Electrochemistry Heinrich Daniel

LIBRARY
OF THE
UNIVERSITY OF CALIFORNIA.
Class
ELECTROCHEMISTRY
I
THEORETICAL ELECTROCHEMISTRY AND ITS PHYSICO-CHEMICAL FOUNDATIONS
BY
DR. HEINRICH
DANNEEL
Privatdozent of Physical Chemistry and Electrochemistry in the Royal Technical High School of Aachen
TRANSLATED FROM THE SAMMLUNG GOSCHEN

BY
EDMUND
S.
MERRIAM,
PH.D.
Associate Professor of Chemistry in Marietta College, Ohio
FIRST EDITION
FIRST
THOUSAND
OF THE
UNIVERSITY
OF
NEW YORK JOHN WILEY & SONS LONDON: CHAPMAN & HALL, LIMITED
1907
55
SRAL'
Copyright, 1907
BY
EDMUND
S.
MERRIAM
ROBERT DRUMMONI), PRINTER, NEW YORK
INTRODUCTION.
THE
science of electrochemistry has
come
to
have a
far wider range of application than formerly.
com-
paratively short time ago it comprised little more than methods of bringing about chemical reactions by means
of electricity,
and the
utilization of chemical affinity for
It has now become the production of an electric current. one of our most important aids in the investigation of some of the fundamental problems of general chemistry.
The measurement
of electromotive forces
is
the safest,
and oftentimes the only, means of determining the chemical force with which reactions take place; conductivity measurements have given us an insight into the nature of
solutions;
electrochemistry has given rise
to
one of the
most
fruitful of the
modern chemical
theories, the theory
of electrolytic dissociation.
has been of immense value.
In practical as well as theoretical line's electrochemistry Aside from the fact that
substances, such as the alkali metals, aluminium,
etc.,
many
magnesium, calcium carbide,
which can only be
made with
greatest difficulty by purely chemical are easily manufactured with the help of elecmeans, tricity, let us remember that electrochemistry gives us
the
'
ia
6232:5
iv
INTRODUCTION.
a nearly perfect means of utilizing the enormous power of our waterfalls for chemical purposes, and enables
us to store up and transport this energy which we receive from the sun. Finally electrochemistry gives us many a quicker, and therefore cheaper, than the old purely chemical processes.
compounds
in
way
Theoretical, or general chemistry, and electrochemistry are not separable; comprehension of one presupposes knowledge of the other. Therefore before we take up
electrochemistry proper
we
will
go over some of the

principles
physical and physico-chemical
which form
the basis of our present ideas in the field of electrowill then discuss the various theories of chemistry.
We
electrochemistry
essary
results
and give such

better
applications,
illustrations as are nec-
for
their their
comprehension.
as well as
Experimental
and
methods
of
measurement,
etc., will
be contained in the second volume.
The
third will be devoted to the technical applications.
TABLE OF CONTENTS.
PAGE
INTRODUCTION
iii
CHAPTER
WORK, CURRENT, AND VOLTAGE.
Kinds
of Energy,
,
I.
and Their Relationships. Work Done by Natural Processes. Principles of Thermodynamics. Maximum Work and Free Energy; Determination of Same. Reversibility. Reaction Velocity and Chemical Force. Ohm's Law. Catalysis.
the Performance of Work by the Expansion of Osmotic Pressure, and Osmotic Work. Semi-permeable Plant Cells, Quantitative Measurements. Work from Walls. Osmotic Pressure. Calculation of Chemical Work from Osmotic
Gas Laws, and

Gases.
Pressure and van't Hoff's Equation.
CHAPTER
II.
CHEMICAL EQUILIBRIUM, STATICS, AND KINETICS Complete and Incomplete Reactions. Equilibrium. Law of Mass Action. Laws of Chemical Kinetics and Statics. Active Mass. Dissociation of Gases. CO and Os- Homogeneous and Heterogeneous Systems. Solution of Salts and Vapor Pressure.
Change of Equilibrium with the Temperature.
Hoff's Equation.
32
CO+O
2.
van't
CHAPTER
III.
THEORY OF ELECTROLYTIC DISSOCIATION

Freezing-point, Boiling-point, and Osmotic Pressure of Solutions. Dissociation. History of Electrochemistry, with the
45
Dissociation
Theory and
its
Basis.
Faraday, Grotthus, Clausius,
VI
TABLE OF CONTENTS.
PAGE
Degree of Dissociation (Table) Law of Mass Action. Applications of the Theory in Chemistry. Dissociation by Steps. Ions and the DissociaPrecipitation. Neutralization. tion Constant of Water. Hydrolysis. SaponTable of Dissociation of Water. Additive Properties. ification.
,
Hittorf, van't Hoff, Arrhenius.
Physiological Applications.
CHAPTER
CONDUCTIVITY Ohm's Law.
cient.
IV.
77
Specific
Conductivity.
Temperature
Coeffi-
Solutions.
Metallic and Electrolytic Conductivity. Conductivity of Charge on the Ions. Velocity of the Ions. Equiva-
lent Conductivity.
pendent "Wandering."
Power (Table).
Conductivity of the Ions and Their IndeWater. Sulphuric Acid. Dissociating Strength of Acids and Bases. Distribution.
Sugar Inversion. Decomposition of Ethereal Salts. Dissociation Constant and Ostwald's Dilution Law. Isohydric Solutions.
Enforced Lowering of Dissociation and Solubility Product. Dissociation by Steps. Conductivity and Temperature. Measurement of the Transport Number. Absolute Ionic Velocities.
Dielectric Constant.
CHAPTER
Difference
of
Potential.
V.
115
ELECTROMOTIVE FORCE AND THE GALVANIC CURRENT

Contact
Electricity.
Galvanism.
van't
Galvani, Volta, Daniell.

Reversibility.
Calculation of Electromotive Forces.
Gibbs-Helmholtz
Formula.
Formula,
Fugacity.
and
Hoff's
Equation.
tial
Nernst's
Solution
Pressure.
Electrolytic Potential.
Daniell Cell.
Gas
Electrodes.
Poten-
of Alloys.
Second Kind.
tration
Cells.
Compounds. Oxidation and Reduction

Diffusion Cells.
Potential of
Electrodes of tHe
Potential.
Concen-
mula.
Solubility.
Applications of Nernst's ForNeutralization Cells. Secondary Elements,
and the Accumulator.
CHAPTER
POLARIZATION AND ELECTROLYSIS
Polarization.
VI.
151
Electrolysis of Water,
Polarization
Capacity.
Residual
Current.
Decomposition
and Deposition
Voltages.
TABLE OF CONTENTS.
Electrolysis of Mixtures.
Vll
PAGB
Overvoltage.
of
Faraday's Law.
Electrolysis.
Table
Atomic and Equivalent Weights.
Secondary
Reactions.
CHAPTER
ELECTRON THEORY
LITERATURE
INDEX.
VII.
169
173
*77
OF THE
f
UNIVERSITY
OF
sf^L'fORNVhs
ELECTROCHEMISTRY,
CHAPTER
I.
THE most important question ior scientific and technical progress is, How much work can a given chemical
This question is of equal or perhaps than the question as to what happens greater importance when two substances are brought together. If we know
reaction perform
?
the
work which a
certain reaction can do, for instance

,
the reaction
CO + O = CO 2
and the temperature
co-
do work, we know at once whether or not the reaction occurs and the conditions necessary We see from the value of the energy, for its occurrence.
efficient of its ability to
that this reaction,
the oxidation of carbon monoxide,
in
takes place at ordinary temperatures with great violence, fact explosively; further, that the reaction is less
complete the higher the temperature, and that at very high temperatures it even goes in the opposite direction;
i.e.,
dioxide
carbon monoxide not only will not burn, but carbon is decomposed into carbon monoxide and oxygen.
We
can distinguish
six
different
kinds
of
energy:
ELECTROCHEMISTRY.
mechanical energy;
2,
i,
volume energy;
3,
chemical
energy; 4, electrical energy; 5, heat energy, and 6, radiant energy. These different forms of energy are transformable and if we have a suitable mechanmutually
ism,
the
transformation
is
quantitative.
;
Heat energy
forms an exception to this rule the complete transformation of heat into electrical or mechanical energy is theoretically
and
practically impossible, although mechanical
or electrical energy
heat.
may
of
be completely transformed into
The
scientific
unit
mechanical work
this
is
=i (
dyne X i
centimetre) and
is the erg the unit of the
C.G.S. system. The practical unit is the kilogram-metre, which is the work necessary to raise 1000 grams through a height of 100 centimetres, or the work
so-called
which a kilogram can do in
falling a distance of i metre.
kilogram weight (not to be confused with the mass of a kilogram) is the force with which the mass of i kilogram = i litre of water at 4 C.) is attracted by the earth. A ( falling body attains as a result of the earth's attraction an
acceleration of 980.6 cms. per second, so that a gram weight represents a force of 980.6 dynes. The unit of
force = of
i i
dyne
is
gram, gives
is
it
that force which, acting on the mass an acceleration of i cm. per second.
Acceleration
Velocity
the
.
increase
of
velocity
is
per
second.
= ~.
distance
kilogram-metre
100000 times
as great as a gram-centimetre, i.e., = 98 060 ooo ergs. The unit of volume energy is the litre-atmosphere. When any body, for instance a gas, which always exerts
a pressure on the walls of the vessel enclosing
it (cf.
p.
is
16)
dis-
expands, the weight of the atmosphere above
it

placed by an
litres
amount corresponding
of
of
expansion
the
gas.
to the number of The expanding gas
therefore does
work against the pressure of the atmosphere.
(In general, every increase of volume taking place against a pressure, or every contraction brought about by a presIn the sure, is accompanied by a gain or loss of work.)
barometer the pressure of the atmosphere forces a column of mercury i sq. cm. in cross-section up to a height of 76
cms.
since
Such a column of mercury weighs 1.0333 kilograms,
the specific gravity of mercury is 13.596. The of one atmosphere therefore is 1.0333 kg. per pressure If then 103.33 sq. cm., or 103.33 kg. per sq. decimetre.
kilograms are raised
decimetre,
is
i.e., if
a body expands
as
by
is
litre,
i
the
work done
is
the
same
when
gram
raised
i
033 ooo cms.
i gr.
cm.
= 980.6
ergs; the value
of
i
litre
atmosphere
therefore
980.6X1033000 =
is
013 200000 ergs.
The
Watt
ordinary unit of electric

the
work
the watt-second.
is
"power"
of
an
electric current of i
ampere
under the pressure of i volt. By power is meant the work done in unit time, i.e.,= work/time. An ampere is the amount of electricity measured in coulombs
coulomb flowing through a conductor in unit time. is the unit quantity of electricity. coulomb in passing through a silver voltameter precipitates 0.001118 gr.
of silver;
a coulomb
is
the electric charge

of
(cf. p.
53)
on
0.01036
milligram
i
equivalents
every
ion
and
will
precipitate this quantity of
any ion on an
electrode.
A
the
current of
ampere
flows through a conductor
when
quantity of electricity passing is i coulomb per second. An ampere is the tenth part of the unit of current in the
C.G.S. system.
ELECTROCHEMISTRY.
Electric pressure or difference of potential is ordinarily in volts. volt is that pressure which suffices
measured
to
send a current of
ampere through a
resistance of
to
ohm
units.
(legal definition).
One
volt
Daniell
cell
has an
i.i
i
equal electromotive
is
io8 C.G.S.
force
or
difference of potential of
volts;
a storage battery
has 2.0
volts.
watt
and a watt-second is is able to do when flowing for of i ohm. A watt-second

ergs.
voltXi ampere (a power), the work which a current of i ampere

is
i
is
second through a resistance therefore io8 Xio~ 1 = io7
Heat energy
quantity of heat
of
i
is
measured
is
in calories.
calorie
is
the
which
water
necessary to raise the

C. to 16
temperature
Since the
gram
of water
from 15
is
C.
not independent of the temperature, the quantity of heat necessary to raise the temperature of i gr. of water i C. is different at different
specific heat of
temperatures.*
The mechanical
by many
follows
:
equivalent of heat has been determined
investigators;
Nernst,f 42 600.
If i
we will use the value adopted by The meaning of this number is as

42 600 centimetres, or
if i
gram
falls
kg. falls
42.6 cms. and the total kinetic energy (vis viva) of the falling weight is converted by impact into heat, this
quantity of heat
of
i
is
just sufficient to raise the temperature
gram
of water
from 15
C. to 16
C.,
i.e.,
one calorie
in use, there are the
* Beside the above-defined calorie, which is the one most generally "mean calorie " = T ^7 the quantity of heat necessary to warm i gr. of water from o to 100, and the "zero-point
calorie," the quantity of heat necessary to
warm
gr. of
water from
o to i.
The "kilogram
calorie"
f Theoretische Chemie, p. 12.
1000 times the 15 Enke, Stuttgart.

is
calorie.

is
evolved.
The energy
of the
gram weight
is
is
then
= 42 600X980. 6 41 777 ooo ergs (980.6

due
to gravity).
is
the acceleration
There
measured
in
no fixed unit for chemical energy, it As yet there volt coulombs.

it
is
is
generally also no
common
With the help

units.
unit for radiant energy. of the following table *
is
easy to
different
express a given quantity of
work
in
any of the
From
the foregoing
is
it
is
clear that
an expression de-
noting work
clearer.
always made up of two
factors.
A summary
of these will perhaps be of use in
making
the relationship
* Table of
H. Steinwehr, recalculated
after Nernst, Zeitschr.
f.
Elec-
trochemie, io, 629, 1904.
ELECTROCHEM1S TRY.
Mechanical work:
Distance
Velocity
Time
Acceleration
Increase of velocity
Time
Force
Work
Power
= Acceleration X mass. = Force X distance.

"
Work
Time'
of fall
Work
Weight
= Mass X length
tion
X acceleradue
to
due
to gravity.
= Mass X
gravity.
acceleration
Work of expansion
Pressure
Electrical
= Increase of volume X pressure.

Weight
*
Surface
work
= Voltage X coulombs.
Coulombs
Current strength
Electrical
Time
of
Chemical
power = Voltage X current. = Chemical potential X quantity work

substance.
of
The
place.
conceptions
chemical and
will
electric
potential
will occur repeatedly
and
be explained in their proper
Work Done by
Fundamental Law.
Natural Processes.
A II processes in Nature whtch take themselves can famish work, and only such procplace of esses occur spontaneously, which, ivith the aid of suitable
apparatus, can be made to perform work. Among such processes are the union of electric charges; movements

of liquid
from a higher to a lower level; all movements of masses in general which occur spontaneously; further,
chemical reactions;
tures, etc.
equalization
of
different
tempera-
The most important question work we can obtain from a given
for us
is,
how much
process under the most " maximum work." favorable conditions, the so-called In order to appreciate the meaning of this term we must
review two laws concerning the relation between heat and work, the two principles of thermodynamics.
First
Law, Principle
of the Conservation of Energy.
Just as no substance can be created from nothing nor be absolutely destroyed (law of the conservation of matter),
so energy can neither be created
hilated.
"Perpetual motion," continually does work without having energy given to

in
is
from nothing nor annia machine which i.e.,

it
scientifically an absurdity. any way, have had such an end in view have who
Many
inventors
tried to achieve
the impossible.
few illustrations will
make
the
meaning
of this law
clear.
a weight of 10 kg. vertically from the floor through a distance of i metre. In so doing our muscles do 10 kg. metres of work. The weight has now a capacity
lift
We
for doing
work, or potential energy, of 10 kg. metres,
if
we disregard the energy it may have had to start with. we let the weight fall again it attains as a result of
earth's
If
the
attraction
a certain
"vis viva"
(the
potential
energy changes to kinetic energy) and when it strikes the If we measure floor this energy is converted into heat.
the heat
we
find
it
to
be 23.5 calories, and

5,
is
this, as
we
see
from the table on
p.
just
equal
to
the
original
ELECTROCHEMISTRY.
denote by
we spent in raising the weight. If we the change in energy resulting from the fall the heat generated (in this case 10 kg. metres) and by the impact of the weight on the floor, then by
10 kg. metres
U = W.
We now tie to the falling weight a cord, lead it over a pulley, and fasten a 9 kg. weight to the other end, so that this last is raised a metre by the fall of the first;
let
the
work necessary
metres).
to raise this
weight be
(in this
case 9 kg.
We
will
now
find that the heat

is
developed by the impact of the first weight on the floor 2.35 calories; if we denote this by W, then
U=A+W.
If
we supply
extra
work
to the process
for instance,
by
accelerating either the 10 or 9 kg. weight by a blow work A' must also appear in the heat developed,
this
W=U-A+A'.
In every case the change in the total energy plus the heat expended and work expended is equal to the work
obtained plus the heat obtained. If we let a chemical reaction take place in such a way that no work is done, we obtain the change in total
energy as heat, which in this case we call the "heat of In the combustion of coal reaction" (Warmetonung).
we
obtain with the
help of a steam-boiler only about
20%
other
of the heat of reaction as mechanical energy; the
goes over into heat which is lost up the chimney and by radiation. If we obtain more work than that
80%

which corresponds
possible in
to
the heat
of
reaction
(which
is
some
cases) the extra heat

i.e.,
must be supplied
mixture cools
by the surroundings,
itself off.
the
reaction
Second Law, Principle of the Transformation of Energy.
We
we can
and
wish, of course, to know how much work out of a given process under the most favorable get
i.e.,
conditions,
after
what the maximum work
is.
Thomson,
travail
Berthelot, proposed the law (principe du maximum) that the maximum work may be
him
calculated from the heat of reaction,
and that the two are

proved that
is
Helmholtz,* however, equal. not the case.
later
this is
fact that heat
The. basis of Helmholtz's theory can do no work when it

it is
the well-known
is at rest.
Just as
and only does so when it falls from a higher to a lower level, and just as electricity can only perform work as it falls from a higher to a lower potential, so heat will only do work when it falls from a higher to a lower temperature/ If heat is to be converted into work we must have To cite an illustration of differences of temperature.
at rest
water can do no work when
Nernst's,
we cannot
utilize
the
enormous
reservoir of
heat in the sea to turn the propellers of the ocean steamers. One might conceive of the ships' engines taking heat from
the ocean water, using it in the performance of work, i.e., in propelling the ship, and then returning it to the
water in the form of
friction. Experience shows that such a machine, which would not contradict the law of the
* Thomson has accepted the views of Helmholtz, but Berthelot and many of the French scientists still cling to the principe du travail maxi-
mum
although
it
has been clearly shown to be incorrect.
10
ELECTROCHEMISTRY.
conservation of energy, is unfortunately an impossibility; such a machine, however, has received the name of
"perpetual motion of the second kind." By a simple thermodynamic cycle

that
it
can be shown
temperain the
when an amount
of heat
at the absolute
the temperature favorable case the quantity of work

falls to
ture *
T-dT*
dA
to
most
is
be obtained
By combining this (cf p. 8) we have

.
equation with the equation
U=A+W
~-^p
is,
however, nothing else than the temperature coof the capacity for doing work,
i.e.,
it
efficient
is
the
amount by which
coefficient
changed one degree.
changes when the temperature is If we represent the temperature
by a, then
A-aT=U.
The formula A
U=T-^
is
the exact expression in one
equation of both laws of thermodynamics.

* The gas laws lower than 273
make
C.
it
probable that there can be no temperature

273
is
therefore called the absolute zero of
Temperatures counted from the absolute zero are deif / is the ordinary Celsius temperature, counted from the freezing-point of water, T=* 273 -H. f An infinitely small value, which is not zero, but approaches zero, is denoted by a prefixed d. dQ is an infinitely small quantity of heat, dU an infinitely small change of total energy, etc.
temperature. noted by T;
II
From
results:
this
i.
equation
is
we can derive
in
total
several very important
The change
chemical reactions
energy U, which in simply the heat of reaction, is only

is is
equal to the work obtainable, or, as it "free energy," when the free energy
the
often called, the
independent of
temperature,
(
i.e.,
when a = o.
always=Z7.
2.
At the absolute
zero
273
C.)
is
i.e., if
the free energy increases
raised,
we may
obtain
the heat of the reaction.
If a is positive, when the temperature is more work than corresponds to The excess must be supplied by
3.
itself off.
the surroundings, and the reaction mixture cools
This happens, of course, only when we do extract the maximum work. 4. If a is negative, excess heat results,
and the system becomes warm, even when the maximum work is obtained. With the exception of No. 2, all
these cases are realized.
The
points.
Daniell
cell
This affords
furnishes a good illustration of these electric energy as the result of the
following equation:
Zn + CuSO 4 = ZnSO 4 + Cu,

i.e.,
copper
is
zinc.
Daniell
precipitated from a solution of CuSC>4 by cell in using up 32.7 grs. of zinc gives
at
C. electric energy equivalent to 25 263 calories;
electrical
measurements further show that the

calorie
free energy
increases 0.786
/.
is
per degree
calories.
rise of
aT = 0.786X273 = 213
therefore
/
The
050
temperature. heat of reaction
= 25 263-213 = 25
cal.
Calorimetric
excellent
gave 25 055 calories, agreement with the calculated value.
measurements
in
12
ELECTROCHEMISTRY.
The
to
questions
now
or,
arise,
How
do we determine the
maximum work?
do
its
How
best?
To do
can we compel a reaction this we must contrive an
arrangement which converts chemical into mechanical

or electrical energy, and which works so perfectly that there are no losses due to secondary causes, such as Further, the reaction leakage, friction, radiation, etc.
must take place in such a manner that we may stop it at any time, and by putting back exactly the same amount
of
work we have already obtained from

original condition.
it,
bring the
system to its a "reversible"
one.
Such a process is called Absolute reversibility would be

if
possible experimentally only
we
ourselves were perfect
beings; since, unfortunately, even electrochemists can make no such claim, we must content ourselves with
approaching the above requirements of reversibility as

closely as possible.
An
arrangement which
is
fulfils
these
In
requirements very perfectly it reactions often take place with practically perfect reversibility, and for this reason the scientific chemist
the galvanic cell (battery).
should realize the importance of electrochemistry. The work which a reaction can do is the point which
has a special interest for us.

electrochemistry
is
One
of the chief aims of
to obtain
work from chemical reactions,
such, for instance, as the combustion of coal; the reaction between zinc and copper sulphate or between lead, lead
Another aim is the comperoxide, and sulphuric acid. of chemical reactions by means of electrical work, pulsion
as in the manufacture of aluminium from
its
oxide, or
the preparation of bleaching solutions from common salt. In the first case we are satisfied when we know the
maximum work which
the given reaction can do;
in the
WORK, CURRENT, AND YOLTAGE.

second
13
we must
learn the
maximum work
of the reverse
reaction.
If
we have
a solution in which two reactions
may
take
and CuSC>4, and wish to obtain the copper electrolytically, we must know which of the two reactions takes place easier; i.e., how
place, for instance a solution of FeSC>4
much work
is sufficient to
precipitate the copper
on the
In cathode, but does not suffice to precipitate the iron. other words, we must know the work necessary for each
reaction.
If
we know
If
the
maximum work
it
of a reaction
we know
also, as
already stated, whether
will take place of itself
or not.
of copper
we know,
for instance, that the displacement
by
zinc according to the equation
Zn + CuSC>4 =
fact
that the reaction will go on of therefore the reverse reaction
Cu + ZnSO4 can perform work, we know from this its own accord, and
which requires the
that
ex-
occur spontaneously; that is, zinc cannot be precipitated by copper from a zinc salt
penditure of
solution.
work
will not
Another example
hydrogen peroxide
is
the following:
When we
2
dissolve
in
water
we
observe no
reaction;
decomposition according to the equation apparently does not take place of itself.
fore
H O 2 =H 2 O + O
It
appear probable that the reverse reaction
would therewould occur
spontaneously.
water,
H 2 O2
is
However, if we pass oxygen gas into not formed in measurable amounts.
Accordingly the only

is
way
of deciding
which of the two

is
reactions, decomposition or
to
formation,
It is
;
spontaneous,
is
measure the work involved.
found that work
necessary for the formation of

its
H2O 2
work can be done by
decomposition and therefore this reaction goes on of
14
itself.
ELECTROCHEMISTRY.
A similar case is found in detonating gas. Hydroand oxygen may be kept together many years without gen
the visible formation of water.
In
this case, also, the only
means
which reaction is spontaneous is the work. The reason why we do not by measuring
of determining
observe either a decomposition of the 2 O 2 or a formation of 2 O lies in the slowness of the reaction.
Reaction Velocity and Chemical Force.
At the end
of the last
paragraph mention was made of
the slowness of a reaction, and
we must now
see
what
bearing the reaction velocity has on the work of a process. In utilizing a chemical reaction for the production of
work
the
first
point to be considered
is
the speed with
which the reaction proceeds. A reaction which can furnish a million kg. -metres can be of no use to us if it
requires a milliard years before it is completed, nor, on the other hand, if it only requires a fraction of a second, for our machines are too imperfect to take care of such a
power, and the greater part would be

of heat.
lost in the
form
ordinary temperatures goes too slow, and at high temperatures,

too fast (explosively).
The
reaction
2H 2 +O 2 = 2H 2 O
at
An
electrochemical arrangement,
however, enables us to regulate the velocity within certain limits, and so quantitatively obtain the work of the reaction.
law similar
to
Ohm's law
regulates the velocity of
chemical reactions.
Reaction velocity =. -. chemical resistance

