X-ray crystallography
results mentioned at the start of this section. If salts are fully ionized in the solid state, it was
argued, then no energy will be required to ionize them when they dissolve. This point is not so
sound as it seemed at the time, and the objections are (i) the dissolution of a salt in water is
accompanied by an energy change, which is sometimes so great an absorption of energy as to
make the salt insoluble: (ii) some electrolyte solutions are formed by the dissolution of molecular
solids or liquids (e.g. H2SO4, AlCl3), yet these processes are often exothermic, despite the
supposed energy of ionization. The misunderstanding lay in supposing that the energy of
ionization would be simply that for the splitting of the molecule into fragments, with the breaking
of bonds; but in fact this energy is more or less regained when the anhydrous ions combine with
water, to give hydrated ions. This is shown in Fig.2.1, which displays diagrammatically the energy
(enthalpy) changes which would accompany a hypothetical route from solute to solution via free
gaseous anhydrous ions. It is not suggested that these free ions are actually formed as
intermediates in the process of dissolution, but such an analysis helps to explain differences in the
solubilities of different electrolytes.
The ionic theory readily explains the conductance of electricity through the bulk of the
molten or dissolved electrolytes, since in these states the ions are free to move, and those with
positive charge (the cations) will move towards the negative electrode, while the negative ions
(anions) drift towards the positive electrode. But what happens when the ions reach the electrode
is another matter; there must be a change from electrolytic to electronic conductance. Therefore
there must be a discharge or creation of ions and an absorption or release of electrons. Fig.2.2
shows the movement and discharge of ions during the electrolysis of ZnI2 solution.

▲
Note that since 'weak' and 'strong' are used to indicate partial and complete dissociation, these words should not
be used to mean 'dilute' and 'concentrated'.

— 11 —
 Free gaseous ions

Energy for
Energy of system increases

bond fission
Lattice Energy
Energy
energy of
of
hydration Energy of
hydration
hydration
Molecular gas

Ionic
solution Heat of vaporization

Molecular
Heat of dissolution solid or liquid Ionic
Heat of dissolution
(exothermic) solution
(endothermic)
Heat of dissolution
and dissociation

Fig.2.1 Analysis of energy changes for hypothetical routes (thermochemical cycles)

for the formation of electrolytic solutions

Practical work
A simple but convincing demonstration of the movement of ions (electrophoresis) is given by
the electrolysis of copper(II) dichromate(VI) solution in a U-tube, with dilute sulphuric acid in the
two limbs (Fig.2.3). As the current passes, a blue colour appear in the acid in which the negative
electrode is placed, due to the migration of Cu2+(aq) ions. Simultaneously, orange Cr2O72- (aq)
ions migrate towards the positive electrode. Even with a potential difference of 20 V, about 15
minutes is required to give clearly visible colours in the limbs of the U-tube, which gives an
impression of the slowness of the drift of ions. Practical details for setting up this demonstration
and also a version for individual work, are given in Appendix II.
A similar but quicker demonstration is provided by the migration of MnO4– when electrodes
with potential difference of about 100 V d.c. are placed each side of a single crystal of potassium
manganate(VII) on a filter paper moistened with dilute sulphuric acid. An elongated purple stain
grows out from the crystal on one side only.
The electrophoresis to separate ions for the purpose of qualitative analysis is the subject of a
project in Chapter 9.

— 12 —
Fig. 2.2 Electrolysis. The process comprising Fig.2.3 Demonstration of the
the electrolysis movement of ions during electrolysis
of aqueous zinc iodide solution

2.3 Chemical changes in electrolysis.

Unlike electronic conduction, electrolytic conduction is always accompanied by chemical
changes at the electrodes. In some cases the electrodes are attacked, but in other cases they are
insert and then the chemical a changes involve only the electrolyte. Despite the variety of
possibilities, certain rules are obeyed in all electrolyses:
(1) At the negative electrode, electrons are forced to leave the metallic (or carbon) electrode and take part in an
electron-absorbing reaction, most commonly the discharge of a metal ion or hydrogen ion. This result in the
formation of a metal plating on the electrode, or the production of hydrogen gas.
(2) At the positive electrode, the externally imposed potential difference causes a deficiency of
electrons, thereby encouraging any electron-releasing reaction such as the dissolution of the
metal electrode in the form of positive ions, or the discharge of negative ions to produce
oxygen, chlorine or another non-metal..
(3) The sum total of these ‘half-reactions’ at the two electrodes is a complete chemical reaction.
But one which would not have occurred without the supply of electrical energy. It is often
the exact reverse of a spontaneously occurring reaction.
The examples which follow will illustrate these general rules.

Examples of electrolysis

1. Molten lead bromide with inert electrodes

This experiment illustrates an electrolysis of no industrial importance, but one which provides
a good introduction to the theory of electrolysis because the result can be interpreted
unambiguously. It is best shown as a lecture demonstration, preferably in a fume cupboard,
because of poisonous nature of the lead bromide fumes and bromide vapour. Routine eye
protection is recommended. .
About 5g dry powered lead(II) bromide is placed in a porcelain ‘boat’ or crucible ,supported
on a drilled asbestos board .Two carbon electrodes, fixed in holes in a wooden bar, are clamped in
place, touching the compound at points 1 to 3 cm apart (Fig 2.4). The d.c. supply ( about 12 to 20
V) with a rheostat and lamp in series, is switched on. No current passes.

— 13 —
 The crucible is heated with a bunsen
flame, suddenly the lead bromide melts, and
the lamp lights up. After this the heating effect
of the current is often sufficient to keep
electrolyte molten. To confirm the point that
solid lead bromide does not conduct even when
in one piece, with good contact with the
electrodes, the current is switched off until the
melt solidifies, and then switched on again, no
current passes until the solids melted.
The current is left on 5 to 10 minutes.
Brown fumes of bromide gas are seen at the
positive electrode and may be tested with Fig. 2.4 Electrolysis of molten lead bromide
starch-iodide paper. Silvery globules of molten
lead may sometimes be seen during the electrolysis, but in any case the lead is easily found, after
cooling, by dissolving away the residual lead bromide in boiling water.
Assuming that, since they appear to be unchanged, the carbon electrodes do not react, there is
only one possible pair of electrode reaction:
At the positive anode: Br– ions arrive and are discharged, 2Br– → Br2 + 2e–
At the negative cathode: Pb 2+ ions arrive and are discharged, Pb2+ +2e– → Pb

2. Molten sodium chloride with inert electrodes

Sodium chloride melts at 8010C, which is inconveniently high. The addition of calcium
chloride lowers this melting point, and in the industrial process (the Downs Cell) a mixture of 42%
by weight NaCl and 58% CaCl2 is used, at 5900C. Despite the high proportion of Ca2+ ions (44
mole %) very little calcium is produced at the steel cathode; the molten sodium floats to the surface
and is drawn off in an inert atmosphere. A steel grid separates the cathode region from the graphite
anode, and prevents the chlorine from reaching the sodium.
The conductivity of the NaCl+CaCl2 melt can be shown with the apparatus in Fig.2.4, but no
sodium metal will be obtained, since at the high temperature it oxidizes in the air instantly, unless
the cathode is protected from air (e.g. by a glass sleeve). As a small-scale demonstration of the
production of sodium or potassium by electrolysis, Humphry Davy’s original experiment with solid
NaOH or KOH may be imitated.

3. Sodium fluoride solution (and other inert electrolytes) with inert electrodes.
In this case the solvent is decomposed, while the ions only carry the current through the
solution. About 0.5 M NaF or KF solution is electrolysed with a carbon or platinum electrodes
(caution: soluble fluorides are poisonous). The products are hydrogen at the (negative) cathode and
oxygen at the anode; these gases may be collected and identified by simple tests. Since neither
element is present in NaF, the overall electrode reactions must be the decomposition of water:
2H2O(l) + 2e–(from cathode) →2OH–(aq) + H2(g)

H2O(l) → 2H+(aq) + 1
2 O2(g) + 2e–(to anode)

— 14 —
 Since fluorides are slightly hydrolysed the solution is already alkaline, and it is not so easy to
show the immediate production of H+ and OH– ions, whereas with a neutral solution, such as
sodium sulphate(VI), this can be demonstrated readily by indicators(see $2.4).
Many electrolytes behave as inert current-carriers, with the decomposition of water as the
electrolytic reaction: these include the sulphate(VI)s, nitrate(V)s, phosphate(V)s, carbonate and
chlorate(VII)s of sodium, potassium, ammonium, calcium, magnesium etc.
The free acids give the same results, though the cathode reaction would be written a little
differently:
2H+(aq) + 2e –(from cathode) → H2(g)
The soluble hydroxides also give hydrogen and oxygen, and the anode reaction is probable the
direct discharge of ionic OH– initially to H2O2, which then be decomposed catalytically at the
electrode surface. The overall half-equation is:

2OH–(aq) = H2O(l) + 1
2 O2(g) + 2e –(to anode)

Practical work
It is highly desirable that the electrolyses of various aqueous solutions should be repeated
individually by all students. The apparatus is cheap and the experiments are easily set up. Details
are given in chapter 2 and Appendix II. As a lecture demonstration, however, or for the more
accurate measurement of the volumes of gases, the electrolyses may be carried out in the Hofman
Voltameter.

4. Sodium chloride solution with inert electrodes

The products of electrolysis of sodium chloride appear to depend upon the concentration.
Concentrated solution with well separated carbon electrodes give hydrogen and chlorine, and the
solution becomes alkaline around the cathode:
2H2O(l) + 2e–(from cathode) = 2OH –(aq) + H2(g)
2Cl–(aq) = Cl2(g) + 2e –(to anode)
It is frequently stated that dilute solutions give H2 + O2, the dilute Cl–(aq) not being
discharged; and that at intermediate concentrations a mixture of Cl 2 and O2 is given at the anode.
The electrolysis of concentrated brine (NaCl) is performed industrially for the manufacture of
H2, Cl2 and NaOH. The diaphragm cell (Fig. 6.12) is designed so that the electrolyte meets the
steel cathode immediately after seeping through the asbestos diaphragm: here the thin layer of
solution is almost completely depleted of Cl– ions, which are attracted back through the diaphragm
towards the positive electrode, and concentrated NaOH solution drips off into the collecting
troughs. The diaphragm also prevents the chlorine from diffusing through the solution and meeting
the alkali, with which it would react.

5. Copper (Ⅱ) sulphate solution with inert electrodes

Oxygen is produced at the anode: the cathode (of any conducting material) is plated with copper,
by discharge of Cu2+ ion :
Cu2+(aq) + 2e–(from cathode) → Cu(s)
The solution becomes more acid and, as the Cu+(aq) concentration decreases, less blue in colour.
The eventual increase in weight of the cathode may be used to measure the original concentration
of copper ion (electrogravimetric analysis). Solutions of Ag+, Pb2+, Sn2+, Cd2-, Hg22+, or Hg2+ and.

— 15 —
with care, Ni2+, Co2+ and Fe2+, also give quantitative deposition of the metal at the cathode
(mercury forms an amalgam). Even quite ‘reactive’ metals such as zinc may be deposited from
solution, though some hydrogen is produced at the same time.

6. Copper (II) sulphate solution with copper electrodes

The result of this electrolysis is that the average concentration of copper (II) sulphate remains
unchanged, while the cathode gains mass (as in example 5) and the anode is eaten away, losing a
mass equal to that gained by the cathode:
Cu2+(aq) + 2e –(from cathode) → Cu(s)
Cu(s) → Cu2+(aq) + 2e–(to anode)
This experiment is often used to determine the relationship between the change of mass of
the electrodes and the amount of electricity passed (2.2). It is also the basis of copper plating (see
8.2 for practical details) and refining (8.10).
The anode reaction is not dependent on the presence of Cu2+ ions already in solution. And a
copper anode is almost invariably attacked during electrolysis. Anodes of lead, silver, zinc, soft
iron, and in fact any soft metal except the very noble metals like gold or platinum, are usually
corroded and produce the corresponding cation. Some hard metals such as steel. chromium, and
nickel can act as inert anodes. And then oxygen may be produced without any visible oxidation of
these anodes. Cathodes, of course, may be made of any metal not attacked by water.

2.4 Summary
Electrolytic conduction is a property of molten (fused) salts and bases, and aqueous solutions
of salts, acids and bases. Ions must be present, and free to move: positive ions (cations) towards
the cathode, which is negative in the case of electrolysis; and negative ions (anions) towards the
anode. This movement of ions constitutes the electric current.
Chemical reaction must occur at both electrodes during electrolysis: at the (negative) cathode
the reaction is always a reduction, that is, a half-reaction which absorbs electrons; and conversely,
an oxidation always occurs at the anode.
The cathode reactions are usually either the discharge of the cation to give the metal, or the
reduction of water to hydrogen, the latter being preferred to the discharge of metals more active
than, say, zinc from aqueous solution. The reactive metals may, however, be produced from their
molten salts.
Anode reactions may be: (1) discharge of simple anions of the less reactive non-metals; (2)
oxidation of water or OH – to oxygen; (3) attack of the anode metal.
Later in the book examples will be given of electrode reactions which involve changes of
oxidation state without production or consumption of free elements (e.g. Chapter 5).

2.5 Exercises
1. The potential difference across the ends of a certain wire is 3.20 V when the current passing is
0.85A.The wire is 300 cm long and 1.0 mm in diameter. What is (a) the resistance, (b) the
resistance per cm, (c) the resistivity, and (d) the conductivity?
2. Solid sodium hydroxide does not conduct electricity, but it becomes conducting either when
melted (m.p 318) or when dissolved in water. Solid malonic acid CH2(COOH)2 does not

— 16 —
 。
conduct nor does molten malonic acid (m.p.135 C): but the aqueous solution is a conductor.
Explain the difference.
3. A saturated solution of calcium hydroxide (0.16 g per 100 g water) has a conductivity of less
than 1/200 that of saturated calcium chloride solution (74 g per 100 g water). Is this evidence
that calcium hydroxide is a weak electrolyte?
4. Predict the products of the following electrolyses and write the half-equations for the
electrode reactions:
(i) Lead (Ⅱ) nitrate solution with carbon electrodes;
(ii) Lead (Ⅱ nitrate solution with a carbon anode and a lead cathode;
(iii) Lead (Ⅱ) nitrate solution with a lead anode and a carbon cathode.
— — —
5. If sea-water contains the following ions: Na+, K+, Mg2+, Cl , Br , and HCO3 , what products
would you expect from the extended electrolysis of this mixture, with carbon electrodes?
6. Explain the following observations: A p.d. of about 2 V was applied across two copper wires
dipping near together in dilute sulphuric acid. At first a gas was given off at one of the wires,
but after a time this ceased although the current did not diminish.

— 17 —
 3. Electrode Reactions

3.1 Redox half-equations

When a current is passed through an electrolyte, causing electrolysis, the overall chemical
reaction is a reduction-oxidation. The reaction is one which would not have occurred without the
current. And since the products appear at separate electrodes there is little doubt that they are the
result of electron gain or loss. For example, the result of the electrolysis of molten lead (Ⅱ)
bromide was:
PbBr2 → Pb + Br2
In fact the same products would have resulted from the electrolysis of an aqueous solution of
the salt. The separate electrode reactions are written thus:
—
Pb2+ + 2e → Pb (reduction, at cathode)
— —
2Br → Br2 +2e (oxidation, at anode)
The converse of electrolysis is galvanic cell action, and this comes about when an oxidant is
present at one electrode of a cell, and a reductant at the other. Lead and bromine would be an
example. And the reactions would be the reverse of those given above. One difference is that in
this case the reaction could be brought about quite independently of the cell, merely by bringing
the reactants into contact and it might not then be suspected that the reaction involved electron
transfer.
Most redox reactions encountered in volumetric analysis, for example, can be shown to take
place by the giving and receiving of electrons, simply by having the two reagents separately in the
limbs of a U-tube, with a platinum (or carbon) electrode in each. A milliammeter will show a
current flowing, with the electrons coming from the electrode in the reductant (Fig. 3.1). After
some time here will be signs that the reaction is occurring ‘at a distance’. For example, if the two
solutions are potassium iodide and iron (Ⅲ) chloride, iodine will be seen around one electrode and
in the region of the other electrode ionic iron(Ⅱ) may be detected by its reaction with
hexacyanoferrate(Ⅲ).
The reactions at the two electrodes, though
separate in space are not independent of each other.
the amounts of reaction being directly related by
the necessity for the number of electrons leaving
the electrolyte in given time to equal the number
entering. No electricity accumulates in any
electrolytic or galvanic cell (not even in an
‘accumulator’!): in other words, the capacitance is
negligible.
The consequence of this is that the
stoichiometric equations for the total chemical
change can be separated into a pair of
half-equations, which are equations containing Fig.3.1 Demonstration of electron transfer
electrons, and so representing either a reduction
(electrons on left) or an oxidation (electrons on

— 18 —
right). The half-equations must each contain the same number of electrons, but on opposite sides.
This useful device can be applied to any redox reaction, whether taking place electrochemically or
not.
For example, the reaction between potassium iodide and iron(Ⅲ) chloride may be considered
to be the sum of the following half-reactions:
— —
2I → I2 +2e (oxidation)
—
Fe3+ + e → Fe2+ (reduction)
Because the numbers of electrons gained and lost must be equal, the second half-equation
must be doubled (or the first one halved) before addition, giving as the full ionic equation:
—
2Fe3+ + 2I → 2Fe2+ + I2
This procedure (or the similar one using oxidation numbers) provides a useful means of
balancing redox equations, which can be very awkward to do by simple inspection.

Worked example
“Obtain the balanced equation for the reaction of potassium manganate(Ⅶ) (permanganate)
with hydrogen peroxide, in acidic aqueous solution.”
The student may care to spend a few minutes trying to balance the following by ‘trial and
error’
—
MnO4 + H2O2( + H– ?) → Mn2+ + H2O + O2
In the systematic method, the two half-equations are considered separately, and balanced for
atoms and then for charges, thus:
— —
MnO4 + H+ + e → Mn2+ + H2O (unbalanced)
—
The four oxygen atoms lost by the MnO4 will require 8H+ to form 4H2O :
— —
MnO4 + 8H+ + 2e → Mn2+ + 4H2O
Now from charge balance (conservation of charge) it follows that z=5.
Similarly we arrive at the half-equation for the oxidation :
—
H2O2 → 2H+ + O2 + 2e
—
So the equation for the oxidation of H2O2 by MnO4 is derived by adding the half-equations,
each multiplied through to make the numbers of electrons equal:
— — 2+
2MnO4 (aq) + 16H+(aq) + 10e → 2Mn (aq) + 8H2O(L)
5H2O2(aq) → 10H (aq) + 5O2(g) + 10e—
+
— 2+
2MnO4 (aq) + 5H2O2(aq) + 6H+(aq) → 2Mn (aq) + 8H2O(l) + 5O2(g)
Two qualifying points should be note:
(1) The fact that any redox reaction can be written as a pair of half-equations should not be taken
to imply that the unconstrained reaction necessarily takes place by a mechanism of transfer of
free electrons (e.g. there could be, in some cases, oxygen atom transfer).
(2) The state of the electron in the half-equation is not defined. Hydrated electrons are known in
the free state, but are highly reactive and short-lived. And it is not this state which is implied
—
by the symbol e in redox half-equations. This uncertainty makes any energy calculations
from a single half-equation meaningless.

3.2 The stoichiometry of electrolysis (Faraday’s Laws)

If the stoichiometry of redox reactions is understood, only one new principle is required in
order to extend the calculations to include electrolysis—namely, the idea of the mole of

— 19 —
electrons. An electron is a particle with a definite mass (though this is negligible in comparison
with atoms), and a definite charge e = 1.602×10-19 coulombs. By historical misfortune, the type
of electrostatic charge which is now known to result from an excess of electrons was arbitrarily
designated ‘negative’, so when a current flows across any potential difference, the electrons move
from negative to positive.
Since electrons are (or at least behave like) separate particles, it is meaningful to speak of one
mole of them—that is, L electrons, where L is ‘Avogadro’s number’, the number of 12C atoms in
12.000g of 12C, found by experiment to be about 6..023×1023.This gives a value for the Faraday
constant, F, which refers to the charge on one mole of electrons:
F = Le = 6.023×1023×1.602×10–19C mol–1= 9.649×104 C•mol–1
The value of F is normally taken as 96500 C•mol –1
Stoichiometric equations, though written as if they represent changes among a few atoms,
molecules or electrons, always have another meaning. If they are multiplied through by L, they
then represent changes in the molar amounts of substances. Thus O2(g)+2H2(g)→2H2O(g)
contains the information that ‘2 moles of steam are formed when 1 mole O2 reacts with 2 moles
H2 ’, and this could be related to massed or volumes of the participants.
In exactly the same way, the half-equations:
Cu2+(aq) + 2e – → Cu(s)
tells us that 2 moles of electrons. 2×96500 C of electricity, can bring about the production of
1mole or 63.55g of copper metal.

Worked example
A current of 250mA was passed for 22 minutes 20 seconds through a copper coulometer
containing copper electrodes in acidified CuSO4(aq), with the addition of 5% ethanol to inhibit
reoxidation of the deposited copper. What changes of mass of the electrodes would be expected?
10 − 3 A
Quantity of electricity passed = 250mA × mA × ((22 × 60) + 20)s
= 335 A•s = 335 C
335
∴Amount of electrons = 96500 mol
The half-equations are : (cathode) Cu 2+(aq) + 2e– → Cu(s)
(anode) Cu(s) → Cu2+(aq) + 2e–

∴ Loss of Cu at anode = gain of Cu at cathode = 1

2 mole Cu per mole of electrons.

g 1
2
mol⋅Cu 335
∴ Changes in mass = 63.55 mol ⋅Cu × mole⋅electrons × ( 96500 ) mol electrons
= 0.11 g
There are two important variations of this calculation:
(a) To calculate the amount of electricity from the change of mass of the electrodes. This can be
used to check or calibrate an ammeter. It was also the basis of the definition of the
international ampere, which was the flow per second of the quantity of electricity which
caused a loss of 0.001118g from a silver anode
(b) Measurements of the amount of electricity and mass changes of some cases may be used to
deduce the half-equation for the electrode process. This applies particularly when the product

— 20 —
 may be in one of several possible oxidation states.
To illustrate this pass a current in series through (1) an ordinary copper coulometer containing
copper electrodes in acidified copper(Ⅱ) sulphate solution; and (2) copper electrodes in boiling
alkaline sodium chloride solution (Appendix Ⅱ). In the second cell a red solid appears at the
anode but does not adhere, and the loss of copper per mole of electrons passed is found to be 63g.
Therefore in the alkaline solution the anode half-equation must contain one electron for every
atom of Cu, and the product must be a Cu(Ⅰ) compound, probably hydrated Cu 2O;
2Cu(s) + 2OH –(aq) → Cu2O(s) + H2O(l) + 2e–

Faraday’s laws
Faraday announced at least three important laws of eletrolysis. The first (1832) was actually a
by-product of researches aimed at proving the essential identity of galvanism (electricity from a
galvanic cell) and electricity from an electrostatic friction machine. Almost incidentally, Faraday
noticed that ‘The chemical power1 of a current of electricity is in direct proportion to the absolute
quantity of electricity which passes’. This law is the basis of our treatment of electrode processes
as gain or loss of electrons; but although it might have suggested the possibility of particles of
electricity associated with atoms, Faraday had no faith in the atom of 1832 (hard, spherical and
incapable of transmitting any influence except during contact). General recognition of the logical
inevitability of the electron had to wait until after Helmholtz’s famous Faraday Lecture to the
Chemical Society in 1881.
Faraday seems to have attached considerable importance to his next law, of April 1833; A New
Law of Electric Conduction; the assumption of conduction power during liquefaction, and the loss
of it during congelation. He observes that compounds become conducting only when they are
melted (e.g. PbBr2). This was a useful generalization. Though recently exceptions have been
found.
The law which is known as the second was published in December 1833 in an extended
discussion, of which the following sentence may be taken as representative.
‘The equivalent weights of bodies are simply those quantities of them which contain equal
quantities of electricity, or have naturally equal electric powers; it being the electricity which
determines the equivalent number, because it determines the combining force. ’
Subsequently the law, as stated in textbooks, was made more operational, or theory free. The
principle of Faraday’s great discovery is implicit in the modern interpretation of electrode
reactions, given earlier in this section. Specifically, from the half-equation
2H2 + 2e- → H2(g)
it is seen that 2 moles of electrons produce 1 mole, or 2 grammes, of hydrogen molecules;
therefore one mole of electrons can produce 1g H2, i.e. one equivalent. For any other element, the
half-equation will be one of the following:
Mz+(aq) + ze– → M(s) (metals)

or X–(aq) → 1
2 X2 + ze- (non-metals)

In either case, 1 mole of electrons (sometimes called one Faraday) will produce 1/z mole of the

1
The word ‘power’ here means ‘measure of the extent of change caused’, and not the modern rate
of transfer of energy.

— 21 —
element, with a mass equal to (atomic mass)/z
It is interesting that this law, which is the foundation for almost all subsequent study of
electrodeposition, was announced on the basis of only three successful experiments, one poor
result, and five attempts which failed to work. The reason is that Faraday thought that only fused
salt electrolyses could give unambiguous quantitative evidence. The contemporary theory of
aqueous electrolysis was that the current was carried by chains of water particles; any metal
produced from solution could be argued to be a product of the reaction of hydrogen (the ‘primary
product’ of electrolysis) with the salt. So the theory would merely prove, in every case, that
hydrogen was liberated in equal amounts by equal amount by equal amounts of electricity— a fact
already known from the First Law. So Faraday proved his new law with three examples: fused
SnCl2, AgCl, and PbCl2; he tried but failed to electrolyse fuse Sb and Bi compounds; and his
results for K were erratic.

3.3 Practical work on simple electrolsis

Required: Electrolysis cell as in Fig.3.2, or a pair of J-shaped electrodes.
10 cm3 measuring cylinder.
Neutral NaCl and Na 2SO4 solutions.
Litmus papers.
6 V d.c. supply (e.g. battery charger)
Milliammeter (0-500 mA).
Rheostat, about 1 A, 100Ω.

Expt.3-1.1 Half-fill the cell with tap

water, and the rheostat half in the
circuit, switch on the 6 V d.c.. Note
the meter reading, and observe the
electrodes. (Gas evolution is a more
sensitive current detector than many
miliammeters!)
Place two test-tubes full of water in
position over the electrodes, then add Fig 3.2 Apparatus for simple electrolysis
a few cm3 of dilute sulphuric acid to
the cell, and stir. Collect the gases evolved, note the relative volumes, and the polarity of the
electrodes. Identify the gases. Write the electrode half-equations.
Expt.3-1.2 Add a little potassium iodide solution to the very dilute sulphuric acid in the
electrolysis cell. Note the different anode reactions at high and low currents, after adjustment of
the rheostat. Suggest an explanation.
Expt.3-1.3 Empty the cell and rinse the electrodes, soak a piece of red litmus paper, and one of
blue, in neutral sodium sulphate solution, and lay them in turn across both electrodes while the
current is a few seconds. Note any acidity or alkalinity resulting from the electrolysis. Explain this
by appropriate half-equations. State a simple empirical rule for discovering the polarity of a d.c.
supply using litmus paper soaked in tap-water(CaSO4 solution).
Repeat the experiment, but use sodium chloride (not sulphate) solution. Note and explain any
differences.

— 22 —
 Expt.3-1.4 Quantitative electrolysis. Starting with fresh water in the cell, fill and invert a
10cm3 measuring cylinder (or a test-tube graduated at 10 cm3). Clamp the cylinder so that it will
collect all the hydrogen evolved at the cathode, but before moving the cathode into position,
switch on, add 50% sulphuric acid and stir, until the current is in the range 100 to 400 mA, and
accurately measurable on the meter provided. Use the rheostat to adjust the current if necessary.
Move the cathode into position, note the time, and read the current. Keep the electrodes and
receiver still, to ensure a steady current. Measure the time required for 10cm3 hydrogen to be
produced. Recode the temperature and barometric pressure.
Calculate the amount n (in mole) of H2 collected, using the ideal gas equation PV = n RT,
where R = 8.31 JK–1mol–1; T is the ‘absolute’ temperature calculated from the ‘common’
temperature θ, thus: T = (θ/℃ + 273) K, and p = partial pressure of H2, that is, atmospheric
pressure minus the saturated vapour pressure of water (see Table 2.1). Since 1 J=1 Nm, p should
be expressed in N m-2 and V in m3. For the conversion of barometer readings, take
1mmHg=133.3Nm-2, or 1 standard atmosphere = 101 325 Nm -2.

Table 3.1 Saturated Vapour Pressure of Water

θ/℃ 10 15 20 25 30

p/mmHg 9.2 12.7 17.5 23.8 31.8

p/Nm–2 1230 1700 2330 3170 4250

Also calculate the quantity of electricity passed, and hence the quantity (in coulombs) which
would produce 1 mole H2.