,
.
impelling force
We
can always calculate the impelling force from the

work which the given
little
15
reaction can do, but
we know
very
about chemical resistance.

all,
ably in
In most reactions, probthe chemical resistance increases as the tem-
perature decreases, and would appear to become infinite at the absolute zero, where all chemical action would
cease.
In
resistance;
this
many cases we can may be done, for
reduce
the
chemical
example, in the case of
formation by constructing a gas cell. The chemical is also lowered by raising the temperature, or divided platinum into the gas mixture. by bringing finely The platinum does not take a visible part in the reaction,
resistance
for
it
H2O
is
the
same
after the reaction as before.
But by
the simple presence of platinum we can increase the reaction velocity at ordinary temperatures till explosion occurs. Such substances which diminish chemical resistance
are
known
as
catalytic agents
or
catalyzers.
Their presence changes neither the impelling force nor In technical work there are the nature of the reaction.
many
reactions which, were
it
not for suitable catalyzers,
would go so slowly as to be commercially worthless. We " contact process" for sulphuric need only mention the acid, in which a number of catalyzers have found application in bringing about the union of sulphur dioxide
and
oxygen.*
*
The
reader will find a collection of the most important technical
reactions in which catalysis plays an important part in an address of Bodlander's, delivered before the Berlin International Chemical
Congress, which has appeared with other collections in "Der deutsche Compare also Ostwald's article on Catalysis in Science and Verlag."
the Arts, in the Zeitschrift fur Electrochemie, 7, 995, 1901.
16
ELECTROCHEMISTRY.
The Gas Laws.
Work
Obtainable from the Expansion

of Gases.
We
will later find that the
work obtainable from

in a solution
of calculating the the expansion of a gas is also
method
applicable in calculating the work done when substances will therechange their concentration.
We
fore briefly go over the gas laws
and put them
in a
form
from which the work obtainable is easily calculated. At constant temperature, when the 1. Boyle's Law. volume of a gas is changed, the pressure varies inversely
as the volume; that
is,
p-v
If
B,
constant.
we
bring into the volume of

.
two, three,
grams
i litre successively one, of oxygen, the pressure increases in

. . . ;
the proportion one, two, three, i.e., each gram of on the walls of the containing vessel as oxygen presses though it were present alone.
Gay-Lussac's Law. If the pressure on a gas is constant and the temperature raised, the gas expands kept
2.
per degree centigrade by an amount which is 0.003663 times ( = -2T-g-) the volume it occupies at o C. If the volume at o C. is v its volume (v) at the temperature r C. is
,
V=v
(i
+ 0.003663
is
T).
On
for
the other hand,
the heating, the
kept constant during pressure increases. Boyle's law holds

if
the volume
any given temperature, and it therefore follows by combining these two equations that
^ = MI +0.0036637).
WORK, CURRENT AND VOLTAGE.

If
i?
both pressure and volume vary,

C.
we
obtain for the
product at the temperature T
p-V
= pQ-V
(l
+0.0036631-).
This equation holds on the supposition that a gas exerts no pressure at the absolute zero, and affords a means of
calculating this temperature.
The
the
value thus found

absolute
is
273
(
C.
If
represents
10)
temperature
= 273 + T)
(cf. p.
we obtain
pv =
L
the equation
^ -- T.
gram
of a gas
273
3.
From
section
it
is
seen that each
exerts a pressure
though it mixture of two or more different gases, and the pressure of a gas mixture is therefore equal to the sum of the
pressure which each gas would
single pressure of each gas
on the walls of the containing vessel as were present alone. This applies also to a
exert
by
to
itself.
This
the.
which goes
of
is
make up
total is called the partial pressure of the
gas in question.
ILLUSTRATION:
sea-level
The
pressure
the
atmosphere at
of mercury,
under normal conditions
760
mm.
of the partial pressures due to nitrogen, oxygen, carbon dioxide, water-vapor, and the rare Air contains about 79.2% nitrogen, 20.8% gases.
and
this is
made up
oxygen, and about

pressure of nitrogen
0.04% carbon
is
dioxide.
The
partial
therefore 760
mm.
of mercury,
and that
20.8 of oxygen 760-
- mm.
4. When gases combine to form a chemical compound the volumes which react are either equal or stand in a
simple numerical proportion to one another, and the
i8
ELECTROCHEMISTRY.
is
same
true of the resulting product
if
it
remains in the
gaseous form.
form the basis of Avogadro's Hypothesis (1811), which states that under the same conditions of temperature and pressure the unit volume of alt gases contains the same number of molecules*
These
facts
ILLUSTRATION:
44
grs.
grs.
of hydrogen,
grs. nitrogen
32
grs.
oxygen,
always occupy the same volume when the temperature and pressure of each has the same value. At atmospheric pressure and o C.
this
is
carbon dioxide, 28
volume is 22.42 litres. Or confined in the volume of i
if
litre, it
a mol of any gas at o C. exerts a pressure of
22.42 atmospheres on the containing walls.

of section 2, therefore,
The
equation
when
applied to i mol,
becomes
litre
273
273
atmospheres.
is the same for all gases is a one. It is called the "gas constant" and very important If we consider n mols instead is denoted by the letter R.
This factor 0.0821 which
of one the equation
is
of course
pv
= nRT.
i
ILLUSTRATION: The average volume of

different gases at o
mol
of the
C. and
litres.
atmosphere pressure has
been found
a
to
be 22.42
different
somewhat
value,
Atmospheric nitrogen gave This led to an 22.34.
investigation into the purity of atmospheric nitrogen and resulted in the discovery of argon and the other rare
gases.
*
mol or gram-molecule
is
is
that
number
i
of
grams
of
i
of
a substance
grs.
which
i
equal to the molecular weight,

grs.
mol
mol (^2=35.45 + 35.45
= 70.9
Zn=65-4
Zn.
grs.
,
chlorine,
63.6 + 32X64 grs.
= 158.6 grs. CuSO 4
mol CuSO 4 =
etc,
19
work obtainable from an expanding = gas one must remember that work pressure X change
calculate the
in
To
volume, provided during the process the pressure does not change. If the volume is kept constant and the
= pressure changes, the work is volume X pressure change. we let a gas under constant pressure and temperaIf
ture
expand from the volume

is
Vi to
volume v 2 the work
obtained
A=p(v 2 -vi).
a quantity of gas at constant temperature and constant volume has its pressure raised from pi to p 2 then
if
Or
A=v(p 2 -p
).
ILLUSTRATION i. Let us consider a cylinder v;hose cross-section is one square decimetre and whose height is about 3 metres, at the bottom of which is i mpl = i8 grs.
Suppose the water is converted into vapor at and under the atmospheric pressure. Neglecting the o volume of the liquid water (0.018 litre) and remembering that at o and atmospheric pressure i mol of every gas
of water.
occupies the volume of 22.42 litres, we find that the weight of the atmosphere above the cylinder is raised through
a distance of 22.42 decimetres. necessary to overcome through the volume of

find the
Since the
work which
is
the
i
pressure of i atmosphere litre is r litre-atmosphere, we
work on evaporation
A =22. 42
If
litre-atmospheres.
is
n mols are evaporated the work
of course n- 22.42
litre-atm.
(cf.
n- 231. 60
kg.-metres,
or
542.34
calories
Table
5).
20
ELECTROCHEMISTRY.
ILLUSTRATION
2.
If
i gr. -molecule
16
of water,
we decompose we obtain 2 grs.
by
of
electrolysis
= oxygen i mol hydrogen + J mol oxygen; these occupy under standard conditions 33.63 litres,
grs.
hydrogen and
of
That
is,
in order to liberate the gas into the
we have done
the chemical
33.63
litre- atmospheres
of work, aside
atmosphere from
work necessary
to
decompose the water.
This consideration frequently enters into the calculation of the work necessary in such reactions where a gas is
evolved or absorbed.
If
we
let
the hydrogen
and oxygen
again combine, the volume decreases by 33.43 litres; i.e., the atmosphere in this case does 33.43 litre -atmospheres of work, which we can obtain as electrical work by using
a gas-battery. In general it
\i\\\
not be true that the volume alone or
If we have a quantity of the pressure alone varies. gas and increase its volume at a constant temperature, the
pressure
tion
falls off at
the
pv = constant.
To
the help of differential result: When a mol of a gas expands from vi to ^ 2 the work obtainable is *
same time according to the equacalculate the work we need calculus, and find the following
A=RTln-.
Vi
Osmotic Pressure and Osmotic Work.

has been shown by van't Hoff that the gas laws mentioned above also apply to substances in dilute soluIt
tions.
*
Ln
is
the symbol of the "natural logarithm."
Briggs or
common
logarithm
it
To change it must be multiplied by 0.4343.

is
to the
The
derivation of the above equation
here given for the benefit of those
WORK, CURRENT, AND VOLTAGE. The pressure of a gas

to
is
21
to
be looked upon as
its
endeavor
expand. Gases expand as far as they can, i.e., they distribute themselves through the whole of the volume
at their disposal
if
there
is
medium
which they can pass.
Such a medium
is
present through the vacuum or
When their expansion filled with other gases. hindered by a medium through which they cannot pass, such as an air-tight wall, they exert on this wall a pressure.
any space
is
All other substances behave in this respect similar to

gases.
as
much
All have the tendency to distribute themselves as possible, but can only do so in a suitable
medium.
Sugar
Water
to
is
a suitable
medium
for cane-sugar.
tries
distribute itself in this

i.e.,
it
medium
to
the
If a
greatest possible degree,
dissolves in water.
layer of pure water
is
carefully put over a solution of
When the gas expands from v to the volthe pressure decreases from p to p dp; the work obtained, dA therefore lies between pdv and (p dp)dv. In comparison with p, dp is infinitely small and can therefore be neglected; i.e.,
who have
studied calculus.
ume v + dv,
dA = pdv.
If
we
insert the value of
p which
is
obtainable from
p-v=RT
in this
equation
we
obtain
v
This, integrated between the values
i)\
and v 2
gives
A = RTln^.
Vi
Since v z :v\= p\: p 2 the equation can also be written

,
P2
If
n mols of gas are used, the equation
is
22
ELECTROCHEMIS7R Y.
an opportunity
for further expansion,
sugar, the sugar has
and
it
accordingly diffuses
upwards against the
force of
gravity till the concentration at all points is the same. If the two layers are separated by a wall which is permeable
water but not to the sugar molecules, the process is reversed, the sugar no longer diffuses upwards, but
to
draws water through the wall
to
itself.
If
the vessel
containing the solution is closed on all sides, very little water can enter, since a hydrostatic pressure is soon developed which prevents the further entrance of water.
This tendency
pressure, and
solution.
to
is
expand has therefore the nature of a
called the osmotic pressure of the sugar
sure
is
The relation between osmotic and gas presclear when we remember that the gas corresponds
and the solvent (water)
to
to the dissolved sugar
the
vacuum.
If
we
avoid the development of hydrostatic pressure,
by allowing the containing vessel to give way, the solution actually draws in a great quantity of water.
To
test
this
substance which
conclusion experimentally we require a is permeable to water but impermeable
to the dissolved sugar molecules.
diaphragm
built of
such a substance
is
called "semi-permeable."
go over the history of our knowledge conosmotic pressure and at the same time become cerning acquainted with many terms and laws which will be
We will first
met
later on.
It is well
dry and
contents.
that plant cells which have become need water can take up water when they are
known
put in contact with
The
permeable
without losing any of the cell it, walls of plant cells are therefore semimembranes. The first investigations on the

osmotic pressure of the solution in plant
'by physiologists.
cells
23
were made
The
cells
were placed in
salt solutions,
it was found that salt solutions of a particular concentration were in equilibrium with the cells, i.e., the If they were put cells neither expanded nor contracted.
and
in a
more
dilute solution, they took
up water and expanded;
put in a more concentrated solution they gave off water and became smaller. Solutions which were in equilibrium
with the
solutions.
salts
cells
were called
"
iso tonic
"
or
"
isosmotic
"
It
was discovered
that solutions of similar
concentration;
were isotonic when they had the same molecular * for instance, normal solution of KNO 3
,
NaNOs, KC1, NaCl

Cell
are approximately isotonic.

Protoplasmic Sac
Wall ,_
Nucleus
As
this
Fig.
is
shows, the
cells are
which
permeable
the
to solutions as well as
surrounded by a cell wall water within

;
permeable to protoplasmic water but not to the salts dissolved in the cell solution.
is
sac
which
is
Th.e cell solution

ess of
is
called the "protoplast,"
and the proc-
fact
expansion or contraction is called "plasmolysis.'' was further discovered which was later explained
electrolytic dissociation,
by the theory of
*
namely, that
Measured
in
mols per
litre.
Cf. remark on p. 18.
ELECTROCHEMIS TR Y.
dilute solutions of the
above-mentioned inorganic
salts
have an osmotic pressure which is practically twice as great as solutions containing an amount of organic subequal in molecular concentration to that of the inorganic salts. It should be mentioned
stances
urea, sugar, etc.
here that the osmotic pressures were later measured in atmospheres and that the ordinary plant cells which contain dissolved glucose, malates of calcium and potassium, sodium chloride,
etc.,
about 4
atmospheres. purposes in plants such as the sugar-beet have a pressure In young plants the pressure of 15 to 20 atmospheres.
is still
to 5
Certain
have an osmotic pressure of cells used for storage
higher.
The
cells of bacteria
high
fact
osmotic
have an especially pressure, which

.
may
perhaps explain their

could only be used
great physiological action.
Plant
in
cells
making comparative measure-
ments; in order to measure the

pressure directly in atmospheres, it was necessary to construct an
artificial
protoplasmic sac,
i.e.,
semi-perrneable
membrane.
impermeable
salts,
A
to
membrane composed
ferrocyanide
is
of copper
sugar and most
permeable to made such a

FIG.
2.
but readily Traube O. 2
membrane -by a solution of 4 Fe(CN),} putting in a carefully cleaned porous cell
and placing the
cell in
a dilute solution of CuSO4-
The
two substances diffuse toward
each other in the cell wall
WORK, CURRENT, AND VOLTAGE

and form, on meeting, a precipitate
of
25
Cu2Fe(CN)6,
.
thus making a durable semi-permeable wall. Using this A cell, measurements were made as follows (cf Fig. 2). solution was put in the cell; the open end was closed sugar
by a rubber cork, through which passed a long glass tube, and the whole was placed in pure w ater. The osmotic pressure of the sugar in solution causes water to be
r
drawn
static
through the walls of the cell till the hydropressure of the column of water in the upright
in
i.e.,
as great as this drawing force, the osmotic pressure of the solution.
tube
is
as great as
The
hydrostatic
of in
easily calculated from the specific gravity pressure the solution and the height of the water column
is
the tube.
An
experiment
made by Ramsay
at
the suggestion
of Arrhenius affords a striking comparison of osmotic
He made an air-tight pressure with the action of gases. cell the bottom of which consisted of a thin sheet of Pt,
attached a manometer,
filled
the cell with nitrogen, and

Plati-
placed the whole in
an atmosphere of hydrogen.
to nitrogen
num
is
impermeable
but permeable to hydro-
gen, consequently hydrogen is drawn into the cell just as is drawn through the copper ferrocyanide membrane, 2
HO
and the increase of pressure can be read off on the manometer. The first quantitative osmotic measurements were made by the physiologist Pfeffer. He measured the osmotic pressure of sugar solutions of various concentrations and
obtained the following table.
Concentration of sugar in i grams per 100 c.c Pressure in atmospheres. ... 0.704 Pressure per gram of sugar 0.704
.
i-34 0.67
2.74 i-97 0.72
4
2 -7S
0.69
6 4.06 0.68
26
ELECTROCHEMISTR Y.
these figures it is clear that the pressure is proportional to the percentage of sugar in the solution, or
inversely proportional to the
From
volume which contains a

Constant
;
gram
which
of sugar in solution
is
p=
= p v Constant,
the expression of Boyle's law. found further that the osmotic pressure rises with a rise in temperature, as the following table shows.
Pfeffer
The
calculated
pressures in the third
column were
obtained from the value for a

the equation
i%
solution, according to
^=0.649(1+0.003671:) atm.;
for
an
n%
solution,
p = n- 0.649(1 +0.003677).
C. the pressure of a 4% solution was 2.74 atmospheres, while the formula gives 2.73. If we calculate
At 13.7
from
this the
molecule of sugar = 342 grs. in equation
value of the osmotic pressure for i grami litre we obtain the
(Gay-Lussac's law),
WORK, CURRENT, 4ND VOLTAGE.
27
where p is the osmotic pressure in atmospheres, v the volume in litres, and T the absolute temperature. Gaysugar
as
it
Lussac's law, therefore, holds for the osmotic pressure of that is, the sugar exerts the same osmotic pressure
;
would exert gaseous pressure and the sugar in the form of a gas.
if
the
H 2 O were absent
and
at the
We
will
now
describe a few experiments which striktransition
ingly illustrate the action of osmotic pressure
same time form a

relation
to
considerations on the
between osmotic pressure and the freezing- or

.is
boiling-points of solutions. i. When a crystal of Feds
thrown into a dilute

of Prussian blue
is
solution of
K 4 Fe(CN)6
membrane
crystal.
is
formed on the outside of the
Inside this
mem-
very high, and water is drawn in from the outer solution, and the membrane is extended till it can no longer stand the pressure from
brane the concentration of FeCls
within.
tion
It
breaks at some point and concentrated solu-
from within bursts out.

this
fresh
membrane
is
is
at
once formed around
and the process
repeated so
that a tree-like structure of Prussian blue gradually grows
up from the
crystal.
Solution
Water
FIG.
3.
2.
If
a,
wall of ice
is
(Fig. 3) in
one side of which
placed in a rectangular vessel is water and in the other
a solution, the ice wall will appear to
move toward
the
28
ELECTROCHEMISTRY.
where the water
side.
is,
side
because on the one side ice melts

a
to
in contact with the solution, while water crystallizes out
on the other
permeable
This
ice wall is in
is
way
a semi-
(An permeable important point in calculating the depression of the

freezing-point.)
3.
wall
which
water.
The atmosphere can

If
also
be considered as a semi-
two beakers, one of which cona sugar solution and the other water, are placed in tains a confined space, it will be found that water distils over
permeable medium.
from the second
to the first.
The atmosphere can be
considered in this case "as a wall permeable to water but not to sugar molecules. (Important in calculating the
elevation of the boiling-point.) " " of Schlierenapparat 4. The so-called
Tammann
is
an arrangement for observing the concentration changes on a semi-permeable wall. If a drop of a concentrated
solution of solution of
K4 FeCy 6
is
is
carefully brought into a dilute
CuSO4 by means
at
of a pipette, a
membrane
of
once formed around the drop. Water Cu2FeCy2 will be drawn in through the membrane on account of
the higher osmotic pressure of the salt inside, and as a result the CuSCU solution in the immediate vicinity of
the drop becomes more concentrated and this heavier solution can be seen falling in a stream away from the
drop.
If
no descending streams are observed, the two

(p.
solutions are iso tonic.*
We
have seen
Just
27) that the gas laws hold for dilute
solutions.
as gases
can do work on expanding,
* For further methods of measuring osmotic pressure, as well as text-books of freezing- and boiling-point changes, see any of the larger
physical chemistry, as Nernst, p. 132
ff.

k
29
it
so a dilute solution can be

is
made
to
perform work when
being further diluted, since dilution is nothing more than the distribution of the dissolved substance through
a greater volume, i.e., expansion. If v is the volume in which n gram- molecules of a simple substance, for instance cane-sugar, are dissolved, and if the osmotic
pressure of these molecules is lowered by dilution from pi to p2, the work which may be obtained is (cf. p. 20)
or, since
osmotic pressure and concentration are directly
proportional,
A=nRTln-, c
2
or, finally, since the osmotic pressure varies inversely as the dilution,
Dilution = volume per gram-molecule =
-.
concentration/
A=nRTln-.
Vi
Vo
With
to calculate the
the help of this equation it is possible in most cases work obtainable from chemical reactions.
Calculation of Chemical
Work from
Osmotic Pressure.
van't Hoff's Equation.
We will
take a reaction of the form
i.e.,
a reaction in which
mols of the substance
unite with
n mols
of thesubstance B, forming o mols
ELEC TROCHE MIS TR Y.
of the substance
C and
q mols of
D.
For instance
in the
reaction
4SbCl 3 + 5H 2 O = Sb 4 O 5 Cl 2 + loHCl,
m = 4, n= 5, = 1,
and
q= 10.
Further,
let
the small
italic
and Greek letters represent the concentrations before and after the reaction and we have the following scheme
:
Lowering of a concentration or presFor the substance A this work is sure can do work.
sinks.
As the and B
reaction
goes on, the concentration of both
mRTln-, a
for
B it is
concentrations of
The
and
are increased
The work to progress of the reaction. this cause is negative, i.e., to increase their concentration
requires work; consequently
by the be gained from
-oRTln-=oRTln->
f
7
31
The
total
work
of the reaction
is
therefore
This
is
the so-called
"
"
energy equation
of van't
HofL
This equation becomes still simpler when we introduce When the reaction goes to the laws of mass action. i.e., till equilibrium between all the reacting completion,
substances prevails
(cf.
following chapter),
and
#= - ^
'
rdq
represents the equilibrium constant, then
A = RTlnK+RTln
Product of active masses* of disaDpeariie: substances
Product of active masses O f resulting substances
When
all
the substances have the
same concentration
at the start, then
A=RTlnK.
* In this equation by "active mass" of a substance is meant the consame raised to a power represented by the number of molecules with which it enters into the reaction.
centration of the
CHAPTER
II.
CHEMICAL EQUILIBRIUM, STATICS, AND KINETICS.

equation on page 31 gives the work of a reaction when it is interrupted at a particular point where the concentrations are a, /?, 7-, d. We will now consider
first
THE
the far
more important
question,
let it
how much work

go on
till
reaction can afford

itself.
when we
it
stops of
to
We
have a fundamental distinction
make
between the so-called complete and incomplete reactions.
An
example of a complete reaction
is
the conversion
of water into steam at atmospheric pressure and tem" peratures above 100, when the water phase" completely
disappears.
The
freezing of water below o

is
reaction. Water no unfrozen remainder.
likewise a complete turned completely into ice, there is

is
The
1 00
evaporation
of
water
at
temperatures
is
and
at atmospheric pressure
below an example of an
incomplete reaction.
till
In
this case
water will evaporate
the partial pressure (cf. p. 17) of the water-vapor attains a value which is just the same as the vapor pressure of water at the temperature which prevails. When
such
concentration
of
the
water-vapor
is
is
attained
just as
much water
evaporates as
formed by condensa
32

tion of the vapor,
i.e.,
33
visible evaporation
is
has stopped.
We
A
"
say the liquid water
in equilibrium with water-
vapor at the corresponding vapor pressure. If too little water is present, it will of course evaporate completely.
classical
ester
example of an incomplete reaction is the formation." When one mol each of alcohol
brought together they unite to form
and
acetic acid are
and water, but the reaction is not complete; mol of water have it stops when f mol of ester and been formed and J mol of alcohol and J mol of acid
ethyl acetate
remain unaltered.
when
The reaction has reached equilibrium the concentrations have attained these values.
will
We
have
It
to
do principally with the incomplete

that such reactions
reactions.
was formerly thought
were exceptional, because the end concentrations were too small to be measured chemically. For instance, before
insoluble.
Davy's time certain substances were considered absolutely It was believed that when solutions of barium
and sulphuric acid were mixed, barium sulphate was absolutely removed from the solution. According In to this idea such a reaction would be complete. there is no such thing as an absolutely insoluble reality
chloride
substance, although in many cases the solubility is so small that chemical methods are unable to measure it.
The
precipitation of substances
It
reaction.
is in reality an incomplete was formerly thought that when zinc in
excess
all
was put in a solution of copper sulphate absolutely the copper was precipitated out of the solution. But this is not the case, the reaction goes on till the concentration of the copper salt
is
io~ 40
Of
course
it is
out of
the question to even demonstrate
by chemical means the
presence of copper in such a dilute solution, but certain
34
electrochemical
ELECTROCHEMISTRY.
methods
is
enable
us
to
measure such low concentrations.

in which one metal
All
approximately such reactions
by another are incomplete. They are also reversible. We saw above that alcohol and acetic acid unite to form ethyl acetate and water. When we dissolve a mol of ethyl acetate
precipitated
in
i
mol
of water the reverse reaction occurs,
i.e.,
alcohol
is
and
acetic acid are formed.

will
But
this
reaction
also
same state of equilibrium as the first, i.e., will stop when J mol of ethyl acetate has been converted into acid and alcohol. Such reactions which can occur in either direction are
incomplete, and
to the
come
denoted by two arrows in place of the equality sign:
C 2H 5 OH + CH 3 COOH
<=>
CH 3 COOC 2H 5 + H 2 O.
We
ceases
have defined an incomplete reaction as one which This of itself when equilibrium is reached.
definition requires
some modification: when equilibrium
is reached the reaction does not actually cease, but the two reactions, from left to right and the reverse, both go
on with the same

reaction
is
velocity, so that although a continual
going on the composition of the equilibrium mixture remains constant. We must likewise assume
a similar condition of affairs before equilibrium is reached. Both reactions take place, but the velocity in one direction
greater than in the other, so that this determines the direction of the total reaction which we observe.
is
much
Keeping
little
in
mind
in
these
considerations
the
we
will
have
difficulty
understanding
very
important
law
of
mass
action.
Let us take the reaction of page
29,
35
in
which the concentrations of

a, b, c,
B, C,
are represented
by
d respectively.
The
kinetic theory *
and
also
practical experience teach that the reaction from right can be expressed by the equation
vi
left to
= kia m b n
i.e.,
is
of the reacting substances.

of the reverse reaction
proportional to the product of the active masses In the same way the velocity
can be expressed:
But the actual apparent
velocity
is
the difference between
these two single velocities:
V=V!-v 2 = kiam b n - k 2 cdq

This
is
the law of chemical kinetics.
When
velocity
equilibrium
is
attained Vi
= v2
and the
total
V becomes o.
Consequently when the equilibrium
concentrations are
a?
If
j#1
=K
represents
the
equilibrium
constant
,
of
the
reaction, then
* The kinetic theory assumes that the molecules of all substances are in a continual state of motion; a reaction can only occur when two
or
more molecules
collide.
See Nernst, Theoretische Chemie, 1903,
p. 427.
36
ELECTROCHEM1S TR Y.
is
It states that for every reaction there exists a state of equilibrium incomplete when the reaction ceases of itself, and this condition is
This
the law of chemical statics.
by the active masses * of the disappearing substances and of those being produced. The equilibrium
regulated
,
constant remains the same no matter what the concentrations of the reacting substances instance, in the reaction
were at the
start.
For
CH3 COOH + C 2H 5 OH <=> CH 3 COOC 2H5+H 2 O

*
We
definitely.
must explain the conception of "active mass" somewhat more By the active mass of a substance is meant its volume conit is the ordinary molecular concenIn the formulae of the law of mass action,
centration; in the case of a solution

tration (gr.-mols per litre).
the energy equation, part in the reaction

for instance, appears reaction.
If
etc.,
is
the active mass of each molecule which takes
used; the concentration a of the substance A, times since molecules of A take part in the
ester formation or in hydrolysis, its active
a solvent takes part in a reaction, as for instance water in the mass should also be introduced. In dilute solutions, however, the change in the active mass of
is
water
its
active
so slight that for practical purposes it may be neglected, and mass be considered as a constant (in all such calculations the
value
mass is the important point rather than the absolute In very concentrated solutions the change in active mass of the solvent can no longer be neglected, but in most of the electrochange
in active
itself).
chemical reactions of importance, concentrated solutions play a minor

part,
and we may nearly always consider the

active
active
mass
of the solvent
as constant.
The
mass
of a solid in contact with a solution in which the
solid reacts is constant.
The active mass of a metal in a galvanic cell, or of a soluble substance in excess in a solution saturated with respect to this substance, is constant, for as soon as any more of the substance is formed or used
up the concentration
changed.
of saturation
is
at
precipitation or solution of the solid,
and the
once reproduced by further active mass remains un-
CHEMICAL EQUILIBRIUM, STATICS, AND KINETICS. 37

if
we
start
with
is
equilibrium
left
i gr.-mol each of acid and alcohol, reached when J mol of acid and alcohol is
and
mol
of ester
and water are formed.
is
therefore
K"
of taking one mol each, to start with, we concentration we please, the reaction will go take any on in any case till the ratio of the concentrations is J.
If instead
For instance,
if
we
take 2 rnols of acid to
of alcohol,
more than J mol of acid left over. If x represents the amount of acid and alcohol which has been used up when equilibrium is reached the quantity of ester and water formed is also x.
there will of course be
i
In equilibrium, then, we have 200 mols acetic acid, x mol alcohol, and x mol each of ester and water,
then
x^
-- = K=.
4
From
this quadratic
equation
we can
calculate x,
and then know how

is
far the reaction
has gone. Another classical example

acid from iodine vapor reaction H^-I-^^^HL
and Here we can* use instead of the concentration the partial pressures of each gas, which
directly
the formation of hydriodic hydrogen, according to the
are
proportional
to
the
concentration.
If
with the corresponding indices represents each particular

partial pressure, then
'HI
ELECTROCHEMISTR Y.
A
and
further example
is
the reaction
Ppci 5
The
or
"
last
two equations have

"
of gases.
to
do with the breaking up

All
dissociation
cases of dissociation
equilibrium whether in gases or in solution are calculated

in a similar
way.
is
very important example
the dissociation of carbon
dioxide.
The union
of carbon
an incomplete reaction; thus,
monoxide with oxygen is 2CO 2 <=O 2 + 2CO, and the
X Pi 2 = P% X Pa2 , equilibrium conditions are given by where PI, P'2, PS are the partial pressures of the three gases If the constant has been determined respectively.
and pressure, the disthe above equation for by any pressure at this particular temperature. The following table gives the percent to which carbon dioxide is dissociated into carbon monoxide and oxygen not only
at
some
particular temperature
sociation can be calculated
for different pressures but also for temperatures
between
1000
and 4000.
Pressures in Atmospheres
39
The
dioxide,
table
shows that
at high temperatures
it
is
im-
possible
to burn carbon monoxide completely to the and that for this reason we are unable to utilize
at high temperatures the full energy of the
of carbon;
we can
see
combustion from the table about how far the

about
combustion goes in different processes. In the iron blast-furnace the temperature

2000 and the partial pressure of carbon dioxide
0.2 of
is is
about
an atmosphere.
about
5%
is
dissociated,
Under these conditions CO 2 is and as a result the efficiency of the

In illuminating flames which
furnace
also
slightly impaired.
have a temperature of 2000 or more, the partial pressure of CO 2 is only about o.i of an atmosphere owing
to the large quantity of
hydrogen.
The
dissociation of
is
CO 2
can then exceed 10%, and the temperature
cor-
respondingly lower, while the illuminating power, which varies enormously with the temperature, is very appreciably decreased. In the case of explosives the temperature
is
sure of
probably between 2500 and 3000, but here the presCO 2 is several thousand atmospheres, and the
is
dissociation very small, so that the combustion

tically perfect.
prac-
great
The law of mass action has been found to hold for a number of reactions for further details, reference is made to the text-books of theoretical and physical chemAs yet we have istry by Nernst, Ostwald, and others.
;
only considered reactions between substances which were same physical condition, i.e., in " homogeneous " systems when all were either liquid or gaseous. We will now consider the " heterogeneous " systems. For the first illustration we will take the solution of a
in the
salt.
If
we bring
solid salt in contact with
water
it
dissolves:
40
ELECTROCHEMISTRY.
NaCl solid
<=
NaCl dissolved
is
The
equilibrium equation solid salt does not change
^C
'
s olid
= C dissolve d;
but the
as solu-
its
concentration
C solid
tion goes
quantity may diminish but the remaining solid salt always keeps the same density or concentration. Csolid is therefore also a constant, and for equilibrium
;
on
its
we have
KI = C d sso ved
i i
This
equation,
however,
is
nothing concentration of the dissolved

salt
less
than a statement that
at equilibrium the
salt is constant, i.e.,
every
has a constant
solubility.
What has been
said for
ordinary salt is true for all solid substances. They do not change their concentration as solids although they
may
expressed when we say the active mass of a solid substance is constant (cf note,
lose in weight.
This fact
is
p. 36).
2.
Another
classical
:
example
is
the
dissociation
of
calcium
carbonate
CaCO 3solid <= CaO solid + CO 2gaSeous.
Here, too, we can include the active mass of the solid substances in the constant of equilibrium and obtain
where p c o 2
is
proportional statement that the dissociation pressure of marble, i.e., the pressure with which it evolves 2, is a constant at
the pressure of the carbon dioxide, and is This is simply a to its concentration.
CO
constant temperature.
to
The same remarks apply
also
liquids. liquid water evaporates, part of it as such, but the density of the' remaining disappears water, i.e., its concentration (mols per litre), is not
When
changed.
We obtain in
this case also

in other words, the
41
vapor pressure of water has at con-
stant temperature a fixed value.
Change
of Equilibrium with the Temperature.

it
In the previous considerations

a
reaction
at
has been understood

If
that the temperature remains constant.

different
we
for
consider
instance temperatures, the formation of carbon dioxide (cf. table, p. 38), we
as
1000
2000
3000
4000
Temperature
FIG. 4.
find
that
the
equilibrium
constants
are
different
for
These facts are clearly shown temperature. the accompanying curves (Fig. 4). The abscissae by
each
represent temperatures,
centage to
and the ordinates give the perwhich carbon dioxide is dissociated. At low
temperatures the combustion for all practical purposes is complete, and the gas mixture contains practically
But the higher the temperature, the less At a temperature of 3000 complete when the pressure of CO 2 is one atmosphere the com-
100%
CO
2-
is
the combustion.
42
bustion
is
ELECTROCHEMISTRY.
only
60%
of
the
whole;
the
till
dissociation
increases with increasing temperature,
finally at very
high temperatures carbon monoxide and oxygen combine to a very slight extent. However, since this reaction, either at high or low temperature, is not absolutely complete,
the curve which represents the relation between degree
of
combination
and
temperature
can
never
actually
touch the two horizontal lines representing o% and 100% dissociation, but can only approach them asymptotically.
This
is
best seen in the curve for o.ooi of
an atmosphere.
The
relations
all
which hold
for this particular reaction are
true for
incomplete reactions;
all cases.
similar curves can be
obtained in
From what has been

ical
said
it
can be seen that the chem-
facts with which we are acquainted are somewhat a matter of chance, since they are governed by the temperature and pressure which happen to prevail on our
burns, uniting with oxygen to form carbon dioxide, and this is true for the comparatively low temperatures of our
planet.
We
are
accustomed
to
say
that
coal
But if we lived on a body stoves or blast-furnaces. whose temperature like that of the sun is in the neighborhood of 10000 our chemical text-books would say that
carbon and oxygen do not combine. Carbon dioxide would be an unknown substance to an inhabitant of the
sun, since at that temperature
dissociated.
it
is
almost completely
Water
is
an unknown body on the sun, since
sun's temperature
of the
at the the equilibrium of the reaction 2H 2 + 2 2 lies at a point where the concentration
O ^2H O
water
is
immeasurably small.
We
consider a
mixture of hydrogen and oxygen unstable, but an inhabitant of the sun would consider water an exceedingly

unstable
ing
it.
43
compound
if
he could ever succeed in obtain-
Our experimental chemistry is the chemistry of the " earth; we cannot write a chemistry of the universe" until we know the equilibrium constants of all reactions
For since all reactions proceed temperatures. toward the point of equilibrium we could then know the
at
all
direction in
ture.
which any reaction would go
at
any tempera-
are indebted to J. H. van't HofT, the master of the science of physical chemistry, for the method of solving
We
important problem. An expression derived by him and known as " van't HofF s Equation " gives the relation between the equilibrium constant, the heat of reaction, and the temperature. This expression, obtained by intethis
grating a differential equation,*
is:
In
this
equation T\ and
T2
are two absolute temperatures, "
KI and
K 2 the equilibrium constants of the given reaction

natural log
at these temperatures, In represents the

(see p. 20, note),
"
is
table on
p. 8).
p. 5),
and
If
we know
q the last-named value and determine
is
the gas constant 1.991 cal. (see " the heat of reaction " (see
the equilibrium constant for any particular temperature
we can calculate the equilibrium for any other temperature. The table on page 38 has been calculated in this
*
(p.
The
9)
equation
is
ential equation
and the energy equation dlnK -q
derived from the second law of thermodynamics (p. 31). By combining them the differ1S
-rr^ ~7^,
obtained.
44
ELECTROCHEMISTR Y.
it
way, sLice
is
experimentally impracticable to measure
the equilibrium at a temperature of 4000. On the other hand, if we know the equilibrium constant
of a reaction at two different temperatures
we can calculate
the
"
heat of reaction."
a- solid
The
the reaction where

is
equilibrium constant of substance dissolves in water
If
equal to the concentration at saturation (see p. 40). Ci=2.SS and 2 = 4. 22 are the solubilities of succinic
C.
(
acid at o
= 273) and
Inci
8.5
C.
= 281.5),
i
then
Inc 2
=q
2\li
( i 7^
\
) .
777-
lz/
find
From
value
since
this
equation
cal.
6900
q
is
we can calculate q\ and The reaction mixture cools
the
itself off,
negative.
6700
cal. as
Berthelot found experimentally the heat of solution, in very good agreement
with the calculated value.
CHAPTER
III.
THEORY OF ELECTROLYTIC DISSOCIATION.
A NUMBER of
later
experimental facts which

to
we
will
mention
the supposition that in the water solution of a salt only a certain fraction of the salt plays a part in electrochemical processes. This active part varies with the nature of the salt, the temperature, the
dilution,
on has led
and the nature
of the solvent.
(Solutions in
solvents other than water have not as yet been systematically investigated.)
The
rest of the salt
remains
in-
active
current.
and has nothing to do in transporting the electric For instance, if we measure the conductivity of a
sodium-chloride solution,
we
find that all the salt does not
take part in conducting the current, but only a fraction; in the case of a normal solution of NaCl this active part
normal solution of AgNO 3 it is only same fraction which is active in in58%. fluencing the electromotive force of an electrode; for instance, in a normal AgNO 3 solution it is 58% of the total salt present. Of every .TOO molecules in the above NaCl solution 67 are in a condition different from the remaining 33, and the same is true of the 58 molecules in
is
of the whole; in a
It
is
this
every 100 in the
AgNO 3
solution.
This active part of the

45
whole
is
found from the conductivity and measurement
46
ELECTROCHEMISTRY.
and
also
of electromotive forces,
from measurements of
the osmotic pressure and changes in the freezing- and boiling-points of the solutions, and all these methods
give practically the
same
values.
of
The chemical conduct
dissolved
salts
seems
to
indicate that these 67 or 58 molecules are just the ones which enter into chemical reactions. In cases where no
if
molecules are present which can transport, the current, or they are present in very small amounts, chemical
reactions
slow.
suffer
do not take
salt
place, or
if
they do, are extremely
on dissolving in water must therefore some change, and the physical conduct of solutions
salt depresses the freezing-point of water and raises the boiling-point. When i gr.-mol of a substance like urea, or boric acid,
shows that the change is very profound. Like all soluble substances, a dissolved
or sugar, which does not conduct the current, is dissolved in i litre of water, the freezing-point of the solution is
1.86.
1.86
is
called the
"molecular lowering of the

however,
"
freezing-point of i gr.-mol of a salt in

current,
of water.
If,
i
we
is
take a solution
litre,
which does conduct the

lowered more
salt
we
find that the freezing-point

It
than 1.86.
seems as though that part of the
which
does not take part in the conductivity acts normally
in lowering the freezing-point, but the rest which is the active agent in conducting the current acts as though its
component
radicals
had parted company and were each
For instance, in a in the solution. existing separately normal solution of NaCl, 33% of the salt affects the
freezing-point as cane-sugar would, lowering it 1.86X0.33 = 0.614; but the remaining 67% acts as though it had
broken up into
Na
and Cl atoms and thus
affects the

freezing-point
47
twice
as
much
as
an equal molecular
X 67 X 1.86 = 2.49. The total lowering is instead of 1.86. In a therefore 2.49 + 0.614 = 3.104 normal AgNOs solution 42% has the usual effect, but the
this
quantity of sugar
would do, so that the lowering from
cause
is 2
rest
has twice the normal
effect,
as
if
this part of the
AgNO 3
had broken up
into
Ag and
NO 3
radicals.
In a
N -
solution of
SO4 about 75%
of the acid takes part in

acts as usual in de-
conduction.
The remaining 25%
pressing the freezing-point, but the 75% has triple the + SO 4 usual effect, as though it had broken up into
H+H
The
o.i
normal acid
it
acts therefore in regard to
its
con-
ductivity as though
to its freezing-point as
were 0.075 normal, but with respect if it were 0.25 normal.

for the lowering of the freez-
The
relations
which hold
ing-point are true also of the rise of the boiling-point or gram-molecule of any lowering of the vapor pressure.
non-conducting substance when dissolved in i litre of water raises the boiling-point a certain fixed amount, no
matter what the substance
a non-conducting solution.
of
is,
provided only that
it
gives
But a
o.i
normal solution
SO 4
raises the boiling-point as
though
75%
of the
acid had decomposed with the formation of three new substances, i.e., as though the solution Were 0.25 normal.
osmotic pressure is affected in just the same way. p. 26 we saw that a normal solution of cane-sugar exerted an osmotic pressure of 22.42 atmospheres. A
The
On
nopnal solution of other non-conducting substances has the same value, but a conducting salt solution has a much
higher osmotic pressure. The ratio of this higher pressure to 22.42 is the same as the ratio of the abnormal
48
to the
ELECTROCHEMISTRY.
Here again had broken
normal lowering of the freezing-point. the conducting molecules act as though they up into their component radicals.
others of a physical and for doubt that a de" " or dissociation composition electrolytic actually takes is dissolved in water, and that place when a salt only the " dissociated atoms or molecules (known as ions ") are
facts, as well as
These
many
chemical nature, leave
little
room
the active agents in conducting the electric current or determining the electromotive force of an electrode. The
percentage of the
called the
salt which undergoes decomposition is degree of dissociation." Aside from the fact that many chemical reactions can
"
only be explained on this supposition, the theory of electrolytic dissociation finds its principal support in the fact
that all the different
degree impossible for the electrochemist to do without the theory

of electrolytic dissociation.
the
of
dissociation.
methods give concordant results for At the present time it is
To
illustrate these facts
measurements.
we give the following table of The numbers state how many molecules
molecule of the dissolved
"
salt as
are formed from one
the result of electrolytic dissociation.
The
this
question
now comes up:

It
What
is
the nature of
cannot be an ordinary separation, separation?" since the union of atoms in forming a compound is
generally accompanied by a great production of energy.
energy would have to appear again, not true in this case. It seems, which apparently therefore, that the chemical affinity which has brought
is
On decomposition this
about the union of the atoms has been compensated for

in
some way
so that the
atoms are
at liberty to separate,
49
DEGREE OF DISSOCIATION AS DETERMINED BY OSMOTIC AND ELECTRICAL METHODS.
we assume
positive
effects and the conductivity that the chemical affinity has been changed to an electrical affinity, in that the atoms take on charges of
Because of the electromotive
and negative
electricity.
The
"
neutral
compound
dissociates into positively
and negatively charged atoms

as
ions."
or radicals, which are
known
In what follows
theory,
we
will review briefly the history of the
and at the same time explain the different conceptions which have been introduced.
History of Electrochemistry. Dissociation and
The Theory
its
of Electrolytic
Foundations.
In order
to
and
its
its
advantages
understand the foundation of the theory a theory which at present is an in-
dispensable part of theoretical chemistry
we
not,
will follow
development
historically.
We
will
however,
confine ourselves strictly to the history of the theory of
50
electrolytic
ELECTROCHEMISTRY.
dissociation,
but will also
take
this
up
that of
to learn
opportunity electrochemistry some of the important laws of electrochemistry.
in
general and use
The
than
our
dissociation theory has
met with more opposition
most theories of a purely hypothetical nature, probably because at first sight it seems to clash with
"
chemical sense."
is
But
is
not the atomic theory
that matter
divisible until the final indivisible particles

still
known
our
"
at ease
as atoms are reached
more
chemical sense
"
And
yet
we
antagonistic to find ourselves quite
where the atomic theory

is
is
concerned.
Possibly
the reason for this
that the physical

for
and nathematical
knowledge required
sociation theory
is
the comprehension of the dis-
atomic theory.
We
not necessary to an understanding of the are probably justified in saying that
most of the opponents of the theory of electrolytic dissociation refrain from accepting it on grounds of conservatism which is simply another name for inertia while others oppose it as they do the atomic theory, because they are unwilling to accept anything which they have not seen c. tested by experiment.
The
ago.
dissociation theory
had
its
beginning a long time

found,
that
Nicholson
the
and
Carlysle
accurately,
and
Davy
confirmed
facts
solutions
which
conduct do not remain unchanged by the passage of the current, as the metals do, but are decomposed; that is,
the chemical affinity which has brought about the union of the elements in the salt is simply overcome by the
action of electricity. The fact that the products of the decomposition are
* Nicholson, Journ. of Nat. Phil., t Gilbert's Ann., 7, 114, 28,
i
4,
179 (1800).
(1808).
and 161

attracted
51
to the electrodes, where they are deposited, that they were already electrically charged before proves deposition, as otherwise there would be no attraction;
and
to
electrode
which move toward the negative must be charged positively and those which go the positive electrode must be negatively charged.
further, the elements
is
Fig. 5
a facsimile of one of Faraday's drawings in

in
which he has written the terms now

These words were made
ogist
common
use.
at his suggestion
Whewell.
He
called
the
by the philol" " electrode negative
Fig.
5.
the cathode," and this is the electrode toward which the " " cations," or the metallic elements in the electrolyte," " " anode is the electrode toward which the move; the " anions " move. The whole process was named " electrolysis."
"
About 1833, Faraday discovered the law of equivalent

deposition,
now
generally
known
is
as Faraday's law.
wrong.
He
The word anode is and o<5oS=road; cathode is ro~n Kard= down and 66 oS (the th in this case comes from the aspirate The word ion is from êyai=to go, and the corresponding in oSo *). words are cation and anion. Cation should have no h.
derived from the Greek words
* Faraday's spelling of "cathion"
dvd=up
$2
ELECTROCHEMISTRY.
ist,
showed:
is
that
is
the
amount
of the electrolyte
which
decomposed which has passed through the solution; and 2d, that when the same current is passed through two different
electrolytes the
proportional to the quantity of electricity
amounts
of the
different substances set
free are chemically equivalent.
ILLUSTRATION: This law can be expressed as follows:

of electricity precipitate equal quantities substances in electrolysis. By equal quantities of substances is meant not equal quantities in grams but
Equal quantities
all
of
in
gram
equivalents.
current of
ampere
precipitates
per second 0.01036 milligram equivalents of any substance;

for instance (cf. table
on p. 163):
107.93X0.01036
or
or
= 1.118
mgr. of
silver,
35.45X0.01036
127
i4.o4
= 0.368
mgr. of chlorine, mgr. of iodine,
X 0.01036 = 1.3 1 6
or
+ Xi6)Xo.oio36 = o.643
mgr. of
is
NO 3
In the case of substances whose valence

i
we must
divide the atomic weight

deposits
greater than the valence. by
One ampere-second
61.6
-^
X 0.01036 = 0.32 94
mgr. of copper,
or
(32.06+4X16)
Xo.oio36
= o.5
mgr. of SO4,
^^
or
3
X 0.01036 = 0.0935
mgr. of Al.
by
Since the precipitation of metals or radicals the law of equivalents, it follows that
is
governed
equivalent

quantities of different
53
compounds are decomposed by one and the same quantity of electricity. Thus i amperesecond decomposes
Xo.oio36 = 0.0933 mgr. of water,
or
Since
lents or
ampere-second deposits 0.01036 mgr. equiva-
gr. equivalents, it is seen that 96 540 are required to deposit i gr. equivalent; ampere-seconds or since i ampere-second = i coulomb, 96 540 coulombs
0.00001036
are required.
This fact proves that one equivalent of
each and every ion carries the same charge of electricity. Faraday's law applies not only to water solutions, but also to solutions in other solvents, and to salts in a fused
state,
and holds
for all temperatures.
The
fact that the
decomposition products of the electro-
lyte, as hydrogen and oxygen, appear at points some distance apart, caused at first a great deal of difficulty.
It
was evident that the two products could scarcely be derived from the same molecule of water or dissolved Several substance, but must come from different ones.
theories
were at
first
proposed to account for the
facts;
for instance, the theory that the
two substances hydrogen and oxygen were not derived from the water at all; that electricity itself was nothing less than an acid.
Von Grotthus * attempted
to clear
He assumed
came from
that the anion which
up the difficulty. was being deposited

to the
the molecule which
was nearest
anode;
* Ann. d. chem. u. Physik, 58, 64 (1806), 63, 20 (1808).
54
cation which was being deposited came from the molecule nearest to the cathode. Just at the instant
the
when
these
were deposited on the electrodes the
re-
mainder of the decomposed molecule appropriated the atom or radical it had lost from its neighboring molecule,
this in turn
robbing
its
next-door neighbor.
This view
was
also apparently held

first to
by Faraday.
The
was Grove.* cell, which derives

molecules
is
point out the shortcomings of this theory From his study of the oxygen-hydrogen
its energy from the union of these two he concluded that a decomposition of the water elements,
not necessary for the evolution of oxygen and hydrogen, but that the molecules are present from the start in a decomposed state.
if a force is Clausius f then followed up this idea to decompose the molecules, electrolysis should necessary
:
not be possible at very low voltages.
But the
electrolysis
of silver nitrate between silver electrodes takes place at
voltages which are far below the voltage which corresponds to the energy of formation of silver nitrate; that is, we
decompose at the expense of a small amount of work a salt which is formed with the liberation of a great deal of energy, a fact which conflicts with the principle of the
conservation
that
"
Clausius concludes therefore energy. the supposition that the components of the moleof
cules of
an
electrolyte are firmly united

is
and
exist in
fixed orderly
wrong." arrangement few years earlier Williamson { had expressed a

similar
somewhat
view.
He
proposed
the
hypothesis
* Phil. Mag., 27, 348 (1845).
f Poggendorf's Ann., 101, 338 (1857). J Liebig's Ann., 77, 37 (1851).