3.4 Concentration change in aqueous electrolysis

For this qualitative discussion of concentration changes (a quantitative treatment, leading to
transport numbers, will follow in Chapter 3), let us consider the cathode and the anode to be in
separate compartments, divided by a porous partition which will allow the movement of ions
under the influence of the electric forces, but which prevents random diffusion.
Several common examples of electrolysis will be analysed, to show that the visible production
of solids or gases at the electrodes are not the only change.
(a) CuSO4(aq), Cu electrodes.
Cathode Partition Anode
Cu2+ + 2e– → Cu Cu 2 + SO42 − Cu2+ + 2e–
←   → Cu →
2+
During the passage of 2 moles of electrons, the cathode compartment loses 1 mole Cu at the
2+
electrode. Meanwhile some Cu ion arrives through the partition, but since the movement of
charge by migration of ions must equal 2 moles e–, and both Cu2+ and SO42– ions carry two
charges, the total movement of both ions together is 1 mole, so the arrival of Cu2+ is something
less than 1 mole. Therefore the cathode compartment diminishes in CuSO4 concentration. By
similar reasoning, the anode compartment gains in concentration.
(b) Na2SO4(aq), Pt electrodes.
Cathode Partition Anode
2H2O + 2e– → H2 + 2OH– 2 Na + SO42 − → + –
←   →
1
H 2 O 2 O2 + 2H + 2e

— 23 —
 At the cathodes, Na+ ion arrives but is discharged; instead, water is reduced to H2 and OH–
ion. So the cathode region becomes alkaline (basic), as can be shown by indicators. In the anode
compartment, SO42– ion arrives, carrying the current, but again the water reacts more readily,
being oxidized to O2 + H+, and so the acidity increases.
From the stoichiometry, the amount of OH– produced at the cathode must equal the amount of
H+ produced at the anode, so if the partition were removed and the solution stirred, its pH would
be the same as before electrolysis.
The stoichiometry also determines the 2:1 ratio of H2 to O2 by amount and hence (by
Avogadro’s Law) by volume.
A variation of the experiment, discovered by Humphry Davy, intrigued a generation of chemists.
Three containers were set up as in Fig.2.3. Each solution also contained an indicator such as
litmus. It was known that Na2SO4 appeared to de separated into NaOH and H2SO4, as discussed
above .But in this variation, when the anode compartment became acid, it had to be assumed that
the H2SO4 had passed through the NaOH without combining with it. A mystery indeed!

(c) NaCl solution with C electrodes.

Cathode Partition Anode
+ −  2Cl-→Cl2+2e
2H2O + 2e - → H2 + 2OH– ←
2 Na
2
→
Cl
 H2O→O2+2H++2e-


Fig.3.3 Based on a Plate from Conuersations on Chemistry by

Mrs Jane Marcet, 1822: Voltaic battery of improved construction
with instances of chemical decomposition by the same

3.5 Galvanic cells

The basic difference between galvanism and electrolysis is this: the galvanic cell reaction
must be capable of proceeding unaided (and not necessarily in the cell at all), and so the free

— 24 —
energy of reaction △G must be negative. In contrast, the reaction brought by electrolysis would
not occur spontaneously, since it has a positive △G, and so there must be an external source of
electrical energy in the circuit, to force electrons to flow through the electrolytic cell.
Otherwise there are many similarities. As we have seen, the electrode processes are in each
case a pair of oxidation-reduction reactions, and the stoichiometry is exactly the same.

Fig.3.4 Some galvanic cells (see text)

A galvanic cell can be based on any reaction which can occur spontaneously, at a reasonably
rapid rate, to produce work. We will consider three examples:
(1) Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
(2) Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
(3) Cl2(aq) + SO32-(aq) + H2O →2Cl-(aq) + SO42-(aq) + 2H+(aq)
In order to generate electricity from these reactions it is essential that the reactants should be
kept apart, to prevent direct reaction: or that conditions be chosen which make direct (local) action
very slow.
If one of the reactants is a metal, it may act as an electrode. Otherwise some inert electronic
conductor (platinum, gold, or carbon) must dip into the solution. For keeping solutions apart, a
porous partition (e. g.. unglazed earthenware) is used for practical cells, or a salt bridge in

— 25 —
experimental cells. The concentration of any reactant can be maintained at saturation, if desired,
by having excess solid present or, in the case of a gas, by bubbling it past or through the electrode.
These principles are followed in the design of cells making use of the three reactions
mentioned above. The half-equations for the electrode reactions are given below each cell.
In the first two cells the zinc rods are amalgamated (by being rubbed with mercury(I) nitrate
solution) to make direct action with the acid very slow. Hydrogen is more readily released ar a
silver surface, where the overpotential is lower than on zinc; and so the first cell needs no partition
Zinc, even when amalgamated, reacts with ionic copper(II) by local action, so in the second
cell the zinc is in dilute sulphuric acid, and separated from the copper sulphate solution by a
partition. The reduction of Cu2+(aq) to Cu takes place at a copper electrode (sometimes the whole
container is of copper, acting as a large electrode); and as this reaction occurs more readily than
the reduction of H+(aq) ion, the second cell is more efficient than the first. It is in fact the Daniell
Cell, once widely used for powering telegraphs.
The third cell is likely to be of theoretical interest only, probably for the purpose of
measuring the cell potential. Little current will be taken from it, so the internal resistance need not
be kept low: therefore a salt bridge of potassium chloride solution ensures that no dissolved
chlorine meets the sulphate(IV).
In each case the polarity of the cell may be deduced from a knowledge of the cell reaction. At
the anode oxidation occurs, which produces electrons: these go into the metallic part of the circuit,
and cause the anode of any galvanic cell to appear negative to a meter connected across the cell.
Similarly, the reduction half-reaction at the cathode absorbs electrons, and tends to leave the
cathode positively charged. Thus the relationship between polarity and the location of oxidation
and reduction (and hence the names of the electrodes) differs for electrolytic and galvanic cells, as
summarized in Table 3.2.

Table 3.2 Electrolytic and Galvanic Cells

Thermodynamic
Electrons Reduction Polarity
Type of cell nature of
enter cell at half-reaction at of cathode
cell reaction
Positive
Galvanic Cathode Cathode Spontaneous
(self-generated)
Negative(imposed
Electrolytic Cathode Cathode Non-spontaneous
by external source)

3.6 Electrode potentials

The measurable potential difference across any galvanic cell is found to decrease as the
current drawn from the cell is increased. It is usual to regard the cell as having an electromotive
force (e.m.f.) which is the potential difference (p.d.) which it would maintain if the transformation
of chemical to electrical energy were taking place with maximum efficiency. This state of affairs is
approached when the current flowing is infinitesimal— for instance when the p.d. is measured by
an electronic voltmeter or a potentiometer. An ordinary moving–coil voltmeter is actually an
ammeter in series with a resistor, and draws some current from the cell: hence the p.d. measured
by a cheaper meter (with a lower resistance) may be considerably, less than the e.m.f. . Since
potential differences of working cells depend upon the physical design (especially internal

— 26 —
resistance) of the cell and the meter, it is convenient to define the cell potential as the p.d. which is
measured at almost zero current— in other words, the e.m.f..
Cells of the Daniell cell type could be constructed (in theory) of any pair of metals each in a
solution of one of its salts. For example, zinc in zinc sulphate paired with silver in silver nitrate
(both solutions 1 M), gives a cell potential of 1.56 V with the zinc negative. Similarly, zinc is
1.10V negative to copper: and copper is 0.46 V negative to silver.
Though only potential differences between pairs of electrodes can be measured, the results
are consistent with the proposal that each electrode has its own potential (on some arbitrary scale)
which is constant, regardless of the other electrode with which it is paired.
So by pairing all metal/metal-ion half-cells against one chosen half-cell, an electrode potential
series could be constructed. A metal high in the series will be negative compared to any lower
metal, because its tendency to form ions, and release electrons, will be the greater. Note that an
element which forms a negative electrode has a strong tendency to change to its positive (ionic)
form, and is therefore said to be electropositive.
Besides the demonstration of the electrode potential series directly, two other experiments are
commonly included at the elementary level. These are the displacement of metals and the reaction
of metals with acids (see Appendix II). For example, pieces of zinc, iron and other metals react
with dilate copper (II) sulphate (VI) solution to produce copper metal, but silver has no effect; but
all these same metals and copper will displace silver from silver nitrate(V) solution. By
considering the extent and speed of such displacement reactions, a series is drawn up such that any
higher member can displace the lower ones from their salts.

K
3.7 The electrochemical series
Na
The electrochemical (or electrode potential) series has Ca
come to be regarded as a unifying principle in elementary Mg
chemistry. Fig. 3.5 is taken from the widely used ‘School Al
certificate chemistry’ by Holderness and Lambert, who were Zn F
the first authors to make extensive use of the E.C.S. in an Fe O
intermediate text. It may be seen from this table that reactions Ni Cl
as diverse as the attack of metals by acids and the Sn
decomposition of carbonates by heat have been brought Pb Br
together by means of the E.C.S. H
The reactivity series is established from the ‘vigour’ of Cu
reaction of the metals with oxygen, and then used for Hg I
predictions of the power of carbon to reduce oxides, and the Ag S
order of displacement of metals from there salts. Au
Pt C
Fig.3.5 The electrochemical
series

— 27 —
 Fig. 2.5 The electrochemical series used as an aid to systematization

Reduction
Action of Action of Character Character Action of Solubility
Combustio Action on Action on of heated
heat on water on of of heat on of
n WATER ACIDS oxides by
oxides oxides hydroxides carbonates nitrates sulphides
Hydrogen

K Soluble and
Soluble in Nitrates Sulphides
Oxides not
water decompose soluble in
Decompose react to decompose
Na therefore to nitrite water
cold water form d by heat
bases and
hydroxides
Ca alkalis
Not
Burn in air Attacked reduced Sulphides
Mg to oxygen by dilute insoluble in
readily acids Stable water bur
Al Decompose when soluble in

— 28 —
steam at heated Insoluble dilute
Nitrates
Zn red heat and hydrochlori
Hydroxides decompose
decompose c acid
in soluble to oxide
d by heat
Fe bases only
Oxides do
Pb not react
Oxidize with water
when Attacked Sulphides
Cu Do not
heated in by insoluble in
air decompose reduced
oxidizing water and
Hg water or acids dilute
steam at Nitrates
Hydroxides Carbonates hydrochlori
Ag red heat decompose decompose
Unaffected not formed unstable c acid
to metal
by oxygen Not
Au
attacked
 It is right to ask how closely reactivity is truly related to electrode potential, and how much of
the agreement is loose or even fortuitous. I would suggest that the term is ambiguous in that it
glosses over the distinction, between the rate of reaction and the position of equilibriums to which
the reaction tends to proceed.
The terms ‘reactive’ and ‘vigorous’ are subjective judgments being based on direct
observation only, and are inevitably a composite of fast and exothermic, neither of which qualities
is necessarily predictable from electrode potentials. Yet it does appear that, for the comparison of
reactions of a similar kind, under closely similar conditions, qualitative predictions from the E.C.S.
are very often correct. And when they are not, this may be explained away in terms of factors such
as hardness, surface oxide films, insolubility of the product, etc.
In the case of electron-transfer reactions in aqueous solution, the connection is definite enough
if metals A and B are both placed in a mixture of soluble salts of A and B, the metal A which is
higher in the E.C.S. (i.e. has the more negative reduction potential) will tend to dissolve, and ionic
B will tend to be reduced to metallic B. The displacement series can be extended to cover the
★
reaction of metals with non-oxidizing acids, since the reduction of the hydrogen ion to hydrogen
gas is closely similar to the reduction of metal ions. However there is a reluctance of hydrogen to
react or to be produced (at ambient temperatures) which is measured by its high overpotential of
about 0.5 V, so that the reaction of metals above H in the E.C.S., but by less than 0.5 V, is
negligibly slow. That is Co, Ni, Sn, Pb and Cd fail to produce H2 from 1 M acids at 298K.
Conversely, hydrogen does not displace metals such as copper from their salts under normal
circumstances, though reaction can be shown to occur under pressure or at a catalyst.
When the E.C.S. is used for predictions concerning redox reactions in the solid state (e.g.
reaction of hot metals with steam, the reduction of metal oxides by CO or C, etc.) the connection
becomes far less straightforward. Firstly it is important to make the distinction between two rather
similar terms, the oxidation potential ( = the ‘electrode potential’ with opposite sign) and the
ionization potential, since the half-reactions to which they refer differ only in the states of the
participants, thus:
﹣
Oxidation potential: M(s) → Mz+ (aq) + ze
﹣
Ionization potential: M(g) → Mz+(g) + ze
Now, while the reactions involving the oxidation of a metal or the reduction of an oxide clearly
have energies which depend upon the ionization potential, they will not be related directly to the
electrode potential because (1) energies other than that of ionization (e.g. lattice energy) must be
incorporated in any comparison, and (2) the electrode potential relates to aqueous solution, and so
incorporates the energy of hydration of the ion, which is irrelevant to the solid metal/oxide system.
It is not intended to give the full thermochemical analysis here, but simply to show that there are
important complicating factors.
In the case of the non-redox decompositions of crystalline solids (nitrates (Ⅴ), carbonates, etc.)
or the solubilities of metal compounds, the accordance with predictions from the E.C.S. should be
regarded as a piece of good luck. The relationship is not one of cause and effect, but rather that of
two different ‘effects’ of a common, more fundamental cause—namely atomic size and charge.

★
Meaning that the anion is non-oxidizing; H+ (aq) is an oxidant in any acid

— 29 —
3.8 Practical cells
Cells which are used as sources of electrical power can be classified into three groups:
(1) Primary or expendable cells.
(2) Secondary or rechargeable cells.
(3) Fuel cells.

This classification is for convenience only, and most primary cells can be reversed to some
extent, but unless the cell is specially designed this regeneration is very inefficient and not
normally worthwhile.
The name Fuel Cell is usually given to a cell which operates by the reaction of oxygen with
hydrogen, hydrocarbons or other organic substances, but the distinctive features are technological
rather than chemical.
The design and manufacture of primary and storage batteries is an important industry, but space
permits a description of no more than the two most important cells, and a mention of some others.

Primary cells
Among the requirements for a well designed primary cell are (a) a high e.m.f. of at least 1 V; (b)
little ‘polarization’ when the cell is under load; (c) long ‘shelf life’; (d) high ratio of electrical
capacity to volume, mass and/or cost.
The first two of these features, at least, are consequences of the chemical system on which the
cell is based. The initial e.m.f. follows from the electrode potentials, but when a current is drawn,
the effective e.m.f. of some cells falls considerably. This effect is known as polarization, and is
partly due to the accumulation of the products of the cell reaction, which cause the e.m.f. to
decrease in accordance with the Nernst equation. Substances which reduce this effect are often
called depolarizers—an unfortunate name (since they increase the polarity of the cell) derived
from an outmoded theory of their action.
All the principles of a good cell are illustrated in the Dry Leclanche Cell, by far the most
commonly used primary cell. It is not really ‘dry’, since the electrolyte is a moist paste of
ammonium chloride solution and starch, with additives. Zinc is the anode (negative), and at one
time served as the container as well. As the cell operates, the metal is oxidized to ionic Zn2+ which
is partly removed by complexing with ammonia:
EΘox = ﹣0.76 V
―
Zn(s) → Zn2+(aq) +2e ;

Zn2+(aq) + 2NH4+ + 2OH (aq) ⇋

﹣
Zn(NH3)22+ + 2H2O

Although local action could result if this oxidation were paired with the reduction of H2O or
NH4+ to hydrogen, it is in fact almost negligible because of the high overpotential of hydrogen on
zinc, especially smooth amalgamated zinc.
The cathode is a carbon rod surrounded by a mixture of manganese (Ⅳ) oxide(dioxide) and
carbon granules, and the predominant electrode reaction seems to be the reduction of manganese
(Ⅳ) to (Ⅲ), though this is still not well characterized even after extensive investigation:
﹣ ﹣
MnO2(s) + H2O + e → MnO(OH)(s) + OH (aq)
﹣
It is the OH ion from this reaction which diffuses to the anode and assists the formation of the
complex ion and when this exceeds a certain concentration, it forms solid Zn(NH3)2Cl2, which

— 30 —
increases resistance. A worn-out dry cell can often be restored to some extent by being kept for a
few hours in a warm place (60﹣80℃) to enable this unwanted product to diffuse away.
The p.d. of the Leclanche dry cell is not very constant, especially during heavy use; it starts at
1.5 V, but falls steadily during continuous discharge to about 0.8 V. After 24 hours rest, however,
the cell may regain a p.d. of 1.3 V or so. These cells are made in several sizes, and in series
batteries for high p.d. But they are not as suitable for miniaturization as, for example, the ‘mercury
cell’ (Zn/KOH(aq)/HgO, C).
Other primary cells of continuing importance are those designed for use as standards for
potentiometry, such as the Weston cadmium cell, and those which maintain an exceptionally
steady p.d. during heavy use, such as the Mallory mercury cell.
Invention of new cells still continues. Among recent developments are cells based on the use of
a metal/insoluble salt depolarizing electrode such as the copper/copper(Ⅰ) chloride cathode in
which the reduction half-reaction is:
﹣ ﹣
CuCl(s) + e → Cu(s) + Cl (aq).
Cells using this cathode and a magnesium anode are manufactured complete except for the
electrolyte, and connected in circuit with a lamp. They begin to operate automatically if immersed
in seawater, for example after a shipwreck.
Most cells have aqueous electrolytes, and suffer from a disadvantage that might become serious
when unusually wide temperature ranges are encountered, such as on the moon or in a space-craft:
that is, they cease to function if the electrolyte freezes or evaporates. This is overcome in one of
the latest innovations, the really dry ‘dry cell’, with a solid electrolyte. Silver bromide and iodide,
in the solid state at elevated temperatures exhibit electrolytic conductance－that is, movement of
ions under an applied potential difference. If a cell is constructed with one electrode of silver, and
the other of carbon surrounded by bromine vapour, in contact with silver bromide (Fig.3.6), some
silver atoms change to Ag+ ions, which migrate into the AgBr lattice; an equal number of Ag+ ions
arrive at the anode where they accept electrons and react with Br2 molecules to form more AgBr.
The e.m.f. is about 1.1 V. Similar cells, with e.m.f.’s of around 0.6 V, can be made for use from
-75℃ to 150℃. These use as the solid electrolyte a mixed crystal of silver and rubidium (or
﹣
potassium) iodides, Rb4AgI5. This has a lattice structure determined by the large Rb+ and I ions,
with the smaller Ag+ ions occupying only a quarter of the remaining ‘holes’－so the Ag+ ions can
move almost as freely as in a liquid.

Fig. 3.6 The solid-state dry cell

— 31 —
 Table 3.3 Secondary Cells

Reduction Oxidation
Electrodes Electrolyte
Cell E.m.f /v Remarks
(for discharge) Solution
(during discharge)

1/2O2+H2O+2e-→ H2+2OH-→
0 Grove Pt.O2 Pt.H2 KOH 1.2 First fuel cell
2OH- 2H2O+2e-

PbO2+SO42-
+4H++2e- Pb+SO42-→
1 Lead-acid PbO2 Pd H2SO4 2.04 See text
→PbSO4+2H2O PbSO4+2e-

Capacity/mass ratio
Ni(OH)3+e→ Cd+2OH-→ twice that of cell 1 and
2 Nickel-cadmium Ni(OH)2 Cd KOH 1.30

— 32 —
Ni(OH)2+OH- Cd(OH)2+2e- less self-discharge.
High current possible

Cheaper than cell 2.

Fe+2OH-→
3 Nickel-iron (NIFE) Ni(OH)2 Fe KOH 1.37 ditto Same advantages but
Fe(OH)2+2e- more self-discharge

2AgO+H2O+2e-
AgO →Ag2O+2OH- Zn+2OH-→ Very high current/mass
4 Silver-zinc Zn KOH 1.50
Ag2O Ag2O+H2O+2e- Zn(OH)2+2e- ratio. Expensive
→2Ag+2OH-

5 Sulphur-sodium Na2S5 Na Solid 2 S52-+8e-→5S2- Na=Na++e- See text

Secondary (rechargeable cells) cells
Secondary cells (often called storage batteries) are electrochemically similar to primary cells,
but the electrode reactions are chosen so that all reactants and products are insoluble in the
electrolyte, and so the electrodes keep their shape during charging and discharging. Only a few
systems have proved fully satisfactory, and the commercially available cells are listed in Table 3.3.
Of these, the lead-acid cell is by far the most widely used, and a short description is called for.
The usual car battery consists of 3 or 6 cells connected in series, giving a nominal 6 or12 V.
Each cell is independent, and situated in a separate compartment of the hard-rubber casing. In
order to provide large surface area for the electrodes, eachone consists of a number (often 6) plates,
connected together at the top. The two sets of plates slot together, and porous separators are
inserted to prevent short-circuits.
Each plate is manufactured as a grid of hard antimony-lead alloy, supporting a paste of lead
sulphate. Then the plates which are to be the positives are made the anode in an electrolytic cell,
and those which are to be the negatives are made the cathode, with sluphuric acid as electrolyte.
Electrolysis under carefully controlled conditions converts the PbO 2 and Pd respectively:
Anode (positive) PbSO 4 + 2H2O = PbO2 + SO42- + 4H+ + 2e-
Cathode (negative) PbSO4 +2e- = Pb + SO42-
There are the reactions which occur during the charging of a run-down cell. Note that H2SO4 is
produced, and so density of the acid increases during charging (and decrease during discharge). If
acid of known density (1.20g cm-3 that is 2.3 mol dm-3) is put into the battery when the plates are
in a fully charged condition. The fall in density is a good guide to the state of discharge. When
1.10g cm-3 is reached the cell potential will have fallen to 1.7V and further discharge may damage
the cell by the formation of a hard unreactive layer of PbSO 4.
On standing, the cell slowly discharges itself by ‘local action’, that is, reaction of the electrodes
with impurities (such as iron) without transfer of electrons to or from the external circuit.This
self-discharge may be 1 to 2% per day, and is made worse if impure water is used to ‘top up’ the
electrolyte. A battery which is to be stored for a long time should be fully charged, and then
drained of its electrolyte.
The search had gone on for secondary cells which have higher energy capacity than the
lead-acid cell, and also higher energy conversion efficiency. Recently a cell which seems to have
commercial possibilities (for electric vehicles) has been developed by exploiting molten
electrolytes and ion-permeable lattices. The sulphur-sodium cell operates at about 300oC, and
consists of two compartments separated by a solid state electrolyte (Al2O3 + a little Na2O) through
which sodium ions can migrate. In one compartment is molten sodium, and in the other, molten
sodium sulphide—each with a graphite current collector. The whole unit is sealed in a stainless
steel case. Charging the cell produces more sodium, and sulphur which remains in solution as
Na2Sx (x=2－5). These reactions are reversed when a current is drawn, and it is claimed that the
stored energy is then recovered at almost 100% efficiency.
3.9 Summary
The net chemical reaction in either a galvanic or an electrolytic cell is invariable an
oxidation-reduction, so it can always be shown as the sum of two half-reactions involving the gain
or loss of electrons. The stoichiometry of these half-reaction require a definite connection between
the amount of substance produced or consumed at an electrode, and the amount of current passed
－a connection first observed by Faraday.

— 33 —
 4. Some Technological Application

4.1 Metal extraction and refining

Electrolytic extraction (electro-winning)
The principal reasons for using an electrochemical method for the extraction of a metal from
its ores are that (1) the reduction with carbon is thermodynamically unfavourable at conveniently
attainable temperature or (2) low grade ores are to be worked, initially by reaction with an
aqueous reagent, giving a dilute solution of a salt of the metal. The first reason applies to sodium,
magnesium, calcium, aluminium etc, and as these active metals cannot be deposited by
electrolysis from any aqueous solution, electrolysis of molten salts is used (though research on
electrodeposition from organometallic compounds in non-aqueous solution appears promising,
especially for aluminium).
Table 4.1 Metals Which Are Extracted Or Refined By Electrolysis
Electrolyte state Electro-winning Refining
Molten Al,Mg,Na,Li,K,Ca,Sr,Ba,Be, Al
B,Th,U,Ce,Ti,Zr,Mo,Ta,Nb
Aqueous Cu,Zn,Co,Ni,Fe,Cr,Mn,Cd, Cu,Ni,Co,Sn,Pb,Hg,Ag,Sb,In
Sb,Pb,Sn,In,Ag

General features of fused-salt electrolyses include (1) the use of mixtures of salts to reduce
the melting-point; (2) the use of the heating effect of the electric current to maintain the
temperature of the melt; (3) the use of graphite anodes, at which the usual product is chlorine
(aluminium electro-winning is an exception); (4) some means of protecting the molten metal from
air and from the anode; (5) applied potential differences are usually 6 to 8 V, and currents may be
as high as 105 A.
It is noteworthy, at a time when world resources of many metals are getting alarmingly low,
that there will never be a shortage of aluminium so long as there is energy to extract it, since on a
molar basis it is the fourth most abundant element in the earth’s crust (after O, Si and H) at 4.8
mole %. However, supplies of high-grade bauxite are becoming exhausted, and the cost of
obtaining aluminium oxide for the electrolytic cells will increase. Recycling of scrap aluminium
will become even more important than it has been hitherto.
The extraction of metals through the electrolysis of aqueous solutions is less widely practiced.
Low-grade copper ores are leached by sulphuric acid, giving copper(Ⅱ) sulphate solution which is
electrolyzed with a copper cathode (which gains mass) and a lead anode (at which oxygen is
evolved, and sulphuric acid reformed). Some zinc is produced in a similar way, the low-grade ore
being roasted to the oxide, then treated with sulphuric acid.

Electrolytic refining
Electrolysis of aqueous solutions is used on a large scale to refine metals produced by carbon
reduction. Copper, nickel, silver, tin and lead are among the metals commonly treated in this way.
Large anodes of the crude metal and thin sheets of the pure metal are set in cells containing a
suitable electrolyte (CuSO4 + H2SO4, NiSO4 + NiCl2, PbSiF6 + H2SiF6), usually acidified to
increase conductivity. As the anode dissolves, impurities with a more negative oxidation potential

— 34 —
remain undissolved (e.g. Bi, Sb and Ag in lead), and are collected in bags hung around the anode,
and later refined. Metals with a more positive oxidation dissolve along with the principal metal, of
course, but they fail to deposit on the cathode. Current efficiencies of 90-95% are obtainable, and
the energy consumption may be as low as 60 kJ·mol-1 (e.g. 0.2kWh·kg-1 for Cu). This is only
one-tenth of the energy required for metal extraction from aqueous solution.

4.2 electroplating
Electroplating, the cathodic deposition of a thin layer of metal on the surface of an object, is
most often carried out for the purpose of enhancing the appearance, or protecting against corrosion,
or both. The metals commonly used for plating are copper, silver, gold, tin, zinc, nickel and
chromium. Electroplate can be thinner than, and yet because of its uniformity just as effective as,
metal plated mechanically, e.g. by dipping. Indeed the rising price of tin would have made
tin-plate uneconomic had it not been possible to change to the electrolytic method of manufacture;
and now tin-plating is, after aluminium and caustic soda/chlorine, the most important
electro-technology.
In most electroplating cells the anode is a piece of the metal being deposited, since this will
dissolve at the same rate as the deposition at the cathode, and the electrolyte solution is not
☆
depleted of its metal content . The plating bath is almost invariably a mixture of a current carrying
but otherwise inert electrolyte and a compound of the metal, in many cases a complex ion. It is
essential that no local displacement of the dissolved metal by the cathode metal should occur,
since the metal coating produced in this way is usually powdery and poorly adhesive. For example,
silver nitrate solution would be useless as a plating bath for a copper object, since copper can
displace silver by local action: the complex dicyanoargentate(Ⅰ) (argentocyanide) is used instead.
A process which is very similar to electroplating is electroforming, which consists of the
deposition of a very thick layer of metal (usually copper or nickel) which, when stripped away
from the original article or ‘former’, reproduces in negative relief all the detail of surface. The
electroformed object then serves as a mould, for example for plastic injection moulding.
Gramophone records are reproduced in this way, as are blocks for printing (electrotype).
Objects to be plated need not be of metal, since the surface can be made conducting by graphite,
painted on as a suspension known as aquadag, or by silver deposited by chemical reaction (a
‘silver mirror’). This procedure permits the electroplating of plaster, plastic, wax, wood, etc.
The best constitution of the plating bath, its temperature, pH, and other factors are often
determined by experiment, and electroplating was for a long time more a craft than a science.
Thorough removal of grease, dirt and oxide films from the surface is always essential. A high
current is desirable, to save time, but too high a current density may produce a loose spongy
deposit, or even a metal powder, or even a metal power. The appearance of the plate may be
enhanced by ‘brighteners’, and other addition agents, usually colloids such as gelatin or glue,
improve the adhesion. These agents encourage the formation of the metal as small crystals, but the
way in which they act is still imperfectly understood.
A most important characteristic of a successful plating bath is that it should have good
‘throwing power’, that is, that the plating should be of uniform thickness at points near to and far

☆
chromium plating is an exception: an inert anode is used, and the chromic(Ⅵ) acid electrolyte has to be
replenished.