that in hydrochloric acid
"
55
not remain quietly attached

of
chlorine,
each atom of hydrogen does all the time to the same atom
but that they are continually exchanging If this is the case, then the places with one another." two radicals must be present separately for a certain
length of time, and this time will be longer the farther apart the molecules are, or, in other words, the more dilute
the solution
is.
This hypothesis was adopted by Clausius, but at that time no experimental means were known for determining
how much
of the electrolyte
was
dissociated, or, in other
words, to determine the ratio of the time during which the molecules were dissociated to the time during which the
atoms remain united.

time Hittorf's* importantwork was published. Hittorf found that during electrolysis changes of concen-
About
this
tration occur at the
anode and cathode, and concluded
that these changes could only be explained

that the anions
by assuming
and
cations
move with a
different velocity.
At the same time Kohlrausch discovered the lawf of the " independent wandering of the ions." He found that
in
dilute
solutions the conductivity of a given salt
is
additively
composed
of two values
is,
which are peculiar

whether
If
it is
to the different ions; that
the potassium ion plays the
same part
in conducting the current
with the chlorine ion or the
NOs
ion.
we add
present to the
conductivity of the potassium ion that of the chlorine ion, which is also independent of the nature of the cation
present with
chloride.
it,
we
This
result
obtain the conductivity of potassium shows that any one ion troubles
* Ostwald's Klassiker, Nos. 21 and 23. f See the chapter on Conductivity.
5^
itself
little
ELECTROCHEMISTRY.
very
about the nature of any other ions which
also be present in the solution. Electrochemical theories had reached this point when van't Hoff in his classic work applied the gas laws to
may
and 46) that the gas laws no longer hold when we consider a salt whose solution conducts the electric current. If p is the osmotic pressure and v the dilution, i.e., the volume in which a gram-molecule is
solutions.
(pp. 20
We
saw
contained,
(cf.
then
pv = RT
for non-conducting
solutions
p.
26).
it
In the case of conducting solutions van't

necessary to multiply
HofT found
RT by a factor
i,
so that
for this class of solutions
p-v = iRT.
Arrhenius calculated from Kohlrausch's measurements

that only a part of the total number of molecules of a dissolved salt is active in conducting the current, and
that this part
is i
i; i.e., if 2
= 1.7, then 70%
of the total
dissolved salt takes part in conduction. Arrhenius then " If we must assume that free ions are present concluded: in the solution, as Clausius and Williamson have shown,
and if the osmotic and other methods show that many more molecules seem to be present in the solution than we have introduced, then we may assume that the salt is
Clausius believed, to a very slight extent, but to such a large extent that this will account for the deviation from the van't HofT gas laws." Now,
dissociated, not
as
and not the whole and since this part corresponds to the extra molecules which van't Hoff has shown to be present, Arrhenius drew the conclusion that the electrolyte is dissociated into ions, the amount of dissociation depending on the concentration of the solution
since only a part of the dissolved salt
is
active in conduction,
and nature
of the salt,
and that the ions are the only
Ê
IV:RSITY
OF
OF ELECTROLYTIC DISSOCIATION.
active
57
agents in conducting the current.

indispensable to
has become
also
This theory electrochemistry, and has
become
of great help in our understanding of general
chemistry.
it
bring ordinary salt in contact with water, * dissolves, but at the same time the reaction
When we
takes place. This is the equation of an ordinary chemical reaction and like all reactions finally reaches a condition
of equilibrium.
In the case of a normal solution of NaCl,
the reaction goes on till 67% of the salt has dissociated into ions, i.e., the degree of dissociation is 67%. Such
a reaction must follow the law of mass action

If
(p. 35).
x represents
that
part of a gram-molecule
which
is
dissociated
when the volume of the solution is v (in the # = 0.67), then at equilibrium the concentration above case
T
/y*
of the undissociated
molecules will be
v
oc
,
'
but the
the law
concentration of each kind of ions will be

of
- and
v
mass action requires

T
'
x
4.
#2
~^2'
ions were formerly denoted by Na and Cl to indicate that we do with a positively charged sodium ion and a negatively charged chlorine ion; substances whose valence is greater than i were denoted
The
to
have
++
SO 4 indicating that the copper or SO 4 ions carry twice the charge of the sodium or chlorine ions. For typographical reasons it ' and the has become customary to replace the + by by printed
by Cu and
,
above and
to the right of the symbol.
53
ELECTROCHEMISTRY.
\
or, in general, if
is
the concentration of the ions
and
cs
that of the undissociated molecules, then
n being
the
i
number
"
of ions
which
salt.
results
from the
"
dissodisso-
ciation of
molecule of the
is
called the
ciation constant
of the salt.
The
occurs
:
following examples will
show how the
dissociation
AgN0 3
^ Ag'+NCV;
Na 2 SO 4
<=
Na' + Na' + SO 4";
But " dissociation by steps " may
also occur, as:
BaCl 2 <=BaClIn many cases we cannot decide from the formula of a how it will dissociate. In the case of KHSO 4 the
salt
following reactions are possible:
or
KHSO 4 <=K'
or
KHSO 4 <=H'
" we can generally transport number determine what the ions are, and Hittorf has applied this
By measuring
method
in a
the
"
number
of cases where the composition of

If
the ions
was doubtful.
we put some potassium

bottom of a
silver
cyanide
KAg(CN) 2
at the
tube and pour
59
water into each arm of the tube, the cations will move to the cathode and the anions to the anode when a current
is
for
passed through the tube. After the current has passed some time we find on analyzing the contents of each
half of the tube that
no
silver
has wandered toward the
cathode, but has gone
in the opposite direction
toward the
of the
This shows that the silver forms part and that the dissociation occurs thus anion,
anode.
:
In a similar way it has been shown that the chromium in the chromates belongs to the anion just as sulphur belongs to the SO 4 ion. In the case of many acid salts,
provided
the solution
is
not
too dilute, the hydrogen
goes as part of the anion to the anode. sulphate then would dissociate
Acid potassium
must not be understood, however, that no further In the above instance of dissociation takes place.
It
KAg(CN)2
the dissociation constant
of the reaction
[KAg(CN) 2 ]
has a very large value, and the dissociation
complete.
is
nearly
On
the other
hand the
dissociation constant
Al
*
[Ag-][CN'f
[Ag(CN) 2 ']
The
concentration of a substance
is
denoted by enclosing
its
sym-
bol in brackets.
60
of
ELECTROCHEMISTRY.
the
reaction
Ag(CN) 2
'
<=*
Ag- + CN' + CN'
is
very
small, so that this second dissociation only takes place to an exceedingly small extent. In such a solution we have very many potassium ions and " complex " silver-
cyanogen
ions,
but free
silver
ions
and cyanide
ions
are present in exceedingly small amounts. It follows therefore that the current is conducted almost entirely
by the potassium and complex ions, while the others on account of their scarcity are practically without effect on the conductivity. As a result we find in the above experiment no silver in the cathode arm of the
tube.
Some
other typical forms of dissociation are:

<=*
Aids
Al-
' '
+ Cl' + Cl' + Cl',
'*
K 6Fe 2 (CN)i2 +
K' + K'-f K
From one
great
are formed,
molecule of potassium ferricyanide seven ions and the dissociated part has seven times as
on the osmotic pressure or lowering of the Other typical freezing-point as the simple molecules. will be given in the following chapters. examples an
effect
* This equation seems to the translator to be incorrect, as Ostwald's "Basicity Rule" shows ferricyanic acid to be tribasic. See Jahn, Grundriss der Elektrochemie, 2d edition, p. 146.
61
Applications of the Dissociation Theory in Chemistry.
In
this
chapter
we cannot
enter into details but
must
limit ourselves to a
few examples which will show the

in our
how we can apply the same time we
and work and calculations. At will touch on a number of physicochemical questions, a clear understanding of which is
usefulness of the theory of electrolytic dissociation
it
necessary to our further study of electrochemistry. The supporters of the theory of electrolytic dissociation
assume that most of the reactions of inorganic chemistry, which, in comparison to organic reactions, take place in a very short space of time, are reactions between the ions.
The
precipitation of silver chloride
from a
silver-nitrate
solution
by ordinary
salt
was formerly explained by the
following equation:
AgN0 3 +NaCl <=> AgCl+NaN0 3

If
we assume
that all the salts except the solid
AgCl
are
dissociated into their ions the reaction
becomes
or subtracting those ions which occur on both sides of the equation,
Ag' + CFÂgCl.
The
essential reaction is the
union of
silver ions
and
old
chlorine ions to form insoluble silver chloride.
The
explanation
to
that
"
chlorine
and
silver react in solution
form
silver chloride" is not strictly correct.
In terms
62
ELECTROCHEMISTRY,
"
chlorine ions
of the theory of electrolytic dissociation
and
in
silver ions
can only
exist together in a
if
water solution
very small concentrations;
the product of their
concentrations,
measured
in
mols
per
is
litre,
should
exceed i.2Xio~ 10 solid silver chloride
deposited until
is
the product of the concentration of the ions to this value."
reduced
Chloroform, for instance, contains no chlorine ions, since it is a non-conductor of electricity, and therefore cannot be electrolytically dissociated; therefore precipitate silver chloride from a solution.
is
it
does not
The same
dissociates
true for
sodium
chlorate>
NaClOs, which
according to the formula
A solution of this salt contains chlorate ions, but no chlorine

ions.
In a solution of KAg(CN)2, which dissociates
after
the formula
KAg(CN) 2
so few silver ions result
^ K'+Ag(CN)
2',
from the further

<=>
dissociation,
Ag(CN) 2
'
Ag- + CN' + CN',
that they can remain in the presence of a large

of
amount
CY
ions without being precipitated.
This accounts
for the fact that
NaCl
2.
will not precipitate
AgCl from
had
a solution of
KAg(CN)
Before the birth of the theory
of electrolytic dissociation
no
satisfactory explanation
been given.
theory explains the slowness of reactions between organic substances on the ground that they are not
The

dissociated to
63
is
any measurable
extent,
and the same
true of reactions between solid substances.

of solid
A
is
mixture
carefully
NaCl and
AgNO 3
from which water
excluded does not react; but as soon as it comes in contact with water the two salts dissolve, are at once
dissociated into their ions,
and reaction
starts.
Salts in a
state of fusion are also dissociated so that
under such
circumstances reaction can easily take place. The old dictum " corpora non agunt nisi fluida "
is
pretty generally true, but not absolutely, since solid substances do react, but with extreme slowness.
Among
hydrogen,
salts
the salts
i.e.,
we must
acids.
include the salts of the metal
the
These are generally very

Just as potassium
strongly dissociated in water solution.
have the
ions, so all
property of giving off -potassium the acids have the property of sending hydrogen
common
ions into solution, as, for instance,
HOMH'+Cl',
or
or
H PO 4
3
<=
H- + H 2 PO 4
'
=*
H-
ions
Acids like sulphuric acid which can furnish two hydrogen per molecule are called dibasic, those which can
furnish three hydrogen ions tribasic, etc.

just
The examples
is
given show
that the dissociation of a molecule
not
necessarily complete but " stepwise."
may
take place by stages, or

the strongly
The
bases are also to be reckoned
among
64
dissociated salts.
ELECTROCHEM1S TR Y.
Just as a
common
characteristic
of
the chlorides
is
their ability to furnish chlorine ions, so
the
bases
have the
common
hydroxyl or
OH
ions.
property of furnishing Acids and bases therefore are

salts.
simply two particular kinds of
Their exceptional
the most universal
importance in chemistry
acteristic
due
to the fact that their char-
ions are also the ions of
solvent, water.
chemical science based on a solvent
which contained neither H* nor

salts.
OH'
ions
would
there-
fore be wholly unable to distinguish acids or bases
from
We
thus arrive at a
now and
salts
exact definition of
an acid or a base.
which are capable of H* ions in solution; bases are salts which furnish forming
Acids are
OH'
is
ions.
We
must now consider the
dissociation of water,
which
one of the most important results of the dissociation theory and the most convincing proof of its value. We can consider water as a dibasic acid which dissociates
as follows:
or also as a mon-acid base, since
it
can furnish
OH'
ions.
rise
The second
to
step of the acid dissociation

is
which gives
O"
is
ions
very
slight, i.e.,
the concentration of
O"
also
ions
exceedingly small.
first
The
dissociation of water into
H* and OH'
is
very slight but of very great chemical importance.

reaction
The
like every other
chemical reaction
is
governed by the law
of
mass
action, thus:
65
" is known as the dissociation equilibrium constant a symbol in brackets is constant of water." (Enclosing
The
the conventional
way
of indicating the concentration of
a substance.)
Now,
active
the dissociation of water
is
very slight, so that the
mass of water is practically unchanged by the dissociation, and we may therefore consider it a constant
and include
along with the reaction constant without causing any appreciable error then
it
;
where k
is the product of the concentrations of both ions. In neutral water neither H' nor OH' is present in excess.
The two
concentrations are equal, so that
if
CQ repre-
sents the concentration of either ion in neutral water,
The last
equation but one must always hold, no matter

of
what the concentrations

whether the
solution
is
H*
or
OH'OH' may
be, i.e.,
acid,
neutral,
or alkaline.
number
22.
of different
methods which we
will consider in
the following have given io~ 7 as the value of CQ at about
Therefore
[H'][OH']=io-
14 .
In an alkaline solution, which contains' 17 grams of ions per litre, [OH']=i, and [H'] must then be io~ 14
such a solution, then,
i
OH
;
in
we would have
a concentration of
gr. of
hydrogen ions in 100
billion litres.
In a o.ooi
,
ormal acid solution [H'] = .ooi and [OH'] = io~ n etc. further application of this formula is as follows:
if
we mix
mol
of
HC1 and
mol
of
NaOH
in a litre
of water, the product
[H']X[OH']
at first will
be=i, a
66

larger value than
is
much
.
possible.
H" and
OH7
will
therefore
the value of [H'j [OH'] becomes io~ 14 The equations for this and other simple reactions of neutralization are:
combine
till
Na' + OH'+H' + Cl' = H 2 0+Na- + Cl',
After subtracting the ions which appear on both sides there remains in every case
The
that
process of neutralization therefore is always based on the same fundamental reaction, provided of course
the
reacting
base and acid are in a solution so
dilute
that
their ions.
they are both completely dissociated into As a result, the heat of reaction of every
neutralization
must always be the same, and must be
independent of the nature of the particular acid or base

used.
This fact has long been known, but previous to the evolution of the dissociation theory no satisfactory
explanation had been given.
The
following table gives
some experimental
results:
67
Hydrofluoric acid is only slightly dissociated in solution, consequently in the reaction
HF + K' + OH'
HF
<=>
K- + F' + H 2
must become further and further dissociated as the
The dissociation of goes on. follows the law of mass action

reaction
HF
of course
K
new ones
[HF]
= [H'][F']
to
and as the H* ions combine with OH' ions
form water
are supplied by the undissociated HF. The heat evolved by the dissociation of the hydrofluoric acid
appears as an excess over that evolved by the union of
The neutralization of hydrofluoric acid 16 270 calories. The difference between this and evolves = 2 570, the ordinary heat of neutralization, 16 270 13 70x3 is the heat of dissociation of HF.
H' and OH'.
question now arises, when either the acid or base a very small dissociation constant, how will this affect has the neutralization? Like all chemical reactions, that
The
of neutralization goes
on
till
a particular condition of
solutions
of
equilibrium
is
reached.
When we mix
and HC1, they do not combine completely to form NaCl, some free NaOH and HC1 remain, but their
quantity
is
NaOH
so small that
of
it
cannot be measured.
of
The
neutralization, incompleteness however, can be measured, as, for instance, that of acetic
acid.
some
reactions
From
influence of
conductivity measurements, or, better, from the sodium acetate on the velocity of the saponifi-
68
ELECTROCHEMISTRY.
cation of methyl acetate,* it has been found that a mixture sodium hydroxide combine of o.i acetic acid and o.i
to the extent of
CH 3 COOH
is it
99.992%, i.e., 0.008% of NaOH and remain in a free state. We may now ask,
possible to calculate this percentage of free acid or hydroxide from the dissociation constant of acetic acid?
o.i
solution of
sodium acetate
in
H2O
must be
decomposed amount (0.008%) and

water
is
into free acid
and base
to exactly this
same
by
this
decomposition of a
salt
The calculation of the hydrolysis." dissociation constant of organic acids from the dissociation
as
known
"
constant of water and the degree of hydrolysis of the salts of the acid, or the reverse, has recently become of such
importance for organic chemistry that we will give a numerical illustration of the method to be followed.
Hydrolysis of sodium acetate: ciates according to the equation
The
acetic acid disso-
CH 3 COOH
and the constant
'
<=
H- + CH 3 COO',
is
of the reaction
given by
K![CH 3 COOH] - [IT] [CH 3 COO'].
From
conductivity measurements the value of KI has to be 0.000018. The relation between [H*] and [OH'] is governed by the dissociation constant of
been found
H 2 0,K
2,
at
25:
The
velocity of this reaction
of th6
ically.
OH'
is proportional to the concentration ions present, which accelerate the saponincation catalyt-
69
Further, there must be just as many positive ions present in the solution as there are negative ions, i.e.,
[H-] + [Na-]
= [CH 3 COO'] + [OH'].

present,
The
two
sodium
compounds
NaOH
and
can be considered as completely dissociated at this degree of dilution, i.e., practically all the sodium is This concentration is present in the form of Na' ions.
then o.i N, since
CH 3 COONa,
we
took that
sodium
acetate.
amounts
of
NaOH
Finally or
much Na in the form of we must remember 'that the

which do not combine which are
set free
CH 3 COOH CH 3 COOH
its
in the reaction of neutralization or
by
the hydrolysis are equal.

dissociated, while the
Since the
NaOH
is
completely
such a small amount that

appreciably affected,
only dissociated to total concentration is not

is
we may
consider
[OH']
= [CH 3 COOH].
:
We haê then four equations

(1) (2)
o.ooooi8[CH 3 COOH] = [CH 3 COO'][H'].
[H'][OH']=i.2Xio-
14
.
(3) [H-] (4)
+ [Na'] = [H-] + o.i =[CH 3 COO']+[OH'].
[CH 3 COOH] [CH 3 COO'J from

(3) in
Substituting the value of

(i) gives
equation
o.ooooi8[CH 3 COOH] = [H']([H-] + o.i
solution of
CH 3 COONa
reacts alkaline;
there
must
is
therefore be
more OH' than H'
present, so that [H*]
7o
ELECTROCHEM1S TR Y.
7.
certainly less than 10
This value
is
so small that
o.i
it
may
this
be neglected in comparison with
(at the most
would only introduce an error of about 0.0001%). Substituting the value of [H*] from equation (2) and then
its
introducing for [OH'] finally obtain
value from equation

n NX
14
(4),
we
-r
o.oooo I 8[CH3COOH]=-
H3COOH]
(o.i-[CH 3 COOH]).
find for the con-
On
solving this quadratic equation centration of 3 COOH,
we
CH
[CH 3 COOH] = 0.0000081.

That
is,
of the o.i
CH 3 COONa,
0.0000081 or 0.0081%
has decomposed
ide;
this agrees
and sodium hydroxvery well with the value 0.008 found by

into free acetic acid
experiment.
We may
of water.
.
also reverse this process
and from the
ex-
perimental value 0.008 calculate the dissociation constant
In
this
way we
find
C = i.iXio- 7
The
at
25.
"
following table contains the degrees of hydrol" of certain salts at 25 when present in o.i normal ysis
solution
:

It is
71
seen that the hydrolysis

It
is
cent.
well
known
may amount to several perthat a solution of potassium
cyanide smells of prussic acid, which can only result from " " a of the salt. A solution of hydrolytic dissociation
ammonium
odor in
carbonate smells strongly of ammonia;
the
this case
hydrolysis. a solution of
3 resulting from being due to the free The slow evolution of carbon dioxide from
NH
sodium carbonate
is
is
another instance.
Still
another example
the conduct of certain salts of bismuth,

in
which precipitate bismuth oxide on being diluted;

the oxide
is
this case the hydrolysis is so great that the solubility of
thereby exceeded. Let us now go back to the calculation of the dissociation
constant of water.
the hydrolysis
consists
The
first
of
sodium
acetate;
method was by measuring a second method
measuring the velocity of the reaction of " When ethyl acetate and sodium hy"saponifi cation.
in
droxide are brought together, sodium acetate and ethyl

alcohol are formed according to .the equation
CH 3 COOC 2 H 5 + NaOH <=> CH 3 COONa + C 2H 5 OH.