— 35 —
from the anode, and that plating should occur in crevices etc., where diffusion may be restricted.
An introduction to throwing power will be obtained from the following experiment.
Expt.4-1 Dependence of plating thickness on current path. For this investigation into the effect
of the length of the current path on the thickness of deposited metal, the cathode is made of two
parallel plates (back B and front F) held tightly together. For example, two pieces of copper foil
may be used, the front one slightly larger, and bent over at the edges to produce a seal. Weigh the
two parts separately before and after the plating, during which this double cathode is set parallel to
an anode of about half its width, and maintain the current at a predetermined value by adjustment
of a rheostat. Record the area of cathode immersed, and the distance between the electrodes, also
the current and duration. Observe the solution closely, in good light, during the electrolysis,
especially around the anode.
With copper electrodes, use (1) acidified, (2) neutral and (3) ammoniacal copper(Ⅱ) sulphate
solutions. Use a fairly high current (say 0.2 A cm-2) and then, if time permits, repeat the series at
one-tenth of this.
Calculate (a) the overall current
efficiency; (b) the ratio of deposit on
F to deposit on B.
In the light of your results and
observations, comment upon the
following accounts of the plating
process.
Account A. During the
electrolysis of acidified copper Elevation Plan
sulphate solution with copper Fig. 4.1 Electrolysis cell with double cathode.
electrodes, the anode dissolves to
form Cu2+ (aq) ions which are attracted by the negative cathode, to which they travel by the
shortest route. On arrival, the ions are discharged, and form a deposit of copper metal.
Account B. When a potential difference is applied between copper electrodes in acidified
copper sulphate solution, the anode, being at a more positive potential than the solution, tends to
ionize to Cu2+ ions, which would diminish or nullify the p.d. between electrode and solution were
it not for the migration of Cu2+ and H+ away from and SO42- towards the anode region. Similarly,
the p.d. between cathode and solution causes the discharge of Cu2+ to metallic Cu. Since the metal
cathode is at one potential throughout, the deposition of metal should be uniform all over.
Further questions:
(i) It may be observed that, at high current densities, a dense solution falls away from the
anode. Does this have any bearing on either of the above accounts?
(ii) Because the solution has an appreciable resistance, the potential of the solution at F will
be more positive than that of the solution at B, when any current is flowing. How does
this fact affect the above accounts? Will high or low conductivity lead to greater
uniformity of deposit?
(iii) If the deposition of copper is susceptible to concentration polarization, activation
overpotential, and variable current efficiency (i.e. some H2 production at high current
density, how would this affect the throwing power?
Expt 4-2 Practical electroplating. Copper plating from acidified copper(II) sulphate solution

— 36 —
is usually successful over a broad range of conditions. However, a coarse-grained structure, and
even a flaky or spongy deposit, will result from too low current density or too high a temperature
(>800), so it is important to maintain a high conductivity. It is found that a nearly saturated
solution containing sulphuric acid (high mobility of H+) at 20-400C is suitable. If the acidity is too
low there is danger of a dark-coloured deposit containing copper(I) oxide . The current density
should be 2-5 A dm-2, and as the throwing power is rather poor, articles should be turned
frequently so that every part spends some time near to the anode.
Recipe: CuSO4.5H2O 200g (0.8mol) or 250g for electroforming
H2SO4 50g(0.5mol) or 75g for electroforming
molasses or dextrin 0.8g
wetting agent few drops
thiourea 0.04g (optional brightener; not <5mg or > 80mg)
water to 1dm3

A copper plating bath with better throwing power, which can be used to plate more
electropositive metals such as iron or zinc, is described in Project 9.2, as are baths for zinc and
silver plating, and the plating of non-metal objects.

4.3 Electrochemical polishing and machining

When a metal is made the anode, at fairly high current density in a suitable electrolyte,
dissolution may occur in such a way as to produce a polished surface. Irregularities and scratches
disappear as the higher points are dissolved preferentially. Electropolishing is often quicker than
mechanical polishing, especially on an intricately shaped object; and since the process causes no
stress, it is preferred for preparing metal specimens for laboratory tests.
Several electropolishing baths are based on phosphoric(V) acid or chloric(VII) (perchloric)
acid, with oxidants such as chromic(VI) or nitric (V) acids to assist ‘passivation’. The current
density to be aimed at is that at which the anode becomes polarized, with no further increase in
current with increased potential (until oxygen evolution commences). It is believed that under
these conditions the recessed areas become passive, possibly due to the formation of a thin oxide
layer, more readily than the elevated areas. A height difference of 10um is sufficient to produce
this differential dissolution rate.

Electrochemical
machining is another
form of anodic
dissolution, but with the
purpose of modifying the
shape of a piece of metal.
It is often used on the
very hard and strong
alloys (such as those
required for aircraft
engines) since these are
extremely difficult to cut Fig. 4.2 The electrochemical machining
or grind mechanically.

— 37 —
 Usually the electrolyte solution is neutral chloride or, better, chlorate (V), and the cathode
reaction is the production of H2+OH-(aq), leading to the precipitation of the hydroxide of the
metal being machined. The cathode is shaped a little smaller than the required cavity and the
electrolyte is circulated mechanically so that the anodic metal hydroxide is swept away (to be
filtered off before the electrolyte is recycled). Very high current densities are necessary----up to
1000 A·cm-2 ---both in order for metal removal to be conveniently fast, and to exceed the
passivating range; and so the gap between the cathode and the surface being cut must be kept very
small. The anodic current diminishes rapidly away from the place nearest to the cathode, and
enters abruptly into the current range at which the metal is made passive; this effect enables the
electrochemical machining to be precise.

4.4 Anodizing
Most metals have a very thin layer of oxide over their surface, formed by reaction with air.
In the case of some reactive metals this film is sufficiently tough and adhesive to give good
protection against corrosion. With aluminium the natural film does not give sufficient protection
for some purposes, but it can be thickened by making the aluminium article the anode for about
30minutes at about 1Acm-2. A film about 0.02mm in thickness develops, which gives protection,
and enhances the appearance. The article is usually ‘sealed’ before used by immersion in boiling
water, which converts the aluminium oxide to a partially hydrated form.
Expt. 4-3. Anodizing of aluminium.
(1) Choose a suitable aluminium object for treatment (e.g. a cheap manufactured article such as a
brooch, or a shape cut from 2 mm aluminium sheet, or machined from aluminium rod). Twist
a wire, preferably of aluminium, around the object so that it provides firm support and
electrical contact, but does not touch any important area of the surface.
(2) Thoroughly de-grease the object by wiping it with a cloth moistened with trichloroethane (or
‘dry-clearer’), and then avoid any further contact with the fingers. Then ensure a uniformly
clean surface by etching it in warm 1M NaOH solution for a minute or so (vigorous evolution
of hydrogen should occur), followed by neutralization in dilute nitric acid (say 0.2M) and a
rinse in clean water.
(3) Suspend the object in an electrolyte of 2 M sulphuric acid (1 vol. concentrated acid added,
with stirring, to 7 vol. water), kept at 25-27℃ by immersion in a large bowl of water at this
temperature. Connect to the positive pole of the d.c. supply.
(4) Arrange a cathode of thin aluminum sheet (or several thicknesses of foil) in the form of a
cylinder surrounding the anode. Using a variable potential control, maintain a current of
10-20mA per cm2 of anode. Stir the electrolyte occasionally. As the oxide layer forms, the
resistance increase and so the applied potential will need to be raised, but should not exceed
15 V. Fifteen minutes will produce an anodized surface. but if it is to be dyed, at least 30
minutes is necessary. Remove and rinse.
(5) Dye at 65-75℃ in solution of about 2g of a suitable dye per dm2, acidified by 5 cm3 1 M
ethanoic acid if necessary . In addition to various common dyes, the Aluminum Federation
has recommended for this experiment the use of Black 2Y, 10 g per dm3 acidified solution, for
a deep black surface; or iron(Ⅲ) ammonium oxalate solution (22 g (NH4)3Fe(C2O4)3• 4H2O)
per dm3, used at 50C) for a gold color. The latter solution should be stored in the dark or
prepared as required by mixing equal volumes of 0.1M FeCl 3 and 0.3M (NH4)2C2O4 solutions.

— 38 —
(6) When the desired intensity of color has been reached, rinse the object and "seal" the anodized
layer by immerse it for 15 minutes in boiling water or, better, a boiling solution of 5g nickel
(Ⅱ) ethanoate and 5g boric acid per dm3 (this treatment converts the aluminum oxide to a
partially hydrated form.) Then rinse, and rub with a clean cloth.

4.5 corrosion of iron

One of the most widespread electrochemical process is also a most unwelcome one: in
Britain alone the corrosion of iron costs an estimated £109 p.a.(3.5%of the gross national product),
of which about one third could be saved by improved protective measures. In the power industries
an estimated £25m p.a. is saved by cathodic protection (see below).
Rusting has been known throughout history, but it was until 1902 that a satisfactory explanation
(proposed by W.R Whitney) was available .It is now generally accepted that the principle cause of
the corrosion is the establishment of a short-circuited galvanic cell, thus:
―
Fe(s) → Fe2+ + 2e
― ―
1
2
O2 + H2O + 2e → 2OH (aq)

followed by two subsequent non-electrochemical steps leading to hydrated iron(Ⅲ) oxide.

Rusting requires liquid water, not merely water vapor, because there must be an electrolyte
solution in contact with the metal if the above cell is to be formed. Pure water is not sufficient, but
it is normally impossible to exclude some electrolyte, if only dissolved CO2; salt from sea-spray or
high ice-clearing is particularly deleterious.
It is found that if oxygen is totally exclude, or destroyed chemically (e.g. by hydrazine)
rusting is prevented. The possible alternative reduction half-reaction, the production of hydrogen,
does not generally occur unless the solution is very acidic. Even so, the presence of water,
electrolyte, oxygen and iron together does not necessarily lead to corrosion .If conditions are
uniform at all points on the metal surface, rusting is extremely slow. It appears that the oxidation
and reduction half-reductions must occur at different sites. One situation which permits this
separation of half-reactions is when the iron is in contact with a more noble metal (e.g. copper),
for then that metal acts as the cathodic site (for the reduction of O2), and the neighboring iron
becomes an anodic site, and is attacked.
However, even in the absence of a dissimilar metal corrosion can occur at points which are
partly hidden from the air, such as under bolts or rivets, under specks of insoluble material, or in a
corner, crack or hole. It appears that rusting, the oxidation of iron, occurs at place further from the
source of dissolved oxygen; and it was to explain this strange behavior that the theory of
differential aeration was devised (for a full account see U.R. Evans, Rusting of Iron: Cause and
Control, Edward Arnold, 1972).
Consider the conditions within a drop of impure water held in a crevice on an iron surface.
Near the water-air interface there will be a plentiful supply of oxygen, but in the remote parts of
the drop there may be a much lower concentration. At the oxygen-rich site, the reduction of
oxygen to hydroxide ions will tend to occur, consuming electrons there, and making the metal
positive relative to the solution. This polarity hinders the oxygen reduction, particularly at sites
where oxygen concentration is low, but encourages the anodic oxidation of the iron metal. Any
hole or crevice tends to deepen.

— 39 —
 The diagram (Fig. 4.3) shows these electrochemical reactions, and also the place where the
products (Fe2+ and OH-), diffusing from the anodic and cathodic sites, meet and precipitate as iron
(Ⅱ) hydroxide, which is rapidly oxidized to the iron (Ⅲ) state. The rust is thus produced away
from the point of attack, and does not protect the metal from further attack. On the contrary, its
water-holding properties promote even more rapid corrosion.

Cathodic protection
Of the various protective measures against rusting, one is very directly related to the
electrochemical mechanism: namely cathodic protection, in which the iron structure is made
cathodic (negative with respect to the electrolyte). There are three ways in which this can be done:
(1) plating with zinc (‘galvanized’ iron); (2) sacrificial anodes; and (3) direct current from a
generator.
In case of galvanized iron, the zinc is constantly under attack (but fortunately the zinc oxide
produced affords a degree of physical protection), but the iron underneath is thereby made
cathodic.
For iron pipes or other underground structures, protection is often given by nearby buried
blocks of magnesium alloy, each electrically connected to the iron. Steel ships are also protected
by sacrificial anodes (following the method devised in 1824 to protect the copper bottoms of the
ships of the Royal Navy). A sufficient number of these anodes must be provided, because
protection ceases where the length of the current path through the electrolyte becomes too great.
(Why? The iron, a good conductor, will be at almost the same potential all along its length.). In
places where a generator and cable may be positioned, it is sometimes cheaper to replace the
magnesium by scrap iron or carbon, and to maintain them at a small negative potential by an
external source.

4.6 Fuel cells

In an earlier section on ‘Practical Cells’ some design features of good cells were mentioned:
high radio of electrical capacity to mass, low internal resistance, a steady potential difference
which does not fall excessively when a current is drawn, and a long shelf life. Three categories
were introduced: primary cells, secondary (rechargeable) cells, and fuel cells, but these categories
are not mutually exclusive and refer to the function and design of the cells as much as to the
electrochemical reactions which occur. Primary cells are portable sources of small quantities (say
1 kJ) of electricity energy, and the price is justified by the convenience rather than by the value of
the electricity. Secondary cells, also, are relatively small, self-contained units, designed so that the
reactants in the current producing reactions may be regenerated in position when a direct current is

— 40 —
passed through the cell in the reverse reaction. The energy which can be stored in a lead-acid cell
of mass 1 kg is about 70kJ, which is about the same as in an equal mass of torch batteries, and less
than a tenth of that in some recently developed rechargeable batteries, such as the sodium-sulphur
battery. However, the lead-avid cell is particularly suitable for use for the starter motor of a
petrol-driven car, because it can provide heavy currents (200 to 400A) for short periods without
suffering damage. As the source of power for driving (rather than starting) the car, lead-acid
batteries are less satisfaction, for they can only provide about 100 W• kg-1 on continuous discharge,
which means that the economic top speed is equal to a brisk walking pace (e.g. milk floats,
fork-lift trucks). For electrically driven vehicles to be viable, the mass and the cost per unit of
power must be reduced to about one-hundredth of those of the present car battery. It now seems
quite possible that the fuel cell will achieve this.
The principles of the fuel cell may be shown by considering one of the simplest systems—the
hydrogen-oxygen sell. Hydrogen is supplied to one of the porous catalytic electrodes, and oxygen
or air to the other. The electrolyte is a concentrated solution of an acid (e.g. phosphoric(V) acid) or,

more commonly, an alkali (usually potassium hydroxide). The overall reaction, H2+ 12 O2→H2O(1),

has ΔGӨ = -237 kJmol-1 and hence Ecell=+1.23 V at 298K. The enthalpy change for the

combustion of H2 to H2O(g) is -242 kJmol-1.Therefore if the fuel cell could be operated at its
maximum (reversible) cell potential, an efficiency of 98% chemical energy conversion would be
achieved. This may be compared with the theoretical maximum efficiency of 40-50% for any
‘heat
engine’ type of energy convertor, with its Carnot limitation of (T2-T1)/T2, where T1 and T2 are the
temperatures of the heat sink and source respectively. This apparent doubling of conversion
efficiency was like a mirage which deluded and eventually disappointed early researchers into fuel
cells.
As was pointed out in §6, the working cell potential is invariably lower than the reversible (or
‘no-load’) potential, by an amount comprising the overpotentials at the two electrodes, together
with any concentration polarization and the ‘IR drop’ due to internal resistance. There can be no
current without overpotential, although the size of the overpotential depends profoundly upon the
catalytic properties of the electrode surface. For this reason research into cheaper and more
effective catalytic electrodes is one of the principle directions that the fuel cell development
programme is taking. There is little hope of finding the ‘perfect catalyst’ (cf. philosophers’ stone),
and the goal of anything like 100% efficiency has now been abandoned— in fact fuel cell
technologist might well be content with the same 40% limit that applies to heat engines, in return
for electrodes that were cheap, durable and easy to maintain. In this respect it appears that fuel
cells will have the important advantage that they can achieve 40% energy conversion even on such
a small scale as a 25kW unit (whereas the modern gas turbine generator does not approach this
unless it is capable of 105 kW) and so their first use may be for small domestic or vehicle units.
If the overpotential of the hydrogen-oxygen cell presents a problem at normal temperatures,
that of a hydrocarbon fuel cell (e.g. CH4-O2) is quite impossible. The rate of reaction is negligible
below about 200℃, yet hydrocarbon fuels, either natural gas or ‘cracked’ petroleum oil, are so
much cheaper (and easier to store) than hydrogen that a considerable part of the $50m fuel cell
effort has gone towards attempts to utilize them. One way is to convert the hydrocarbon to

— 41 —
hydrogen immediately before use, by catalytic reaction with steam:

e,g. CH4 + H2O → CO + H2 (ca. 900 oC)

CO + H2O ⇌ CO2 + H2 (ca. 300oC)

The technical difficulties of the conversion and purification are serious but not insuperable.
The other solution to the unreactivity of hydrocarbons is to raise the temperature of the cell,
to 650oC or so, by using a molten salt electrolyte such as mixed lithium and sodium carbonates. At
these high temperatures the overpotentials are low, and no expensive catalytic electrode are
necessary. For this reason, high temperature hydrogen-oxygen fuel cells have also been designed,
either using molten carbonates, or a very concentrated potassium hydroxide solution under
pressure (as in the first practical fuel cell, build by Bacon and Frost at Cambridge in 1959). In all
such cell, corrosion is one of the most serious obstacles, and most of the construction materials of
the most of the advanced Pratt and Whitney cells have been developed specially for the purpose in
the last 7 years.
A heavy duty fuel cell which consumes carbon monoxide at 1000oC is being designed by
Westinghouse, and uses a solid state electrolyte of ZrO2 containing a little Y2O3 (which gives it an
O2- deficiency). To avoid corrosion troubles at this high temperature, the air electrode is made of a
solid state conductor (SnO2) rather than a metal.
It must not be thought that low temperature aqueous cells are being neglected, however. Esso
in the U.K, and Exxon-Alsthom (U.S.A./France) are developing methanol fuel cells which will
require electrodes of high specific catalytic power and large surface to volume ratio. That a low
temperature fuel cell is possible was proved in the General Electric Company’s hydrogen-oxygen
cell which provided the electric power in the Gemini spacecraft; but this, using an ion-exchange
resin electrolyte and platinum-coated PTFE electrodes, was far too expensive for terrestrial use.
Fuel cell technology is part science, part economics.
Exp: 4-4. A methanol fuel cell. Prepare the fuel cell anode by platinizing a piece of fine nickel
gauze, about 6×10 cm, by making it the cathode (negative) in chloroplatinic acid solution. A
cheaper alternative plating solution is 0.5% palladium chloride in 1 M hydrochloric acid. Curve
the gauze around the outside of a porous pot.
Prepare the cathode by silver plating a similar piece of nickel gauze, simply by letting it stand in
dilute silver nitrate solution for an hour or so. Curve the gauze so that it fits inside the porous pot,
and arrange for oxygen or air bubbles to pass upwards over it (O2 bubbled through a sintered glass
disk is best, but air from a cheap aquarium aerator will suffice).
An alternative arrangement, described by K.R. Williams in Ref.9 below, consists of a porous
carbon rod with a blind hole drilled along its axis, to which oxygen is supplied via a plastic tube.
The rod should be activated by heating to redness followed by quenching in water, and it may be
silver plated for extra efficiency.
When the cell is assembled, with 6 M KOH electrolyte (CARE— caustic, wear goggles), but
without fuel, check that no spurious potential is arising from galvanic action of the nickel. Then
add methanol (or hydrazine) to the outer part of the cell to give a concentration of about 2%
by-volume. Mechanical stirring is desirable.
Measure the cell potential with a high-resistance voltmeter, both on open circuit and when
various currents are being drawn. How steadily is the cell able to supply 1 mA ?

— 42 —
 5 Secondary Batteries— Lead-Acid Batteries

5.1 History
The lead-acid battery, which still represents the most important electrochemical system for
energy storage, reached a rather high level of technical perfection by the end of the 19th century,
when the production of lead-acid batteries was started in factories. Before that, in 1854 J.
Sinsteden reported that lead electrodes immersed in diluted sulfuric acid could be used as a
coulometer. The first accumulator in fact was developed by Plante in 1859, who applied the
repeated charge-discharge procedure which is still used today to produce battery electrodes. The
pasted plate which is most common today was patented concurrently by Faure and Volkmar in
1881.

5.2 General Theory

In principle the lead-acid battery
consists of two electrodes immersed
into a common electrolyte as shown in
Figure 1. The characteristic feature of
such a cell is the conversion of electron
conduction into electrolytic conduction
at the phase boundary electrode-
electrolyte. This change in conductivity
is established by the electrochemical
reaction, i.e., a chemical reaction
combined with the exchange of electric
charge. As assumed, for example, in
Figure 5.1, a reduced substance may be
oxidized at the left-hand electrode. The
electrons liberated in this reaction are
consumed by the corresponding
reduction reaction at the right-hand (nSred→nSox+ze-) (pSox+ze-→pSred)
electrode. When the outer circuit is
closed the electric current flows until Fig.1 The Galvanic Cell
one of the substances nSred and pSox (or
both of them) is exhausted.
The electrochemical reactions specify the most important parameters of the cell: the cell voltage
determined by chemical affinity of the reacting substances and the capacity defined by amount of
electrode material which can be converted.

— 43 —
5.2.1 The Basic Electrochemical Reactions

For the lead-acid battery both reactions (shown schematically in Figure 1) are:

Positive electrode: ⇌ (1a)

― ―
PbO2 + 3H+ + HSO4 + 2e PbSO4 + 2H2O
(reduction reaction
negative electrode: ⇌ (1b)
― ―
Pb + HSO4 PbSO4 + H+ + 2e
(oxidation reaction)
overall reaction: Pb + PbO2 + 2HSO4– + 2H+ ⇌ 2PbSO4 + 2H2O (1)

Read from the left to the right (top arrow) Eq. (1) represents the discharge reaction, i.e., lead
dioxide is reduced to lead sulfate at the positive electrode, while metallic lead is oxidized at the
negative electrode. Reversal of the current reverses Eq. (1) and recharges the cell.
To calculate the equilibrium cell voltage the change in free energy (ΔG) can be used, which is
derived as the difference of the standard free energies of the substances involved in the reaction.
For Eq. (1) this difference turns out to be
△G = -372.5 kJ/mol (2)
And the standard equilibrium cell voltage (emf) is
372.5
E0 = = 1.930V (3)
2 × 96500
On account of the concentration dependence of △G the equilibrium cell voltage changes with the
concentration or activity of the reacting species except those present in solid state (α=1)
according to the Nernst equation:

RT α H + α HSO4 −
E = E0 + ln (4)
F α H 2O
E0 represents the standard equilibrium cell voltage, αthe activity (mol/liter).
5.2.1.1 Dependence of Cell Voltage on Acid Concentration
The dependence of cell voltage on acid concentration is shown in Figure 2. In battery practice
the approximation E = d + 1.84(d is density in g/cm3) is often used. This dependence on acid
concentration is a disadvantage of the lead-acid system because the H2SO4 consumption during
discharge [Eq. (1)] causes a decrease of cell voltage, even though the load is extremely low. This
can be seen in Figure 3., where the top curve shows the decrease of equilibrium cell voltage with
discharge for a commercial motive power cell. To minimize this effect, stationary batteries are
often provided with a large quantity of excess acid, which is not possible for motive power
batteries because of the extra weight and volume.
5.2.1.2 The Heat of Reaction
The electrochemical reaction [Eq.(1)] is combined with heat exchange. The fundamental
equation is
△G = △H ― T△S （5）
Where △G represents the already mentioned change in free reaction energy, while △H and △S
are the changes in heat energy and entropy, respectively. T△S indicates the amount of heat
absorbed or liberated by Eq. (1).
Since ΔH = –360.1KJ/mol. the heat of reaction comes to
TΔS = 124 KJ/mol (T=25℃) (6)

— 44 —
Or referred to the free energy ΔG of the reaction
T∆S
= –3.3% (7)
∆G
Thus about 3% of the energy produced by reaction (1) is converted into heat. The negative
sign in Eq. (7) means that heat is absorbed. When the discharge takes place (ΔG negative ),and
that the same amount of heat is liberated during charge. On the whole this heat of reaction is rather
small and always covered up by irreversible heat production. Especially during discharge, when
theoretically a cooling effect should be observed. [cf. Eq. (13)].
5.2.1.3 The Power-Weight Ratio
The power-weight ratio of the lead-acid battery can be estimated starting with Eq. (1). The
weights of the species involved amount to 642.4g, while the converted electric energy [Eqs. (1a),
(1b)] comes to 2×F = 53.61 Ah. Using the equilibrium cell voltage 1.930 V [a hypothetical figure
in this case, because Eo in Eq. (3) is based on the assumption that the activities of the reacting
species are 1mol/liter. Which of course is not true in pure H2SO4], the theoretical power-weight
ratio is
(53.61)(1.930)
=161 Wh/kg (8)
0.6424
In practice only one quarter of this can be attained. To explain this great difference between
theory and practice the proportionate weights of the different construction elements are compiled
in Figure 4. The scale on the left shows the weights, which are needed per kWh, while the
reciprocal numbers (Wh/kg) are plotted on the right.
The bottom block in Figure 4 contains Eq. (1), which leads to the figure calculated in Eq. (8).
Which means that a weight of 6 kg would be able to store 1kWh. However, pure H2SO4 is nor an
electrolyte; the acid has to be diluted to achieve adequate conductivity. Furthermore there must be
some excess of acid to keep conductivity
even when the battery becomes discharged
completely. Therefore the pure
electrochemical system provided with the
correct acid requires 11.5 kg/kWh.
Additional weight is caused by the fact
that only a fraction of the active material
can be utilized. At extremely low
discharge rates mass utilization may be
increased to about 70%, but at the usual
rates (on the order of magnitude of hours),
this figure decreases to about 35%,
reducing the available power-weight ratio
to nearly 50 Wh/kg. The limited mass
utilization is comprehensible when it is
kept in mind that chemical reactions occur
at the electrode. During discharge, e.g., Fig. 4 Weight contributions of the different
lead is dissolved at the negative electrode constrution elements (example: motive
and lead sulfate precipitated. While at the power cell)
positive electrode PbO2 is reduced and

— 45 —
dissolved Pb2+ ions give rise to lead sulfate precipitation. These reactions produce isolating layers
on the active material, which prevent further discharge. Furthermore dismantling of charge
material by inhomogeneous attack will reduce the electric contact between parts of the active
material and the grid, also restricting further discharge.
In addition to the facts discussed up to now, much extra weight is added by passive
construction elements which are unavoidable in the actual lead-acid cell. So the grids supporting
the active material and conducting the current usually contribute nearly as much weight as the
active material itself does. But the acidic environment and corrosive potentials exclude the
substitution by lightweight metals. The same is true for the so-called top lead; i.e., the conducting
bars on top of the plates and terminals. Finally, the cell has to have a jar which (as well as the
isolating separator between the plates) does increase the weight.
Therefore in practice, even cells for electric vehicles, which are developed especially for low
weight, deliver less than 40 Wh/kg and (as can be seen in Figure 4) little margin is left for further
increase.

5.2.2 Discharge Performance

When current is drawn, the cell voltage is influenced by additional parameters. Limited rates
of electrochemical or diffusion processes cause displacement of cell voltage called over-voltage
Eη; furthermore a voltage drop due to the ohmic resistance Ri of the cell is also present. Thus
when current flows the cell voltage is described by
E(i) = Eo – Ep – i·Ri (9)
In practice it is difficult to distinguish over voltage from ohmic voltage drop; therefore both terms
in Eq. (9) usually are combined and called polarization (Ep); thus
E (i) = Eo – Ep （10）
The discharge curves in Figure 3 illustrate the influence of current on discharge performance. The
capacity of a lead-acid cell is determined by a specified end-of-discharge voltage. The capacity,
therefore, is not a constant value and the nominal capacity is valid only for a specified discharge
rate (see e.g. the 5-hr rate in Figure 3). Standardized rates have been set, e.g., 6-and 5-hr rates for
motive power batteries, 8- and 10-hr rate for stationary batteries in the U.S.A. and Europe
respectively.
Both polarization and internal resistance change with temperature. Therefore discharge
voltage and capacity also depend on temperature. The empirical equation for capacity is
Actual capacity (T℃)
Corrected capacity (25℃) = (11)
1 + a(T-25℃)
The temperature coefficient a for different standards and cell type is between 0.0045 and
0.008 per ℃.
The heat released during discharge is described;
W = –TΔS + i2Rt +iEηt = –TΔS + iEpt (12)
(t is time of discharge).
The heat of reaction was mentioned above [Eqs. (6) and (7) ]. The second term in Eq.(12)
usually exceeds TΔS and the cell temperature is increased upon discharge as well as charge e.g.,
the temperature rise for a motive power cell during a 5-hr discharge is on the order of 5-10 ℃,
while an 8-hr charge raises the temperature of the cell by about 8-12℃, depending on the amount
of heat carried away.

— 46 —
5.2.3 Charging Performance

Reversal of reaction (1) in principle describes the charging process. However, the following side
reactions emerge during charge more and more until at the end of the charging process water
decomposition consumes the current completely.
Oxygen evolution at the positive electrode:
―
H2 O → 1
2 O2 +2H+ + 2e (13a)

Hydrogen evolution at the negative electrode:

―
2H+ + 2e → H2 (13b)
Together

H2 O → H 2 + 1
2 O2 (Eo= 1.23 V) (13a)

As marked by the dotted areas in Figure 5 gas evolution is favored by the position of
equilibrium potentials. However, the rates of both hydrogen and oxygen evolution are very slow at
lead and lead oxide, respectively, and therefore gas evolution according to Eqs. (13a) and (13b)
accompanied by simultaneous discharge [Eqs. (13a) And (13b)] is very slow during discharge or
open circuit (self-discharge). During the changing process, however, especially when a constant
current is impressed on the cell, the electrode potentials are raised, whereupon gas evolution
becomes favored. Finally, when the rechargeable material is exhausted, Eq.(13) remains only.
As can be seen in Figure 5 the potential of the positive electrode increases from the very
beginning of the charging process, which indicates that oxygen evolution accompanies the entire
recharging process. The negative electrode, on the contrary, accepts charge during the first stage
nearly completely until a sudden step in the charging curve signifies the beginning of hydrogen
evolution.
In any case, the side reactions (13a) and (13b) reduce the efficiency of the accumulator and
cause water loss [Eq.(13)]. In view of these facts it is important to know that the hydrogen
overvoltage at the negative electrode can be reduced by many substances, which would cause an
increase of gassing. Most effective are well-known catalysts like platinum or palladium, which
therefore have to be carefully excluded from lead-acid cells. Well know is the disadvantage effect
of antimony, which still is the preferred alloying element for battery grids, especially in motive
power batteries submitted to extensive charge-discharge cycling. For low-maintenance batteries
special alloys are selected which reduce or avoid antimony addition.

5.3 The Actual Appearance of Lead-Acid Batteries

Although lead-acid batteries always have the same design in principle, specific demands for
different applications have resulted in a multitude of types. Within the scope of this chapter only a
few examples can be described to gain a superficial insight.