In
this reaction the ester
CH 3 COOC2H 5
The
is
said to be
of
this
saponified
reaction
is
by the base
is
NaOH.
velocity
dependent on the concentrations of the reacting
substances and
presence of
H'
ions
further catalytically accelerated by the On the other hand, the (cf. p. 15).
number of OH' ions present also influence the velocity, and it has been found experimentally that the OH7 ions It saponify an ester 1400 times as fast as the H' ions. is easy to see that when we successively diminish the concentration of the
reach a
OH' ions, the velocity of the reaction will minimum when the concentration of the H' ions
72
ELECTROCHEMISTRY.
1400 times as large as that of the OH' ions. If this is determined experimentally and the amount
is
minimum
of free acid at that point determined,
we have
In
this
manner
van't Hoff has calculated the dissociation

,
constant of water, and obtained as the value of c

c
= i.2Xio~ 7
at
25.
third
method
that
for calculating the dissociation of
H2 O
consists in
alkali cell;
measuring the electromotive force of the acidis,
of
electrodes saturated with hydrogen, one of

in
an element made of up two platinum which is placed

in
an acid and the other
an alkaline
solution.
We shall
when
see later that the electromotive force of a metal
placed in a solution of one of its salts depends not only on the nature of the metal but also on the concentration of
the ions of the metal present in the solution For any one metal the electromotive force varies inversely as the logarithm of the concentration of the ions of the metal
in
solution.
We may
consider
platinum
electrode
saturated with hydrogen as an electrode of the metal hydrogen, and its electromotive force is therefore depen-
dent on the concentration of the hydrogen ions in the

solution.
If
we measure
the electromotive force of the
and determine by titration the concentration of the H' ions on one side and that of the OH' ions on the other, we can calculate from this result the concentration In a normal of the H' ions in the alkaline solution. solution of NaOH where the concentration of the OH'
acid-alkali cell
ions
is
nearlv =
i it
has been found that the concentration

of the solution
73
in this
H*
ions
is
about i.44Xio~ 14
..
That
is,
[H'][OH']= 1.44X10-1*,
or
The
method.
the
conductivity
of pure
water furnishes a fourth
The measurements made by Kohlrausch on

water obtainable have given the following
co
purest
figures:
= o.78Xio~ 7
~"
at 18
and
7 at
25.
were obtained
will
(The method by which these
results
be
on Conductivity.) These four independent methods have given the following results for the dissociation of water:
discussed later, in the chapter
i.iXio" 7
If
i.2Xio~ 7
as
and
,
we
take the constant for 25
^T=i.2Xio~ 14 we can
calculate the value of the constant for other temperatures by means of van't Hoff's equation, since the heat of the v -t-OH r = reaction is cal. From these
H2O
13700
has been calculated that the conductivity of the water should increase 5.81% per degree rise of purest Kohlrausch found that the increase was temperature.
results
it
5.32%. The following table gives the dissociation of water at different temperatures
:
74
ELECTROCHEM1S TR Y.
number
of purely chemical problems
which cannot be
satisfactorily explained
without the help of the theory of
equilibrium will be discussed in the chapter on Conductivity, after we have learned the different methods of
measuring
dissociation
constants.
Among
these
are:
influence of the strength' of acids

fication of esters,
and bases on the saponion the inversion of sugar, and on the
hydrolytic dissociation of salts; distribution of an acid between two bases, or of a base between two acids;
rapidity of solution of metals, carbonates, and oxalates the influence of dissolved salts on one another,
etc.
in acids;
The dissociation
a reaction occurs
theory disposes of the question whether
when solutions of salts which have no common ions are brought together; for instance, are KC1 and NaBr formed when solutions of KBr and
NaCl
takes
are
mixed?
The absence
would go
to
of
absorption of heat
place.
is
show
any evolution or that no reaction
The
dissociation
meaningless. question contain the ions K*, Na', Cl' and Br'; and after mixing, the resulting solution contains the same ions unchanged.
theory shows that the Before mixing, the solutions
No
reaction can have occurred.
According to the dissociation theory it is self-evident that the properties of such mixed solutions are additively
built
up
of the properties of the original solutions.
The
specific gravity, for instance, is simply obtained specific gravities of the original solutions.
from the We can go
one step farther, since the

a single substance
to the ions.
effect of
is
specific gravity of a solution of
additively
If
we know
each ion on the
made up of values peculiar number representing the specific gravity, we can calculate
the

by simple addition the
specific
75
gravity of a mixture of
any
salt.
ions, i.e., the specific gravity of a solution of
In a similar manner
the
it
any has been shown that the

the
internal
friction,
compressibility,
capillarity,
the index of refraction, the magnetic rotation of the plane of polarization, and the light absorption of solutions are
additive properties.
These few examples have shown
some
of the applications of the dissociation theory to
chemical phenomena, and will suffice for the present. We need only mention that the conduct of indicators in
titration
tion
has been explained satisfactorily by the dissociaAlso many analytical reactions, such as theory.
of
the
sulphides by hydrogen sulphide, can easily be understood from a knowledge of the (Cf. solubility products and the state of dissociation.
precipitation
metallic
chapter on Conductivity, p. 103). Finally a few words must be added on the application
of the dissociation theory to physiological problems.
The
theory has widely increased our knowledge of the poisonous action of certain classes of substances. The acids are
more poisonous and have a greater physiological action

according as their dissociation constant
is
The
ions of mercury are very poisonous.
great or small. If a salt con-
effect is
taining mercury is taken into the stomach, the poisonous more intense the higher the salt is dissociated.
Corrosive sublimate
slightly soluble
is exceedingly poisonous, while the calomel which gives rise to few mercuiy
ions
is
less
poisonous although physiologically active.
on the other hand, which contains Cyanide two active poisons' mercury and prussic acid, is itself the not very poisonous. This is accounted for by the fact
of mercury,
that cyanide of
mercury
is
practically undissociated, as
76
cLEC TROCHE MIS TR Y.

been
has
shown by conductivity measurements.
An
every-day example of the application of the osmotic theory

to physiology is the following:
The
cells of the
human
body contain dissolved substances and have therefore a certain osmotic pressure. When a wound is washed with " water, the cells, whose walls are semipermeable," draw
in water
and
burst, giving rise to continued bleeding.
To
avoid this the
wound should be washed with
a solution
whose osmotic pressure is the same as that of the solution in the cells. Such a solution is the 2% solution of boric If a 2% solution of NaCl were used, this would acid.
cause smarting, since NaCl is completely dissociated and has twice the osmotic pressure of the boric acid,
which
salt,
is
practically undissociated.
A i%
solution of
the so-called
"
physiological salt solution," is there-
fore used for cleansing
wounds.
with water causes pain, use of a 1% solution
Washing out the nose but this may be avoided by the A swimmer of common salt.
unpleasant to open the eyes under fresh water, but in sea-water, which has nearly the same osmotic
that
it is
knows
pressure as the solution in the cells of the eye, the eyes
may be
kept open for a long time without smarting.
CHAPTER
IV.
CONDUCTIVITY.
JUST as water
lower
level,
descend from a higher to a or as heat tends to pass from a higher to a

strives to
lower temperature, so electricity tends to sink from a higher to a lower "potential." In these three cases the
tendency
or in
falls
is
greater, the greater the difference in level,
and consequently the quantity which is governed by the difference of A quantity of water is measured in litres, potential. a quantity of heat in calories, and a quantity of electricity
potential,"
in
"
unit
time
in
coulombs.
is
The
time
governed by the
quantity of water flowing in a given size of the pipe through which the
water flows, as well as by the difference in level. The quantity of water per unit of time is greater, the greater the
cross-section of the pipe;
and
smaller, the longer the pipe.
This quantity can be measured by determining the number of litres per unit of time which flows in at the top
This same amount must or out at the bottom of the pipe. of the pipe in unit time. The also pass any cross-section amount of water is further dependent on the friction of In other words,
the water against the material of which the pipe is made. it is directly proportional to the reciprocal
of the value of this friction,
which we might
call
77
the
78
ELECTROCHEMISTRY.
conductivity for water of the pipe material. Exactly similar relations hold for the conduction of heat and of
electricity.
When two
quantities of electricity
which have
a different potential are connected by a conductor, a certain quantity of electricity per unit of time will pass
through the .conductor. This amount per unit of time, or current, will vary directly with the cross-section of the conductor and inversely with its length and with the
friction
which the material of the conductor offers to passage of the electricity. These relations are expressed
in
Ohm's Law
Current =
Amount -
of electricity in coulombs J .
Time
Eq = * = -i.
Iw
In
formula E represents the impelling electromotive or difference of potential, q the cross-section of the force, conductor, / its length, and w is a value which varies from
this
substance to substance, and expresses the resistance which each .substance offers to the passage of electricity. The
current
force
is
therefore
proportional
to
the
electromotive
and the
the reciprocal of the conductivity for the of cross-section and length, and is the resistance unit
is
the length and resistance "; it
inversely proportional to " resistance, is called the specific specific

cross-section,
and
which a cube of the conductor

offers to the
centimetre in thickness
If
passage of the current.

i
we put 'a
ampere,
difference
of potential of
volt
on two opposite
is
sides of this
it
cube
and find that the current flowing

from the above equation that the
conductor
is is i.
follows
specific resistance of the
The
reciprocal of the specific resistance
the specific
conductivity.
The
specific
conductivity
CONDUCTIVITY.
of a substance
i
79
is
when
volt will send a current of

i
a difference of potential of i ampere through a cube of
the substance
resistance
is
centimetre in diameter.
i
The
specific
then
distinction
ohm. was formerly made between good, bad,

This distinction, however, cansince we have conductors of every order
gives
:
and medium conductors.

not be adhered
of
to,
magnitude.
conductivity of a
The following table number of substances

OHMS
AT 18.
the
specific
SPECIFIC CONDUCTIVITY IN RECIPROCAL
or A CENTIMETRE
CCBE
'=
K 18
is
the specific conductivity; o ls = K

(T 18
is
the specific resistance;
<7
18
10 ooo
millimetre in cross-section;
gives the resistance of a wire i metre in length and i square a is the temperature coefficient; if T is the
<7
temperature, then
metals.
=a
ls [i
+ a:(T
18)].
The
figures apply to
pure
soft
Approximate values.
Silver
is
which
is
the best conductor known, although copper, used most extensively, is not far behind. Alu-
8o
ELECTROCHEMISTRY.
lately
minium, which has
come
into
prominence as a
material for power transmission cables, conducts only about half as well as copper, but has the advantage of lightness.
Impurities in a metal always diminish its conductivity, consequently all alloys have a lower conductivity than the
metals themselves.
at
1
Thirty percent sulphuric acid has a conductivity of about f, at 40 of about i; i.e., a centimetre cube of sulphuric acid of this strength has a
8
i ohm. A complete list of substances could be given whose resistances lie between those of nickeline and hard rubber, which shows that all degrees of resistance
resistance of
are possible. The temperature coefficient of the resistance of all the metals and most of the alloys is positive, i.e., In the the resistance increases as the temperature rises.
case of practically all liquid conductors the temperature coefficient of the conductivity is positive, and in the case
of water solutions
its
value would indicate a conductivity
of zerjo at about
It is
30.
make a sharp distinction between good and bad conductors, but another very important distinction can be made. All conducting substances may
impossible to
be divided into two classes the first includes all substances which remain unchanged by the passage of the current;
:
in this class belong all the metals, practically all solid
conductors and a few liquids.

prises all
The second
definitely
class
com-
substances
which are
changed by the
i.e., salt
passage oj the current; to this class belong the electrolytes, solutions and salts in a state of fusion.
The
metallic
rule has
been proposed that a substance shows
conduction
is
when
the
temperature
electrolytic
coefficient
of
its
conductivity
negative;
positive.
conduction
hen the
coefficient is
This
rule,
however, does
CONDUCTIVITY.
81
not always hold, for gas carbon, which conducts like a metal, has a positive temperature coefficient of conductivity
(or negative temperature coefficient of resistance).
Cer-
tain solutions
conductivity.
alloys
show a negative temperature coefficient of Even among the metals there are certain
coefficient of
which have a positive temperature

difference
if
conductivity.
The
will
be clearer
between the two kinds of conductivity we assume that in a metallic conductor
the atoms touch each other,
and there are everywhere
present bridges over which the electricity may pass. In an electrolyte the dissolved substances which conduct
the,
if
current are
is
electricity
to pass
more or less widely separated, so that from one atom to another these
traverse a certain distance in order to
atoms must
first
come
less
in contact.
rise of
temperature causes metals to
expand and thus the contact between the atoms becomes In the case of intimate and the resistance increases.
electrolytes,
however, the
to
rise in
temperature diminishes
are
subject in their
the
friction
which the atoms
motions and the conductivity increases.

Conductivity of Solutions.
In the study of electrochemistry we have
to deal princi-
pally with solutions of salts in water, and we will therefore consider more closely the mechanism of the conduction of
electricity
through a solution.
p.
We
saw on
into
58 that salts
electrically
when
dissolved in water
ions.
dissociate
charged
When
two
electrodes are connected with the poles of a battery so that
one
is
charged positively and the other negatively and

salt,
the electrodes dipped into a solution of any
the.
82
ELECTROCHEMISTRY.
an attractive force on the negacharged ions and a repelling force en the positively charged ions, while at the other electrode the positive ions
positive electrode exerts
tively
are attracted
and the negative
repelled.
As a
result the
negatively charged anions
move
to the positively
charged
anode and the positively charged cations go to the cathode. At the electrodes the ions are discharged; i.e., they
neutralize a part of the electricity with
which the electrodes
are supplied, and either remain as neutral matter on the electrode or enter into further reactions. The charges on the electrodes which have been neutralized by the
ions are of course immediately
renewed by the battery. As a result of the pull exerted on the ions by the charges on the electrodes the ions move through the solution, and
since -they themselves are electrically charged they thus
As was seen transport a current through the solution. on p. 52, each gram equivalent of any ion always carries the same amount of electricity, 96 540 coulombs, i.e.,
the anions carry 96 540 coulombs of negative electricity per mol, and the cations the same amount of positive
electricity
per mol.
When
mol of K' ions and
mol
of
CY
ions pass through a plane perpendicular to the
2 X 96 540 coulombs are transported and the current strength is 193 080 amperes, since it makes no difference whether positive electricity moves in one direction or negative in
direction of the current in one second, then
the
other.
If
instead of
mol i/iooooo mol passes

is
through the plane per second the current

amperes.
only 1.931
must now consider the all-important question: What is the relation between the conductivity of an electrolyte and the number and nature of the ions?
We
CONDUCTIVITY.
Let us consider two metallic
placed
Since
parallel to
83
plates, serving as electrodes,

i
each other at a distance of

to
centimetre
between these we pour the solution

all
be considered.
the ions are either attracted or repelled by the electrodes, and since they all take part in transporting the
current,
the
greater the
more
conductivity of the solution will be i;ms there are between the electrodes;
two equivalents of the ions will give twice the conductivity of one equivalent.*
conductivity will also depend on the amount of electricity which each ion can carry; this, however, is
the
The
same
for all ions since they all carry 96 540
coulombs
per equivalent. Finally, the conductivity is dependent on the velocity with which the ions move, i.e., is conditioned
by the different degrees of friction which the ions must overcome as they move through the solution. If we
represent by
friction,
and by
the conductivity of our solution, by r the the number of equivalents present,
then
mX 96540
If
we
represent by
by 96 540,
i
A the reciprocal value of r multiplied then when m=i, i.e., when we are dealing with
equivalent of the ions,
L = A.
is
called the equivalent
conductivity.
The
i
therefore equal to
* "
when an
equivalent conductivity of a salt is electromotive force of i volt
Gram
of the substance obtained
equivalent," or simply "equivalent," is the number of grams by dividing the atomic or molecular weight
i.e., it is
by the valence,
words,
it is
mol
(see p. 18) divided
by valence.
In other
the weight in grams of a substance which carries a charge of 96 540 coulombs. The atomic weight of the bivalent element zinc,
for instance, is 65.4
and
its
equivalent
is
32.7 grs,
84
suffices to
ELECTROCHEMISTRY.
send a current of
i
ampere between two
elec-
trodes which are
cm. apart,
i
when
gram
the solution be-
tween the electrodes contains

ion of the dissolved salt.*
equivalent of each
In
this definition
no account
is
taken of the volume of
is is
the solution between the electrodes, the only provision that they are i cm. apart. Whether the gram equivalent
present in a small or large volume of solvent the pull exerted on the ions by the electromotive force of the
electrodes
w ill always be
r
the same, and the
same
is
true
just
of their velocities
and
electric charges.
What has
been said in regard to the salts can be applied to each kind of ion. The conductivity of any sort of ion will be
high according as
the friction
is
its
concentration
to
is
high and the

in
less
which the ion has
overcome
moving
through the water. Let k' represent the conductivity of the cation, m' the
number of equivalents present, =1 the friction), and 96 540
U its velocity (reciprocal of

',
and
let &',
m', V,
and
'
be the corresponding values for the anion, then

Conductivity of the cation " " anion
=k' = m' Uq6 540 = m'l

f
',
"
=k = m'Vg6 $4o = m'l<f, " " solution = & =m'l '+m'l

'.
In the solution of a
the
salt
m'
is
always equal to m', since
number
of equivalents of cations
must necessarily
Any changes
current
and which may

later.
at the electrodes brought about by the passage of the result in a back electromotive force are not con-
sidered in this definition.
considered
Any
difficulty arising
This phenomenon of "polarization" will be from this source can be avoided

See Book
II,
by suitable methods of measurement.
CONDUCTIVITY.
equal
the
85
of
number
of
equivalents
anions;
then
if
or
if
m=i
(i
equivalent in solution),
Each
the
"
ion,
then, has a particular value
IQ
known
as
molecular conductivity of the ion," and by adding them together the conductivity of any salt may be obtained.
Since the ions lead a rather independent life and any one ion bothers itself very little about what the others
may
be doing
it
follows that
IQ
has the same value in
all
solutions.
take an example, the conductivity of the K' ion is 65.3, the molecular conductivity of KC1 is 131.2, conse= 65.9. quently the conductivity of the CY ion is 131.2 65.3
Since the conductivity of NaCl is 110.3, we nn d that the value for the Na* ion is no. 3 65.9 = 44.4. Further, since
the conductivity of NaNOs is 105.2 and therefore that of ' = is 60.8, the conductivity of 3 3 is 65.3+60.8
To
NO
KNO
126.1.
This law, that the conductivity 0} any one kind of
independent of the nature of the ions of opposite be present in a solution, was called by .charge
ion
is
which may
its
discoverer, Kohlrausch, the

of the ions."
"
law
of the Independent
for the
wandering
A table of the values of IQ

II.
different ions will different values of

salt.
be given in Book
IQ
By adding
A
for
the
we
obtain the value of
any
Thus far we have known quantity of
ions.
considered only solutions containing But in general we are not sure
of the quantity of ions present,
we simply know
the total
$6
ELECTROCHEMISTRY.
quantity of salt. As we saw on p. 48, however, all salts are not entirely dissociated into ions, but only to an extent which generally represents a large fraction of the
whole.
This fraction can be determined by measurements of the osmotic pressure, or of the freezing- or
Let a be the degree of
for the
boiling-points of the solution.

dissociation
y rml per c.c., i.e., mol present a mols have dissociated into ions for every and the salt is iooa% dissociated. For every mol present then i a mols remain as undissociated salt, and we
concentration
find as the conductivity of the solution, not k
= m(l Q
'
+/o')>
but k = ma(l
'
l ').
Thus
far
we have
of solution
not considered any particular volume between the electrodes. The specific con(cf.
ductivity of our solution
p.
79)
is
ic
=
,
where q
is
Since in this particular case / = i, the volume of the solution, v = q and k = KV. Further, the conthe cross-section.
centration in mols per c.c.
is
v
or
or
if
7)
= i mol per c.c.,
of the salt for A^ is called the equivalent conductivity This equation is used very often to the concentration i).
determine the degree of dissociation.

of the solution specific conductivity
We
and
measure the
if
divide this by
the equivalent concentration of the solution,
i.e.,
= A v and
CONDUCTIVITY.
this gives the equivalent conductivity.
87
We then introduce
p.
the values for
'
and
/o'
from the table mentioned on
85 and obtain
the equivalent conductivity of the salt completely dissociated into its ions.
is
when
it
is
From what has been

AQ = I Q + IQ
'
said
it
is
clear that the value of

i;
can only be found when a =
that
is,
when
all
the dissolved molecules are dissociated into their ions.

solutions, however,
Such
do not
exist in reality, since the
incomplete and proceeds until a state of equilibrium is reached. Nevertheless the law of the independent wandering of the ions holds for solutions when dissociation is net
reaction of dissociation
is
is, in a way, an additive property, a law of independent dissociation of the ions which, while not as exact and of such general application
complete.
Dissociation
and there
is
as the other,
is still
of great use in calculation.
It states
that the degree of dissociation of a dissolved substance may often be calculated from numbers which are peculiar
to
each ion.
*
From
the two laws
it
follows that the values
of a/
and
'
a/o' are definite alrf
for a given concentration.
Let al Q
= lc and
'
lc
be the conductivities of the ions

for the equivalent
at the concentration c
and we obtain
conductivity at the concentration c:
i.e.,
the equivalent conductivity at the concentration c is equal to the sum of the conductivities of the ions. It
must always be kept
in
mind
that the degree of dissociation
88
is
ELECTROCHEMISTRY.
always included in the values of
*
'
lc
and
/</,
but not in the
values of
/
for all ions
and and
IQ.
for all concentrations
complete table of the values of is given by Kohlis
rausch and Holborn.*

II of this series.
This table
also given in
Book
of
The
/o
question
/
now
arises,
how
are
the
values
and
determined experimentally?
equivalent conductivity of a wf
KC1
measuring the solution we find it to
On
be 98.2, then
^Kci = ^K + fa = 98-2.
Using a n NaCl solution we find
= ^Na + fa = 74-45
also
= 66. 0,
,=6 7 .8.
In these four equations there are five unknown quantities, fe, ^Na> Âg> fa> ^NO 3 and without further data the single
,
values cannot be found.

is
The
"
fifth
necessary equation
furnished by measuring the gives the value of
transport number," which
For the transport number of KC1,

fa
IK
+ lei
The
value 0.503 has been found by experiment.

Teubner,
is
* Kohlrausch and Holborn, Leitvermogen des Elektrolyt.