— 47 —
5.3.1 Electrode Designs

All kinds of electrodes have been designed to gain a large surface area for the active
material combined with high electric conductivity. The Plante-type plate consists of pure lead cast
with fine lamellas to increase the geometric surface area. Lead dioxide as an active material is
produced by electrochemical oxidation of a thin surface layer. The most common are pasted plates
consisting of a grid (of lead or lead alloy) filled with a paste of porous active material (Pb; PbO2).
This grid can be recognized in Figure 6, which shows an assembly of positive and negative plates.
The grid may be manufactured by casting, punching or expanding. For improvement of
mechanical strength, alloys (e.g., Pb-Sb; Pb-Ca) are used. A section of a tubular plate (positives
only) is shown in Figure 7. The grid in this case is represented by vertical rods (spines) surrounded
by the active material. A tube of fabrics retains the active material, which therefore can be rather
porous to provide high utilization. In most cells the plates are assembled as shown in Figure 6 (cf.
Figures 9-11). Very thin electrodes may be wound up combined with the separators to form
cylindric cells as shown in Figure 8.

5.3.2 Design of Cells and Batteries

In addition to the described electrodes, electrochemical passive parts are needed to form a
complete cell. Porous sheets of plastics or rubber, the separators, are used to avoid short circuits
between the narrowly spaced plates (even for tubular plates as can be seen in Figure 10).
The so-called “top lead” which mainly consists of lead bars connecting the plates and the
terminal posts, can be seen in Figures 6, 9, and 11. Figure 9 represents a stationary battery, which
may be used as a standby battery for telephone systems, power stations, or emergency lights to
provide electric current in case the mains break down. These batteries usually are joined with the
electric circuit in parallel connection, therefore nearly always a (very low) overcharge
(2.15-2.25V/cell) is impressed. As mentioned above, water consumption may be reduced by using
grid alloys containing no or extremely small amounts of antimony.
The cut section of Figure 9 shows negative and positive grid and a separator in between them.
In the foreground a specially formed plastic body keeps the distance to the wall and defines the
pressure of the plate assembly. The jar in this case consists of very rigid (usually transparent)
plastics, because these batteries are usually installed without any support.
Since the lifetime of stationary batteries is expected to be very high, the positive plates hang
on special beams on the wall (Figure 9) to neutralize grid-grow effects.
The connecting bars and terminal posts can also be seen in Figure 9. To achieve sufficient
high rate performance, two terminal posts are used in parallels.
A special vent furnished with a filling funnel protects the cell against fire hazards caused
mainly by electrostatic discharges, e.g., when waiting personnel touch parts of the battery and the
hydrogen-oxygen mixture inside the cell ignites.
The motive power cell used for driving forklifts, electric tractors, and other vehicles is built
much more compactly (Figure 10), because the stored energy per volume is the most important
figure. The example shown in Figure 10 is equipped with tubular positive plates. Positive as well
as negative plates rest on special supports at the bottom. The jar is usually made of polyolefin
yielding rather low wall thickness. Mechanical support therefore is necessary, which is achieved

— 48 —
by a tray made of steel or resin.
An automotive or SLI battery (starting, lighting, and ignition of motorcars) is shown in Figure 11.
The construction principle of including the whole battery in one jar is applied for smaller types of
stationary and motive power cells too. The very short connections between adjacent cells
contribute to a very low internal resistance, which is needed (or achieving the high cranking power
for car engines (even at low temperatures). This starting requirement is the reason for using
extremely thin plates and a very low distance between them. When the car is running, the battery
is charged by the generator with constant voltage.

— 49 —
 6. State-of-the-art of alkaline rechargeable
batteries

6.1 Introduction
Recently, boosted by advances in electronic devices, significant technological progress has
been occurring in the technical field of small rechargeable batteries for consumer use. Up to the
1980s, rechargeable batteries used for cordless electronic and electric equipments were
exclusively Ni–Cd batteries. Currently, however, Ni–MH batteries (a new family of alkaline
rechargeable battery) and Li-ion batteries are available and are widely used for information and
communication equipment such as mobile phones and notebook computers. Among these, an
increase in the energy density of Li-ion batteries has been outstanding. The performance,
production quantities and application areas of Ni–Cd and Ni–MH batteries, especially in small
size are also increasing. Alkaline rechargeable batteries will continue to play an important role in
future society using mobile devices for advanced network and emission-free portable energy
sources.
In this paper, we focus on the current technological achievements and projected future trends
with Ni–Cd and Ni–MH batteries, which are currently boasting the largest production and
outstanding marketability among small rechargeable batteries for consumer use.

Fig. 1. Trends in production of small alkaline rechargeable batteries in Japan.

— 50 —
6.2 Alkaline rechargeable batteries
The Ni–Cd battery is well-established in the market place. After the invention of sealing
technology by Neumann et al. in the late 1940s, the manufacture of this battery began in the late
1950s in Europe and USA. In Japan, Sanyo started the production and marketing of the similar
battery design based on an indigenous sealed construction using sintered electrodes in 1963. Until
the Ni–MH battery was commercialized in 1991, Ni–Cd batteries were used as the power supply
on virtually all portable electronic equipment. During the course of its development, the Ni–Cd
battery has made a remarkable advance and much experience about the application of this
technology has been accumulated. In short, the Ni–Cd battery has led and expanded the market for
cordless electronic and electric equipment.
The Ni–MH battery is a unique rechargeable battery type employing a negative electrode
consisting of a metal alloy that stores hydrogen at high density, and this battery was successfully
commercialized by Sanyo and Matsushita in Japan in 1990. A Ni–H battery had already been
developed before the Ni–MH battery, and was used in a limited quantity for special purposes. This
type one does not fit with the requirement of commercial applications. A Phillips Laboratory
discovery of LaNi2.5Co2.5 in 1984 suggesting a new type of negative electrode material for
rechargeable batteries triggered the development of nickel metal hydride batteries. R&D on alloy
compositions has been pursued extensively and has resulted in Mm(Ni–Co–Mn–Al)x as a current
AB5 metal alloy of choice. The energy density of a battery adopting this composition, as a result
of the high negative electrode capability, is enhanced by 30–50% over that of Ni–Cd batteries.
The composition of much of the Ni–MH battery is identical to that of Ni–Cd batteries, i.e. a nickel
oxide as a material for positive electrode, electrolyte, configuration and sealing principle are
identical to Ni–Cd.
Changes in the production of these alkaline rechargeable batteries in Japan in the past 10
years are listed in Fig. 1. As is shown, both the quantity and value of Ni–Cd battery sales are
decreasing. This is due to the shift of production in Japan to Ni–MH batteries as well as due to a
transfer of production sites outside Japan. The quantity and value of Ni–Cd battery production are,
however, still increasing world-wide. At the same time, a rapid expansion in the use of mobile
electronic devices such as personal computers and mobile phones, is encouraging both the
quantity and the value of Ni–MH battery production to increase also. Thus, the market of alkaline
rechargeable batteries appears to be set to expand further.

6.3 Ni–Cd batteries

6.3.1 Composition and features

Three fundamental components of Ni–Cd battery are the nickel species as the positive
electrode active material, the cadmium species as the negative electrode active material, and the
aqueous alkali solution as electrolyte. The battery shows a nominal voltage rated at 1.2 V. The
charge–discharge reactions of this battery are described by the following equations.
Charge:
Positive electrode : 2Ni(OH)2 + 2OH– → 2NiOOH + 2H2O + 2e–

— 51 —
 Negative electrode : Cd(OH)2 + 2e– → Cd + 2OH–
Discharge:
Positive electrode : 2NiOOH + 2H2O + 2e– → 2Ni(OH)2 + 2OH–
Negative electrode: Cd + 2OH– → Cd(OH)2 + 2e–
Total:

2NiOOH + Cd + 2H 2O ⇋ 2Ni(OH)2 + Cd(OH)2

The forms of the active materials during the charge operation are NiOOH for the positive
electrode and metallic cadmium as the negative electrode: during the discharge operation, these
are Ni(OH)2 and Cd(OH)2, respectively. The sealed technology is one of the most important
features of Ni–Cd battery. Sealed operation was accomplished by transferring oxygen evolved on
the positive electrode in overcharging through the separator to the metallic cadmium negative
electrode which reacts with the oxygen to form Cd(OH)2. In order to ensure the sealing by means
of the oxygen absorption by the negative electrode, the capacity of the negative electrode is
designed to be larger than that of the positive electrode so that the negative electrode does not
reach a state of full charge. When the design capacity of the negative electrode is low so that the
electrode reaches the fully charged state, a sharp pressure rise occurs in the battery. Since the
reaction of oxygen with hydrogen evolved during over-charging of negative electrode is slow,
hydrogen evolution itself causes a serious pressure rise inside the battery.

Fig. 2. Enlarged view of sintered nickel and foam nickel substrates.

Two different kinds of electrode are manufactured for Ni–Cd batteries: sintered and
non-sintered. The sintered electrode has a nickel substrate involving innumerable fine pores
(several mm diameter), which are filled with an active material composed of mostly Ni(OH)2 or
Cd(OH)2 prepared by chemical or electrochemical conversion from aqueous nitrate solutions.
Owing to its high electrical conductivity, the sintered electrode can display a large current
discharge characteristic and quick charge characteristic. The non-sintered positive electrode is
manufactured by filling directly a foam-type nickel substrate (which has three-dimensional porous
texture) with an active material that is granular Ni(OH)2 powder. The non-sintered negative
electrode is obtained by coating a Ni-plated pierced steel sheet with an active material paste
composed mostly of cadmium oxide. Fig. 2 illustrates an enlarged view of both the sintered-type
nickel substrate and the foam-type nickel substrate. The non-sintered electrode is advantageous in

— 52 —
attaining a higher capacity, but is inferior to the sintered electrode in terms of electrical
conductivity.
The shapes of Ni–Cd batteries can be roughly categorized into cylindrical, prismatic, and
button types. Commercially available shapes are usually limited to the cylindrical and prismatic
types.
A cylindrical Ni–Cd battery is produced by winding three layered thin sheets of positive and
negative electrodes sandwiching a separator (made from a synthetic fiber material made of
polyamide or polypropylene), and then loading the roll into a cylindrical metal casing followed by
pouring in an alkaline electrolyte. The battery is next sealed by using a gasket and a seal plate
which is equipped with a self-resetting gas vent.
The prismatic Ni–Cd battery has a construction of stacked sandwiching a separator. The
stacked electrode composites are placed in a prismatic metal casing and then an alkaline
electrolyte is poured in. The casing is sealed by welding with laser.
Ni–Cd batteries show the outstanding features of long durability and excellent high power
performance, and very quick discharging and charging. Another advantage of Ni–Cd batteries is
the wide variety of the product line up which permits a diversity of applications. This wide line up,
includes more than 30 cell sizes with a capacity range of from 45 to 20,000 mAh. Moreover,
various kinds of purpose-specific batteries have been developed, each of which features high
performance optimized for a focused application. These batteries are basically identical in
composition, but are designed to meet the varying requirements of various applications by
selecting an optimal combination of electrode manufacturing process, component design, and
parts. The development history of purposespecific Ni–Cd batteries is summarized in Table 1,
while examples of the range of Ni–Cd batteries are shown in Fig. 3.
Table 1 Development history of purpose-specific Ni–Cd batteries
Year Purpose-specific battery type Applications
1973 High-temperature battery Guide lamp, emergency lighting
1975 Memory backup battery Cash register
1978 Quick-rechargeable battery Power tools
1979 Heat-resistant battery Medical instrument
1986 High-capacity battery Camcorder
1990 Extended service life battery Cordless phone

Fig. 3. Ni–Cd battery product line. Fig. 4. Capacity increase over time.

— 53 —
6.3.2 Trends in Ni–Cd battery technology

Efforts in developing Ni–Cd batteries have been focused on the applications that utilize the
advantages of Ni–Cd batteries, such as power tools, standby power supply for electrical equipment,
and motor power uses. The major challenges in the future development of Ni–Cd batteries will
involve larger discharge current characteristics, larger capacity and longer durability under severe
operating conditions such as continuous recharging. The high drain discharge performances are
required to satisfy the requirements of power tools and motor power uses. The trends for greater
capacity and higher power are described below in discussing the development of technology for a
high power type battery. Fig. 4 illustrates the history of the increase in the capacity of SC size
batteries that are most commonly used for power tools. As can be seen, the capacity has
approximately doubled in 20 years. The energy density of this type of battery is not so high as that
of batteries employing the sintered-type positive and negative electrodes. For example,
CP2400SCR can output a current as large as approximately 30 A. Its capacity is rated at 2400
mAh, and its size is 22 mm in diameter, 42.5 mm in height. Its weight is approximately 60 g.
When designing a Ni–Cd battery of a higher capacity, it is required to pack active material as
densely as possible into the electrodes. Also, it is required to increase the utilization of active
material. A high volume ratio occupied by the positive and negative electrodes in the total volume
of the battery gives a high capacity. Therefore, the separator, winding core space, casing and seal
parts are required to occupy as small a volume as possible. Among these, it is a major challenge to
reduce the space of a winding core for the positive and negative electrodes. We have focussed on
the increased utilization of the Ni(OH)2 active material for the positive electrode, and the
suppression of the volume for several parts.
First, the increased utilization of the Ni(OH)2 active material for the positive electrode is
discussed. It is known that the utilization of active material is increased by coating the surface of
the active material with Co(OH)2 by a chemical or electrochemical process after formation of the
sintered electrode . But this could not be applied to the commercial sintered electrode because of
poor reproducibility of the effect. A reproducible effect was finally achieved by controlling the
crystalline structure and morphology of the Co(OH)2. Cobalt coating technique has been utilized
since the successful development of the (CP-2400SCR) battery.
This improvement in the utilization of the active material is caused by the oxidation of the
Co(OH)2 coating layer on the electrode to CoOOH during the first charging operation so that it
forms a path of higher electrical conductivity. Since this oxidation takes place at a more negative
potential than the potential of the nickel positive electrode and this oxidation is an irreversible
reaction, so that the above-mentioned effect remains valid even after repeated charge–discharge
cycles. The conductivity of the positive electrode drops during the discharging process because
less conductive Ni(OH)2 is formed from conductive NiOOH. However, the CoOOH coating layer
makes up for this loss in conductivity, and enables a thorough discharge of the positive electrode.
This increase in utilization of the positive electrode is proved by measurement of the average of
valence change of nickel in the positive electrode, i.e. changes of the average nickel valency from
3.05 to 2.18 with the cobalt coating during discharge, while it changes from 3.05 to 2.25 without
the cobalt coating. The addition of 1.5 wt.% cobalt causes an 8% increase in the nickel utilization.
The data in Fig. 5 exhibit that the cobalt-coating effect remains even in high density loading
electrodes.

— 54 —
 New types of separator have been developed with materials made of non-woven polyamide
or polypropylene fabrics reinforced with fibres of high mechanical strength. This development has
decreased the separator thickness by 30% while maintaining its liquid-tightness and strength.
The size of the winding-core has been reduced by 55% compared with the conventional
winding-core. This change, on the other hand, has made the conventional arc welding to connect
the casing to the negative electrode collector inappropriate because this technique requires an
auxiliary electrode rod. To overcome this issue, a laser welding technique has been developed,
where a laser beam is irradiated from outside the casing to weld the collector. The schematic
diagram in Fig. 6 illustrates the method for laser welding on the bottom of the case. These new
techniques, including thinning the other components, have increased the energy density by
approximately 25% .

Fig. 5. Utilization of added Co and normal

active materials vs. material density. After Fig. 6. Laser welding of current
addition Co (surface addition: 1.0 wt.%): collector to can bottom.
(●). Before addition Co: (○). Note: the
utilization of active material density of 2.6
g/cm3-void no added Co is considered 100
(index).

Fig. 7. Discharge characteristics at 30 A discharge.

Typical characteristics of this battery are illustrated in Fig. 7. As shown in the figure, this
new Ni–Cd battery can meet the requirements of power tools. Variations of this type of battery
have been produced and used in many devices such as power-assisted bicycles, powered
wheelchairs, scooters, carts, and small power lifts.
The market for power-assisted bicycles started in 1994 in Japan and is expanding. For
power-assisted bicycles, a battery pack is typically used that is composed of twenty 5.0 Ah Ni–Cd

— 55 —
cells connected in series. When the load on riders becomes heavy at an upward slope, an assisting
motor powered by the battery pack helps to decrease the load on the rider. At the end of 2000,
approximately 500,000 power-assisted bicycles had been marketed in Japan.
The other promising market for Ni–Cd batteries is as a standby power source for
telecommunication equipment like WLL (wireless local loop), UPS, security equipment, POS
(point of sales) equipment, etc. These are sometimes employed in conjunction with solar cells as
power shutters, burglary-prevention lighting, traffic signs, etc. Hitherto, standby battery packages
coping with sudden power failure have been incorporated into various parts of
telecommunications systems. While lead–acid batteries have been used so far for this purpose,
Ni–Cd batteries have been gradually expanding in this application field because of their smaller
size and higher performance. This market requires a hightemperature trickle charging performance,
such as was required and developed for emergency lighting and guide lamps, and a wide range of
temperature performance with high reliability. Examples of the developments for hightemperature
trickle charged performance are: the adoption of the separator made of polypropylene, which is
more stable against heat and oxidation; optimization of the electrolyte; and inhibition of Cd
migration based on an improved negative electrode .

6.4 Ni–MH batteries

6.4.1 Composition and features

The Ni–MH battery is composed of nickel oxide as the positive electrode, metal hydride as
the negative electrode and an aqueous alkali solution (such as KOH) as electrolyte. As described
above, its positive electrode material and battery configuration are practically identical to those of
Ni–Cd batteries. In charging, a hydrogen atom deposits on the surface of the hydrogen storage
alloy by electrolysis of water. The hydrogen atom diffuses into the metal and is stored there, i.e.
the metal is reduced to a metal hydride. On the positive electrode, Ni(OH)2 is oxidized to an
NiOOH. In discharging, vice versa

Positive electrode : Ni(OH)2 + OH–⇋ NiOOH + H2O + e–

Negative electrode : M + H2O + e–⇋ MH + OH–

Total reaction : Ni(OH) 2 + M ⇋ NiOOH + MH

In this battery, the true active material in the electrode reaction is hydrogen, and the hydrogen
storage metal alloy is a medium for hydrogen storage.
The progress of improvement of the negative electrode material (hydrogen storage metal
alloy), which is the most outstanding feature of this battery type, is described below. The
optimization of the composition of the hydrogen storage alloy for batteries is illustrated in Fig. 8.
After replacing a part of Ni in LaNi5 with Co, prevention of fine pulverizing of the metal alloy and
capacity increase were achieved by replacing a part of Ni with Mn. The oxidation resistance of the
metal during the electrode manufacturing process was improved by replacing a part of Ni with Al.
Furthermore, it was clarified that replacing the La with a mixture of rare earth metal elements Mm
(misch metal) not only enhances the alkali resistance of the metal alloy, but also reduces the cost

— 56 —
of metal alloy. Finally, the stoichiometry of the basic composition of the AB5 series alloy was
reviewed over the range up to A:B = 1:5, and it was found that A:B = 1:4.76 is the most favorable
ratio to attain high capacity. The metal alloy composition MmNi3.2Co1.0Al0.2Mn0.6, which is
most widely used currently, shows high corrosion resistance and high capacity. The metal alloy of
composition, ABx, where x = 4:76, gives a discharge capacity of 330 mAh/g which is 10% higher
than that obtained for the composition of x = 5.
Avariety of Ni–MHbatteries is shown in Fig. 9. Basically, as in the case of Ni–Cd batteries,
their types are classified into two types: cylindrical and prismatic. Their internal construction is
very similar to that of Ni–Cd batteries.

Fig. 8. Process optimizing the composition of hydrogen storage alloys for batteries.

Fig. 9. A section of Ni–MH batteries. Fig. 10. Charging characteristics of Ni–MH

batteries. Model: HR-4/5AU; charge: 1 C for 1.3 h;
0.5 C for 3.2 h; 0.1 C for 16 h.

— 57 —
 The charge characteristics of Ni–MH batteries are summarized in Fig. 10. As is shown, a
quick charge operation can be completed in approximately 1.3 h after a full discharge. The charge
control methods are generally based on the peak voltage control (detecting the maximum value of
the battery voltage) and dT/dt control (detecting battery temperature increase appearing at full
charge).
The most outstanding advantage of Ni–MHbatteries is the high volume capacity, reaching a
value of 1.3–1.5 times that for comparable Ni–Cd batteries. Their other features are roughly
identical to those of Ni–Cd batteries; their discharge voltage is the same as that of Ni–Cd batteries.
Thus, Ni–MH batteries can easily replace the Ni–Cd battery.

6.4.2 Trends in Ni–MH battery technology

The progress of increase in energy density for Ni–MH batteries, cylindrical 4/3 A size
batteries (diameter: 17 mm and height: 67 mm) and prismatic C1 size batteries (width: 17 mm,
height: 35.5 mm and thickness; 6.1 mm) is summarized in Fig. 11.

Fig. 11. Capacity increase of the Ni–MH battery (HR-4/3AU, HFC1U). HR-4/3AU (cylindrical): (●; HFC1U (prismatic): (◆)).

Fig. 13. Charge–discharge cycle characteristic before

Fig. 12. Limiting current density before and after
and after surface treatment. After surface treatment:
surface treatment. After surface treatment: (●);
(●); before surface treatment: (○).
before surface treatment: (○).

Since coming on to the market in 1990, our Ni–MH batteries have met market needs for
higher energy density (an increase of approximately 1.7 times during these 10 years based on 3/4
Asize battery, and approximately 1.8 times based on C1 size). Requirements for small and lighter

— 58 —
weight batteries with high capacity have been increasing recently, especially for application to
notebook computers and mobile phones. To satisfy this requirement, development and
improvement of battery materials are necessary. In particular, enhancement of the hydrogen
storage capacity of alloys has been of vital importance.
The target for advanced hydrogen storage alloy is to enhance the hydrogen storage capacity
and to protect against fine pulverization as well as oxidation-induced deterioration that occurs as a
result of repeated expansion/shrinking during charge–discharge cycles. To achieve this, the
composition of this alloy has been extensively examined as discussed above. One of the current
interests for the improvement of the performance is to prepare a homogeneous alloy that
suppresses segregation of manganese and eliminates the lattice distortion occurring during
quenching of the alloy. The reactivity of the alloy surface is moderated by a treatment with acid or
alkaline aqueous solution . The influence of acid treatment is described in Fig. 12. The treatment
enhances the limiting current density (per weight), which leads to an increased power capability of
the electrode . The influence of acid treatment on capacity is shown in Fig. 13, which shows that
the increase in capacity is limited to about the fifth cycle .
One of the key technologies to enhance Ni–MH battery capacity is to develop a Ni-based
positive electrode with a higher capacity. Adding to the technologies described in Section 3,
further improvement has been accomplished by the air-oxidation of Co(OH)2 in the alkaline
electrolyte containing NaOH, which leads to the formation of a cobalt oxide more conductive than
CoOOH. The cobalt oxide formed containing Na shows electric conductivity 4 orders of
magnitude higher than the conductivity of CoOOH. Recently, the addition of rare earth oxides to
the nickel positive electrode has been shown to increase the utilization of the positive electrode.
The addition of Y 2O3 increases Ni(OH)2 utilization as shown in Fig. 14 .

Fig. 14. Influence of the amount of Y2O3 on Fig. 15. Endurance in overcharge cycles at high
active material utilization. temperature. PP separator: (●); nylon separator:
Charge: 0.1 C, 16 h; discharge: 1/3 C (cut-off (▲); charge at 0.2 C at 608C; discharge at 1 C
voltage 1.0 V). (cut-off voltage 1.0 V) at 258C.

Some of the oxygen evolved during overcharging oxidizes the separator. Then the charge
reserve of the negative electrode decreases and the cycle durability of the battery is decreased.
Oxidation of the separator must be strictly avoided. The use of an oxidation-proof PP separator
enhances the durability of the battery. Typical durability during overcharge cycles at high
temperature as shown in Fig. 15.
Some new kinds of hydrogen storage alloys such as the AB2 type, Mg–Ni type and bcc type
represented by V3Ti are being investigated, which are expected to offer a larger capacity (in
particular, the capacity of the bcc type is two times larger than that of AB5). However, some

— 59 —
problems to be solved for these new alloys remain; these new alloys are easily corroded in an
electrolyte and this causes serious deterioration during cycling. Nevertheless, research and
development on these alloys is in progress although they have not yet been brought into practical
application. The problems to be solved for the new high-capacity alloys are summarized in Fig.16.
The world production of Ni–MH batteries has continuously increased and reached
approximately 1.2 billion in 2000. The increase in the market for electronic equipment such as
notebook computers and mobile phones, and the continued endeavor to meet the demands from
such equipment have kept production increasing. The merit of high performance and excellent
environmental compatibility will accelerate the further expansion of Ni–MH batteries in new and
current application areas including HEVs, UPS, power-assisted bicycle, and others in the future.

Fig. 16. New high-capacity MH alloys.

6.5 Conclusion
Ni–Cd batteries, which do have environmental issues, also have many advantages, e.g.
high-power output, super-rapid charging, low cost, and high durability. Although new
rechargeable batteries such as Ni–MH batteries and Li-ion batteries have been commercialized,
Ni–Cd batteries still boast the largest production throughout the world even 30 years after their
first commercial marketing. It is expected that Ni–Cd batteries will keep their share of this market.
Ni–MH batteries has reached an energy density of 91 Wh/kg and 340 Wh/l. As compared with
lithium ion batteries, the former parameters is less but the latter (volumetric energy density) is
equal. The Ni–MH battery shows much higher safety than Li-ion. The merits of volumetric energy
density and safety will sustain a help to expand the application of Ni–MH batteries further, for
example, is HEVs, dispersed electricity storage, a UPS. Furthermore, new hydrogen storage alloys
are expected to bring a new break-through in their performance.
R&D of these alkaline rechargeable batteries is directed both to common applications and to
specific uses and remarkable progress is expected in both directions.

— 60 —
 7. Fundamental Principle of Electroplating

7.1 Introduction
Electroplating is the process of depositing coating having a desirable form by means of
electrolysis. Its purpose is generally to alter the characteristics of surface so as to provide improve
appearance, ability to withstand corrosive agents, resistance to abrasion or other desired properties
or a combination of them, although occasionally it is used simply to alter dimensions. Electrolysis
is carried out in a bath which may consist of fused salts or of solutions of various kinds; in
commercial practice it is almost invariably a water solution.
The laws of electrolysis, formulated by Faraday in1833, afforded the first quantitative
demonstration of the electrical nature of matter, and have long defined the unit quantity of
electricity. Today, unmodified by newer discoveries, they remain among the foundations of
physical science. For the electroplater, Faraday’s laws specify the current time product required to
produce a definite weight of diposit. One Faraday (96,490+2.4 amp-sec) of electricity yields 1
gram-equivalent of substance. The gram-equivalent is obtained by dividing the gram-atomic
weight of the deposited metal by the number of electrons required per atom (see Table 6,
Appendix).
If more than one substance is deposited, as in alloy plating, then Faraday’s laws apply to the
total number of equivalents of all the substances produced but do not specify proportions. No
exceptions have been found, but electrode processes do not invariably lead to deposition of metal
or gas; Fe3+ ion, for example, may be reduced to Fe2+ ion at the cathode, or the reverse process
may proceed at the anode, accounting for corresponding amounts of current.
To complete an electric circuit through the bath, two electrodes are required, an anode and a
cathode, and each may consist of several pieces; Faraday’s laws apply separate to each electrode.
When a soluble anode is used, the same number of equivalents of metal dissolve from the anode as
deposit on the cathode, if no other reactions occurred. In this way, the bath would be maintained at
its original concentration, if side reactions did not interfere and no losses of solution occurred. In
practice, however, solution is carried out of the bath on plated work-pieces as they are removed
(“drag-out”); consequently replacements of chemicals and water are required. Furthermore, since
secondary reactions often consume certain constituents, replenishment is generally not as simple
as restoring a fresh portion of the original bath; it is discussed in following chapter for individual
baths.
A simple example of a plating cell comprises two copper electrodes immersed in a water
solution of copper sulfate and connected externally to a source of direct current, such as a battery,
generator, or rectifier. It is usually considered that copper sulfate is completely ionized, so that
only copper ions and sulfate ions are found in the bath# (together with minute quantities of
hydrogen and hydroxide ions resulting from the ionization of water; in commercial copper sulfate
baths, however, sulfuric acid is also added). Electrons are supplied to one electrode, imparting a
negative charge, and removed from the other, at which a positive charge therefore remains. A

#
This picture is too simple for solutions as concentrated as plating baths, but the concepts of ion pairs, unionized
molecules, of semiordered structures proposed for such solutions have not yet proved advantageous in considering
deposition mechanisms.

— 61 —
copper ion in the bath, being positively charged, is attracted by and attaches itself to the negative
electrode or cathode, accepting two of the surplus electrons; that is, it is discharged and thus
becomes a copper atom. At the opposite electrode, or anode, a copper atom, gives up two electrons
in response to the positive charge and so becomes an ion, passing into the solution. These
※
reactions are written
–
Cathode: Cu++ + 2e → Cu
– ++
Anode: Cu → 2e + Cu
The anode process is, accordingly, oxidation of copper metal to the ion, and, conversely, the
cathode process is reduction of the ion to metal. The sulfate ion plays no direct part in the
△
electrode processes . Since equivalent changes must occur simultaneously at anode and cathode in
order to maintain net electrical neutrality in the solution, another copper ion enters the bath
whenever a copper atom is deposited. Therefore the system undergoes no total change, except for
the disappearance of a copper atom from the anode and the appearance of another at the cathode.

7.2 Electrode Potentials

A piece of metal dipping into a solution containing its ions establishes a definite electrical
potential, characteristic of the metal and of the concentration of the metal ion in the solution. Such
☆
potentials for certain solutions are listed in the Appendix Table 3+ Copper, for example, shows a
potential 0.345 V more positive than hydrogen. If the potential of the electrode is diminished to,
say, 0.340 V by application of a negative external potential, copper ions become attached to it, that
is, are deposited, If a positive potential is applied, and the electrode potential rises to, say, 0.350 v,
copper ions become separated from the metal. Thus, a total external potential of 0.10 V or less
between cathode and anode is sufficient (neglecting polarization and ohmic resistance, which are
described later) for plating, but larger potentials are needed for sizable currents.
The hydrogen ions which are also present are not discharged, because the potential must be at
least 0.345 V more negative for this to happen (in molar acid; about 0.6 V if no acid is added). In
fact, overvoltage (discussed later) increases the required potential to about 1.3 V more negative

※
The symbol Cu++ represents the copper(Ⅱ) ion together with coordinated water molecules. In most chemical
reactions the coordinated water molecules are not significant. They are important, however, in electrochemical
–
kinetics, and the equations should preferably be written Cu(H2O)4++ + 2e = Cu + 4H2O, and the reverse; the
subscript 4, although not known with certainty, is considered probable.
△
The anion may, however, influence the character of the deposit and the efficiency of the process, as will be
explained later.
☆
The solutions are defined as containing 1 gram-ion/1,or more precisely as having unit molar activity at 25oC.
Potentials are strongly influenced by the presence of complex-forming substances, or by the passage of current, as
is explained later. Because only relative electrode potentials can be measured, values given in the table are relative
to the hydrogen electrode, the potential of which is arbitrarily considered to be zero for a hydrogen pressure of 1
atm, hydrogen ion at unit activity, and at 25oC. Since at least two electrodes must appear in any plating cell, this
convention introduces no difficulties. There are two conventions regarding the signs of the potentials; many
American chemists use a positive sign when electrons are produced in the electrode more readily than in the case
of hydrogen (for example, zinc), and a negative sign if the reverse is true; this sign indicates the potential of the
solution relative to the electrode. Such tables are published in many texts and reference words. In this volume, to
conform with general electrochemical practice, the opposite sign is used (zinc negative with respect to hydrogen);
it represents the potential of the electrode, relative to the solution. In order to avoid the ambiguity introduced by
the concurrent use of two contradictory sign conventions, many authors prefer the unambiguous terms “noble” and
“base”. Certain electrode potentials which are not easily measured are computed from thermodynamic data. The
determination of potentials at the individual electrodes is made by means of suitable reference electrodes, as
described in texts on electrochemistry[13]

— 62 —
than that needed to deposit copper. Since these potentials cannot be attained without depositing all
the copper, hydrogen is not produced in this bath.
If the cathode potential is not more negative than the least negative potential at which any of
the possible reduction reactions can occur, no reduction can take place, and consequently no
current can flow through the cell. Often, as with the example given, the reduction requiring the
least negative potential is the only one which proceeds. Thus, the aluminum reduction potential is
about 0.8 V more negative than the hydrogen potential (allowing for overvoltage); hence, in
aluminum solutions, hydrogen is produced exclusively. For this reason, the potential required to
deposit aluminum cannot be attained in the presence of water; therefore aluminum can be
deposited only from nonaqueous baths.
At the anode, the oxidation reaction which requires the least positive potential will occur;
unless this potential is exceeded, oxidation cannot take place and current cannot flow. Often
oxidation of the metallic anode occurs, so that metal ions enter the bath, but oxidizable ions or
water may also be oxidized. In the example given, copper is dissolved at a potential about 2.5 V
less positive than that required to evolve oxygen from water.
Electrode reactions with potentials differing by less than about 0.05 V may proceed
simultaneously. In this way two or more metals are codeposited as an alloy; hydrogen is also
codeposited with certain metals. The relative amounts of each of the simultaneous reactions
depend on kinetic factors as well as on the reduction (or oxidation) potentials.
Electrode potentials are substantially altered by polarization and passivation; thus, lead anodes
in chromium plating baths become passive by forming a film of lead oxide, and then oxidation of
water occurs in preference to dissolution of lead. A similar effect occurs with nickel anodes unless
the bath contains chloride ions.
The ratio of the weight of metal actually deposited to that which would have resulted if all the
current had been used for depositing the metal is called the cathode efficiency with respect to
◇
metal deposition . An efficiency of 92﹪ in nickel plating means that 8﹪ of the current was used
in depositing hydrogen or in other reductions (such as that of Fe3+). With respect to the sum of all
electrolytic processes occurring at an electrode , the efficiency is, of course, 100﹪, in accordance
with Faraday’s laws. Similar efficiency quotients apply also to the anode.
When metal ions are complexed, deposition usually proceeds less readily, as expressed in a
more negative electrode potential. The changes are sometimes as great as 0.6-0.8 V, and they
result in substantial alterations in relative positions in the familiar “electromotive” or “activity”
series. For example, the electrode potential of copper in cyanide baths is more negative than that
of zinc, so that displacement deposits are not formed on zinc base die castings as they are in
▽
sulfate baths ; it is, in fact, so close to that of zinc that codeposition of zinc and copper in the form
of brass becomes possible. On the other hand, in solutions containing zinc and copper sulfates, the

◇
some electroplaters have referred efficiency to metal actually deposited on the work-pieces, as distinguished
from that deposited on contacts and racks, or in trees which become detached, together with hydrogen evolved.
Since such figures depend on operating details they vary from job to job and gave no fundamental significance.
▽
In copper plating on a steel surface, the situation may seem similar; displacement deposits of copper are formed
from sulfate but not from cyanide baths. Nevertheless, the very low activity of Fe2+ in a cyanide solution should,
according to the Nernst equation, produce an electrode potential even more negative than that of copper;
accordingly displacement deposition would be expected. Actually, the electrode potential observed is indefinite
and is determined by other, unpredictable reactions rather than by oxidation of iron to Fe(CN)64-; the latter process
is evidently so slow as to be completely negligible. The absence of immersion deposits is therefore the result of
kinetic rather than thermodynamic factors. As is well known, cyanide copper baths are entirely suitable for plating
directly on steel, whereas acid copper baths are not.

— 63 —
potentials are separated by more than 1.0 V, and all the copper would be deposited at a much less
negative potential than that needed to deposit zinc.
╬
The effect of concentration changes on electrode potential is given by the Nernst equation:
RT
E = E M0 n + + ln a M n +
nF
In which E is the electrode potential, E0 is the standard potential for unit activity of the simple
metal ion, Mn+; R is the gas constant, T is the absolute temperature, F is the Faraday, n is the

formal charge of the ion, and a M n + is the activity of the metal ion in the solution.**

The formation of a complex may be represented as

M n + + qX p−
→ MX qn − pq

In which q is the coordination number and X the complexing ion of charge p; and the Nernst
equation may be written

RT RT a MX n − pq
E = E M0 n + − ln e K f + ln e q q
nF nF a X p−
Where Kf is the thermodynamic formation constant for the complex and a represents activities of
the species denoted by subscripts. In some instances (in which activity coefficients roughly cancel
out) it is possible to obtain useful approximations by substituting concentrations for activities. It
can be seen that the term involving Kf will usually determine the region in which the potential lies,
and since Kf will be large for any stable complex, the potential will be shifted by a substantial
negative quantity.

7.3 Bath Constituents

More is required than a specified weight of deposit. It should have the desired distribution
(generally uniform thickness is wanted); it should adhere satisfactorily to the substrate; pores,
cracks, and other discontinuities in the coating are usually undesirable; and the deposit should
have the required brightness, smoothness, hardness, ductility, stress, and resistance to corrosion.
The bath constituents are chosen to permit achievement of these objectives at reasonable rates and
costs.
Deposition on the surface does not proceed by laying down atoms successively from one edge to
the other, as a mason builds a brick wall. It commences at relatively few favored sites on the
substrate, apparently at defects or patches of adsorbed foreign substance. According to recent
studies, metal ions become attached to certain positions on the face of the growing metal crystal,
and subsequently diffuse or move along the surface to kinks, edges, steps or other discontinuities,
where they become incorporated into the metal lattice. As these growth sites travel across the face

╬
This equation is known to be valid at equilibrium, whereas electrodeposition is, of course, a nonequilibrium
process. It is customary to assume that the equation holds also during deposition and dissolution, and to assign
observed deviations from the equilibrium potential to various types of polarization as discussed later; this
assumption permits satisfactory treatment of electrode kinetics, and appears to be justified by the consistency of
the deductions based on it.
*
A useful approximation for RT/F, multiplied by 2.3 to convert to common logarithms, is 0.059 V per electron at
25 oC.

— 64 —
of the crystal it is built up layer by layer.
Growth proceeds not only normal to the substrate but also laterally, until the growing faces meet
each other. Because neighboring crystals usually have different orientations, the lattices do not
merge, but form a boundary, and continued growth must be outward. At some stage in growth a
surface imperfection becomes the nucleus for growth of a new crystal; a composite or
polycrystalline structure results. Since the crystals ordinarily cannot develop symmetric faces,
they are called grains. The production of large single crystals by electrodeposition has not been
achieved.
Under some conditions the grain structure of the deposit continues that of the basis metal, but
more often it passes within a few atom layers into a form characteristic of the depositing metal. It
is of primary importance in controlling mechanical properties. If grain boundaries contain little
foreign material but are formed by the approach of neighboring lattices to within atomic
dimension, cohesion and tensile strength comparable to that of the metal in massive form resulting
from solidification of a melt are often developed. Grain boundaries ordinarily contain material
excluded from the growing lattices, and the strength of the metal is influenced by the nature and
amount of this material and the bonds which exist between it and the metal grains.
In some solutions (AgNO3, SnCl2), outward growth of grains is much more rapid than lateral
growth, and produces unconsolidated, needle-like crystal with little integrity as a coating. In other
solutions (for example, cyanide silver or stannate), outward growth is less rapid, and satisfactory
coating result. The reason for such differences is not clear, but it appears to be connected with
preferential adsorption of anions (for example, cyanide or chloride) or the mode of occurrence of
lattice dislocation and its influence on the growth rate of certain crystal faces. Thus it has been
suggested that needles result from the rapid growth of screw dislocations in specific faces.
Whatever the mechanisms, anions often profoundly alter and therefore influence the choice of salt
to provide metal ions.
Because some plating baths contain complex ions, it has been supposed that complexing favors
good deposits, but this is not a general rule; many complexes give very poor results.
Transformation of complex ions to simple cations seldom occurs in the deposition process; the
concentration of uncomplexed metal ions is not significant, as was once believed.# Even the
so-called “simple” cation is actually coordinated with water molecules, and the deposition process
consists in part of conversion of its bonds from coordinate to metallic functions with concurrent
removal or “stripping ” of the coordinated groups. No essential difference exists between plating
from “simple ” and from complex ions.
In respect to the deposition process the distinction between acid and alkaline baths has little
significance. Baths containing simple salts of those metals which are commonly plated must be
acidic, since most of these cations are hydrolyzed to insoluble hydroxides, or hydrous oxides, at
pH exceeding about 5.5. In commercial practice plating baths containing complex ions of the
desired metal are mostly neutral or alkaline (except the chromium, halide tin, and certain gold,
platinum, and rhodium baths). The potential for hydrogen discharge is less negative in strongly
acid baths; if it approaches the metal deposition potential (as in zinc or nickel sulfates), the current
efficiency will drop. Hydrogen evolution is, however, more common in certain alkaline baths

#
On the other hand, the thermodynamic stability of the complex, as measured by its dissociation constant, may be
important through its effects on the reduction potential.

— 65 —
(cyanide copper, cadmium, or zinc) where, because of complex formation, the metal deposition
potential has become nearly as negative as the hydrogen discharge potential. The pH range to be
used influences the choice of materials for tanks and other equipment.

Simple salt or “acid ” baths; effect of the anion

Since enough metal ion (usually 0.2-2.0M) must be present to avoid rapid depletion in the vicinity
of the cathode, only the more soluble salts can be employed. Nitrates are generally soluble, but
nitrate is reduced at about +0.7 v, and hence it cannot ordinarily be used with metals more active
(that is, reduced at more negative potentials) than silver.
Although halides are not reducible, bromides and iodides are relatively costly. Chlorides are
occasionally used for nickel, iron, tin, and some other metals, and chloride solutions show less
polarization and greater conductivity than sulfate baths. Nickel deposits from chloride baths
generally have higher internal stress than those from sulfate baths. Because many chlorides are
more soluble than the corresponding sulfates, more concentrated baths, which permit higher
currents and faster plating, can be prepared. The ability of chloride ion to facilitate the deposition
process is apparently related to its tendency to form coordinate bonds.$ The baths, however, are
strongly corrosive to equipment, and therefore tend to become contaminated readily. Furthermore,
with some metals brighteners for chloride baths are not as readily found as for sulfates. Chlorides
are, however, always added to nickel sulfate baths to promote dissolution of the anode by
preventing its passivation. With copper, the coordinating tendency of chloride stabilizes the
copper(I) chloride complex, so that the cathode process is largely or entirely the production of
solid copper(I) chloride, rather than of metal.
The sulfate ion has little tendency to form stable complexes, and deposition from sulfate baths
△
apparently occurs from “simple ” hydrated cations. For copper, nickel, zinc, tin, iron, and cobalt
sulfates, solubilities are high enough to sustain good rates of deposition. Such baths are widely
used. Occasionally mixed sulfate-chloride baths are advantageous.
Perchlorates are quite soluble and make good plating baths, but their cost and explosive hazard
have prevented their use. The perchlorate ion has almost no tendency to form complexes; it should
be relatively easy to find suitable brighteners.
Fluoborates are costly but have some use where high plating rates are desired, because the
solubilities permit high concentrations. Deposition apparently occurs from the simple (hydrated)
metal ion. Excess boric acid is added with fluoborates to suppress hydrolysis to hydrofluoric acid,
which would precipitate metal fluorides. Baths usually contain free fluoboric acid, which, together
with the high salt concentration, gives unusually high conductivity and reduces power
requirements. These salts are also used for depositing metals like lead (and its alloys), for which
the chloride and sulfate have too limited solubility. Fluosilicates are similar to fluoborates but are
less stable and have hound little use in plating, though they are used in electrorefining because of
their lower cost.
Salts of sulfamic acid are use for depositing lead, indium, and nickel. Apparently there is no
tendency to form complex ions. The baths decompose slowly because of hydrolysis of the anion,

$
It has been suggested that chloride ions form electron-conducting bridges to the cathode which are important in
the deposition process; the superior coordinating tendencies of bromide or iodide might sometimes prove to be
advantageous.

— 66 —
although this is negligible if temperatures are sufficiently low. Advantages claimed for sulfamate
nickel (low porosity and low stress) are not easily accounted for. Various organic sulfonates and
trifluoroacetates have been used occasionally, particularly for tin and zinc. Because these salts are
unusually soluble, high concentrations of the metal ions can be attained, which accordingly permit
higher rates of plating than in sulfate baths, for example. Specific advantages which result from
less common salts are described in chapters on the various metals.
In general the effect of the anion is exerted first through its control of the solubility of the salt, and
thus on the concentration of the metal ion; and second through its ability, if any, to coordinate with
the metal ion and also to interact with the cathode surface, thus influencing the deposition process
by adsorption or bridging effects.

Complex ion baths

The most important complex ions in electroplating copper, cadmium, gold, silver, and zinc are the
cyanides. Because most cyano complexes are decomposed by acids (with evolution of the
exceedingly poisonous gas, hydrogen cyanide), baths must be alkaline; however, the cyano gold
complex is sufficiently stable to exist in acidic solutions, but still not too stable to give deposits, as
are cyanide of iron and cobalt. With other metals, when hydroxides are not added, the baths are
alkaline by hydrolysis of excess (“free”) cyanide. Cyanide baths usually contain several different
―
complexes; the copper bath, for example, contains di- and tricyanocuprate(I), [Cu(CN)2] and
―
[Cu(CN)3]2 , and possibly the tetracyano complex as well. At least at low currents and in dilute
solution, deposition proceeds from the dicyano complex, which is in mobile equilibrium with the
other forms. Calculation of so-called “free” cyanide based on the assumption that only one type of
complex is formed, however useful it may be for control purposes, has no foundation in the
chemistry of the solution.
In general, deposition appears to occur from the complex ion containing the fewest coordinated
★
cyanides, even though it may exist only in relatively small concentrations, except, possibly, at
the surface of the cathode. More highly coordinated ions are evidently readily converted to this
form.
Deposits from cyanide baths are usually finer-grained than those from the corresponding acid
baths; and cyanide solutions have poorer micro- but better macro-throwing power, as a
consequence of interaction between the several forms of complex ions at the cathode surface,
resulting in variations of cathode efficiency and of polarization with current density. Thus
decrease in current efficiency and increase in polarization at high current density make the rate of
deposition more nearly equal to those obtained at lower current densities.
Because the baths are alkaline, they absorb carbon dioxide from the air. The resulting carbonate
ion has little effect until its concentration becomes high enough to precipitate a salt with one of the
cations in the bath. Then the crystals become included in the deposit, producing gross roughness.
The higher solubility of potassium carbonate compared to sodium carbonate defers this difficulty
and is one reason for the preference for potassium salts in such baths as silver. In copper and silver
baths, carbonate reduces anode polarization; this may be the result of temporary formation of

△
In the high sulfate nickel bath, sulfato complexes probably account for its special characteristics.
★
Deposition from cyanide zinc baths proceeds from Zn(OH)2[2]. The hydroxide can exist only at the cathode
surface, since it would be attacked by cyanide ions in the bath itself; the question of its “solubility” in the double

— 67 —
carbonato complexes or of buffering at the anode surface, which can influence the nature of the
complexes formed.
At a copper anode, the dissolving copper may form the insoluble cyanide salt CuCN as a
nonconducting film, with the result that current flow ceases. Dissolution of this salt from the
anode may be promoted by adding more cyanide to dissolve it as a complex, but this reduces the
cathode current efficiency by diminishing the concentration of the dicyano ion. The use of
tartrates (Rochelle salts) or other additives to prevent formation of this film by forming temporary
complexes which do not affect the cathode because they do not reach it is explained in chapter 7.
When alkali metal hydroxide is added to cyanide baths, it prevents formation of hydrocyanic acid
and consequent loss of cyanide by reacting with carbon dioxide entering the bath from the
atmosphere. It also improves conductivity. In the zinc bath some zinc is converted to zincate, that
is, the tetrahydroxy complex. Deposition occurs more readily from this ion than from the cyano
＃
complex, even though the latter still controls the form of the deposit. Cyanide ions undergo slow
hydrolysis, yielding ammonia and formate. These substances appear to have no effect on
deposition from cyanides except in brass baths. Ammonia, of course, readily volatilizes from
alkaline baths. Electrochemical oxidation of cyanide to cyanate has been suggested as a path by
which cyanide is lost, but is has not been demonstrated analytically in electroplating baths.
The stannate bath contains the hydroxy complex of Sn(Ⅳ). At the cathode this is doubtless
reduced to the hydroxy-stannate(Ⅱ) complex (stannite), from which the metal is immediately
＊
deposited. Sodium or potassium hydroxide is added to suppress hydrolysis of the complex, to
prevent precipitation of hydrous stannic oxide (tin hydrate) by the reaction of carbon dioxide
absorbed from the atmosphere with stannate ion, and to improve conductivity.
The nature of the complex ions and deposition mechanisms of many complex baths, such as
pyrophosphates, is not completely elucidated. In the familiar chromium bath, reduction of the
dichromate complex, Cr2O72-, appears to result in precipitation of an oxide, which in turn is
reduced to lower oxides, and finally to metal; it has been shown that chromium (Ⅲ) ions do not
enter the deposit from the solution. This is not a typical deposition process; in part, it may be
chemical reduction by hydrogen.
Many other complexes give good deposits. Gold is deposited from the tetrachloroauric(Ⅲ)
complex. Deposits of various metals (Sn, Cd, Zn) from sulfur complexes (for example,
thiostannate( Ⅱ ), thiosulfate, thiocyanate) generally include substantial amounts of sulfur.
Complexes formed by ammonia or amines of various types often give good deposits. The iodide
complex has been recommended for silver. Baths based on tartrates and citrates have also been
described. None of these baths has been used extensively, presumably because ordinary baths are
satisfactory and less costly.

layer is ambiguous. Mixed hydroxo-cyano complexes apparently do not occur.

＃
This is probably not the effect of potential (thermodynamic) relations, but of kinetic factors. The stability
constants of the zincate and cyano complexes indicate that the latter are more stable, and hence have more negative
electrode potentials; accordingly zinc will be present almost entirely in cyano complexes, provided of course that
sufficient cyanide is present, which is usually not the case in technical baths. Even with excess cyanide, however,
deposition at low current densities occurs from a hydroxy complex, apparently Zn(OH)2. evidently retes of
transformation to this complexes and its subsequent electro reduction are sufficiently large that little reduction
from the cyano ion occurs. Since the actual electrode potentials must be identical for thermodynamic equilibrium
between the complexes, the reason that deposition occurs only from zincate in spite of its much smaller
concentration must be kinetic; presumably this would be true also in technical baths.
＊
Accumulation of stannite in the bath is deleterious; it produces spongy deposits apparently by
disproportionating.

— 68 —
Wetting agents

If bubbles of hydrogen gas adhere to the cathode surface, plating is prevented around the bubble
and a pit in the coating results. Wetting agents are added to some baths, such as bright nickel, to
promote detachment of bubbles and eliminate pitting.

Conducting “salts” and buffers

Sulfuric acid is added to copper sulfate baths mainly to increase electrical conductivity; in tin
sulfate baths too, acid affords improved conductivity, although its primary purpose is to prevent
hydrolysis. The addition of sodium hydroxide to cyanide baths has been discussed earlier.
Carbonates are added to cyanide copper, silver, and gold baths, their purposes are not clear, but it
has been claimed that they increase conductivity, function as buffers, and increase polarization at
the cathode while decreasing it at the anode. The improvement of conductivity in silver baths has
been established, but there is little effect in copper except in preventing excessive anode
polarization. Some baths are operated with carbonate as low as can be readily maintained.
Boric acid in nickel baths is usually termed a buffer. Solutions of the acid in water, however, are
buffered only at pH exceeding 9, which cannot be achieved in nickel baths, even at the cathode
surface. Since a weak buffer action has been observed, it must be ascribed to the effect of
unrecognized complex ions. Acetates, citrates, and tartrates buffer at operating pH ranges, but
have had little use except with gold; on the other hand, formates are used in certain nickel,
cobalt-nickel, and gold baths.
Acetates and aluminum salts are used to buffer zinc sulfate baths. Although pH is not a critical
factor in operation, the use of buffers is convenient for control purposes.

Additions to promote anode corrosion

Chlorides in nickel baths, tartrates and carbonates in cyanide copper baths, and hydroxides in
stannate baths are added to obtain proper dissolution of the anodes. They tend to dissolve films
(NiO, CuCN) which interfere with normal dissolution.

7.4 THE PLATING PROCESS

According to modern concepts, a metal crystal or grain consists of metal ions located in
regular lattice positions, together with a cloud of moving valence electrons, equal in number to the
charges of the metal ions. The valence electrons are more or less free to distribute themselves
among the ions according to certain distrihution laws. Each ionic charge is neutralized by the
electronic charges when aver aged over a period of time or over a number of ions; but individual
valence electrons are not confined to any particular ion. According to Pauling, this arrangement
gives use to resonating bond forces responsible for cohesion and the resulting physical properties
of the crystal. On immersion in water a few metal ions leave their lattice sites, become hydrated,
and diffuse out into solution as dissolved cations. The corresponding electrons, however, remain
as part of the electron "atmosphere" of the solid metal, and this surplus of electrons constitutes a
negative charge in the metal: The dissolved cations are attracted by this charge, and some

— 69 —
re-enter the metal, occupying vacant lattice sites.' As the charge in the metal increases, the rate of
return of ions to the metal is accordingly increased, and soon becomes equal to the rate of
dissolving, which is diminished by the accumulating negative charge on the metal. This
balanced condition in rates con stitutes a dynamic equilibrium, with the metal negatively charged
relative to the solution. The negative potential so produced is related to the conventional electrode
potential but is not numerically identical with it; a positive reversible electrode potential means
only that the true potential is less negative than that of the hydrogen electrode
The number of ions released in building up this potential is usually too small to be detected
chemically. Many are held in the interface between the metal and the solution by electrical
attraction. The negatively charged metal is thus enveloped by a film of solution containing mostly
╳
positive ions. This arrangement constitutes an electrical double layer, the capacitance of which
can readily be measured. The flow of ions to and from the metal at equilibrium (zero net current)
is equivalent to a current termed the exchange current. Methods of measuring this quantity have
recently come into use.
The magnitude of the electrode potential reflects the algebraic sum of two quantities of energy:
╬
lattice energy, required to remove the ion from its crystal lattice, and hydration energy available
from its interaction with solvent or complexing agents in the solution, Lattice energy depends
partly on orientation of the crystal face from which the ion is removed; in the randomly oriented
polycrystalline metal usually dealt with in technical electroplating, slightly differing potentials
from several faces are mixed. Energy of hydration or coordination depends in part on the
concentrations, or more correctly the activities, of the reacting species, which are related to
potential by the Nernst equation.
The magnitude of the exchange current density is determined by the potential difference and
the activation needed to permit the dissolution and deposition reactions to proceed. This last
quantity, which may be considered a potential barrier to be surmounted, depends on the nature of
the mechanisms by which the ions react. In turn, these apparently depend in part on the number,
location, and nature of growth sites in the metal lattice. Finally, both electrode potential and
exchange current may be profoundly influenced by the presence of adsorbed material at the
interface, either intentional (addition agents) or unintentional (contaminants).
In the plating cell used earlier as an example, the copper electrodes, being identical, have equal
potentials and the net potential is accordingly zero; hence no net current flows if the electrodes are
connected (short-circuited). If an external potential is applied between the electrodes, added
negative potential at the cathode increases the rate of transfer of ions across the double layer to the
electrode, where they are deposited. At the same time, excess negative potential diminishes the
rate of metal dissolution (at the cathode).* As a result, deposition of metal prevails over

╳
This Helmholtz double layer, because its outer layer is charged positively, in turn attracts a layer of anions,
which is, however, considerably more diffuse, and this in turn attracts a still more diffuse layer of cations
(Gouy-Chapman layer). The resulting alternating structure grades into the quasi-ordered structure of the solution
itself, which is far too concentrated to fit the familiar Debye-Huckel- Onsager considerations. The diffuse layer
is nearly inconsequential in solutions as concentrated us plating baths, but doubtless it has a minor influence on
electrode processes. Because the double layer is the consequence of charge attraction, it is made up of cations of
whatever kinds are present in the solution and is not limited to those originating from the electrode itself.
╬
In the metal, as already explained, atoms are already ionized, at least in part. The energy of removal (lattice
energy) may, however, be calculated by adding the sublimation energy (to remove an atom from the lattice as a
gaseous atom) to the ionization energy of the gaseous atom.
*
The extent to which the available excess potential is effective in accelerating the deposition process, as compared
to that which slows the dissolution process, is given in kinetic studies by a fraction known as the transfer

— 70 —
dissolution, and plating takes place. At potentials used in technical processes, dissolution is
completely negligible. At the anode, the situation is reversed in most but not all aspects.

Polarization

For current flow, therefore, added potential is required at the electrode. This excess potential,
over the idle or rest potential of the electrode, is termed overpotential, overvoltage, or polarization.
⊿
These terms are often regarded as synonymous. The difference results in part from depletion of
depositing ions in the immediate vicinity of the cathode, after a short period of electrolysis. If the
potential of the electrode, is measured immediately after current is interrupted, it is found to be
mere negative than before electrodeposition took place, and it gradually returns to the original
value as the ion concentration in the double layer is replenished by diffusion of ions from thc main
portion of the bath.
This change in potential is explained by the diminished concentration of depositing ions in the
double layer which decreases the rate of their transfer to the electrode, whereas the rate of their
dissolution from the metal is increased. The balance in these rates, which determines the
potential of the metal (on open circuit), is therefore altered and makes the potential more negative;
its new value is given by the Nernst equation when concentrations prevailing at the electrode
surface are inserted. The negative shift in potential due to these concentration changes is termed
concentration polarization. At soluble anodes, essentially similar changes occur, but in the
opposite direction.
Concentration changes are not confined to the double layer, but extend about 0.10 to 0.25 mm
into the bath as a concentration gradient, depending on the rapidity of replenishment by diffusion
and convection. The region in which a significant gradient persists during electrolysis is
commonly referred to as the diffusion or cathode film; but it is to be regarded as a region of altered
concentration rather than as a film in the usual sense.
The rates at which metal ions are transferred across the double layer from solution to metal
and vice versa are determined by two factors: the kinetics# of the process, and activation produced
by means of a portion of the total polarization potential, called activation or chemical polarization.
Finally, films of material at the electrode surface, whether adsorbed from the bath or produced by
the electrode process, offer resistance to current flow differing from that of the bath. The
potential corresponding to the IR drop in the film is called ohmic polarization, or "pseudo-ohmic
resistance," which is not to be confused with the potential equivalent to the IR drop in the solution
proper, sometimes called resistance polarization.
The total change in potential necessary to maintain a steady current through the cell is
accordingly given by the sum of the three polarization voltages at each electrode, and the potential
corresponding to the IR drop across the solution:

coefficient α. At technical plating rates, this fraction must approach unity very closely.
⊿
According to the American Standard Definitions of Electrical Terms, polarization is the difference between the
dynamic electrical potential and the static potential, whereas overvoltage is the difference between the dynamic
potential and the reversible electrode potential. In many instances, the two are identical. The term overvoltage is
commonly used when gas is evolved at the electrode,
#
The exchange current density provides an indication of the speed and nature of the reaction as already discussed,
but it must be remembered that the mechanisms which prevail at technical plating rates may not be identical with
those which determine the exchange current density near zero net current.