Leipzig.
f The letter n means "normal." times normal; etc.
o.i
is
tenth normal; 3 n
three
CONDUCTIVITY.
From
solution,
this,
i
and from the conductivity

i )
of a
normal KC1
found
to
A KC = lK + l C = ()8.2
the value of
/ C1 is
be 49.4.
With the help of this figure we obtain the following values for the conductivities of the five unknown quantities
IK
/Cl
/Na
/N0 a
/Ag
48.8
49.4
25.0
41.0
26.8
/
In exactly the same way the values for
may be found
n they are
for other concentrations, for instance, for o.oi
61.3
It
62.0
40.5
56.8
51.9.
must not be forgotten that these numbers represent not the velocities of the ions alone, but the velocities
multiplied by the degree of dissociation. In order to determine the values of /
*
and
'
we must
t1
Concentration
FIG.
Dilution
6.
know
If
the value of
AQ
is
This cannot be measured directly,

infinite dilution.
since dissociation
complete only at an
plot the value of A in its dependance on the concentration we obtain a curve similar to Fig. 6. In this
we
the abscissae represent the dilution
and the corresponding
equivalent conductivities are plotted as ordinates.
As
90
ELECTROCHEMISTRY.
the dilution increases the curve approaches asymptotically
but which
it
maximum which we cannot reach experimentally, may be found by extrapolation. In this way
.
Since the possible to determine the value of A Q number remains essentially the same for all transport
is
concentrations
late /o,
we may
f
use the value found to calcu-
=nA
and
/o'=/o".
Pure substances conduct poorly:
the specific conis
ductivity of ordinary distilled water at 18
about io" 6.
this low conductivity is not the conductivity of water, but is due almost entirely to small amounts pure of dissolved substances. Although the amount of these
But even
dissolved impurities
may be so small as to escape any they have a very marked influence on the conductivity. Glass may be dissolved to a very slight extent Dy water, also carbon dioxide from the air
chemical
tests,
still
when
dissolved in water furnishes ions which
may impart
a marked conductivity to the water.

very careful distillation and other methods, Kohlrausch was able to obtain water so pure that its specific
By
conductivity
even this
in
was only 0.0384 Xio~ 6. Probably a part of low figure is due to dissolved impurities, but
part, as the following calcula-
any case not a very large
tion shows:
the specific conductivity K ( = reciprocal of the resistance of a centimetre cube of water) and
From
the values of the velocities of the ions
H* and OH',
we
of
obtain as the
this
number (m) of H' and OH' ions in i In i litre, then, water m = o. jSXio~ w
f
c.c.
the
CONDUCTIVITY
concentration of
9
7 at
H* and OH'
ions
is
o.ySXio"
18.
The
fact that several other
methods
for determining the
value of this concentration have given as an average 7 0.78 Xio~ at 18 proves that 0.0384X10" must be very nearly the actual conductivity of absolutely pure water,
A
way
number
of other pure substances
behave in a similar
at ordinary temperatures.
They have a very low
conductivity and consequently can contain very few ions. For instance, pure anhydrous sulphuric acid is very weakly dissociated according to the scheme
when
mixed;
the
two pure substances
HO
2
and H2SO4 are
i.e., if
H 2 SO4
more
is
is
solution conducts
dissolved in water, the resulting or less readily.
According
very few
to the views
the reason for this

ions,
developed in the preceding pages, that the pure substances alone contain
but mixing or dissolving the two substances in some way gives rise to the formation of a large
number
of ions.
An instructive example of this general fact is furnished by the conductivity of sulphuric acid of different strengths. The accompanying curve (Fig. 7) shows the relation
between the concentration and conductivity of H 2 SO 4 conductivity being plotted on the vertical axis and concentration
,
on the horizontal.
zero, i.e., in zero.
At the concentration
ductivity
is
pure water, the conthe concentration of
practically
As
then
H2SO4
increases, the conductivity increases rapidly
and
at
32%
a
reaches a
is
maximum.
It
falls off until at
82%
minimum
reached, the solution at this point having
a composition corresponding to the formula
SO4-H 2 O.
ELECTROCHEMISTRY.
This monohydrate
is to be considered as a comparatively conductor. When more sulphuric acid is added the poor curve rises again (the following solutions may be considered as a solution of 2 SO 4 in the hydrate, 2 SO 4 -H 2 O), at
92%
to
reaches a
o at 100%.
maximum and then falls off practically If SO 3 is added to the anhydrous H 2 SO 4 a
10
.20
30
40
50
60
70
80
90
100
FIG.
7.
new curve with another maximum

in the figure
is
obtained, as
shown
above 100%.
although frequently the solubility
to allow the
is
Solutions of all other conducting substances behave in a

similar way,
not
high enough
maximum
conductivity to
be
NaCl shows (Fig. 7). The more soluble LiCl, however, shows the maximum. The question now arises, does a conducting solution,
attained, as the curve for
i.e.,
mixture
one containing many ions, always result from the of two different substances? This must be
in
answered
on Water
The dissociation depends negative. the nature of the two components of the solution.
the
possesses the property of forming with most of the
CONDUCTIVITY.
acids, bases,
i.e., it
93
and
salts solutions
which conduct very well;
compels the dissociation of these substances.
We
r say that water has a great "dissociating pow er"; but all substances dissolved in it are not necessarily dis-
sociated.
For instance, sugar, urea, boric
acid,
and
many
ions.
organic substances
when
non-conducting solutions,
dissolved in water give which therefore contain no
Another
solvents,
class
of substances,
solvent
though by no means power decreases with an increase in molecular

Liquid ammonia
is
the alcohols, are good as good as water; their
weight.
almost as good a solvent as
water;
it
dissolves
many
substances and gives solutions
which conduct very well. In order to compare solvents with respect to their dissociating power two points must be kept in mind.
dependent not only on the degree of dissociation of the dissolved electrolyte but also on the resistance or friction which the ions must overcome
of a solution
is
The conductivity
in
moving through the

power may
solution.
solvent of low disso-
ciating
give a solution of higher conductivity
than a second solvent whose dissociating power is greater. If the friction which the ions have to overcome in one
this may more than compensate number of ions in the other solution. Water for the larger and liquid ammonia are two such solvents: the first
solution
is
low enough,
possesses the higher dissociating power, but the latter presents much less resistance to the movements of the
ions, as
ity
might be expected from the mobility and of liquid ammonia.
volatil-
Nernst has proposed the following explanation of the

ability of different solvents to dissociate dissolved salts
94
into the ions.
ELECTROCHEMISTRY,
The
electrostatic attraction of the oppositely
must evidently tend to diminish the dissociaof a given salt, and acts in opposition to that force tion which strives to dissociate the compound, and whose nature is as yet entirely unknown. The rivalry between
charged ions
these two opposing forces regulates the actual equilibrium The dissociation must therefore increase of dissociation.
if
of
is diminished. The study has shown that two bodies having electricity opposite charges of electricity attract each other with a force which varies inversely with the dielectric constant
the electrostatic attraction

static
medium which surrounds the bodies. According view those solvents which have the highest dielectric constant must have the highest dissociating power. This
of the
to this
rule, which was proposed simultaneously by Thomson and Nernst, holds very well in most cases, as is shown by the following table of Nernst.*
The
values of the different dielectric constants and a table showing
the relation between the dissociating power and a number of the solvents will be given in Book II. physical properties of the different
CONDUCTIVITY.
95
Apparently most of the physical properties of solvents, " such as association," dissociating power, etc., are in some way connected. Dutoit and Aston have found that
solvents with a high dissociating
power are
in general
inclined to polymerization in the liquid state.
Polymeri-
generally noticed in the case of substances which contain an element of variable valence, such for instance
zation
is
NH which contains the or H 2 O, which contains the

as
3,
tri-
or pentavalent element di- or tetravalent element
oxygen.
therefore
The occurrence
would seem
to
of these elements in a
compound
dissociat-
be connected with the
ing power.
Aside from the dissociating power and internal friction

there
are
other influences at
are
work concerning whose

Formic acid, and accordingly
nature
we
completely
in the dark.
for instance, has a dielectric constant of 62,
should have a high dissociating power, nevertheless HC1 dissolved in formic acid gives a practically non-conducting
although salts like NaCl, KBr, etc., conduct very well in formic acid. In this case the hydrochloric acid probably unites directly with the formic acid and is
solution,
In gennot only on the solvent depends but also on the nature of the dissolved substance. The
therefore unavailable for conducting purposes.
eral the dissociation
tendency of the different elements and 'radicals to take up an electric charge a tendency which makes itself evident in the electromotive force of the elements and the
deposited on an electrode, plays an important part in determining the relative dissociation. The tendency of elements to pass
ease or difficulty with which they
may be
is closely related to the general chemical properties of the elements, and thus the degree
into the ionic condition
96
ELECTROCHEMISTR Y.
becomes an important factor
in determining
of dissociation
the chemical activity of a dissolved substance.

therefore consider the relations of dissociation
We must somewhat
is
more fully. As we have seen on
p. 87, the
degree of dissociation
a.
calculated according to the equation
ô
f.
The
folio w-
ing table shows

typical
how the degree of dissociation of certain electrolytes when dissolved in H 2 O changes with
the concentration.
The
c
first
vertical
column contains the concentration
(reciprocal of the dilution), the others contain the degree of dissociation of the different substances at these
HC1 is dissociated the most, particular concentrations. and the dissociation of the other strong monobasic acids
as
HNO
3,
HC1O, HBr, HI,
etc.,
follows that of
HC1
closely; the bases NaOH. KOH, LiOH, T1OH, etc., are The i i salts are slightly also just as highly dissociated.
:
less
dissociated;
still
less the
1:2
salts,
while the
2:2
salts like
*
ZnSO 4
:
are the least dissociated.*

meant one derived from a monobasic acid and a
By a
salt is
CONDUCTIVITY.
97
The
is
strength of the acid and base from which the salt derived has considerable influence on the degree of
dissociation.
The
salt of the
weak
acetic acid
is less
dissociated than the corresponding salt of the stronger hydrochloric acid. This fact is still more evident when we
compare the acids and bases themselves,

acetic with hydrochloric acid:
for
instance,
ammonia with potassium
hydroxide; etc. Since the H* ion is common to all acids and always has the same tendency to take up an electric
charge the difference in the degrees of dissociation can only be due to the fact that chlorine has a much higher
tendency to pass into the ionic condition than the acetic" acid radical, i.e., it has a higher electro-affinity."
Strength of Acids and Bases.
The
degree of dissociation
is
of the highest importance
in determining the chemical activity of The common characteristic of all acids of
an acid or base.
is
the formation
H*
ions in a water solution, consequently in all re-
actions which may be brought about by any acid and which therefore depend on the presence of the H* ion, the concentration of the H* ion is of decisive importance. In
a similar way the

ability to
common property of all bases is their form OH' ions in a water solution, consequently
more vigorously according as
high or low.
their degree
is
the bases will act

of dissociation
strength of a base or acid makes itself felt in the reaction of distribution. If we add to a solution of 3
The
NH
monacid base; 1:2 are derived from a monobasic acid and diacid base, or vice versa, as BaCl 2 or Na 2 SO 4 etc. 2:2 are such as ZnSO4
, ,
MgCO
3,
etc.
98
ELECTROCHEMISTRY.
and
to
KOH an amount of HC1 which

this
is less
than
sufficient
neutralize both bases,
acid will be distributed
between the .two bases.

the stronger.
chloride will be formed, but
Both potassium and ammonium more of that salt whose base is

is
In the same way a base
distributed
between two
acids, so that the larger part falls to the lot
of the stronger acid.
weak
base, such as
Further, if we add to the NKUCl, the stronger base
salt of
a
a
KOH,
takes place, the the acid from the ammonia, the latter is set free
redistribution of the
HC1
KOH
takes
and may
further,
be driven out of the solution by

if
boiling.
Still
we add hydrochloric acid to a solution of sodium acetate In all these cases, the HC1 displaces the acetic acid.
till
however, the displacement takes place only
a state of
equilibrium is reached, and this equilibrium is determined by the value of the dissociation constants of the acids and
bases.*
It
has been found that the ratio of distribution
is
equal to the ratio of dissociation of the two acids or bases

at the dilution in question.
The
certain class of reactions celerated

is
strength of an acid also makes itself felt in a " " which are accatalytically
by the presence
of
H*
ions.
Such a reaction
the inversion of cane-sugar into levulose and dextrose, which causes a good deal of trouble in the refining of
sugar, since the two resulting The reaction to crystallize.
compounds are very hard
proceeds very slowly in a neutral solution, but This accelerated by the presence of acids.
is
greatly
catalytic
* For the relation between the dissociation constant and the distribution,
cf.
Nernst, Theoretische Chemie, 1903, p. 506.
CONDUCTIVITY
acceleration
is
99
greater according to the
number
of
H*
ions
which a given acid can supply; in other words, the acid

accelerates this reaction
more or
less
according as
it
is
(
If the acids are arranged strongly or weakly dissociated. in the order of their conductivity this same order represents
also their relative activity in accelerating the inversion
of sugar.
A similar case is furnished in the decomposition

CHaCOOCsH,,
+
of the ester:
CH 3 COOH + C 5H lo
acids.
This reaction
is
accelerated to
a different degree by
strongly and weakly dissociated
The
reaction of saponification.
of a base the faster
fatty acids.
it
strength of a base regulates the velocity of the The higher the dissociation
will saponify the ethereal salts of the
As
yet
we have
considered the connection between the

of
dissociation
and strength
an acid or base only
in a
qualitative way.
relations ?
How can we
obtain definite quantitative

to the reaction of dissoIf
The law
ciation, as
of
mass action applies

all reactions.
it
does to
we write the equation
for the dissociation of acetic acid,
CH 3 COOH ?=* CH 3 COO+H',

and apply
to this the mass-action
law
we have
ca
represents
the
Ci
concentration
of
the
undissociated
molecules and
that of the ions.
(In any solution the
concentration of the two different kinds of ions must
100
ELECTROCHEMISTR Y.
necessarily be equal.)
is
the dissociation constant.
If
the value of
is
known
the dissociation
may
any acid or base the value of be at once calculated for any dilution,
for
'
and also the conductivity, if the values of / and / known, van't Hoff and Reiche give the following
for acetic acid:
'
are
table
MOLECULAR CONDUCTIVITY OF ACETIC ACID AT 14.1.
The first column contains the dilution in litres per mol, the second the observed molecular conductivities A v the
,
third
the value of
calculated from the conductivity

cc
measurements by means of the formula

fourth column are the values of
= -~.
ô
In the
calculated from the

as the value of
equation Kv(i
K.
c8
a)=a using 0.0000178 The equation c = Kci 2 is identical

,
with this since
- and c\=
In regard
to the physical signifi-
cance of
K
is
the following
(i.e.,
may be
said: in the case of a
binary electrolyte
ions)
one which dissociates into two
equal to half the concentration at

is
which the
electrolyte
* This
is
50%
dissociated.*
substituting 0.5 for
readily
shown by
in the equation.
CONDUCTIVITY.
Strange to say, this law, which was
101
Ostwald and
is
known
as the
first derived by Ostwald dilution law, holds
only for electrolytes which are weakly dissociated. does not at all fit the case of highly dissociated salts.
possible reason for this is the dissociation we tacitly
of the ions
It
the following: in calculating
assumed that the mobilities
were independent of the concentration, and that the friction they meet with on the part of the
/</
V and
solvent
is
molecules and other ions.

for
not affected by the presence of the undissociated Since Ostwald's law holds
electrolytes
weak
where a great many undissociated
molecules are present, it has been argued that these must be without effect on the velocity of the ions. In the case
where very many ions are some disturbing factor is present, and it seems as present if the ions have some mutual influence on each other's
of the strongly dissociated salts
velocity.
Still it is
quite possible that the undissociated
molecules have a favorable effect on the mobility of the ions; with a slightly dissociated electrolyte, where the
relative
slightly
number
increased
of
as
undissociated
the
molecules
is
only
concentration
increases, this
may have an
unnoticeable effect on the value of K, but
with a strong electrolyte the effect may be very great. The whole matter has not yet been satisfactorily cleared
up.
From
derived
:
the law of
mass action the following

is
rule has
been
For a binary
electrolyte the ionic concentration
and consequently the conductivity,
square root of the total concentration is not very strongly dissociated.
when
proportional to the the electrolyte
For highly dissociated
electrolytes van't
Hoff has found
empirically that the following expression holds true:
102
ELECTROCHEMISTRY
-^2 Cs
=a
constant,
and from
this the conductivity
may
be calculated.
Acis
cording to this the
cube of the concentration of the ions
proportional to the square of the concentration of the undissociated molecules.
The
dissociation
constants
of
different
electrolytes
may
of
have widely differing values, as the following table

affinities
"
"
of a
number
of acids aixd bases shows:
K
Acetic acid, 3 Mono-chlor-acetic acid,
Tri-chlor-acetic acid,
CH COOH CH C1COOH
2
o 0000180
.
0.00155
1.21 o 000023 o 00050
. .
CC1 3 COOH
3
NH OH Methylamine, NH CH OH Aniline, NH C.H OH Carbonic acid, HCO H

Ammonia,
4
iX io- 10
Hydrogen sulphide,
Boric acid, Prussic acid,
HSH
H BO
3
10 3Q4oX io~ 10 57oX io~ io- 10 iyX

i3 i
.
CNH
Phenol,
C GH 5 OH
X io- 10 10 3 X io-
One
action
is
very important consequence of the law of mass the following: the dissociation of acetic acid
follows the equation
CH 3 COOH ^ CH 3 COO' + H\
The law
of
mass action requires
If
an excess
of either of the ions
is
introduced into the
solution of acetic acid, for instance

*
CH
COO', by
is
the
The
concentration of any
compound or
radical
indicated
by
enclosing the symbol in brackets.
CONDUCTIVITY.
addition of
103
of a
strong right-hand side to of the equation becomes too large and in order for remain constant the dissociation must decrease.
acid, the equilibrium
is
CH 3 COONa
or
H* by addition
disturbed.
The
If
two solutions have a
common
ion
and
their concen-
tration with respect to this ion are the same, then their
solutions
may be mixed and no change
in the state of
dissociation of either of the substances will occur; " solutions are called isohydric."
such
Two
acids
solutions of acids
for
whose
dissociation follows the
law of mass action
instance acetic
and propionic
i.e.,
are without effect on their mutual dissociation,
isohydric inverse ratio of their dissociation constants.
are
when
their
concentrations
stand in
the
This forcing back of the dissociation by the addition of a solution containing a common ion is of great importance
of
in
many
analytical
operations.
dissociation
many
has explained the empirical chemical receipts.
mode
For
The theory of action of

instance,
is
the
dissociation of a
normal solution of
if
acetic acid
0.4%,
but this
is
reduced to 0.0018%
is
sodium acetate
added
to
a gram equivalent of the solution. Since the
strength of the acid, or the intensity with
which
it
takes
part in reactions or accelerates

of sugar, p. 98)
is
them
is
(cf.
the inversion
determined by the concentration of the
H* ions,
by
of
it is
evident that acetic acid
the addition of
CH 3 COONa.
very much weakened The same is true of
other acids and bases.
For instance, the precipitation
ZnS by H^S the H* ions of

number
is
prevented by the addition of acid, for the acid cause a great decrease in the
dissociation of the
2S
of S" ions.
with a consequent decrease in the For the same reasons the precipita-
104
tion of
ELECTROCHEMISTRY.
Mg(OH) 2 by NH 4 OH is
ammonium
is
prevented by the previous
addition of
dissociation
salts.
The
forcing back of the
also of great importance in all reactions of

If
Ag* ions by Cl' ions and add an amount of chlorine which is exactly
precipitation.
to precipitate
we wish
equivalent to the silver, then a quantity of silver corresponding to the solubility of AgCl remains in solution.
This
o.ooooi i mol., contains o.ooooi i X ro8

is
i.e.,
a saturated solution of
AgCl
In washing a silver-chloride precipitate an appreciable error might be

mgr. of
silver.
= i. 2
introduced owing to the solubility of the precipitate. The law of mass action requires for the reaction of solution
#[AgCl solid ] = [AgCl disso ved ] = o.ooooi i

i
In
this
very dilute solution

is
we may assume
that the disso-
ciation
practically complete, so that
Then
"
solubility
is
the
"
product
of silver chloride.
is
If
we
to
add KC1 so that the solution

the chlorine ions, then, since
normal with respect

is
a constant, the con-
centration of the silver ions will be reduced to 1.2
Xio~ 10
a value too small to be of any analytical importance.

is
It
customary therefore to add an excess of KC1 for the precipitation, and to wash with a solution containing
Cl' ions, as dilute
HC1.
For similar reasons a number
of sulphide precipitates are

.ing
washed with water containin the case of
2 S.
These
PbCi2.
facts
If
may
easily
be demonstrated
of a strong
a few drops
solution of
NaCI
CONDUCTIVITY.
105
are added to a saturated solution of PbCl2, a heavy white precipitate forms; the dissociation is forced back by the
addition of the chlorine
PbCl2
results
and more undissociated than corresponds to the solubility, and this

ions
excess appears as a precipitate.
The examples cited above of the precipitation of Mg(OH) 2 by ammonia and of ZnS by H 2 S depend on the reverse process. The addition of an ammonium salt to the
ammoniacal magnesium
of a large share of
its
salt solution robs the
NH OH
4
*
basic nature;
ions can only exist in a solution in
and NH 4 such amounts as are
OH'
ions
On 4 OH. governed by the dissociation constant of 4 ions in the form of a salt, the concentration adding
NH
NH
'
of the
OH'
ions
is
greatly reduced,
and consequently
in
the mass action equation
the
right-hand
side
will
much more Mg"

were present.
go into solution than
becomes too small, and therefore if no NH 4 salt
quantitative relations may be obtained when we consider the matter as a question of distribution (p. 97).
The
When
salt,
a strong base such as the anion of the salt
NaOH
is
is
added
to
Mg
Mg
distributed between both
the
of
Na and the weaker Mg, consequently a large amount Mg(OH) 2 is formed and appears as a precipitate.
The
addition of
NH 4 OH, however, which has been weakened by NH 4 salt, is no longer able to displace
its salts.
the
the
Mg
from
yet
considered only such dissociations as But with many take place according to one equation. The salts two stages in the dissociation are possible.
As
we have
106
ELECTROCHEMISTRY.
dissociates ac-
most important example is water, which cording to the two equations

(i)
and
(2)
H 2 0<=H'+H-
The second
dissociation, however, takes place to a very
slight extent, or, as
constant of the
that of
we may also put it, the dissociation second H" ion is very much smaller than
Similar reactions
are possible with
the
first.
many
other substances, for instance

(i)
(2)
(i) (2)
BaCl 2 <=BaCl-
It
sometimes happens that two molecules unite and

" steps."
then dissociate by
With CdCl 2 the following

:
modes
of dissociation are possible
2 CdCl 2 <=>
Cd 2 Cl 2 " + Cl' + Cl'
3 ',
etc.
This polymerization of the molecules is the cause of many of the deviations from the laws of solutions.
CONDUCTIVITY.
107
Conductivity and Temperature.
The temperature has

of
a great effect on the conductivity

coefficient
is
the
electrolytes,
and the temperature

i.e.,
practically always positive,
as
the
temperature
,
rises.
Two
the conductivity increases causes must be dis-
tinguished.
The
dissociation of
most
salts
decreases as
the temperature rises, small should lower the conductivity.
and
this decrease
the mobility of the ions is to increase the conductivity.
though generally the other hand, much increased and this tends
On
The temperature coefficient of most salts hi water has such a value that at about 30 the conductivity would
be zero.
internal friction)
Since the fluidity of water (reciprocal of the follows a temperature formula which
also gives zero as the value for
30,
it
seems clear that

is
the influence of temperature on the conductivity

to the effect of the
due
temperature on the internal friction
of water.
At ordinary temperatures the temperature coefficient of dilute solutions of salts is from 0.02 to 0.023, e tne con"
i->
ductivity
ture.
by 2 2.3% for i degree rise in temperaFor acids and some acid salts the coefficient is
is
raised
0.009 to 0.016, for alkalies
it is
0.019 to 0.02.
The temperature
concentration.
coefficient
all
depends but
cases
it
little
on the
In nearly
decreases slightly
as the concentration rises,
and then
rises
again at higher
concentrations.
and
nitrates of
With K and
certain salts such as the chlorides
NH4
the decrease persists even in
the stronger solutions.*

* A classic work on the conductivity of the electrolytes is the book by Kohlrausch and Holborn, published by Teubner of Leipzig, which
Io8
ELECTROCHEMISTRY.
The high temperature coefficient of substances which conduct electrolytically is of especial importance in the
case of solid
salts.
At ordinary temperatures these are

but at higher temperatures and salts in a state of
practically non-conductors,
the conductivity increases greatly, fusion are
substances
among the best conductors. when highly heated may show

is
Even
solid
considerable
A good example conducting power. " " of the Nernst light. glower
furnished by the
The Transport Number.
We
If
will consider first a binary electrolyte, say
NaCl.
unit quantity of electricity through this solution both ions take part in transporting the current?
we send a
and
since the concentrations of the two ions are equal
and
the pull exerted by the electrodes is the same for both, the part taken by each in the conduction will be proportional If E' is the quantity of electo the velocity of the ions.
transported by the anion and E' the part transported the cation, then by
tricity
E'+E' = E
where
and
E':E' = V:U,
and
V are
the velocities of the cation and anion
respectively.
We
then obtain
E':E=V:U+V
The phenomena
will
and
E':E=U:U+V.
attending the passage of the current be better understood from Fig. 8. A tube which is divided into three compartments by two porous diaphragms contains at one end the anode and at the other
contains the theory of the methods of measurement and extended
tables.
CONDUCTIVITY.
the cathode.
109
the electrolyte has the same concentration throughout the tube as is indicated by the
At
first
upper
series of
salt,
signs.
Every
sign represents a gram-
molecule of
signs represent the cations, and the the anions. Let us assume that the velocity of the signs send 16 cation is to that of the anion as 5:3.
the
We
F*
through the solution, which results in the separation of

Before
Anode
Diaphragms
FIG. 8.
Cathode
16
mols of cations
at the
cathode and 16 mols of anions
at the anode.
In the actual transporting of the current the ions take

part in the ratio of their velocities,
i.e.,
E-:E' = icF:
6F
E".E = ioF:i6F E':E = 6F:i6F.