— 71 —
E − E static = (η concn. + η activ. + η ohmic ) anode + (η concn. + η activ. + η ohmic ) cathode + IRbath

Mass Transfer Processes

Three processes operate to supply metal ions to the depleted solution at the cathode, and to
remove them from the enriched solution at the anode. In the following, only the cathode is
considered, but analogous processes occur at the anode. First, diffusion causes ions to move from
the unchanged bulk of the solution to the impoverished region at the cathode, according to the
usual laws. Second, electrical migration of cations is superimposed on diffusion (the motion is
reversed with an anionic complex). Ordinarily, migration is very much less important than
diffusion. Third, convection currents tend to move the depleted solution away from the cathode,
and replace it with fresh solution from the unaltered bath.
In unstirred baths, the fact that the diffusion film is less dense than the bulk of the bath,
because it has lost metal ions through deposition, results in upward flow (the motion is downward
at soluble anodes because the density is increased). This convective flow mitigates depletion
noticeably. Thermal convection currents are produced by localized heating due to passage of
current, and by cooling at the surface of the bath, tank walls, or cooling coils. Furthermore, high
rates of flow along portions of an irregularly shaped cathode surface may result from
concentration differences in the diffusion film caused by local variations of current density. *
Stratification of plating baths, with solution density increasing irregularly with depth,
sometimes results from convection currents produced at the electrodes. Mechanical stirring, or
agitation, prevents stratification; but its primary purpose is to induce convection currents which
replenish the diffusion film. The limiting current density, and hence the permissible rate of
plating, is substantially increased. Moving the cathode pieces may be as effective as pumping or
circulating the bath. In baths such as copper or zinc cyanide, in which hydrogen is codeposited
with metal, rapid formation and detachment of gas bubbles is extremely effective in providing
stirring. In other baths, this effect may be approximated by bubbling air into the tank if the air
bubbles are comparable in size and number and if the bubbles reach significant surfaces of the
cathode. The air must be free from contaminant, including substances which would react with
constituents of the solution, such as carbon dioxide in alkaline baths.
Ions, then, are carried to the diffusion film mainly by convection or agitation (induced
convection), since migration under the electric field prevailing in the bulk of the bath is relatively
very slow. They pass through the film to the double layer largely by diffusion, which so far
outweighs coulombic forces that anions move to the double layer nearly as readily as cations; in
spite of charge repulsion. Entry into the double layer depends partly on specific electrostatic
attraction or adsorption and may involve distortion or chemical modification of the entering
species in the more intense electric field.

Activation Of Electrode Reactions

Unequivocal studies of the activation of electrode reactions have been made only at low

*
Although strictly a diffusion phenomenon, it differs from usual diffusion processes at the electrode and resembles
convection. "Maxima" in polarography are due to the same kind of effect.

— 72 —
polarizations and with mercury electrodes. The results appear, however, to be suggestive for solid
electrodes. Deposition of cadmium, tin, and lead from simple ions is very rapid (high exchange
currents) and activation polarization is small; but the latter is quite large with nickel and iron (low
exchange currents). Zinc and copper are intermediate. Rapid electrode reactions often lead to
deposits with large grain size. Addition agents or complex ions may interfere with the formation
of large crystals and increase polarization. Activation polarization is often about equal at the
anode and cathode for a given current density, because the potential barriers to be crossed are
nearly the same.
Some metals (titanium, vanadium, molybdenum, and tungsten) form such firm coordinate
bonds in all their ions that either the deposition potential is greater than the hydrogen discharge
potential, or the bonding presents such kinetic hindrances that hydrogen discharge occurs
preferentially.$ Since the strength of bonds reflects the electronic structure of the metal ion, these
considerations explain why metals which can be plated from aqueous solutions are located in
definite regions of the periodic table. All metals can be deposited from fused salt baths and
presumably also from suitable nonaqueous solvents, provided discharge potentials of competing
reactions are not exceeded.
In the discharge of hydrogen, polarization is exceptionally high at most metal surfaces. This
hydrogen overvoltage is due largely to activation required for discharge. It is strongly influenced
by the nature of the surface; fin and lead, for example, show higher hydrogen overvoltages than
◇
nickel or platinum, doubtless because the latter catalyze the discharge reaction. Hydrogen
overvoltage depends also on the nature of the solution, the nature and surface condition of the
cathode, the current density, the temperature, and any extremely minute traces of impurities in the
solution. Extended discussions may be found in monographs on electrochemistry.
Hydrogen overvoltage is of special significance in plating when the metal reduction potential
is nearly equal to or more negative (less noble) than that of hydrogen. Thus in zinc sulfate solution
the metal reduction potential is about -0.76 V; whereas the reversible hydrogen reduction potential
is only -0.34 V (at pH 5.5, which gives the most negative hydrogen potential attainable without
precipitating zinc hydroxide). Consequently hydrogen would be discharged preferentially except
for its overvoltage, which exceeds 0.7 V on zinc. The result is that actual hydrogen discharge
requires at least -1.04 v, (-0.34-0.7), and accordingly zinc may be deposited at -0.76 to -0.9 v with
current efficiency exceeding 99.98% even at pH as low as 2.5. Traces of nickel or cobalt and some
other impurities on the cathode lower hydrogen overvoltage and reduce efficiency at low current
▼
density.
In cyanide baths, hydrogen overvoltage is considerably lower and its discharge potential is close
to that of zinc or copper. Hence hydrogen discharge competes with metal deposition and current
efficiency is commonly less than 100%. On cast iron cathodes the presence of graphite, which has

$
For example, thermodynamically, tungsten, molybdenum, and germanium should be deposited from acid
solutions, but this does not occur. It is well known that complexes of the first two are quite slow to react, in part
because of their tendency to polymerize. These metals are, however, deposited as constituents of certain alloys;
and there is a possibility that certain complexes may be suitable for depositing the pure metals. Still others are on
the border line; thus nickel can be deposited from the ammonia complex, but not from the cyanide complex.
(There is a question as to deposition of nickel from cyanide baths. If it; occurs at all, the efficiency is extremely
low. In properly purified solutions, efficiency does not exceed 0.01% on nickel cathodes, and no deposit is
visible. Nickel may be deposited alloyed with other metals from cyanide solutions, and it is possible that
unrecognized metallic impurities account for apparent deposition.)
◇
It is noteworthy that metals which are generally deposited with low overvoltages show high hydrogen
overvoltage, and vice versa; no satisfactory explanation of this fact has been advanced.
▼
Such considerations are extremely important in electrolytic zinc refining, where the physical form of the deposit
and its tendency to redissolve exercise profound effects on reported cathode efficiencies.

— 73 —
low hydrogen overvoltage, sometimes allows the entire current, to produce hydrogen, and no zinc
is deposited.
Little is known of ohmic polarization resulting from the resistance of electrode films. In the
anodizing of aluminum it may be very large.

Ohmic Resistance of the Bath; Resistance Polarization

Apart from the electrode interfaces, cell resistance is determined by the specific resistance of
the solution, the effective areas of the electrodes, the distance between them, and the geometry of
the cell and electrodes, in accordance with well-known principles. Specific resistance depends on
the nature and concentration or activity of conducting ions, viscosity, and temperature. Hydrogen
ions are by far the best conductors; hydroxide ions are good, but all others are much less effective.
Discussion of electrolytic conductance may be found in works on electrochemistry.

Mechanism of Deposition

The means by which depositing ions reach and enter the double layer have already been
considered, but the steps by which they subsequently become incorporated into the cathode crystal
lattice are still unknown. The coordination sphere of strongly associated ligands (in the case of
"simple" ions, the ligands are water molecules) is probably modified in the electric field of the
double layer. The following processes are suggested:
―
1. Electron transfer across the double layer, possibly by means of a bridging group (CN , H2O;
―
Cl ) which is temporarily linked both to the ion and to the cathode. On neutralization, the ion
releases its ligands, and in this stripped state is adsorbed on the cathode surface.
2. Dissociation of one of the ligands followed by interaction of the vacated bond function with
an atom on an active site, with participation in metallic resonance giving partial metallic character.
As ions enter neighboring positions in the lattice, the remaining coordinate bond functions release
their ligands and are transformed to metallic linkages to the incoming ions until complete metallic
character is established.
3. Adsorption of the coordinated ion directly on the active site by means of an additional bond
function which is metallic in character, followed by release of ligands and conversion of
coordinate to metallic bonds.
Migration of adsorbed ions, or "ad-ions," along the surface from the original site of attachment
to a growing step or dislocation in the lattice face may occur after any of these processes, possibly
before complete removal of the ligands. As yet, unequivocal distinction between these
mechanisms has not been achieved experimentally, but recent studies suggest the second, followed
by migration to growth sites, for certain baths. Other mechanisms may operate under different
conditions.
Activation may represent energy required for the incoming ion to penetrate the double layer,
dissociation energy of one or more coordinate bonds, association energy to effect coordination
with the cathode, transformation energy to convert from coordinate to metallic resonance, or
energy required to expel released ligands back through the double layer, or some combination of
these. It may also be necessary to displace a ligand previously coordinated with the active site on
the cathode. Surface diffusion requires activation energy, particularly if adsorbed ions or

— 74 —
molecules must be displaced. It is clear that the presence of adsorbed species or alterations of the
double-layer structure can have profound effects on the activation energy and the resultant
structure of the deposit. The final crystallization process itself has already been discussed.

"Burned" or Powdery Deposits: Diffusion Current

If increasing potential is applied to the cathode, the current, increases; Ohm's law is obeyed if
electrode polarization is deducted from the applied potential. If the concentration of nondepositing
ions is large, and the depositing ion is relatively dilute, as in solutions used in polarography, a
point is ultimately reached when further increases in potential result only in increased
concentration polarization, and the current remains unchanged. This constant-current behavior
occurs when the depositing ions are plated out as fast as they reach the cathode surface, and thus it
depends on the rate of diffusion; the current is called a diffusion or limiting current, and the
concentration of the ion in the double layer is substantially zero. At sufficiently negative potentials,
a new cathode process such as hydrogen discharge may appear, and the current will rise again.
Similar limiting currents are possible, at least in theory, in electroplating baths; but technical
usage refers to the limiting current density as the highest at which "good" deposits may be
obtained. Beyond this point deposits are generally noncoherent, dark, and powdery; they have a
burned appearance. It has been believed that such deposits are due to hydrogen discharge, with
consequent increase of pH at the cathode surface to the point where metal hydroxide or basic salts
are precipitated and become included in the deposit. The use of buffers in nickel baths counteracts
this tendency.
"Burning" may occur, however, at potentials well below the hydrogen discharge potential (as
with copper sulfate); hence the basic film hypothesis does not always apply. Measurements of
pH in the diffusion film indicate that it is too low to precipitate basic material except when very
substantial amounts of hydrogen are produced. Within the double layer pH has not been
determined; because the dielectric constant is substantially altered, ordinary solubility products
and ionization constants do not apply. It may be that the rate of decoordination of water
molecules from the metal ions is so slow that some Water remains coordinated and is included in
the deposits. Analyses of inclusions suggest water rather than hydroxide. Inclusions interfere with
growth of a coherent crystal lattice, and affect the mechanical properties of the deposit. Strongly
adsorbed anions or organic materials are also found in inclusions.
Inclusions are not confined to burned deposits; they are found in trace amounts (in the order of
0.01% or more) in almost all coatings, especially if addition agents are used. When as much as
10-20% of sulfur or phosphorus occurs in smooth deposits, these should be classified as alloys.
Burned deposits may be avoided by lowering the current density or by providing higher mass
transfer rates, as by agitation or stirring, higher temperature, or higher concentration of metal.
The buffer action of boric acid at the cathode surface reduces burning in nickel baths: presumably
by repressing formation of basic precipitates.

Effect of pH

The pH of the bath influences the hydrogen discharge potential, the precipitation of basic
inclusions, the composition of the complex or hydrate from which the metal is deposited, and the

— 75 —
extent of adsorption of addition agents. Since it is not possible to predict these factors, the best pH
range must be determined empirically. The effect of pH on stress and hardness is probably exerted
mainly through the nature and distribution of inclusions. In baths containing complex ions, pH
may influence equilibria between various complexes present and must be considered in relation to
concentrations of metal and cyanide, for example.
When anodes are insoluble, the bath becomes depleted in metal ions (which must later be
replaced), and simultaneously becomes more acid, because the anode reaction usually is
―
2H2O → O2 + 4H+ + 4e
The resulting acid solution may be replenished in the case of the zinc sulfate bath, for example, by
chemical reaction with scrap zinc metal, zinc oxide (as in a roasted zinc ore), or zinc carbonate. To
add more zinc sulfate would not remove the acid formed during plating.
On the other hand, hydrogen evolution at the cathode is accompanied by the production of
hydroxide ions: Therefore, if the current efficiency is greater at the anode than at the cathode, the
bath becomes more alkaline and accumulates metal ions (unless the pH becomes high enough to
precipitate the hydroxide). Inequalities in electrode efficiencies may be detected by changes in pH;
increasing pH means that cathode efficiency is lower than anode efficiency, decreasing pH the
reverse.

Addition Agents

The addition of small amounts of certain substances, often organic, may profoundly influence
the form or structure of the deposits. Adsorption at the cathode surface during electrolysis is
apparently essential; one added molecule may affect many thousands of metal ions. Generally the
effects are undesirable, but when a bright or leveled surface is produced or internal stress reduced,
the added substance is no longer classed as a contaminant. Increases in activation over-potential
are usually observed, but decreases have been found for carbon disulfide in the cyanide silver bath,
and for thiourea in the cyanide copper bath.
Colloids such as glue have been used for many years to produce smoother deposits with
smaller grains and to suppress the formation of trees and nodules. The newer agents enhance
brightness and smoothness by causing metal to deposit more rapidly in pits and depressions and
less rapidly on peaks and ridges than on level portions of the cathode surface, and they modify
internal stresses as well. Bright plating reduces or eliminates the expense of hand buffing and may
diminish the need for high finish of the basis metal. Zinc and cadmium coating, which are never
buffed, and which may not retain their brightness in service, are nevertheless more marketable
when bright.
Bright deposits have high specular and low diffuse reflection; the term does not refer to the
amount or wavelength of the light reflected. The essential requirement is that the surface be
smooth and free from sharp submicroscopic irregularities. The term leveling is used to denote
microscopic smoothing of surface irregularities which has a secondary effect on brightness,
whereas brightening implies submicroscopic smoothing resulting in a substantial increase in
specular reflection; it is not always accompanied by leveling. The nature of leveling and
brightening is discussed in the following section.
Metallographic preparation and etching of sections of bright or leveled deposits almost
invariably reveal a banded or laminated structure . This seldom, if ever, causes structural weakness

— 76 —
and merely indicates differences in rate of etching, due perhaps to trace impurities or minor
differences in structure. Bright plating baths usually require more or less close control of
brightener content, pH, current density, temperature, and bath composition. Furthermore, some are
quite sensitive to very small amounts of impurities. The deposits are generally more brittle than
those made in the absence of addition agents. The corrosion resistance of bright plates is
sometimes slightly inferior to that shown by ordinary "dull" or mat-finish deposits. If the latter are
buffed, however, loss in protection due to removal of metal may exceed the loss incurred in
depositing metal in the bright condition. The action of brightening agents is associated with
certain molecular groups or structures, and other compounds having similar structures produce
similar effects, if other factors are unchanged; however, it is not generally possible to predict what
structures will produce brightening.

7.5 Distribution Of Thickness Of Deposits

Current Distribution

The laws governing the flow of electric current preclude the possibility of producing a deposit
of uniform thickness except on cathode shaving the simplest shapes, and even then the geometry
of the plating set-ups must be carefully arranged. Edges and projections receive higher current
densities than the average surface, and hollows or recesses lower. The variations may be many
fold.
The current distribution in the absence of polarization is termed primary. It prevails only at
the first instant of current flow, and can be calculated exactly from potential theory, although the
computation may become very complex; it may be measured experimentally by the use of probes
in the cell, with alternating current of a frequency high enough to eliminate the effects of
polarization; or it can be determined by models of the cell using conductive paper. It depends on
the conformation of the various electrodes, the spaces between them, and the distances between
them and the walls of the cell, and the surface of the bath; it is independent of absolute size.
Optimum spacing for the best uniformity is often a few times the diameter of the significant
portion of the cathode. Primary current distribution is of course not affected by characteristics of
the electrolyte.
The primary, current distribution is modified by polarization, which often makes the secondary
current distribution (that is, that which prevails after the onset of polarization), more uniform than
the primary. If polarization is known as a function of current density, secondary current
distribution can be calculated, although the computations are usually cumbersome and may need
correction for the effects of stirring. It may be determined experimentally in the cell by the use
of suitable probes, or by measuring local thicknesses of deposit on cathodes; or dissolution of
anode metal, provided current efficiencies are known as a function of current density. The
relative effect of polarization versus ohmic resistance in the electrolyte is most marked in small-
or micro-scale profiles, where the secondary current distribution is essentially uniform if the same
polarization function applies to all points. This will be true when electrocrystallographic
differences or local variations of diffusion rates resulting from concentration changes or other
factors do not interfere.

— 77 —
According to Wagner, the equalizing effect of polarization depends on the ratio of the product of
the specific conductivity by the absolute slope of the polarization curve to the characteristic
dimensions of the profile. On larger-scale profiles both activation and concentration polarization
are effective in improving uniformity; but on profiles of the order of thickness of the diffusion
layer (0.25 mm), concentration polarization varies both with current density and with the local
effective thickness of the diffusion layer, and high concentration polarization (extensive depletion
of metal ions) produces poor micro-throw.

Effect of Cathode Efficiency

The uniformity of the deposit is also strongly affected by variations in cathode current
efficiency. In some cyanide copper, zinc, and cadmium baths, especially those with a high
cyanide-to-metal ratio, efficiency drops sharply as current density is increased; accordingly
thicknesses in regions of high current do not exceed the average as greatly as would otherwise be
expected.
In chromium plating baths, on the other hand, cathodic current efficiency increases with
current density, within certain limits, producing exaggerated nonuniformity of metal distribution.
Variations of efficiency influence metal distribution whatever the scale of profile, but on
small-scale profiles current efficiency varies not only with current density but also with local
variations in effective thickness of the diffusion layer.
In summary, metal distribution depends on the shape and dimensions of the object, the
geometry of the plating cell arrangement, the conductivity of the bath, the shapes of the
polarization and current efficiency curves, and the effect of agitation on them. Since a change in
conditions may affect several of these factors in opposite ways, predictions are uncertain.
Changes favorable for one shape may be unfavorable for another.

Throwing Power

The ability of a bath to produce deposits of more or less uniform thickness on cathodes having
macroscopic irregularities has long been termed throwing power. The property of plating into
grooves, pores, and scratches less than about 0.25 mm in dimensions has recently been called
micro-throwing power. There is no sharp distinction between this property and leveling.
Finally, this same effect applied to submicroscopic irregularities appears to be related to
brightening. The term "covering power" has not been defined clearly and is therefore
ambiguous.
Throwing power has been studied by using the Haring-Biam cell, bent cathodes, and cavity
scales. Since it is not exclusively a property of the solution, however, these devices have limited
value. For example, macro-throwing power is poor and micro-throwing power good in zinc or
copper sulfate baths, whereas the opposite is true of the corresponding cyanide baths.
Micro-throwing power is profoundly influenced by addition agents, which may produce a high
degree of leveling or smoothing, whereas tile effect on macro-throwing power is usually
negligible or unfavorable.
Although quantitative measurement of throwing power is of limited value, in a general way it
may be stated that alkaline baths, particularly cyanide solutions, have good macro-throwing power,

— 78 —
and acid baths have relatively poorer; the zinc sulfate and chromic acid baths are extremely poor
in this respect (negative throwing power on the Haring-Blum scale).
Micro-throwing power is governed by the diffusion layer. When recesses in the cathode surface
are comparable in size to this layer, it does not reflect the surface contour in detail; consequently
its thickness varies substantially over the profile. Diffusion rates through the layer then vary
correspondingly. Where polarization is strongly influenced by the diffusion of metal ions or
addition agents, or by "back"-diffusion of complexing ions (CN-) liberated in the deposition, it
will depend on these different thicknesses. Consequently, although primary current distribution is
nearly uniform, the secondary is much less so, and the micro-throw is poor. This is the case for all
baths at high current density, and for cyanide baths even at moderate currents.

Leveling and Brightening

In either bright or leveled deposits, inclusions of sulfur and carbon from the addition agents are
found. By using radioactive tracers, Beacom and Riley have shown that the inclusions are more
pronounced at micro-peaks in the surface than at valleys, evidently the result of more rapid
diffusion through the thinner diffusion layer at the peaks. It is presumed that the greater
concentration of adsorbed material at the peaks inhibits deposition there more than in the valleys.
Consequently deposition occurs more rapidly in the valleys, and in time they become completely
filled in. It is possible that brightening is produced by leveling on a still smaller scale, but other
factors may be involved.
The manner in which adsorbed material inhibits deposition is unknown. It has been attributed to
ohmic differences, potential differences, or interference with migration of ad-ions after deposition.
Probably the adsorbed material covers growth sites progressively until few remain available on the
peaks, while deposition proceeds relatively unhindered in the valleys, which contain less adsorbed
material and therefore more uncovered growth sites. As diffusion continues, however, the
growth sites become blocked in the valleys as well, and finally a stage is reached in which fresh
sites must be nucleated over the entire surface for deposition to continue. As the cycle is repeated,
the adsorbed material is buried in layers under the growing deposit, giving rise to "laminations".
Beacom and Riley and Trivich have shown that addition agents are "cleaved," or broken down
chemically, during nickel deposition. Hydrocarbons derived from the added organic substances
appear in the gas evolved at the cathode, whereas sulfur and carbon remain in the deposit. These
agents are not reduced or cleaved by ordinary, cathodic treatment nor are they adsorbed at
uncharged metal surfaces, which shows that cleavage is the result of involvement in the deposition
reaction itself. Presumably cleavage products are produced by electrolysis and immediately
absorbed at rates adequate to maintain an inhibiting film on the surface peaks, but not in the
valleys, at least for a considerable time.
Laminations in nickel are 0.35-0.62 μ thick, and require about a minute to form, in accord
with the differential diffusion hypothesis outlined before. Any cyclic fluctuations of current or
potential associated with them are masked by larger, more frequent variations from other sources;
it is hardly to be expected that these cycles would be simultaneous over the entire cathode area.
The diffusion hypothesis accounts for the observation that inclusions are less concentrated in
deposits made at higher current densities.
The increased brittleness of these deposits is due to the inclusions, which may either increase,

— 79 —
decrease, or even reverse the internal stress. The nature of this action is not understood.

7.6 Growths In Deposits

As electrodeposits become increasingly thicker, the surface roughness increases. The most
common appearances are the development of trees or nodules. The latter consist of rounded
projections of metal and are sometimes quite firmly attached. Trees are more angular, dendritic, or
many-branched. They are evidently the result of rapid growth of favored crystal faces, possibly
because of the effect of screw dislocations in the lattice. As the tree develops, the concentration
of current flow to the relatively sharp point resulting from the angular shape, the decrease in
distance from the anode, and the decrease in polarization owing to induced stirring of the
electrolyte around the tree, cause its rate of growth to increase; occasionally a tree reaches the
anode and short-circuits the cell. Its thin structure prevents development of any considerable
physical strength, and trees are usually not very firmly attached. The thickness of deposit which
may be obtained without trees and nodules depends on the composition of the bath and on its
freedom from suspended matter and other impurities; for example, although silver nitrate and
stannous chloride baths produce trees almost immediately, smooth deposits more than 0.05 mm (2
mil) thick are readily obtained from cyanide silver or stannate baths. These growths are
suppressed by colloids and by brightening and leveling agents. Nevertheless, in many baths the
development of nodules puts a limit on the thickness of acceptable deposit., particularly in
electroforming, electrowinning, and electrorefining.

7.7 Adhesion
It is usually stated that surfaces must be "clean" before they can receive a plated coating which
will be adherent. If, however, cleanness means that the metal surface contains no other atomic or
molecular species, it is hardly attainable even in the laboratory. If imperceptible residual films or
soils are removed in the plating bath so that the deposit approaches the basis metal within atomic
dimensions, then normal atomic bonding occurs and the resultant structure is one integral piece of
metal. The work of Linford and others has shown that high orders of adhesion are also obtained
even though residual films are not removed, provided these are not too thick and have good
strength and adherence of their own; in other instances oxide films are reduced electrochemically
before deposition occurs. In any event it is often simple to obtain bonding, at least on common
metals, so strong that failure in adhesion tests occurs in the basis metal or deposit more readily
than in the interface between them, and in principle this degree of adhesion can always be secured.
Peeling of electroplates is avoidable.

7.8 Deposition by Displacement

Potentials generated by chemical reaction with the bath at a metal surface may produce
electrodeposits without an external source of current. For example, an iron surface in a sulfate
solution tends to establish a potential (relative to the solution) greater than that required to deposit
copper. If copper ions are present, as in copper sulfate solution, they are therefore deposited.

— 80 —
The actual potential cannot become much more negative (less noble) than that of copper as long as
copper ions are present, for then electrons are transferred from iron atoms to copper ions,
depositing them, and the resulting iron(II) ions enter the solution: Cu++ + Fe = Cu + Fe++. Thus
iron displaces copper ions from solution. As iron (II) ions accumulate, the iron potential is
diminished; and as copper ions are depleted, their deposition potential rises. If the two potentials
become equal, action ceases.
The submicroscopic regions from which iron is being dissolved are anodic; the cathodic
deposit covers the remainder of the surface, presumably leaving tiny pores at the anodes.
Electrons flow from anode to cathode through the basis metal; the action is that of a
short-circuited voltaic cell. Since the resistance of the basis metal is relatively very low,
momentary current densities may reach the limiting value and produce burning, although this may
be too thin to be detected visually. For this reason, the deposit is seldom adherent; perhaps, too,
the basis metal is partly dissolved from under the initial layers of deposit. Occasionally, however,
deposits are sound and exhibit good adhesion.
After the first reaction the concentration of dissolving ions may become quite high in the
anodic pores of the deposit, with consequent decrease of potential, since convection is somewhat
blocked. Similarly, the solution at the surface of the basis metal may become relatively depleted
of the depositing ions. Furthermore, as the surface becomes covered with the deposit it assumes
the potential of that metal; consequently, deposition practically ceases after periods ranging from a
few seconds to several minutes. Semibright copper deposits may be made on steel from acidified
solutions of copper sulfate. The addition of complexing substances such as
ethylenediaminetetraacetic acid (EDTA) increases deposition potentials to values nearer the
anodic potential in some cases and helps to avoid extreme surges of current which cause burning;
or the complexes may produce compact deposits by the nature of their discharge mechanisms, or
by their control of anodic dissolution. Good deposits are obtained on aluminum from zincate
baths; from stannate baths, immersion deposits are adequate for purposes of lubrication, but are
not sufficiently adherent to support subsequent electroplated coatings, nor to be soldered.
These deposits are termed immersion, displacement, galvanic, or (improperly) cementation
coatings. Obviously thickness is limited, and rarely exceeds 0.01 mm for compact deposits; thus,
tin deposits 0.005 mm (0.2 mil) thick can be deposited on aluminum from a stannate bath.
Spongy coatings such as those from copper sulfate on zinc surfaces often attain a greater weight
and thickness than the more coherent types of deposit.
Because most displacement deposits have burned or unsound structure, they do not afford a
satisfactory basis for subsequent electrodeposits. Thus copper plated on steel directly from a
sulfate bath is almost never adherent because of the displacement deposit which forms
immediately on immersion, even when an external potential is applied, unless the copper is quite
dilute and the bath strongly acid. In practice, therefore, the initial electrodeposit is made from a
cyanide bath. Similar considerations apply to zinc surfaces in copper sulfate or ordinary nickel
baths, or to brass surfaces in ordinary silver or gold baths. The silver "strike" bath (Chapter 14)
has an exceedingly high cyanide-to-silver ratio. In depositing on steel, it might be thought that
the purpose of the strike is to avoid displacement deposition, but as has already been explained,
displacement by iron in a cyanide bath does not occur. The high ratio greatly reduces the cathode
efficiency so that it is necessary, after initial coverage, to transfer the article to the normal silver
bath to build up a thicker coating.

— 81 —
 Aluminum has so high a potential that displacement occurs with any of the metals used in
coatings; it is common first to apply a displacement deposit of zinc, since adherent deposits may
be made from zincate baths, and then to deposit further coatings as on any zinc surface. Plating
on magnesium likewise requires special procedures to avoid displacement.
Large quantities of steel wire are copper- or copper-tin-plated by displacement from acid sulfate
solutions; the thin plate serves as a lubricant in drawing. Displacement tin coatings on aluminum
pistons protect them during "running in."
The treatment of bright zinc baths with zinc dust is based on displacement to remove all metals
having potentials less negative than that of zinc; purification can be made virtually complete.
The metal dust method does not work well for other metals, because the more negative cations are
not removed and may be quite deleterious, whereas, if zinc dust is used, the zinc dissolved in the
bath is usually undesirable. Moreover, some metals, such as nickel, are so sluggish as electrodes
(small exchange currents) that displacements are seldom complete.

7.9 Effects of Impurities

It is so extraordinarily difficult to obtain and maintain electroplating baths truly free from
impurities that this is hardly ever achieved, even in the laboratory. Accordingly the effects of
impurities need to be recognized. Those which are insoluble, such as dust, debris from polishing
or other preparatory treatments of the metal surfaces, lubricants, undissolved material from the
anodes, and fragments of deposited "trees", frequently occur as suspended particles which may
attach themselves to the cathode. The deposit grows around them, and a pit is left if they later
fall out, or a nodule if they become completely embedded. Agitation of baths may stir up
particles which have previously settled to the bottom.
It has long been felt that pores and discontinuities which account for the failure of nickel and
other coatings to show the same corrosion resistance as solid sheets of the pure metal result from
suspended matter. Efforts to obtain pore-free coatings by scrupulous filtration and protection of
the bath have had only limited success. Actually, defects in the coatings may have structural
origins even in the absence of suspended matter.
Soluble organic substances (which are necessarily somewhat polar) are more or less strongly
adsorbed at the cathode, with undesirable effects in most instances. Fortunately the tendency to
be adsorbed makes them removable at a surface if sufficient area is available to adsorb enough of
the impurity. Activated charcoal or clay provides suitably large surface areas with relatively
small bulk. Bright-plating baths are especially sensitive if the contaminant is preferentially
adsorbed; they are treated periodically or continuously to remove such substances. Brightening
agents are also removed and must be restored to the bath.
Anionic impurities have very specific effects. If, like phosphates, fluorides, or carbonates in
high concentration, they cause precipitation of metal salts, they produce suspended matter, if, like
nitrates, their reduction potential is less negative than that of the metal, they are reduced at the
cathode, lowering the efficiency and often altering the structure of the deposit; or they may
oxidize addition agents. Chlorides or cther halides usually alter polarization and affect the
internal stresses in the deposits.
Cations with less negative reduction potentials than the metal to be deposited, although quite
deleterious, are usually plated out fairly rapidly, mainly by displacement on both anodes and

— 82 —
cathodes. During this process displacement deposits may become detached and form suspended
particles in the bath with resultant roughness of the electrodeposit. When present in very small
amounts, such metals may be deposited as alloying constituents and may influence the form and
structure of the deposit. If these metals occur as impurities in anodes, they enter the bath
continuously and their effects therefore persist.
The ions of metals of more negative potential than the main metal are not, usually deposited,
but they may have profound effects. Small concentrations of zinc and cadmium in nickel baths
produce brightness and streaking in the deposit. The action of brightening agents may be either
interfered with or enhanced. Even ions such as sodium, potassium, and ammonium, which cannot,
be deposited, influence internal stresses through their roles in the double layer. Some metals are
removed by operation at low current densities on "dummy" cathodes; but this will only be
effective if the anodes are free from the undesired metal.
Finally, iron (III) ion may be reduced at the cathode to iron(II) ion, which becomes reoxidized
either at the anode or by oxygen from dissolved air. Repetition of this alternate reduction and
oxidation constitutes nonproductive use of current and lowers efficiency. Inasmuch as iron salts
are continually introduced on the surfaces of steel parts as residues from cleaning operations, iron
is almost always present. It may be removed from acid baths by oxidizing it, raising the pH to
precipitate the hydroxide, and filtering it off; often other impurities are also removed, adsorbed on
the hydroxide. Fortunately, this difficulty is seldom troublesome in practice, since the reduction
potential, determined by the ratio of Fe+++ to Fe++, generally lies beyond the range of actual
cathode potentials.
In research on electrode kinetics, exacting and tedious purification procedures are essential to
obtain reproducible results on which interpretation can be based. On the other hand, the technical
plater must deal with systems badly contaminated (from the kineticist's point of view) by
unknown substances. Consequently, technical practice must continue as an empirical art to some
extent; yet many deductions from kinetic studies (for example, the composition of the double layer)
will be of great significance when transferred to technical situations.

7.10 Anodes
At the anode metal usually dissolves in its lowest stable oxidation state. If, however, the metal
can form an impermeable, insoluble film of oxide or other compound, it may do so, especially if
the potential at the anode becomes somewhat high. The filming of copper anodes in cyanide
baths has already been discussed. Nickel may form oxide films (passivity); these conduct current,
but oxidize water rather than dissolve metal, because access of the solution to oxidizable metal is
excluded; the bath accordingly becomes depleted in nickel while the acidity increases. Chloride
ions are added to prevent formation of the passive film. With stannate baths the oxide film gives
rise to a higher potential so that tin dissolves in the 4-valent state. The insolubility of lead anodes
in chromic acid baths is due to lead oxide films and in sulfate baths to lead sulfate films. Oxide
films account for the passivity of the noble metals (such as platinum) as anodes, and of more
active metals, such as iron, in alkaline baths.
Even the purest anodes are more or less prolific sources of suspended matter, which may lead to
nodules and trees, or to roughness caused by inclusions in the deposit. This behavior results
from the fact that certain grains or grain boundaries in the anode metal are dissolved more rapidly

— 83 —
than others, with the consequence that other grains are undercut before being completely dissolved.
After they are loosened, they may become attached to the cathode and cause nodules or holes in
the deposit. Less active impurities in the anode may also form undissolved particles. The use of
anode bags, diaphragms, and continuous filtration of the bath is intended to control these and other
particles.
Anodes may undergo chemical attack both during idle periods and when the bath is in use.
Thus in Sulfate baths zinc anodes are dissolved by acid; and copper anodes are oxidized by
dissolved atmospheric oxygen in the presence of the customary acid. In cyanide baths dissolution
of the anodes may be quite marked, depending on the amount of available cyanide ion and the rate
at which oxygen diffuses from air at the surface of the bath through the solution to the anodes.
Since in these baths current efficiencies are often higher at the anode than at the cathode, metal
may dissolve more rapidly by these two processes than it is lost from the bath by deposition and
drag-out. Hence in certain instances insoluble anodes are used to diminish the metal
concentration.
The use of such insoluble anodes at the same potential as soluble anodes will not serve to
correct high metal concentration because the potential required to liberate oxygen (usually the
only reaction at these anodes) is about 1 V more positive than that required to dissolve the soluble
anode; consequently all the current will flow from the soluble anodes alone and dissolve them as
rapidly as if the insoluble anodes were omitted (unless a new reaction sets in). The decrease in
soluble anode surface will diminish chemical attack; but the insoluble anodes are useless even to
improve current distribution for they cannot carry current unless a higher potential is supplied
through a separate circuit. This same effect permits the use of lead-covered contacts anodes in
sulfate baths; no current will flow from the contact as long as there is a soluble anode in the circuit.
At the same time, the conducting lead cannot function as a cathode during idle periods, which
function would allow zinc, for example, to displace hydrogen from the bath, because of the high
overvoltage of hydrogen on lead; this prevents contact with lead from accelerating the attack of
the bath on the zinc, as copper would.
Many difficulties with anodes may be averted by using insoluble anodes, and by replenishing
the bath separately with appropriate chemicals. This method, which may become economical
when the metal oxide is sufficiently less costly than the metal itself, incurs difficulties in control of
pH at the cathode.

7.11 Periodic Reverse Current

In recent years periodic reversal (PR) of current has been practiced in certain baths. The
reversals are commonly made at intervals of a few seconds and of course involve fewer coulombs
(although usually comparable current densities) than those used for depositing. During reverse
flow, polarization effects are partially dispelled, particles which may have attached themselves
owing to their charges may be thrown off, and prominent crystals starting, to rise above the level
of the cathode surface are in part dissolved and leveled. Films of brightening agents are
modified. These effects depend on diffusion and migration, which are relatively slow; hence the
superimposition of ordinary 60-cycle alternating current, although occasionally recommended, has
had little acceptance, and more extended reverse periods are better. In general, periodic reversal is
employed to improve leveling, distribution, and brightness of the deposit, on both micro- and

— 84 —
macro-scales.

7.12 Hydrogen Embrittlement

With many metals hydrogen is codeposited, although perhaps in traces. Since hydrogen is
produced first in the atomic state, it is readily adsorbed by the basis metal. Steels are more or
less susceptible to embrittlement by absorbed hydrogen, depending on analysis and metallurgical
treatment. The nature of the embrittlement is not understood, but at least in part it is the result of
interference of the hydrogen atoms with the normal flow or slip of the lattice planes under stress.
If microscopic voids occur in the basis metal, hydrogen may accumulate in molecular form at
pressures exceeding the tensile strength of the metal, and develop blisters within it. If
weaknesses exist in the bond between the plate and the basis metal, blisters may also develop here.
Hydrogen embrittlement is most marked in deposition from cyanide baths; acid baths generally
give less trouble. Hydrogen embrittlement may result largely from acid dips in the cleaning
cycle; the gas does not diffuse out before the coating is applied and is therefore sealed in by such
deposits as zinc or cadmium, which are relatively impermeable. Baking partially relieves the
difficulty. The hydrogen embrittlement problem is complex, apparently involving several
mechanisms.

— 85 —
 Appendix
Appendix 1. Chemical Compounds

Name Formulas Formula weight

Acid
Acetic CH3COOH 80.05
Arsenious As2O3 197.82
Boric H2BO3 61.84
Chlorosuric HAuCl4•4H2O 412.10
Chloroplatinic H2PtCl4•6H2O 518.08
Chromic CrO3 100.01
Citric H2C2H4O7•H2O 210.14
Formic HCOOH 48.03
Fluoboric HBF4 87.83
Hydrobromic HBr 80.92
Hydrochloric HCl 36.46
Hydrofluoric HF 20.01
Molybdic MoO3 143.95
Nitric HNO3 63.02
Oxalic H2C2O4•2H2O 126.07
Perchloric HClO 4 100.46
Perrhenic HReO4 251.32
Phosphoric H3PO4 98.00
Pyrophosphoric H 2 P 2 O7 177.99
Silicic SiO2• X H2O
Sulfamic HSO2•NH3 97.09
Sulfuric H2SO4 98.08
Tartaric (CHOHCOOH) 2 150.09
Tungstic WO2 231.92
Aluminum Al 26.97
Chloride, anhyd. AlCl3 133.34
Chloride AlCl3•6H2O 241.43
Oxide Al2O3 101.94
Potassium sulfate AlK(SO4)2 258.19
AlK(SO4)2•12H2O 474.38
AlK(SO4)2•24H2O 690.57
Sulfate, anhyd. Al2(SO4)3 342.12
Sulfate Al2(SO4)3•18H2O 666.41

— 86 —
Ammonium sulfate
Acetate NH4C2H2O2 77.08
Aluminum sulfate (NH4)Al2(SO4)4•24H2O 906.64
Bifluoride NH4HF2 57.05
Carbonate (NH4)3CO3•H2O 114.09
Chloride NH4Cl 53.50
Fluoborate NH4BF4 104.86
Hydroxide NH 4OH 35.05
Molybdate NH4MoO4 195.08
Nitrate NH4NO3 80.05
Persulfate (NH4)2S2O6 228.20
Sulfamate NH4(SO3•NH2) 114.13
Sulfate (NH4)2SO4 132.14
Sulfide (NH4)2S 68.14
Thioeyanate NH4CNS 76.12
Thiosulfate (NH4)2S2O3 148.20
Antimony Sb 121.76
Trichloride SbCl 3 228.13
Trifluoride SbF3 178.76
Trioxide Sb2O3 291.52
Sulfide, tri Sb2S3 339.70
Sulfide, penta Sb2O5 403.82
Arsenic As 74.91
Trichloride AsCl3 181.23
Trioxide As2O3 197.82
Barium Ba 137.36
Carbonate BaCO3 197.37
Chloride BaCl2•2H2O 244.31
Cyanide Ba(CN)2•2H2O 225.42
Hydroxide Ba(OH) 2•8H2O 315.50
Nitrate Ba(NO3)2 261.38
Sulfate BaSO4 233.42
Sulfide BaS 169.42
Bismuth Bi 209.00
Trichloride BiCl2 315.37
Trioxide Bi2O3 466.00
Cadmium Cd 112.41
Cyanide Cd(CN)2 164.43
Fluoborate Cd(BF4)2 236.05
Nitrate Cd(NO2)2•4H2O 308.49

— 87 —
 Oxide CdO 128.41
Sulfate CdSO4 208.47
Calcium Ca 40.08
Carbonate CaCO3 100.09
Chloride, anhyd CaCl2 110.99
Chloride CaCl2•2H2O 147.03
Cyanide Ca(CN)2 92.12
Fluoride CaF2 78.08
Hydroxide Ca(OH)2 74.10
Nitrate Ca(NO3)2•4H2O 236.16
Oxide CaO 56.08
Sulfate 2CaSO4•H2O 200.30
CaSO4•2H2O 172.17
Chromium Cr 52.01
Potassium sulfate Cr2(SO4)2•K2SO4•24H2O 908.84
Trioxide CrO3 100.01
Cobalt Co 58.94
Ammonium sulfate Co(NH4)2(SO4)2•6H2O 395.24
Carbonate CoCO3 118.95
Chloride CoCl2•6H2O 237.95
Fluoborate Co(BF4)2 232.58
Sulfate CoSO4•7H2O 231.11
Copper Cu 63.57
Cupic
Acetate Cu(CH3COO)2•2H2O 199.67
Carbonate, basic CuCO3•Cu(OH)2 221.17
Chloride CuCl2 134.38
Cuprosulfite CuSO3•Cu2SO3•2H2O 336.36
Fluoborate Cu(BF 4)2 237.21
Nitrate Cu(NO3)2•3H2O 241.63
Oxide CuO 79.57
Pyrophoaphate Cu2P3O7•3H2O 355.15
Sulfate CuSO4•5H2O 249.71
Cuprous
Chloride CuCl 99.03
Cupricsulfite Cu2SO3•CuSO3•2H2O 393.38
Cyanide CuCN 89.69
Gallium Ga 69.72
Hydroxide Ga(OH) 2 120.75
Gold Au 197.2

— 88 —
 Auric
Acide chloride HAuCl4•4H2O 412.10
Chloride AuCl3 303.57
Chloride, dihydrate AuCl 3•2H2O 321.59
Aurous
Cyanide AuCN 232.65
Potassium cyanide, anhyd. KAu(CN)2 288.33
Potassium cyanide KAu(CN)2•2H2O 324.36
Sodium cyanide NaAu(CN)2 272.21
Hydrogen H2 2.016
Peroxide H 2 O2 34.02
Indium In 114.76
Chloride InCl2 221.13
Fluoborate In(BF 4)2 375.22
Hydroxide In(OH) 2 165.78
Sulfamate In(SO3•NH3)3 403.03
Sulfate In2(SO4)2 517.70
Iridium Ir 193.10
Tetrachloride IrCl4 334.93
Trichloride IrCl 3 299.47
Iron Fe 55.85
Ferric
Chloride, anhyd. FeCl3 162.22
Chloride FeCl3•6H2O 270.32
Fluoride FeF3 112.85
Fluoborate Fe(BF 4)3 316.31
Nitrate Fe(NO3)3•9H2O 404.02
Oxide Fe2O3 157.70
Potassium ferricyanide K3Fe(CN)3 329.25
Ferrous
Ammonium sulfate FeSO4(NH4)2SO4•6H2O 392.16
Chloride, dihydrate FeCl2•2H2O 144.78
Chloride, tetrahydrate FeCl2•4H2O 198.83
Fluoborate Fe(BF 4)2 230
Potassium ferrocyanide K4Fe(CN)4 422.39
Sulfate FeSO4•7H2O 278.03
Lead Pb 207.21
Acetate Pb(CH3COO)2•3H2O 379.35
Basic carbonate 2PbCO 3•Pb(OH)2 775.67
Dioxide PbO2 239.21

— 89 —
 Fluoborate Pb(BF4)2 380.85
Fluosilicate PbSiF4 463.27
Monoxide PbO 223.31
Nitrate Pb(NO3)2 331.24
Sulfamate Pb(SO3NH2)2 399.39
Magnesium Mg 24.32
Carbonate MgCO3 84.33
Chloride MgCl2 95.23
Fluoride MgF2 52.32
Hydroxide Mg(OH) 2 58.34
Sulfate MgSO4•7H2O 246.50
Manganese Mn 54.93
Potassium permanganate KMnO4 158.03
Manganic
Dioxide MnO2 86.93
Manganous
Chloride MnCl2•4H2O 197.91
Sulfate MnSO4•H2O 169.01
Mercury Hg 200.61
Mercuric
Chloride HgCl2 271.52
Cyanide Hg(CN)2 252.65
Nitrate Hg(NO3)2•H2O 342.65
Oxide HgO 216.61
Sulfate HgSO4 298.67
Mercurous
Chloride HgCl 236.07
Nitrate HgNO3•H2O 280.63
Sulfate Hg2SO4 497.28
Nickel Ni 58.69
Acetate Ni(CH3COO)2•4H2O 248.84
Ammonium sulfate NiSO4(NH4)2SO4•6H2O 394.99
Carbonate, basic 2NiCO3•3Ni(OH)2•4H2O 587.58
Chloride NiCl2•6H2O 237.70
Cyanide Ni(CN)2•4H2O 182.79
Fluoborate Ni(BF 4)2 232.33
Formate Ni(HCOO)2•2H2O 184.76
Hydroxide Ni(OH) 2 92.71
Oxide NiO 74.69
Sulfamate Ni(SO3•NH2)2 250.85

— 90 —
 Sulfate
Hexahydrate NiSO4•6H2O 262.85
Heptahydrate NiSO4•7H2O 280.87
Palladium Pd 106.7
Chloride PdCl 2•2H2O 213.65
Chloride, sodium PdCl 2•2NaCl•3H2O 348.57
Cyanide Pd(CN)2 158.72
Nitrite, potassium K2Pd(NO2)4 368.92
Platinum Pt 195.23
Chloride PtCl4•2HCl•6H2O 518.08
Diamminonitrite Pt(NH2)2•(NO2)2 321.31
Potassium K 39.10
Acetate K(CH2COO) 98.14
Acid tartrate KHC4H4O6 188.18
Bifluoride KHF3 78.10
Bisulfate KHSO4 136.16
Carbonate, anhyd. K2CO3 138.20
Carbonate K2CO3•3/2H2O 165.23
Chlorate KClO4 122.58
Chloride KCl 74.55
Chromate K2CrO4 194.20
Copper cyanide K2Cu(CN)3 219.78
Cyanide KCN 65.11
Dichromate K 2Cr2O7 294.21
Ferricyanide K3(FeCN)5 329.25
Ferrocyanide K4(FeCN)6 422.39
Fluoborate K(BF4) 125.92
Fluoride, anhyd. KF 58.10
Fluoride KF•2H2O 94.13
Gold cyanide, anhyd. KAu(CN)2 288.33
Sodium Na 23
Phosphate
Monobasic NaH2PO4•H2O 138.01
Dibasic Na2HPO4•7H2O 258.09
Tribasic Na3PO4•12H2O 380.16
Potassium tartrate NaK(C6H6O6) •4H2O 282.23
Pyrophosphate, anhyd. Na4P2O7
266.02
(tetrasodium)
Pyrophosphate (tetrasodium) Na 4P2O7•10H2O 446.11
Sesquicarbonate Na2CO3•NaHCO3•2H2O 226.04

— 91 —
 Sesquisilicate Na2Si2O7•11H2O 504.28
Silicate
Meta Na2SiO3 122.05
Ortho Na4SiO4 184.05
Stannate Na2Sn(OH)4 266.74
Sulfamate NaSO3•NH3 119.09
Sulfate Na2SO4•10H2O 322.21
Sulfide Na2S•9H2O 240.20
Tetraborate Na 2B4O7•10H2O 381.43
Tetraphosphate Na 4P4O12 470.09
Thiocyanate NaCNS 81.08
Thiosulfate Na2S2O3•5H2O 248.21
Tripolyphosphate Na 2P3O10 367.93
Tungstate Na2WO4 293.91
Zincate Na2ZnO2 143.38
Tin Sn 118.70
Stannic
Potassium stannate K2Sn(OH)6 298.94
Sodium stannate Na2Sn(OH)6 266.74
Stannous
Chloride SnCl2•2H2O 225.65
Fluborate Sn(BF4)2 292.34
Sulfate SnSO4 214.76
Oxide SnO 134.70
Chlordide, chloride SnCl 2 189.61
Zinc Zn 65.38
Ammonium chloride ZnCl2•2NH4Cl 243.29
Chloride ZnCl2 136.29
Cyanide Zn(CN)2 117.39
Fluoborate Zn(BF4)2 239.02
Oxide ZnO 81.38
Sulfate ZnSO4•7H2O 287.56
Tungsten W 183.92
Sodium tungstate Na2WO4 293.91
Trioxide WO3 231.92

— 92 —
 Appendix 2. International Atomic Weights

Atomic Atomic Atomic Atomic

Element Symbol Element Symbol
number weight number weight
Actinium Ac 89 227 Neodymium Nd 60 144.27
Aluminum Al 13 26.98 Neon Ne 10 20.183
Americium Am 95 241 Neptunium Np 93 237
Antimony Sb 51 121.76 Nickel Ni 28 58.96
Argon A 18 39.944 Niobium Nb 41 92.91
Arsenic As 33 74.91 Nitrogen N 7 14.008
Astatine At 85 210 Osmium Os 76 190.2
Barium Ba 56 137.36 Oxygen Os 8 16.0000
Beryllium Be 4 9.013 Palladium Pd 46 106.7
Bismuth Bi 83 209 Phosphorus P 15 30.975
Boron B 5 10.82 Platinum Pt 78 195.23
Bromine Br 35 79.916 Plutonium Pu 94 239
Cadmium Cd 48 112.41 Polonium Po 84 210
Calcium Ca 20 40.08 Potassium K 19 39.10
Carbon C 6 12.010 Praseodymium Pr 59 140.92
Cerium Ce 58 140.13 Promethium Pm 61 147
Cesium Cs 55 132.91 Protactinium Pa 91 231
Chlorine Cl 17 35.457 Radium Ra 88 226.05
Chromium Cr 24 52.01 Radon Rn 86 222
Cobalt Co 27 58.94 Rhenium Re 75 186.31
Copper Cu 29 63.54 Rhodium Rh 45 102.91
Curium Cm 96 242 Rubidium Rb 37 85.48
Dysprosium Dy 66 162.46 Ruthenium Ru 44 101.7
Erbium Er 68 167.2 Samarium Sm 62 150.43
Europium Eu 63 152.0 Scandium Sc 21 44.96
Fluorine F 9 19.00 Selenium Se 34 78.96
Francium Fr 87 223 Silicon Si 14 28.09
Gadolinium Gd 64 156.9 Silver Ag 47 107.88
Gallium Ga 31 69.72 Sodium Na 11 22.997
Germanium Ge 32 72.6 Strontium Sr 38 87.63
Gold Au 79 197.2 Sulfur S 16 32.066
Hafnium Hf 72 178.6 Tantalum Ta 73 180.88
Helium He 2 4.003 Technetium Tc 43 99
Holmium Ho 67 164.94 Tellurium Te 52 127.61
Hydrogen H 1 1.0080 Terbium Tb 65 159.2
Indium In 49 114.76 Thallium Tl 81 204.39
Iodine I 53 126.91 Thorium Th 90 232.12
Iridium Ir 77 193.1 Thulium Tm 69 169.4
Iron Fe 26 55.85 Tin Sn 50 118.70
Krypton Kr 36 83.8 Titanium Ti 22 47.90
Lanthanum La 57 138.92 Uranium U 92 238.07
Lead Pb 82 207.21 Vanadium V 23 50.95
Lithium Li 3 6.940 Wolfram(Tungsten) W 74 183.92
Lutetium Lu 71 174.99 Xenon Xe 54 131.3
Magnesium Mg 12 24.32 Ytterbium Yb 79 173.04
Manganese Mn 25 54.93 Yttrium Y 39 83.92
Mercury Hg 80 200.61 Zinc Zn 30 65.38
Molybdenum Mo 42 95.95 Zirconium Zr 40 91.22

— 93 —
 Appendix 3. Commonly Used Names For Chemicals

Commonly Used Chemical Names or Commonly Used Chemical Names or

Names Compound Names Composed
Alum Potassium aluminum Gypsum Calcium sulfate, CaSO4·2H2O
sulfate K3Al(SO4)4·24H2O Hypo Sodium thiosulfate, Na2S2O3•5H2O
(varies) Lime Calcium oxide, CaO
Litharge Lead monoxide, PbO
" Aloxite" 
Alumina  Aluminum oxide, Al2O3 Liver of sulfur Potassium polysulfide, KS
" Alundum"
Marble Calcium carbonate, CaCO3
Aqua fortis Nitric acid Metao Sodium metasilicate,
Aqua regia Nitric acid(1 part) + Na 2SiO2·5HO2
Hydrochforic acid(3 Parts) Milk of lime Calcium hydroxide, Ca(OH)
Baking soda Sodium bicarbonate, Muriatic acid Hydrochloric acid, HCl
NaHCO3 Oil of vitriol Acid sulfuric,H2SO4
Bleaching powder Calcium hypochlorite, Pearl ash Potassium carbonate, K2CO3
CaOCl2 Plaster of Paris Calcium sulfate, 2CaSO4·H2O
Blue dip Solution of mercury salt Quick lime Calcium oxide, CaO
Boracic acid Boric acid Quicksilver Mercury

Blue atone
}
Blue vitriol
Copper sulfate, CuSO4·5HO2
Rocbelle salt Sodium potassium tartrate,
NaK(C4H4O4) ·4HO2
Borax Sodium tetraborate, Rouge Iron oxide, Fe2O3
Na2B4O7·10HO2 Sal ammoniac Ammonium chloride, NH4Cl
Butter of antimony Antimony trichloride, SbCl3 Single nickel salt Nickel sulfate,
Calcite Calcium carbonate, CaCO3 NiSO4·6HO2 or NiSO4·7HO2
Calomel Mercurous chloride, Hg2Cl2 Slaked lime Calcium hydroxide, Ca(OH)2
“Carborundum” Silicon carbide, SiC Soda ash Sodium carbonate，Na2CO3
Caustic potash Potasaium hydroxide, KOH Sour water Dilute sulfuric acid
Caustic soda Sodium hydroxide, NaOH Sugar of lead Lead acetate, Pb(CH4COO)2
Chalk Calcium carbonate, CaCO3 TSP Trisodium phosphate, Na3PO4
Chevereul salt Cupro cupricsulfite Washing soda Sodium carbonate, Na2CO3·10HO2
Cu2SO4CuSO4·2HO2 Water glass Sodium ailicate solution
Chloride of lime Calcium hypochlorite, Wood’s metal Low melting - temperature alloy,
CaOCl2 e.g, 4pts Bi,2pts Pb,1pt Sn, 1pt Cd
Common salt Sodium chloride,NaCl Vienna lime Calcium carbonate, CaCO3
Copperas Ferrous sulfate, FeSO4·7HO2 Glauber’s salt Sodium sulfate, Na2SO4·10H2O
Cream of tartar Potassium acid tartrate, Epsom salt Magnesium sulfate, MgSO4·7HO2
KH(C4H4O4) Flowers of sulfur Sulfur, S
Double nickel salt Nickel ammonium sulfate, Emery Aluminum oxide, Al2O3
NiSO4(NH4)2SO4·6HO2 Fluorspar Calcium Suoride, CaF2

— 94 —
Appendix 4. Greek Letters

Appendix 5. 常用数学符号

a2 a square 或 a squared
b3 b cube 或 b cubed
c4 c (raised) to the fourth (power)
f –1 f to the minus one
0.4 zero(或 nought) point four
0.01 point(或 decical) nought one
10.34 ten point three four

40 the square (或 second ) root of forty

3 the cub（或 third）root of one hundred and twenty

120
10×8 feet ten by eight feet (意为：十呎长，八呎宽)

— 95 —
≌ be congruent with; approximately equal 全同于，近似于
～ equivalent to 相当于
Π=3.1415926536… the ratio of the circumference of a circle to the diameter 圆周率
e=2.7182818285… the base of natural logarithm 自然对数的底
∞ infinity 无穷大

i= − 1 the unit of imaginary numbers 虚数单位

n! the factorial of n ｎ的阶乘

[x] the greatest integer not greater than x 不大于ｘ的最大整数
∝ varies directly as 正比于

log a, log10 a common logarithm 常用对数

ln a, log e a natural logarithm 自然对数

﹙a,b﹚ the open interval a<x<b 开区间

［a,b］ the closed interval a<=x<=b 闭区间
﹙a,b］ the interval a<x≤b 半开区间
［a,b］ the interval a≤x<b 半开区间
n n

∑
i =1
,∑
1
sum to n terms ｎ项的和

n n

∏i =1
,∏
1
product to n terms ｎ项的乘积

lim sup, lim superior limit 上极限

lim inf, lim inferor limit 下极限
f(x) the function of x x 的函数

lim f ( x) the limit of f(x) as x approaches to a

x → a
当 x 趋近于 a 时 f（x）的极限

Δy the increment of y y 的增量

dy the differential of y y 的微分
dy the derivative of y with respect to x
, y' , Dx y
dx y 对 x 的导数

d n y ( n) the nth derivative of y with respect to x

,y
dx n y 对 x 的 n 阶导数

表示
lim U n
Un=o(Vn) n → ∞
Vn

sin sine 正弦
cos cosine 余弦
ta tangent 正切
cot, ctg cotangent 余切

— 96 —
 sec secant 正割
csc cosecant 余割
arcsin,sin-1 arc sine 反正弦
arccos,cos-1 arc cosine 反余弦
arctan, arctg, tan-1,tg-1 arc tangent 反正切
arccot, arcctg, cot-1,ctg-1 arc cotangent 反余切
arcsec,sec-1 arc secant 反正割
arccsc, csc-1 arc cosecant 反余割
sinh hyperbolic sine 双曲正弦
cosh hyperbolic cosine 双曲余弦
tanh hyperbolic tangent 双曲正切
coth hyperbolic cotangent 双曲余切
sech hyperbolic secant 双曲正割
csch hyperbolic cosecant 双曲余割