While the
tion the
distribution
Fig. 8.
ions all
ions
is
move 5 units of length in one direcmove 3 units in the other. The final shown by the lower series of signs of
mols have been set free at each
in the
i gr.
It is seen that 16
electrode, the concentration
middle compartment
equivalent of ions or 96 540
* In honor of Faraday the charge on
coulombs
is
represented by F.
i 1
ELECTROCHEM1S TR Y.
remaining unchanged, while that in each electrode compartment has changed to a different degree. The changes
in the salt concentration in each of the electrode
com-
which have
partments are to each other as the velocities of the ions In this case the left those compartments.
is
change at the cathode
to the
is
change at the anode as
the velocity of the anion as 3 is to 5.
to the velocity of the cation cr
The
known
value of
-^
can therefore be found by sending a
quantity of current through a suitable form of apparatus and determining before and after the concentrations in the electrode
the concentration in the
compartments. The fact that middle compartment does not
change
result.*
is
a proof that diffusion has not influenced the
only applies when the ions are or otherwise removed from the solutions. If precipitated instead of the ion which has transported the current,
is set free, it is necessary to calculate by law (p. 52) how much of the first ion should Faraday's have been removed by the electrolysis and subtract this
The above method
some other ion
from the concentration found before we can

ion. If the original concentration
tell
how
the
concentration has been affected by the wandering of this
after electrolysis are c' at
and the concentrations the cathode and c f at the anode,

is c,
so that the losses at the electrodes are c

respectively, then
c'
and
V:U=c-c':c-c
f
.
* For more detailed information concerning the methods of measure-*
W ent and calculation of reûl^
cf,
5Q9fe
JJ,
CONDUCTIVITY.
U:
ill
is
the ratio between the velocities of the two ions.
Hittorf (1856),
who was
,.
the
first to
investigate this subject,
called the fraction
the anion."
Since
V ==n the "transport number of ,y U V ,, v and rr, v together are equal

is
to
one,
=in
of this
the transport
number
of the
cation.
With the help
new term we may now summarize
the most important formulae concerning the conductivity of an electrolyte. If y represents the concentration in
mols per
the degree of dissociation, then a y is the concentratiorrbf the ions and the specific conductivity K is
c.c.,
K =arjF(U+V).
'
Putting
= FU
and
1Q
'
= FV
(cf. p.
84), then
K=ar)(l '+I
').
Now
the molecular conductivity
is
A=
and we obtain
= i, consegreat dilutions a quently if we represent by A the molecular conductivity at extreme dilutions then AQ = IQ'+IQ'.
A = a(lo'+lo).
At
very
'
= nA
and
are
'
IQ
= (I
n)A
These
last
equations
of Kohlrausch's law of the independent

ions,
the mathematical expression wandering of the
H2
ELECTROCHE MIS TR Y.
Absolute Velocity of the Ions.
The
velocities or mobilities
/'
and
/'
are based
79).
on the
to
ohm
as the unit of resistance
(cf.
p.
In order
obtain
and F, the acutal velocities with which the ions move in a second
of potential
is
in centimetres per
field
where the
fall
volt per centimetre,
we must remember
it
that each
gram
equivalent of ions carries with
96 540
repre-
coulombs, and since the conductivities sent velocity X charge we have
and
/</
96 540(17+ F)-/o'+V.
Accordingly
we
obtain the actual velocities
and
in
96 540.
centimetres per second by dividing the mobilities / by For infinite dilution the following are the cal-
culated absolute velocities of
some
of the ions at
18.
It is possible to calculate the force which must be exerted on an ion to give it a velocity of i centimetre per second. This force is about io 10 i.e., a force represented
,
by the weight of io ooo ooo coo kilograms.
We may
CONDUCTIVITY.
easily see that
113
such a force is necessary when we remember a finely divided precipitate often requires many hours to settle, on account of the friction against the
that
solvent
which the
particles
must overcome.
It
is
not
surprising therefore that the ions, which are very many times smaller than the finest particle of a precipitate,
meet
with
such
an
enormous
friction.
The
acturl
measurement by a method first worked out by Whetham and Masson, and later improved by Abegg and Steele. The observed
velocities of the ions are
capable of direct
and calculated
results are in perfect
agreement.*
Dielectric Constants.
Two
attract each other,
bodies carrying an opposite charge of electricity and the force of this attraction varies
with the nature of the

bodies.
in a
If k is the attraction
k'
medium surrounding the two when the bodies are placed

some other medium,
vacuum and
k
the attraction in
then the dielectric constant
DC
of this
i
medium
is
is
given
= by JDC T>.
greater than
attraction
For the vacuum

i
DC =
and
but slightly
for the different
gases.
i.e.,
In water the
the dielectric
is -gV
of that in a
is
vacuum,
i.e.,
constant of water
80.
The
capacity
of
it
a condenser,
is
the
quantity of
electricity
which
necessary to
add
in order to give
the two plates a difference of potential of i volt, varies directly with the dielectric constant of the medium which
occupies the space between the two plates of the condenser. If c is the capacity when air is used, the capacity is cDC
* For details
cf.
Book
II.
1 1

dielectric
when a substance whose

used.
constant
is
DC
is
According to the theory of electric vibrations the velocity with which electric waves travel along wires varies
inversely as the square root of the dielectric constant of
the surrounding
medium.
of
measuring the dielectric constant are founded on these two laws. The quantity of electricity is measured which is necessary to charge a given condenser;
bridge.
this is best
The methods
done by the use of the Wheatstone

the needle of a quadrant
Or
the deflection of
is
electrometer
medium
in question,
observed once in air and again in the and thus the difference in the force
between the needle and the quadrants is Another method, directly determined for the two media. worked out by Drude, depends on the determination of
of attraction
the length of electric waves along wires surrounded by A table of the values of the dielectric different media.
constants of a
number
of substances
which can be used as
solvents for electrolytes will be given in Book II, and also a more complete description of the methods of measure-
ment.
CHAPTER
CURRENT.
V.
ELECTROMOTIVE FORCE AND THE GALVANIC
To
aid in forming a clear idea of the relations between
current and voltage
we
will
make
use of an illustration,
all
although this illustration, like comparisons, does not hold

at all
points.
Suppose we
air.
have an
tube
point
air-tight ring-shaped
filled
with
At a
place a
in Fig. 9
we
pumping arrangement which draws in air on one side and As a expels it on the other. result a partial vacuum is
created to the right of the pump and the pressure of
the air
raised.
on the other
side
is
The
this
air
seeks
to
equalize
difference
in
pressure by flowing around FIG. 9. through the tube from left to right, and the pump strives to keep up the difference
pressure.
in
As a
result a stationary
condition
is
arrived
"5
n6
at
ELECTROCHEMISTRY.
the quantity of air flowing around through the left to right is the same as that brought over
right to
left.
when
tube from
by the pump- from
From
right to left along
the tube the difference in pressure gradually falls off, as is indicated in the figure by the different lengths of the arrows. In the narrow part of the tube where the
air finds the greatest resistance the pressure falls off
most
rapidly.
If
the tube
is
closed at
any point the
pump
continues working for a short time and forces air over till the difference in pressure between the ends of the tub e
is
the
same
as the pressure
which the
pump
can
exert.
Let us now take, in place of the tube, a wire through which electricity can flow, and replace the air-pump by an electricity pump which takes in positive electricity on
out on the other (or what amounts thing, gives out positive electricity on one side and negative on the other). For this purpose we may use
one side and gives

to the
it
same
a battery or a dynamo.
pressure on the
raised
left
In the
raised
first illustration
the air
was
and on the
right lowered;
in this case also the electric pressure, or
"
potential,"
is
on the
left
and lowered on the

seeks
to
right.
this
The
electricity
equalize
difference
of
potential by flowing around through the wire, while the battery strives to maintain the constant difference of
potential.
The potential falls off along the wire from pole around to the right, and it decreases most rapidly at those points where the electricity finds the greatest friction, i.e., where the resistance of the circuit
the
left
is
If we cut the wire at any point so that eleccan no longer flow, the battery still continues to tricity work for an instant, but only until the difference of
highest.
potential between the ends of the wire
is
the
same
as the
ELECTROMOTIVE FORCE AND GALVANIC CURRENT,

electromotive
electricity
force
is
of
the
battery.
The amount
of
which
necessary to bring the
ends of the wire
up
to this potential is
is
the capacity give a difference of potential of i volt. If the circuit is closed so that a current can pass,
equal to one,
known as the capacity of the wire; when i coulomb is required to

Ohm's
If
law applies
s is
to every portion of the circuit (cf. p.
78).
the difference of potential the between any two points,
resistance,
and i the quantity of

per second,
Fig. 10,
electricity passing
= iw. If, in and P_ represent

then
e
e
the poten-
tials
on the
is
left-
and right-hand
sides of the battery

circuit
open, so that
when the P -P_
represents the electromotive force of the battery, then the

potential will gradually fall off
FIG. 10.
along the wire from P e to when the circuit is closed.

points along the wire be
P_
Let the potential at different
the value of each be indicated 'by the length of PQ represents the original potential of the wire before the battery was attached and the direc-
and
the
let
arrow.
tion of the arrows
point
If
is
higher(
\ )
shows whether the potential at any or lower ( j ) than at P

.
the
electromotive
(represented
force
at
the
terminals
in
of
10)
the
is
battery
by
and P_4
is
Fig.
measured while the battery
in action
we no
longer
1 1
ELECTROCHEM1STR Y.
cell
obtain the true electromotive force of the
P-
since part of the voltage is used in sending current through the cell itself. This loss of voltage in the battery is given by i=iwi, where w\ is the internal
resistance.
is
If the
i
measurement
then
1
is
made when
of
the circuit
open,
true
when
=o
is
also zero
and we obtain
the
battery.
the
electromotive force
P -P_
e
In measuring the electromotive force of a cell, then, we obtain the true value only when no current is flowing.
value
is
slightly
smaller
is
obtained
when
the
current
are
very low, and
for this reason all voltmeters
current
a high resistance. If any appreciable taken from the cell the voltage measured at the terminals may be much lower than the true voltage
is
made with
of the
cell,
and the error
will
be larger the greater the
internal resistance of the cell.
Contact Electricity.
different
difference of potential is always present when two substances are brought in contact and the
is
surface of contact
Positive
collected
thing,
electricity
the seat of the electromotive force.

is
taken from one
substance
to
and
on the
other, or,
what amounts
charged
reactions
the
same
one substance becomes

negatively.
positively, the
other
Chemical
are
undoubt-
edly the cause of this contact electricity,
but their nature
has not been determined in

of substance
all
cases.
The amounts
under
which enter
into chemical reactions
these circumstances are so excessively small that the
quantity of electricity produced It is a well-known fact that
is
also very small.

is
when one substance
rubbed with another, both become
electrified (frictional
ELECTROMOTIVE FORCE AND GALVANIC CURRENT.

electricity).
119
When
sealing-wax
is
rubbed with a piece of

;
wool the wool becomes positively electrified when glass is rubbed with silk, the silk becomes negatively charged.
simple law without any exceptions has yet been with regard to contact electricity. Substances may, however, be arranged in a series so that
discovered
No
a body rubbed with any of those following

series
it
in the
positively charged; the charges so produced are larger the farther apart the substances stand. Such a series is the following: glass, wool, silk, wood,
becomes
.metal,
amber, hard rubber,
sulphur,
shellac,
sealingto
wax.
have two substances are pretty general application: brought in contact, the one whose dielectric constant
Coehn has discovered a law which seems
When
is
higher becomes positively electrified. Since contact and frictional electricity
are
of
very
little
importance in chemistry
on account of the very
small
amounts of
electricity
mention one
fact in this
concerned, we will only connection, which has lately
become of technical importance. If we suspend in water some very finely divided material such as powdered glass, precipitates, dyes, peat, etc., and introduce two
electrodes
tricity,
we
which are connected with a source of elecfind that the particles which become nega-
charged are attracted to the cathode and deposited This movement of the suspended particles is there.
tively
called
"
" Endosmosis " or Cataphosesis."

is
If
an
electric
current
sent through peat
mud,
the positively charged
water moves
to the negative pole,
and
this fact
may
be
used for expelling water from peat. On the other hand, water when pressed through a porous diaphragm carries positive electricity with it, and so gives rise to a current.
I2O
ELEC TROCHEMIS TR Y.
Galvanic Production of Current.

If
we wish
to
obtain larger quantities of electricity
(without using a dynamo) we must use some arrangement in which the chemical energy of large quantities This can of material is converted into electric energy.
be done by using a galvanic
cell.
The
early experiments
of
Galvani on the twitching

electric-spark
also
of a frog's nerve under the influence of
discharges showed that those same occurred when two metals touched
also
movements
each
other
attributed
and
to
the
nerve.
Galvani
wrongly
itself.
this
an
electric force in the
nerve
Volta found, how-
ever, that the twitching did not occur
when
the
same
metal touched the nerve at two points, but that two His classic experidifferent metals were necessary.
+
Cu
,
Zn
,
Cu
Zn
Cu
FIG. ii.
ments showed further that two metals and a simple
salt
He believed solution are sufficient to produce a current. that the force producing the current lay at the junction
of the
two metals, but found further that a
series of
metals connected one with another could give no current in the absence of moisture, although they became
electrically
charged.
On
the
basis
of his
discoerievs
121
Volta built his well-known Voltaic Pile, which consisted of a number of pairs of Zn and Cu plates having between each pair a pad soaked in ordinary salt solution. One
end of this arrangement he found was strongly charged with positive electricity and the other end with an equal
amount
due
to
of
negative.
The production
This
of
electricity
is
which becomes oxidized.
a reaction between the solution and the zinc, "

Fig.
is
pile," like the battery
shown
in
n,
rapidly loses its electromotive force

it.
when
current
taken from
of copper
Volta placed in each of a number of beakers a strip and one of zinc, filled the beakers with dilute
sulphuric acid and connected each copper with a zinc pole as shown
in
Fig.
ii.
The
electromotive
force of this battery falls off rapidly,
since
hydrogen
is
evolved on
the copper. furnished the current
The
reaction which
is
In order
of
to avoid the evolution
hydrogen Daniell used a comwell-known
bination of two metals and two

solutions, forming the
Daniell element.
lain
cell
is
filled
porous porcewith a soluFlG

I2
tion
this
this
copper sulphate and in is placed a rod of copper; cell is then placed in a soluof
tion of
ZnSO 4
contained in a glass jar and a zinc rod
is
122
ELECTROCHEMISTRY.
placed in the ZnSO 4 .* When the two metals are connected by a wire electricity flows through the wire from
the copper to the zinc. The reaction which occurs in the Daniell cell
is
or written in the ionic form,
Zn+.Cu" -Cu+Zn".
is displaced from its salt by zinc; the zinc over from the metallic state into the state of ions, passes and copper passes from ions into the metallic state.
Copper
The arrangement
of the above cell
Zn/ZnSO 4 - CuSO 4 /Cu

shows that
as
at the left position ions go into solution
at the right position ions are precipitated,

just
much
positive
is
electricity
is
and and thereby taken away from
the zinc electrode as
given up to the copper electrode.

circuit is closed, until
This process goes on, before the

the
electrostatic
electrodes
repulsion between the and ions prevents any more ions from enterattraction
or
ing
or
leaving
the
stops electrodes
as soon as
solution. The process* therefore the electromotive force between the
corresponds to
is
the
cell
energy of the reaction.

the difference of potential
i . i volts.
In the case of the Daniell

between the electrodes
about
* In Fig. 12 is shown the arrangement of a Bunsen cell, which is similar to the Daniell except that in place of copper in copper sulphate a carbon rod in
HNOs
is
used.
A number
of other cells, with the
reactions taking place in them, will be given in
Book
II.

As soon as the
electrodes are
123
connected by a wire,
the two kinds of electricity flow through the wire and The chemical reaction seeks to maintain the unite.
two electrodes at a difference of potential of i.i volts, so that an uninterrupted current flows through the wire
from copper
to zinc.
Calculation of Electromotive Forces.
The
electromotive force of a chemical reaction can
only be calculated in such cases where the process is a reversible one (see p. 12); that is, when the chemical
energy
trical
is
converted entirely and without loss into elec-
energy.
The
is
various formulae no longer hold when insulation faulty, or when unknown secondary chemical reactions
are involved.
A
made
chemical
to
reaction
is
reversible
when
it
can be
go backward and the system be restored to its original condition by the exact quantity of electrical work which the reaction has furnished. The process If we at an electrode of Cu in CuSCU is reversible.
send current through
is
the
electrode
in
one direction,
> Cu". dissolved according to the scheme Cu copper current is sent in the opposite direction copper is If
Cu precipitated The reaction at

:
"
>
Cu
an aluminium
electrode,
Al
Al"',
is
not reversible, because the reverse reaction, Al"' >A1, does not take place in a water solution. Aluminium cannot be deposited on an electrode by the electrolysis
of a water solution of
an Al
salt.
The H*
ions are dis-
charged
instead.-
24
ELECTROCHEMISTRY.
saw on
p. 10 that there is a relation
its
We
between the
If the
heat of a reaction and
electromotive force.
formula which was derived,
true of any given reaction, then we may be sure that our experimental arrangement fulfils the condition of In order to use this equation in electrical reversibility.
is
calculations
it
must be remembered that the

of
transfor-
mation of
gram equivalent
in the production of 96 540
any metal into ions results coulombs of electricity. In

where the elements Cu and
the case of the Daniell
cell,
Zn
are divalent, 2 Xg6 540 coulombs are produced for every atomic weight in grams of zinc which is dissolved.
2
When
of
X 96
540 coulombs pass through the

grs. of
Zn are dissolved and 63.6 The work done by the cell is
Cu
cell 65.6 grs. are deposited.
therefore coulombs X vol-
tage
(cf.
p. 6),
and
A =96
where n
is
540 nE,
the valence.
Consequently
E = ~96540^
+ T^
dT
This
is
the well-known Gibbs-Helmholtz equation.
Another method of calculating the electromotive force

of chemical reactions
equation
(p.
31).
furnished by van't Hoff's energy Copper is precipitated from the

is
solution until equilibrium
is
reached.
If Ci
the concentration of the
Zn
ions, c^ that of the
represents Cu ions

in the cell at the start,
125
and
c 0z
if
the concentrations of
is
Zn"
and Cu" are
c 0l
and
all
after equilibrium
reached
when
practically
the
Cu
has been removed from
solution, then van't Hoff's equation gives
If
is
the valence of the reaction (in this case 2)
we
obtain
#96
I
Substituting the value of
(cf.
R
the
in watt-seconds,
= 8.3 167
Briggs
p.
5),
and
changing
natural to the
logarithm by multiplying by 2-3026
we have
log
n 96 5403 = 8.3167 X2.3026T
a .22S23 r
og
For the ordinary temperature of 18 have
(T = 273 + 18) we
The
if
values of c 0l and c 0z are called the equilibrium
concentrations of the ions.
They may be determined

till it
we
allow the reaction to continue
stops of
itself,
and then measure the

cases,
different concentrations.
In most
however, our chemical methods are not delicate
126
ELECTROCHEMIS TR Y.
enough, for many reactions go on until one of the substances seems to entirely disappear.
The
ratio of the
two concentrations
>
J2i,
a
however,
may
often be determined by electrical methods; for example, by measuring the electromotive force when the concentrations c\
and
are known.
ILLUSTRATION:
ions are
If the concentrations of
if
Zn and Cu
they are simply made equal whatever their values, then c\ and c 2 cancel in
made
equal to i, or
the equation and
we have
c 02
has been found to be
i.i
volts, so that log
-^C
z
=38
c or -^-
= io 38
that
is,
when we put
zinc into a solution
of
CuSO 4
the
copper will be precipitated until the

is
concentration of the zinc ion
io 38 times that of the

analytical purposes this
remaining copper ions.

precipitation
this small
is
For
all
remainder
absolutely quantitative; but theoretically is of very great importance, since
otherwise the energy of this reaction would be infinite. As a second example we will calculate the electro-
motive force of a Daniell

then
cell in
which c\
=i
and
c%
= o.ooi
we have
= 0.02-9 lg
or
Io38
>
12= i.i +0.029 log o.ooi

In a similar way,
if
= 1.013
volts.
we know
the electromotive force
ELECTROMOTIVE FORCE AND GALYANIC CURRENT.

for for
127
some
particular concentration
we can
"
calculate
it
any concentration. Nernst has given the

"
to
name
electrolytic
.
solution
of
pressure
the values c 0l and c 02
The meaning
this term will be considered in the next section.
Nernst's Formula.
fro"
Every substance has a certain tendency to change over the condition in which it happens to be to some
i
been given the name of For instance, liquid water has a tendency fugacity." to pass over into water vapor, and water vapor, on the other hand, strives to condense and reform liquid water.
of "
er.
This
tendency
has
If the first
tendency prevails evaporation actually takes
fugacity is dependent on the temperature, but at constant temperature is higher the higher the
place.
The
concentration, or in the case of condensation, the higher the vapor density. When a 'solid soluble salt
is brought in contact with over into the dissolved condition.
is
water
it
strives to pass
The
concentration of the solid salt
constant and con-
On sequently the fugacity of a solid salt is constant. the other hand the salt which has already dissolved has a tendency to leave the solution and go back to the
solid state,
and
this
tendency
is.
is
concentration of the solution

causes the salt to dissolve
is
greater the higher the The actual force which
tween the two
fugacities
and
is.
is
equal to the difference betherefore smaller the more

Finally the concentration where the two fugacities
concentrated the solution
of the solution reaches a value
balance, then no
more
salt dissolves
and the solution
is
128
saturated. solution
ELECTROCHEMIS TR Y.
is too high, i.e., if the the tendency to take the solid supersaturated, overcomes the tendency to dissolve and the re-
If the concentration
is
form
action goes in the reverse direction. Very similar relations hold for the metals.
They
ions,
is
all
have a tendency
this
to pass over into the
form of
and
tendency
is
constant as long as solid metal

of a metal
is
for the active
mass
constant.
On
present, the other
hand, the ions strive to pass back into the metallic condition, and their tendency to do so varies according to their concentration. We represent the first value by P, the
solution pressure, as
will
P Zn PCW PAS
,
etc.;
the deionizing
is
p, nothing less tendency than the osmotic pressure of the ions. The osmotic pressure and deionizing tendency both strive to make
be represented by
and
the solution
more
dilute.
salt
As
in the
reaction of a
going into solution, a
precipitation of the metals actually takes place, according or p has the higher value, but the one essential as
point of difference lies in the fact that the* metals can only go into solution in the form of positively charged
Conpositive electricity with them. sequently the passage of the metal from the solid to the dissolved state leaves the remaining metal negatively
ions
and thus carry
if p > P, the resulting solid metal is positively and the electrostatic attraction (or repulsion) charged) thus produced soon puts a stop to any further solution
charged (or
(or deposition).
The
following three cases are possible, illustrated by
Figs. 13, 14,
and
15.
IiP>p
traces of metal will go into

If
it
solution
and the metal takes on a negative charge.
P<P
a few ions separate out on the metal and give

a
positive
129
If
charge,
leaving
the
solution
negative.
P=p
If
no changes occur. we can arrange so as

the solution
to
conduct the
electricity
away from
and the
electrode, the influence
of the electrostatic charge disappears
and considerable
be deposited,
represented by
quantities of metal
may
go into solution or
are
according as the
Fig. 13 or Fig. 15.
conditions
those
These two processes can furnish a certain amount of
work.
When
the
a substance
to
to
work
changes be obtained is
its
pressure
from
A=RTlnj
(cf.
p.
21).
Since the solution or deposition of i equivalent of any metal is accompanied by the passage of 96 540
coulombs, and that of a mol of any metal by 96 540^,
where n
is
the valence,
is
and
since,
further,
the
work
measured by the the number of coulombs, we have

obtainable
electromotive force
p
.
If
simplify this expression in the same corresponding one on p. 121 we obtain
we
way
as the
13
Now it is possible to find a concentration, c at which the osmotic pressure of the ions just balances the solution pressure of the metal, and the condition of things is as represented in Fig. 14. c corresponds to the solution
,
pressure P, and if c represents the concentration at which the osmotic pressure of the ions is p, then
and
E=
E
to
is
the electromotive force with which the metal seeks
go into solution when the concentration of the ions
is c,
and
is
the electromotive force in a solution

i.e.,
i
when
the ions
Utre.
have a concentration of one,

is
mol per
E\
called the electrolytic potential of the metal.
If the concentration of the ions of a metal

by a power of 10,
tlie
is
changed
volts
potential changes by
at ordinary temperature.
We
will
now combine two
systems,
each consisting
its salts,
of a metal dipping in a solution of
one of
the
two solutions being separated by a porous diaphragm which hinders the two solutions from mixing, but does
not prevent the passage of the current.
of the system
is
The
condition
as follows (Fig. 16):

its
metal I becomes
pressure
charged
negatively, since
solution
P\
is
ELECTROMOTIVE FORCE AMD GALVANIC CURRENT.
13*
greater than the osmotic pressure p, of the metallic ions in the solution; metal II becomes positively charged, There will therefore be since p 2 is greater than P 2
.
a certain difference of potential between the