Appendix 6. 度 量 衡 表

1. Length 长度
micron(µ) (微米) =1/1,000,000 m =10 -6m (米)
centimillimetre(cmm) (忽米) =1/100,000m =10 -5m (米)
decimillimetre(dmm) (丝米) =1/10,000m =10 -4m (米)
millimetre(mm) (毫米) =1/1,000m =10 -3m (米)
centimetre(cm) (厘米) =1/100m =10 -2m (米)
decimetre(dm) (分米) =1/10m =10 -1m (米)
metre(m) (米) =1m(米)
decametre(dam) (十米) =10m =10m (米)
hectometre(hm) (百米) =100m（米的百倍）=102m (米)
kilometre(km) (千米) =1,000m（米的千倍）=103m (米)

2. Area 面积
square millimeter (mm2) (平方毫米) =1/1,000,000(平方米)=10-6 m2
square centimeter (cm 2) (平方厘米) =1/10，000(平方米)= 10 -4 m2
square decimeter (dm2) (平方分米) =1/100(平方米)= 10-2 m2
square metre (m2) (平方米) =1(平方米)=1m2
square decametre (dam2) (平方米) =1(百平方米)=102 m2
square hectometre(hm2) (万平方米) =1/100(平方公里)= 10 2m2
square kilometre(km2)(平方公里) =1(平方公里)= 1km2
square metre (m2) (平方米) =1 centiare(公厘)
centiare（ca）(公厘) =1/100 are(公亩)
are（a）(公亩) = 1/100 hectare(公顷)
hectare（ha）(公顷) =100ares(公亩)

— 97 —
3.Volune 体积
cubic millimetre (mm3)(立方毫米)
cubic centimetre (cm3)(立方厘米)
cubic decimetre (cm3)(立方分米)
cubic metre (m3)(立方米)
=1/1,000 cm3(立方厘米)=10-9m3
= dm3(立方分米)=10-6m3
=1/1，000 m3(立方米)=10-3m3
=1,000 dm3(立方分米)=1m3

4.Capacity 容量
milliliter(ml) (毫升) = 1/1,000 l（升）
centiliter(cl) (厘升) = 1/100 l（升）
deciliter(ml) (分升) = 1/10 l（升）
liter(l) (升) = 1 l (升)
decaliter(dal) (十升) = 10 1（升）
hectoliter(hl) (百升) =100 1（升）
kiloliter(kl) (千升) =1,000 1（升）

5.Weight 重量（质量单位同）
milligramme(mg) (毫克) =1/1,000 g (克)
centigramme(cg) (厘克) =1/100 g (克)
decigramme(dg) (分克) =1/10 g (克)
gramme(g) (克) =1 g (克)
decagramme(dag) (十克) =10 g (克)
hectogramme(hg) (百克) =100 g (克)
kilogramme(kg) (千克) =1000 g (克)
quintal(q) (公担) =100 kg (公斤)
metric ton (M,T,),tonne(t) (公吨) =1,000 kg (公斤)

Appendix 7. 度量衡比较表

1. Length 长度
公 制 市 制 英 美 制
1 meter (米) = 3 chi (市尺) = 1.0935 yd. (码)
10 meters (米) = 3 zhang (丈) = 10.936 yd. (码)
1 kilometer (km) (公里) = 2 li (市里) = 1,093.6 yd. (码)

市 制 公 制 英 美 制
1 chi (市尺) = 1/3 meter (米) = 1.0936 ft. (呎)
1 li (里) = 0.5 kilometer (公里) = 0.3107 mile (哩)

英 美 制 公 制 市 制
1 in. (吋) = 2.54cm (厘米) = 0.762 cun (市吋)
1 ft. (呎) = 0.3048 m (米) = 0.9144 chi (市尺)
1 yd. (码) = 0.9144 m (米) = 2.7432 chi (市尺)
1 mi. (哩) = 1.6093 km (公里) = 3.2187 li (里)

— 98 —
2.Area 面积
公 制 市 制 英 美 制
1 square meter (平方米) = 9 sq. chi (平方尺) = 1.196 sq. yd. (平方码)
1 are (公亩) = 900 sq. chi (平方尺) = 119.6 sq. yd. (平方码)
1 square kilometer(平方公里) = 4 sq. li (平方里) = 0.386 sq. mi. (平方哩)
1 hectare (ha.) (公顷) = 15 mu (亩) = 2.471 acres (英亩)

市 制 公 制 英 美 制
1 mu (亩) = 1/15 hectare (公顷) = 0.1644 acre (英亩)

英 美 制 公 制
1 sq. in. (平方吋) = 6.452 cm2 (平方厘米)
1 sq. ft. (平方呎) = 929 cm2 (平方厘米)
1 sq. yd. (平方码) = m2 (平方米)

英 美 制 市 制 公 制
1 acre (英亩) = 6.07 mu (亩) = 40.4687 ares (公亩)
640 acres (英亩) = 10.36 sq. li (平方里) = 2.59 km2 (平方公里)
1 sq. mi. (平方哩) = 2.59 km2 (平方公里)
1 township (区) = 93.24 km2 (平方公里)

3. Capacity 容量
公 制 市 制 英 美 制
1 deciliter (分升) = 1 he (市合)
1 liter (升) = 1 sheng (市升) = 0.264 U.S. gallon (美制加仑)
= 0.9081 dry quart (干量夸脱)
= 1.0567 liquid quart (液量夸脱)
10 l. (升) = 1 dou (市斗)
100 l. (升) = 1 shi (市石) = 2.838 bushels (蒲式耳)
= 26.418 gallons (加仑)

市 制 公 制 英 美 制
1 sheng (升) = 1 liter (升) = 0.22 British gallon (英制加仑)

4. Weight 重量
公 制 市 制 英 美 制
1 gram (克) = 2 fen (市分) = 0.0355 oz. (唡)
100 grams (克) = 2 liang (市两) = 3.55 oz. (唡)
1 kilogram (公斤) = 2 jin (市斤) = 2.2046 lb. (磅)
1 quintal (公担) = 2 dan (市担) = 2,204.6 lb. (磅)

— 99 —
 市 制 公 制 英 美 制
1 liang (两) = 50 grammes (克) = 1.7657 oz. (唡)
1 jin (市斤) = 0.5 kg. (公斤) = 1.1023 (磅)
1 dan (市担) = 50 kg. (公斤) = 0.0492 long ton (英吨)
= 0.0551 short ton (美吨)

英 美 制 公 制
1 lb. (磅) = 0.4536 kg. (公斤)
1 short ton (美吨) = 0.90713 metric ton (公吨)
1 long ton (英吨)
=1.120 short tons (美吨)

5. Density
1 g. per cu. cm. (克/ 厘米 3)
1 kg. per cu. meter (公斤/米 3)
1 lb. per cu. in. (磅/吋 3)
1 lb. per cu. ft. (磅/呎 3)
= 0.03613 lb. per cu. in. (磅/吋 3)
= 0.06243 lb. per cu. ft. (磅/呎 3)
= 27,680 g. per cu. cm. (克/ 厘米 3)
= 16.018 (公斤/米 3)

6. Force 力
1,000,000 dynes (达因) = 2.2181 lb. (磅) = 1.020 kg. (公斤)
1 kg. (公斤) = 2.2046 lb. (磅) = 980,665 dynes (达因)
1 lb. (磅) = 0.4536 kg. (公斤) = 444,822 dynes (达因)

7. Pressure 压强
1 bar (巴) = 106 (达因/厘米 2)
1 ft. of water (呎水) = 62.4 lb. per sq. ft. (磅/ 呎 2)
= 0433 lb. per sq. in. (磅/ 吋 2)
1 in. of mercury (吋汞) = 1.134 ft. of water (呎水)
= 0.4912 lb. per sq. in. (磅/吋 2)
1 atmosphere (大气压) = 1.013 (巴) =1,013 (毫巴)
= 14.697 lb. per sq. in. (磅/吋 2)
= 33.9 ft. of water (呎水)
1 lb. per sq. ft. (磅/呎 2) = 4.8824 kg. per sq. meter (公斤/米 2)
1 lb. per sq. in. (磅/吋 2) = 0.07031 kg. per sq. cm (公斤/厘米 2)
1 kg. per sq. cm (公斤/厘米 2) = 14.223 lb. per sq. in. (磅/吋 2)
= 32.8 ft. of water (呎水)
1 ton. per sq. ft. (吨/呎 2) = 13,889 lb. per sq. in. (磅/吋 2)

8. Energy 能量
1 ft.-lb. (呎-磅) = 1,356 joules (焦耳) 或 watt-sec. (瓦特-秒)

— 100 —
 1 joules (焦耳) = 10 7 ergs (尔格) =107 dyne-cm. (达因-厘米)

1 horse-power-hr. (英制马力-小时) = 1.98×106 ft.-lb. (呎-磅)

= 0.7457 kw-hr. (千瓦-小时)
= 2544 Btu. (英国热单位)
1 kw-hr. (千瓦-小时) = 1.341 horse-power-hr. (马力-小时)
= 3,411 Btu. (英国热单位)
= 2.654×106 ft.-lb. (呎-磅)
1 Btu. (英国热单位) = 778.4 ft.-lb. (呎-磅) =0.252 kg-cal. (仟-卡)
1 meter-kilogram (米-千克) = 7.233 ft.-lb. (呎-磅)

9. Power 功率
1 horse-power (英制马力) = 33,000 ft.-lb. per min. (呎-磅/分钟)
= 550 ft.-lb. per sec. (呎-磅/秒)
1 horse-power (英制马力) = 0.7457 kw. (千瓦)
= 0.7066 Btu. per sec. (英国热单位/秒)
1 kw. (千瓦) = 1.341 h. p. (英制马力) = 737.5 ft.-lb. per sec. (呎-磅/秒)
1 horse-power = 1.0139 metric horse-power (公制马力)

10. Speed 速率
1 rad. per sec. (弧度/秒) = 9.5496 rev. per min. (转数/分)
= 0.15916 rev. per sec. (转数/秒)
1 rev. per min. (转数/分) = 6 deg. per sec. (度/秒)
1 ft. per sec. (呎/秒) = 0.6818 miles per h. (哩/时)
1 mile per h. (哩/时) =183 ft. per min. (呎/分) = 1.4667 ft. per sec. (呎/秒)

11. Circle 圆周
1 circle (圆周) = 4 quadrants (象限)
1 quadrant (象限) = 90 degree (度)
1 degree (°) (度) = 60 minutes (′) (分)
1 minute (′) (分) = 60 seconds (″) (秒)
1 rad (弧度) = 1/2π circle (圆周)
= 57.2958 deg. (度)
= 3,437.75 min. (分)
= 206,265 sec. (秒)

12. Temperature 温度
Deg. C. (摄氏度数) = (Deg. F. －32)×5/9
Deg. F. (华氏度数) = (1.8×Deg. C.)+32
或:
n ℃ (摄氏度数) = (n×1.8)+32 (华氏度数)
m ℉ (华氏度数) = (m－32) ×5/9 (摄氏度数)

— 101 —
Appendix 8. 美国《化学文摘》中常用缩写词

A ampere 安（培）
Å angstrom unit(s) 埃（波长单位）
abs. absolute 绝对的
Abs. EtOH Absolute Alcohol 无水乙醇
abstr. abstract 文摘
Ac acetyl(CH3CO2 或 CH3COO) 乙酰基
ac alterating current 交流电（流）
Ac.H. acetaldehyde 乙醛
AcOH acetic acid 乙酸
Ac2O acetic anhydride 乙酸酐
AcoEt ethyl acetate 乙酸乙酯
add additive 附加物
addn addition 加成，添加
addnl additional 添加的
alc. alcohol, alcoholic 醇
aliph. aliphatic 脂族的
Al. Hg. aluminum amalgam 铝汞齐
alk. alkaline (not alkali) 碱性的
alky alkalinity 碱度，碱性
am amyl (not ammonium) 戊基
amorph amorphous 无定形的
amp ampere(s) 安（培）
amt. amount (as a noun) 数量
anal. analysis 分析
anhyd. anhydrous 无水的
AO atomic orbital 原子轨道
app. apparatus 仪器，装置
approx approximate, approximately 近似的，大概的
approxn approximation 近似法，概算
aq. aqueous 水的，含水的
arom. aromatic 芳族的
as. asymmetric 不对称的
assoc. associate(s) 缔和
assocd associated 缔合的
assocn association 缔合
at. atomic (not atom) 原子的
atm atmosphere(s), atmospheric 大气压
ATP adenosine triphosphate 三磷酸腺苷酶
at. wt. atomic weight 原子量
av. average (except as a verb) 平均

— 102 —
 沸腾(后面的数字表示温度,
b. (followed by a boils at, boiling at (similarly b13, at 13 mm
figure denoting pressure 同样 b13 表示在 13 毫米压力
temperature) 下沸腾)
bbl barrel 桶（液体量度单位，英国＝
163.5 升，美国＝119 升
BCC. body-centred cubic 体心立方
Bev or Gev billion electron volts 十亿电子伏，千兆电子伏，109
电子伏
BOD biochemical oxygen demand 生化需氧量
μB Bohr magneton 玻尔磁子
b.p. boiling point 沸点
Btu British thermal unit(s) 英制热量单位
Bu butyl (normal) 丁基
bu. bushel 蒲式耳（＝36.3 升）
Bz benzoyl (not benzyl) 苯甲酰
BzH benzaldehyde 苯（甲）醛
BzOH benzoic acid 苯甲酸
C concentration 浓度
Cal. calorie(s) 千卡，大卡
cal. 卡，小卡
calc. calculate 计算
calcd calculated 计算的
calcg calculating 计算
calcn calculation 计算
CC cubic centimeter(s) 立方厘米
CD circular dichroism 圆振二向色性（物）
c.d. current density 电流密度
cf. 参见
chem.. chemical (as an adjective) (not chemistry 化学的
nor chemically)
Ci curie 居里（放射单位）
clin. clinical (ly) 临床的
cm centimeter(s) 厘米
CoA Coenzyme A 辅酶 A
C.O.D. chemical oxygen demand 化学需氧量
coeff. coefficient 系数
col. colour, coloretion 颜色
com. commercial 工业的，商业的，商品的
comb. combustion 燃烧
compd. compound 化合物，复合物
compn. composition 组成，成分
conc concentrate (as a verb) 提浓，浓缩
concd concentrated 浓的
concg. concentrating 浓缩（的）

— 103 —
concn concentration 浓度
cond conductivity 导电率，传导性
const. constant 常数
contg containing 包含，含有
cor corrected 校正的，改正的，正确的
cp. constant pressure 恒压
C.P. chemically pure 化学纯的
crit. critical 临界的
cryst. crystalline (not crystallize) 结晶
crystd crystallize 使结晶
crystg crystallizing 结晶
crystn crystallization 结晶，结晶化
cu. m. cubic meter(s) 立方米
Cv constant volume 恒容
d density 密度
D debye unit 德拜单位，电偶极矩单位
d. dextrorotatory 右旋
d. c. dirext current 直流电
decomp. decompose(s) 分解
decompd decomposed 分解的
decompg decomposing 分解
decompn decomposition 分解
degrdn degradation 降解
deriv. derivative 衍生物，导数（数）
det. determine 测定
detd determined 测定的
detg determining 测定
detn determination 测定
diam. diameter 直径
dil. dilute 稀释，冲淡
dild diluted 稀释的
diltg diluting 稀释
diln dilution 稀释
diss. dissolves, dissolved 溶解
dissoc dissociate(s) 离解
dissocd dissociated 离解的
dissocn dissociation 离解
dist. distil, distillation 蒸馏
distd distilled 蒸馏的
distg distilling 蒸馏
distn distillation 蒸馏
dl deciliter 分升
dm. decimeter(s) 分米
DMF dimethylformamide 二甲基二甲酰胺

— 104 —
DNase deoxyribomuclease 脱氧核糖核酸酶
d.p. degree of polymerization 聚合度
dpm disintegrations per minute 水解量／分钟
DTA differential thermal analysis 差热分析
E.D. effective dose 有效剂量
EEG electroencephalogram 脑电流描记术，脑电图
e.g. for example 例如
elec electric, electrical (not electrically) 电的
e.m.f. electromotive force 电动势
e.m.u. electromagnetic unit 电磁单位
en. ethylenediamine (used in formulas only) 乙二胺
equil equilibrium(s) 平衡
equiv. equivalent 当量
esp. especially 特别，格外
est. estimate (as a verb) 估计
estd estimated 估计的
estg estimating 估计
estn estimation 估计
et ethyl 乙基
ET2O ethyl ether 乙醚
η viscosity 粘度
e.v. electron volt(s) 电子伏
evac. evacuated 抽空的
evap. evaporate 蒸发
evapd evaporated 蒸发的
evapg evaporating 蒸发
evapn evaporation 蒸发
examd examined 检验过的，试验过的
examg examining 检验，试验
examn examination 检验，试验
expt. experiment (as a noun) 实验
eaptl experimental 实验的
ext. extract 提取物，萃取，提取
extd extracted 提取的
extg extracting 提取
extn extraction 提取
F farad 法拉第（电量单位）
fcc face centered cubic 面心立方体
fermn fermentation 发酵
f.p. freezing point 冰点，凝固点
FSH follicle-stimulating hormone 促卵泡激素
ft. foot, feet 英尺
ft-lb foot-pound 英尺磅
g. gram(s) 克

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gm 克
gal gallon 加仑
geol. geological 地质的
gr. grain (weight unit) 谷
（1 谷＝1/7000 磅＝0.64799
克）
h hour 小时
H henry 亨（利）
ha. hectare(s) 公顷
homo- 均匀，单相
hr. hour 小时
hyd. hydrolysis, hydrolysed 水解
hz hertz (cycles/sec) 赫（兹），周／秒
ID infective dose 无效剂量
in. inch(es) 英寸
inorg. inorganic 无机的
insol. insoluble 不溶的
ir infrared 红外的
irradn irradiation 照射
iso-Bu isobutyl 异丁基
iso-Pr isopropyl 异丙基
IU 国际单位
J joule 焦（耳），
K kelvin 绝对温度，开式温度
Kcal. kilocalorie(s) 千卡
Kg kilogram(s) 千克
kv kilovolt(s) 千伏
KV-amp. kilovolt-ampere(s) 千伏安
kw. kilowatt(s) 千瓦
kwh kilowatt-hour 千瓦小时
l. liter(s) 升
lab. laboratory 实验室
lb pound(s) 磅
LCAO linear combination of atomic orbitals 原子轨道的线性组合
LD lethal dose 致死剂量
LH luteinizing hormone 促黄体发生激素
liq. liquid 液体，液态
Lm mumen 流明（光通量单位）
LX lux 勒克斯，米烛光（照度单位）
m. meter(s) 米
M. mega- 大，兆，百万
M molar 克分子
m. melts at, melting at 熔融
m molal 克分子的
ma milliampere(s) 毫安

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manuf. manufacture 制造
manufd. Manufactured 制造的
manufg. manufacturing 制造
math. Mathematical 数学的
max. maximum(s) 最大值，最大的
Me. methyl (Meoh, methanol) 甲基
mech. Mechanical 机械的
metab. Metabolism 新陈代谢
m.e.v. million electron volts 百万电子伏
mg milligram(s) 毫克
mi mile 英里
min. minimum [also minute(s)] 最小值
min minute 分钟
misc. miscellaneous 其他
mixt. mixture 混合物
ml milliliter(s) 毫升
mm millimeter(s) 毫米
mμ millimicron(s) 毫微米
mo molecular orbital 分子轨道函数
mol molecule molecular 分子，分子的
mol. wt. molecular weight 分子量
m. p. melting point 熔点
mph miles per hour 英里/小时
μ. micron(s) 微米
mv. milillivolt(s) 毫伏
mx. maxwell 麦克斯韦
n 折射率
index of refraction (n 20D for 20o and sodium

light)
n newton 牛顿
n normal(as applied to concn.) 当量（浓度）
neg. negative (as an adjective) 阴性的 负的
no. mumber 号，数
obsd observed 观察，观测
org. organic 有机的
oxidn oxidation 氧化
oz. ounce 盎司（常衡=28.35g）
，英两
P poise 泊(粘度单位)
p- pico- (10-12) 微微
p.d. potential difference 势差, 电位差
Pet. Et. petroleum ether 石油醚
Ph. phenyl 苯基
phy. physical 物理的
physiol. physiological 生理学的

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p.m. post meridiem 午后
polymd polymerized 聚合
polymg polymerizing 聚合
polymn polymerization 聚合
pos. postive(as an adjective) 阳性的,正的
powd. powered 粉末的,粉状的
p.p.b (ppb) parts per billion 亿万分之(几)
p.p.m(ppm) parts per million 百万分之(几)
ppt. precipitate 沉淀, 沉淀物
pptd. precipitated 沉淀出的
pptg. precipitating 沉淀
pptn. precipitation 沉淀
Pr Propyl (normal) 丙基
prac. practical 实际上
prep. prepare 制备
press. pressure 压力
prepd. prepared 制备的
prepg. preparing 制备
prepn. preparation 制备
psi pounds per square inch 磅/平方英寸
psia pounds per square inch absolute 磅/平方英寸(绝对压力)
pt pint 品托
purifn purification 精制
Py pyridine (used only in formulas) 吡啶
qt. quality 质量
qual . qualitative (not qualitatively) 定性的
quant. quantitative (not quantitatively) 定量的
red. reduce 还原
red reduction 还原, 减小
ref. reference 参考文献
rem roentgen equivalent man 人体伦琴当量, 雷姆
rep roentgen equivalent physical 物理伦琴当量
repr. reproduction 再生产, 再生
res. resolution 分辨, 分解, 离析
resp. respectively 分别的
rpm revolution per minute 每分钟转数
RNase ribonuclease 核糖核酸酶
sapon. saponification 皂化
sapond saponified 皂化过的
sapong saponifying 皂化
sat. saturate 使饱和
satd. saturated 饱和的
satg saturating 饱和的
satn. saturation 饱和, 饱和度

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sec second(s) 秒, 仲, 第二的
sep. separate 分离
sepd separated 分离出的
sepg separating 分离的
sepn separation 分离
sol. soluble 可溶的
soln solution 溶液
soly solubility(solys. for solubilities is not 可溶性，溶解度
approved)
sp. gr. specific gravity 比重
sp. ht. specific heat 比热
sp. vol. specific volume 比容
std. standard 标准
suppl. supplement 补篇
sym. symmetrical 对称的
tech. technical 技术的
temp. temperature 温度
tert. tertiary 叔［指 ch3c(ch3)2—型羟基］
thermodyn. thermodynamics 热力学
titrn. titration 滴定
unsym. unsymmetrical 偏，不对称
U.V.. ultraviolet 紫外线
V volt(s) 伏（特）
vac. vacuum 真空
vapor. vaporization 气化
vol. volume(not volatile) 体积
vs. versus 对
w. watt(s) 瓦特
wt. weight 重量
wk week 星期

Appendix 9. 专利国别缩写

专利国别 简称
Australia AU 澳大利亚
Austria OE 奥地利
Belgium BE 比利时
British GB 英国
British Amended Brit, Amended 英国修改
Canada CA 加拿大
Czechoslovakia CS 捷克斯洛伐克

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Finland SF 芬兰
France FR. 法国
French Addition Fr. Addn. 法国增补
French Demand Fr. Demande 法国申请说明书
French Medicinal Fr. M. 法国医药
French Addition to Medicinal Fr. CAM 法国医药增补
Germany (east) DL. (east) 东德
Germany (west) Patentschrift DS. 西德
Germany (west)
DT. 西德展示说明书
Auslegeschrift
Germany (west)
Ger. Offen. 西德公开说明书
Offenlegungsschrift
Hungary HU 匈牙利
Hungarian Teljes Hung. Teljes 匈牙利 Teljes
India IN 印度
Israel IL 以色列
Italy IT 意大利
Japan JA 日本特许
Japan (kokai) Japan Kokai 日本公开特许
Netherlands NL 荷兰
Netherlands Application Neth. Appl. 荷兰申请
Norway NO 挪威
Poland PO 波兰
Rumania RU 罗马尼亚
South Africa ZA 南非
Spain ES 西班牙
Sweden SW 瑞典
Switzerland CH 瑞士
U.S.A. United States US 美国
U.S. Reissue U.S. Reissue 美国再版说明书
U. S. Defensive Def. Publ., U. S. Pat. Off. 美国防卫性公告
U. S. S. R. SU. 苏联

Appendix 10. 常用的一些词尾

词 尾 章 义 词 例
Ⅰ名词词尾
-age 表示抽象概念，如 voltage 电压
性质、状态、行为
等
-al removal 除去
-ance(-ence) resistance 电阻，difference 差别

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-ancy(-ency) brilliancy 度亮，efficiency 效率
-cy accuracy 精确性
-dom freedom 自由
-hood 1ikelihood 可能性
-ic (-ics) logic 逻辑学，physics 物理学
-ing reading 读数
-ion(-tion，-sion， action 作用，expansion 膨胀，connexion 连结
-xion)
-ism communism 共产主义
-ment movement 运动
-ness hardness 硬度
-ship relationship 关系
-th growth 生长
-ty(-ity) certainty 肯定，probability 概率
-ure mixture 混合物
-y factory 工厂
-er 表示人或物 worker 工人，computer 计算机
-or 表示人或物 director 指导者，tractor 拖拉机
-ist 表示人 Marxist 马克思主义者
Ⅱ形容词词尾
-able(-ible) 表示可能性 movable 可移动的，visible 看得见的
-al 表示"…的" national 国家的
-ant(-ent) important 霉要的，dependent 从属的
-ar(-afy) drcular 圆形的，secondary 次的
-ed aged 老化(了)的，large-sized 大尺寸的
-en 表示“制[质]的” golden 金(色)的
-ful 表示“充满” useful 有用的
-ic (-ical) 表示“属于” atomic 原子的，physical 物理的
-ish 表示"稍微有点" reddish 稍带红色的
-ive 表示性状 active 活泼的
-less 表示否定 useless 无用的
-like 表示相似 glass-like 玻璃似的
-ly friendly 友好的
-ory 表示性状 refractory 难熔的
-ous various 各种的，numerous 许多的
-y woody 木质的，handy 灵便的

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 Ⅲ 副词词尾
-ly 表示方式、程度 automatically 自动地，extremely 极度地
-ward (s) 表示方向 backward(s)向后
-wise 表示方向、样子 clockwise 顺时针方向，likewise 同样地
Ⅳ 动词词尾
-en 表示“使…” broaden 加宽，harden 硬化
-fy amplify 放大，verify 证实
-ize(-ise) oxidize 氧化
V 几个常见的构词成分和后缀
-fold …倍的，成…倍地 three-fold 三倍的，成三倍地
-free 无…的，免…的， oil-free 无[不含]油的，rust-free 无[不]锈的
不…的
-gram 表示记录下的东 spectrogram(光)谱图
西
-graph 表示记录工具或 autograph 自动记录仪，手稿
结果 spectrograph 摄谱仪
-graphy 表示根据记录图 spectrography 摄谱学[法]
象来研究的方法
和学术
-meter 表示计量仪表 spectrometer 分光计[仪]
-metry 表示计量方法或 spectrometry 度谱术，能谱测定法
技术
-ology …学(科) geology 地质学
-proof 防[不怕]...的 water-proof 防水的，不透水的
-scope 表示观测仪器 spectroscope 分光镜[仪]
-soppy 表示观测方法或 spectroscopy 光[能，波]谱学
学术
-tight 不透…的 air-tight 不透气的，气密的
-tron 表示(电子)管、仪 plasmatron 等离子管，等离子流发生器，等离
器装置 子电焊机

Appendix 11. 国际电化学相关杂志及网址：

Electrochimica Acta
http://www.elsevier.nl/inca/publications/store/2/0/5/
Journal of Power Sources
http://www.elsevier.nl/inca/publications/store/5/0/4/0/9/3/
Journal of the Electrochemical Society

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http://www.electrochem.org/journal.html
Solid State Ionics
http://www.elsevier.nl/inca/publications/store/5/0/5/6/7/7/
Journal of Alloy and Compound
http://www.elsevier.nl/inca/publications/store/5/2/2/4/6/8/index.htt
Electrochemistry Communications
http://www.elsevier.nl/inca/publications/store/6/0/1/4/4/9/
Journal of Electroanalytical Chemistry
http://www.elsevier.nl/inca/publications/store/5/0/4/0/8/7/index.htt
Journal of Applied Electrochemistry
http://www.wkap.nl/jrnltoc.htm/0021-891X
Materials Chemistry and Physics
http://www.elsevier.nl/inca/publications/store/5/0/4/0/9/7/index.htt
Applied and Theoretical Electrophoresis
http://www-lmmb.ncifcrf.gov/ESAB/journal.html
Bioelectrochemistry and Bioenergetics
http://www.elsevier.nl/locate/bioelechem
Biosensors and Bioelectronics
http://www.elsevier.nl/locate/bios
Electroanalysis
http://www.vchgroup.de/vch/journals/2049/index.html
Electrochemical and Solid State Letters
http://www.electrochem.org/letters.html
Electrochemical Society Interface
http://www.electrochem.org/interface.html
Electrophoresis
http://www.vchgroup.de/vch/journals/2279.html
International Journal of Hydrogen Energy
http://www.elsevier.nl/locate/ijhydene
Journal of Electroanalytical Chemistry
http://www.elsevier.nl/locate/jelechem
Journal of New Materials for Electrochemical Systems
http://www.polymtl.ca/journal/material.html
Journal of Solid State Electrochemistry
http://link.springer.de/link/service/journals/10008/index.htm
Transactions of the Institute of Metal Finishing
http://www.uk-finishing.org.uk/IMF/transactions.html

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