If the
two metals.
metals are connected for an instant by a wire,
The electrothe charges on the two electrodes unite. static repulsion and attraction at the electrodes dis-
FIG. 16.
and
appears, and traces of metal I again go into solution traces of metal II are precipitated until the electro-
static forces
again
stop
the process.
If
we
allow the
electrodes
will flow
to
remain connected a continuous current
dissolved
cell is
and metal II
through the wire, metal I will continue to be The Daniell to be precipitated.
How much work

is its
an arrangement of this sort. can such an element do, and what

Evidently
!
electromotive force?
-577
log
Pi -
0.0577
log
If the
two metals have the same valence (ni=n 2 =n)

cell,
as in the Daniell
then,
if
we put
c :c
= P:p,
log B
132
ELECTROCHEMISTRY.
is
which
If
identical with van't Hoff's equation

also greater than
on
p. 125.
P2
is
for the second metal, then
or,
since
log
log
2 ~~
this
this
p2
*2
In
equation
is
identical
with the one
first
given.
case the two metals

is
are both negatively charged before the circuit
closed,
but to a different degree, and

the
this
difference
causes
current
positive
on completing the circuit. The current flows through the wire from the metal
to
flow
P
having the lower value of
therefore dissolves
to the other;
this latter
When
and the first is deposited. the concentration of the ions is the

cell,
same
in
both compartments of the
=i and we have
____ E= 0.0577 log _

l
The
electromotive force
of such
cell
furnishes a
p
means
of calculating the f ratio of -5-. f2
PI and
tion
is
In order to determine the actual separate values of P we must use some combination of metal and
solution
where
P = p.
Unfortunately no such combina-
known with
same
certainty,
and we are obliged

is
to resort
to the
principle
i.e.,
which
used in deciding on the
atomic weights,
we must
fix
an arbitrary
unit.
We
UNlvtKbllY
OF

do not know the actual weight of the atoms;
measure
is
133
what we
the relative weight. arbitrarily take 16 as the atomic weight of oxygen and use this as the
We
standard.
Following a suggestion of Nernst's, we arbitrarily take the solution pressure of hydrogen as one t so that
0.0577 log 1=0.
To
other
determine the electrolytic solution pressure of the metals we measure the electromotive force of
cells built
up
in this
'
way:
wMetal* solution|Metal.
solution
platinum electrode over which bubbles of hydrogen
gas are passed, dipping in an acid solution whose H' ion concentration is i (normal), is combined with a metal
dipping into a solution of one of its salts of such strength that the ionic concentration is one and the electromotive
force of the
whole combination
is
measured.
platinum
electrode saturated with hydrogen gas behaves as regards its electromotive force as if made of the metal hydrogen
(cf. p.
136).
If
we
find that the combination
Pt H JH--nAg-
Ag
0.771 -volt,
has an electromotive force

electrolytic
is
of
is
then the
potential of silver
0.771.
The minus
used because hydrogen has a higher solution sign pressure than silver, and the current flows in the connecting wire from the silver to platinum.
In the com-
bination
Pt H2 nR'-nZn' |Zn
134
the voltage
is
ELECTROCHEMISTRY.
+0.770; here the current flows in the From these two values we find
opposite the electromotive force of the combination
direction.
Zn\nZn"
to
is
wAg'|Ag
volts.
be 0.770
0.7 71)
= 1.541
The
positive sign
given to the potential of those metals
is higher than that of a greater power for taking on a positive charge; metals whose solution pressure is less than that of hydrogen,
pressure
whose solution hydrogen, since they have
also elements or radicals .which take on a negative The same thing is charge, have a negative potential. " " of the metals; meant when we speak of the nobility
and
silver is
more noble than

etc.
zinc,
and
zinc
is less
noble than
hydrogen,
Now the hydrogen electrode is not so easily reproducible

as certain other electrodes which are known, and which would naturally be chosen as standards in determining
the exact values of the different potentials.
electrode to
potential
is
The
easiest
make, and one which always has the same " normal calomel electrode," the
The
form
calomel
electrode
has
potential
of
0.283
against the hydrogen electrode,
i.e.,
an element of the
solution -wKCl + HgCl|Hg
has an electromotive force of
0.283 volt, and in
it
the
* (Cf. p. 18 and the chapter on Methods of Measurement in Book II for details concerning the calomel electrode and certain other normal
electrodes.)

positive
135
current
to
goes
through
the
solution
from the
hydrogen
the mercury electrode.

in the following table
The numbers
have been obtained
with the help of such normal electrodes.
Column
contains the electrolytic potentials of the different elements; the second column contains the same values all
shifted
0.277 v
lt
order
to
refer
them
to
another
standard proposed by Ostwald.* We can obtain from this table the electromotive force
of
any
cell
nickel element, in
of the Daniell type. For instance, a copperwhich the concentration of the metallic
* According to a theory of Helmholtz, the surface tension of polarized mercury has a maximum value when there is no difference between its This theory, however, has not been potential and that of the solution.
satisfactorily
proven;
it
polarized mercury are
appears that the surface-tension phenomena more complicated than Helmholtz supposed.
of
36
ELECTROCHEMISTRY.
is
ions of each salt
equal, has an electromotive force of

volt.
i.e.,
+ 0.288
voltage
0.329)
0.619,
= 0.557
Zn
If
A Zn-Pb
the
cell
has a
of
Cu,
Daniell
cell,
has
1.099 volts, Gas Electrodes.
Cu Ag
0.442
volt, etc.
we
take an electrode of platinum
which has had deposited on it a coating of finely divided platinum and allow bubbles of hydrogen to pass up
over
it,
some
of the gas dissolves in the platinum

if it
and the
electrode behaves electrochemically as

of the metal hydrogen.
gases,
were composed
Every chemist knows that most
hydrogen particularly, are chemically much more
active in the presence of finely divided platinum " (Pt sponge "). This is probably due to the fact that hydrogen dissolved in Pt is partially dissociated into
atoms,
= H + H, and
the atoms enter into reaction
The quantity 2 molecules. readily than the of hydrogen which dissolves in the Pt, i.e., its concen-
much more
tration
or active
is
which
mass, is dependent on the pressure exerted on the hydrogen above the solution.
This follows from Henry's absorption law, which states

that the solubility of a gas in a liquid or solid is proportional to the concentration of the gas, and this in
turn, according to
Boyle's law, is directly proportional to the pressure on the gas. To calculate the electromotive force of gas electrodes
we
again
make
use of van't Hoff's equation, but
we must
of the
remember
that in previous cases the active
mass
metals were constants and therefore cancelled out in
In the case of gases, however, the fraction after the log. the active masses do not thus disappear; they are not
constants, but are dependent
on the pressure.
Let us consider two hydrogen electrodes at atmospheric

pressure in a solution whose
ci,
137
is
H* ion concentration
then
E=
CA
is
RT 2
In
CA
C\
RT 2
In
CA =
Ci
o.
is
the active
mass
of the
at atmospheric pressure P.
hydrogen dissolved in the Pt The 2 in the denominator

has a valence of
2.
due
to the fact that
H2
If
we
combine an electrode under atmospheric pressure with another under the pressure p, in which the active mass
of the
hydrogen
is
C PJ we
have
E=
or since
RT 2
p In 2
RT 2
In
CA
,
Ci
Ci
C P :C A =
the current in the solution goes from the p electrode if p < P it goes in the opposite that is, the electrode which has less hydrogen direction,
If
p>P
electrode to the
gets
more from the passage

till
of the current,
and
this will
continue
the same.
the
pressure at both
electrodes
becomes
If the pressures
p and
are kept constant
the cell
Pt with
under pressure P\ solution |Pt with
under pressure p
will furnish
a steady current.
The
2
reactions at the elec-
trodes are
-> 2 H-
or
H-^H 2
This
is
according to the direction of the current.
13&
ELECTROCHEMISTRY.
cell
"
concentration
"
in
which the current
is
due
to
dif-
ference in concentration of
electrodes.
the substances forming the
If the pressure is
.
changed by a power of
0.029 vo ^to
10 the potential
is
changed
0.058 =
Other gases when dissolved in Pt act similarly
hydrogen in their electrochemical relations. A platinum electrode saturated with chlorine behaves like an electrode
of the element chlorine,
and
its
potential,
which
is
1.35
at atmospheric pressure, changes with the pressure in the
same way as
but
that of the hydrogen electrode.

its
The oxygen
electrode also
we
potential with the pressure, changes remember that in this case the molecule must
O2 has a valence of four. From the values for the

as given in the table
potentials of the metalloids
on
;
p.
135
we can
derive the electro-
motive force of any
cell
for instance, the cell
Zn|ZnCl 2 |Pt C 2
i
has an electromotive force of 2.12 volts; the voltage with which chlorine displaces iodine from a solution of
an iodide
is
of chlorine
1.35 0.52=0.83 volt when the concentration and iodine ions is normal.
gas-cell,
The Grove
O 2 solution |H 2
1
has a voltage of 1.12. This value for the potential of O 2 refers to a solution when the concentration of H* cannot calculate the true potential of oxygen in a solution which is normal with respect
ions
is
normal.
We
ELECTROMOTIVE FORCE AMD GALVANIC CURRENT.

the
139
O"
ions, for
at present
we do
any
not
know
the con-
centration of the
of certainty.
O"
ions in
solution with any degree
Potential of Alloys.
The dependence
concentration
is
of
the electro-
motive force on the forming the electrodes
of
the
substances
also seen in the case of metals

cell
which form
electrodes are
alloys.
Suppose we have a
of dilute zinc
different,
whose
composed
are
zinc
concentrations
is
amalgams whose and in which the

the electromotive
electrolyte
a solution of
is,
ZnSO 4
force of such a cell
as above,
Here
and PI are the solution pressures of the zinc amalgams, and since, as in the case of Pt and H 2 we may consider zinc as the dissolved substance and mercury as the solvent, we have P^'-Pi^c^Ci, where
in the
,
P2
and
Ci
are the zinc concentrations in the amalgams.
We
have therefore
This
formula
has
been
verified
experimentally.
We
have assumed in the above formula that the molecules

of the dissolved zinc are
this
were not the
say,
RT
composed of single atoms. If and the molecules were composed, case, of two zinc atoms, Zn 2 then we would have to divide by 4 to get the electromotive force. But since the
,
formula as written represents the experimental facts, this in itself furnishes a proof that the zinc molecules
when
dissolved in mercury are
composed of
single atoms.
HO
The amalgams,
1.
ELECTROCHEMISTRY.
or
in
general
the
alloys,
may be
Such
divided into three classes:
The
metals
form
mechanical
"
mixtures have the potential of the less noble metal. For instance a mixture of Zn and Fe has the potential
of pure zinc.
2.
mixture. "
metals form a solution (amalgam or alloy). " metal solution is always nobler," i.e., has a potential
of-
The
nearer that
oxygen, than
its
least noble
and the greater the amount
of
work which
results
its
component, from
potential
the formation of the alloy the nearer will approach that of oxygen.
3.
The
metals form a chemical compound.

its
In
this
case the electrode has

sure,
the
and the ions it same proportion
particular solution pressends into solution are formed in
own
as the elements exist in the elec-
trodes.
These various conditions have
to
be considered
in
the electrolytic solution of impure metals; for instance, in the refining of crude copper, silver, and gold. Details the solution of alloys and the refining of concerning the metals will be given in Books II and III. Potential of Compounds. Case 3, mentioned above,
has
a very general application. Every element when a compound attains an entirely different potential. entering
For instance, chlorine has a very

according as
it
different
potential,
present as the free element, or a as solution in platinum, or as a chloride, and its potential is changed to a larger degree according to the amount
is
of free energy developed in the formation of the
compound.
chlorine
As may be seen from
the table on p. 135,
AgCl has a
lower potential of formation than CuCl,
i.e., its

potential
clearer
is
141
when we remember
higher than that of CuCl. This will be that the reaction
like all reactions, goes
librium
is
reached.
a certain state of equiAll the chlorine does not enter into

till
on only
combination, but an excessively small quantity of Ag and Cl2 remains free. This small remainder may react
like chlorine at
silver chloride will
an exceedingly low concentration, and have a chlorine potential correspondi.e.,
ing
to
this
concentration of C\2,
its
electromotive
force will be that of a chlorine electrode at very low The more stable a compound is, i.e., the pressures.
higher the voltage of the
cell
Metal solution of the chloride of the metal chlorine

j
|
is,
the
more complete
is
the reaction
and the lower the

its
chlorine pressure and chlorine potential. An electrode made of a metal covered with
chloride has
versible
solid
is
perfectly
definite
potential
and
re-
with
respect
to
chlorine.
For instance, the
electrode
Hg/HgCl + wKCl
has a potential of
left to right
0.283 volt.
is
If current passes
from
HgCl
formed;
if
in the reverse direction,
trodes
chlorine goes into solution and HgCl disappears. Eleclike this which are reversible with respect to
the anion are called electrodes of the second kind, while
those reversible with respect to the metal are called Electrodes of the second electrodes of the first kind.
142
ELECTROCHEMIS TR Y.
kind are very often employed in potential measurements on account of their constancy. The calomel electrode
is
the one most used.
The
concentration of the
to the
CY
potential varies with the ions in the solution according
same formula
as for the metals,
n
where
the
ti
log
is
the potential of the electrode
when
is
i.
concentration of the
electrodes
for
CF
ions in the solution
Reversible
other metalloids
;
or
radicals
can be made in the same way
for instance,
etc.
Ag/Agl + KI
Salts
or
Hg/Hg 2 SO 4 +H 2 SO 4
The
which are the
least soluble in
water are naturally

following
chosen for use in normal

table gives the potentials of
electrodes.
some
electrodes of this sort:
The
same
sisting
values given in this table are to be used in the way as those given on p. 135, so that a cell conof
Zn
in
ZnSC>4 combined with a mercurous
= sulphate electrode will have a voltage of 0.77+0.644

1.414 volts.
143
The
to
so-called
oxidation and reduction potentials are
be considered in a similar way. A Pt electrode covered with potassium chlorate (KC1O 3 ) has a perfectly
to the incompleteness of the reaction
definite potential, for the chlorate
pressure, due
has a definite oxygen which
has produced the chlorate. The Pt electrode becomes charged with oxygen at this pressure and thus becomes an oxygen electrode, which can bring about reactions of
oxidation. electrode
The
potential of such a secondary oxygen
corresponds to the pressure with which the The potential oxidizing agent tends to give up oxygen. of a Pt electrode in a solution of an oxidizing agent,
is due simply to a charge of gaseous oxygen furnished by the oxidizing agent, as Nernst has proven
therefore,
experimentally. The reduction potential of reducing agents is Reducing agents give exactly similar causes.
to
due
to
up H2
a Pt electrode, or, what amounts to the same thing,
they abstract oxygen, until the gas concentration, and consequently the potential, reaches a value corresponding to the reducing power of the substance. If we bring
together on a Pt electrode an oxidizing agent, such as KMnC>4 and a reducing agent, such as FeC^, the permanganate gives up oxygen to the electrode and the
FeCl 2 takes
it
away; that
is,
the second substance becomes
The potential with which this oxidized by the first. reaction takes place is simply the difference between the oxidation potentials of the two substances. These
potentials
are dependent
on the concentrations
of the
oxidizing and reducing agents and may be calculated by Nernst's equation. Data and information concerning
the use of a
number
of oxidation
and reduction electrodes
44
ELE C TROCH^ MIS TR Y.

be given in Book
II.
will
is
The Grove
gas-cell, for instance,
an oxidation-reduction cell, consisting of the oxidizing agent oxygen and the reducing agent hydrogen.
Concentration
differing
Cells.
A
139
is
kind of concentration
the following:
cell
from that on
p.
Ag|A gN03-AgN0 3 |A g
ci
2
i.e.,
electrodes of the
same metal dipping
into solutions
of a salt of the metal having different concentrations.
The
current through the solution flows from the less On concentrated to the more concentrated solution.
one side
silver
is
dissolved,
on the other
sides
is
precipitated,
If
until the concentration
on both
of
its
the same.
we
as
neglect
on account
smallness the difference of
potential at the point of contact of the
two solutions
electromotive
we have always done

is
hitherto
the
force at 18
given by
E = RTln = 0.0577
C-2
log
2
The
solution pressure of the metal, being the same at each electrode, does not appear in the formula.
In many cases the electromotive force at the junction of the two solutions may be neglected, but not always.
The
following consideration will show the cause of this electromotive force and how to calculate it. Two so-
lutions of different concentration
fuse into each

at
all
other
till
always strive to difthe concentration is the same

salt
points.
When
a dissolved
diffuses
the ion
of
having the highest velocity tends to
move on ahead

the other.
MS
In the case of acids this is the hydrogen ion has the highest velocity of any of the ions. This which of the ions can only take place to an partial separation
immeasurable extent, for since the more dilute solution

has an excess of H' ions, the electrostatic attraction of the ions gives rise to a force which compels the two kinds of
ions to remain together.
As a
is
result, in the diffusion of

is
salt the
more rapid ion
held back and the slower
accelerated.
This tendency of one ion to hurry on ahead
of the other gives rise to
an electromotive force which,
as Nernst has shown, can be calculated from the velocity

of the ions.
If
represents the velocity of the cation
and v
that of the anion, then
C2
being the difference of potential at the junction of two the salt in solutions whose concentrations are c\ and c<2
e
;
each solution
the ions
all
supposed to be completely dissociated and This formula holds only for 1:1 univalent.
is
salts (cf. p. 96);
the formulae for others are

of
plicated,
and most
that
more comthem have not been derived.*
From
follows
of
the theory of the diffusion of electrolytes it this electromotive force at the junction
different
two solutions of
concentration
practically
disappears of another salt whose concentration
when each
solution contains equal

is
amounts
higher.
much
To
avoid this somewhat uncertain contact-electromotive
* For further particulars see the list of text-books named at the close of this volume: in particular Nernst, Theoretische Chemie, 4th edition,
p. 699.
146
force a large
ELECTROCHEMIS TR Y.
excess
of
some
indifferent
salt
is
often
added.
Applications of Nernst's Formula.
The formula on
p.
144 has been experimentally verified in a great number of cases, and may be used to determine the solubility of
certain difficultly soluble salts in cases
is
where the
solubility
too small to be
measured by chemical means.
We
find, for instance, that the electromotive force of the cell
Ag|o.ooi n
is
AgNO 3 + i.owKNO 3 -i.o n KNO 3 +AgI|Ag

The
;
0.22 volt.
left is
concentration of the silver ions on

that
the
o.ooi
let
on the
right
be
where
c is the
value sought.
From
0.22
the formula
o.ooi
=0.0577 log
a
litre
we
Agl
find that c =
i.6Xio~ 8
i.e.,
of a saturated
mols of Agl = 0.000003 5 This agrees very well with the value i.5Xio~ 8 gr. Agl. obtained from conductivity measurements.
solution contains 1.6
8 i o~
Another very important application of the measure-
ment
on
of concentration cells
is
in determining the disso-
ciation constant of water, a

p. 72.
cell
method already mentioned
The
Pt H2
is
|NaOH-HCl|Pt H2
"
called the
"
neutralization cell
is
because the reaction
of neutralization
the one which furnishes the current
NaOH + HC1 = NaCl + H 2 O,

or
more
correctly, as
we saw on
p. 66,
14?
The
voltage of this cell with o.i
solutions
is
0.6460 at
To this 0.0468 volt must be added, because at the 25 contact of the two solutions there is an opposing electromotive force of
"
this
value.
The
voltage
of
the
cell
without this voltage would therefore be The concentration of the H' ions in a o.i n 0.6928.
diffusion
"
solution of
HC1
is
solution of
NaOH
to
0.0924, that of the OH' ions in a o.i is 0.0847, as found from conductivity
measurements.
The
cell
is
be considered as a concentration
cell
with respect to the H* ions, and therefore follows the formula on p. 144. Introducing the different values
we have
0.6928
= 0.05898
log
o - 0024.
c
,
where
c is the concentration of the

c is
solution,
found to
H' ions in the NaOH be i.66Xio~ 13 Therefore

.
[H'][OH']=i.4o6Xiowhich
is
14
and
= i.i87Xio-7
in excellent
agreement with the values obtained

65 and also
p. 91).
by other methods
(cf. p.
Secondary Elements and the Accumulator.
The secondary
elements do not differ in principle nor
in the calculation of their electromotive forces
from the
primary elements which

are
we have
just
studied.
They
nominally distinguished from the first, however, because after they are once used up they may be revived or recharged by sending a reverse current of electricity
through them, and
it is
not necessary to rebuild them of
48

material as in the case of primary
cell
cells.
fresh
The
oxygen-hydrogen
Pto 2 |solution|Pt Ha
may be
considered as a secondary cell if the gases resulting from the electrolysis are collected at the electrodes and then used to produce a current.
The most important

lead
of the secondary elements is the accumulator or storage battery. If we put two
lead electrodes in a solution of sulphuric acid a small amount of PbSCU is formed by chemical action on the
If we pass a current through surface of the electrodes. the solution, the PbSC>4 on the cathode becomes reduced
to metallic lead,
and
at the
anode
is
oxidized to lead
peroxide element (cf. p. 152) of the form
(PbO2), so that
we now have
a polarization
Pb|H 2 SO 4 |PbO 2
This can furnish a current and has an electromotive

force of about 2 volts.
Since the formation of PbSC>4
was very slight, very little Pb and PbO 2 was formed and the cell can only furnish a small amount of electricity.
To
increase the capacity, large amounts of PbO 2
i.e.,
,
to allow of the
formation of
the electrodes should expose
as large a surface as possible.
This
may be
accomplished,
according to Plante*,
by
electrolyzing first in one direction
and then in the other, which causes the electrodes to become somewhat porous; or, according to Faure, a paste of lead oxide and red lead is spread on a grating of lead and when this is electrolyzed we obtain spongy
149
lead at the cathode and lead peroxide at the anode. When such an element furnishes a current PbSO 4 is
formed -at both electrodes.

In "Charging," the tive pole," is reduced
occurs *
:
PbSO 4 on
to
negaPb, and the following reaction
the cathode, or
"
This
which sends At the anode or (cf. p. 141). " " SO 4" ions are set free, which through positive pole the agency of water ,act on the PbSO 4 forming PbO 2
is
an electrode of the second
-kind,
SO 4"
ions into solution
and
SO 4
In
"
Discharging," the lead pole):
SO 4"
is
liberated at the
anode (now
Pb + S0 4" + 2=PbS0 4
At the cathode (now the
PbO 2
:
pole)
H'
act
ions are dis-
charged and with the help of the
SO 4
on the
PbO 2
and convert
it
into
PbSO 4
PbO 2 + 2 H" + H 2 SO 4 + 2
Summing up
these equations
= PbSO 4 + 2 H 2 O.
obtain as the chemical
we
process which produces the current the equation
PbO 2 + Pb + 2 H 2 SO 4 <=
PbSO 4 + 2 H 2 O.
electricity,
* In equations the symbol represents 96 540 coulombs of positive the same quantity of negative
ELECTROCHEMIS TR Y.
Read from
right to left this represents the reaction on from left to right the reaction on discharging. charging, In charging 2PbSO 4 and 2H 2 O disappear and TbO 2 Pb, and 2H 2 SO4 are formed; the reverse is true on dis,
charging.*
the application of the different thermodynamical and electroII, and also the " The excellent work of F. Dolezalek, Theory of the Lead Accumula-
On
chemical theories to the lead accumulator, see Book
or," Wiley
&
Sons.
CHAPTER
VI.
POLARIZATION AND ELECTROLYSIS.

IN
facts
this
chapter
we
will discuss briefly a
number
of
which are of the greatest importance to the experimental and technical side of electrochemistry and which
be easily understood from what has been The way in which a said in the previous chapters.
will
conducted through a solution and the part the different ions has been discussed in the played by
current
is
chapter on conductivity.
arriving at the electrodes the ions give up their charges, and are either precipitated as neutral substances, where they remain in a solid state as in the case of the
On
metals, or, as in the case of the gases, escape into the atmosphere or dissolve in the solution; on the other hand,
they
may
react at once with the surrounding solution as
set free, and thus give rise to oxidizing or reducing effects. As a result of electrolysis either the electrode or the solution around the electrode is changed, and conditions are produced which result in an electro-
soon as they are
motive force opposed to that which
is
sending the current
through the solution; in other words, the electrolytic cell becomes " polarized."
15*
ELECTROCHEMISTRY.
Polarization.
If
we
electrolyze a solution of
HC1
with an electro-
motive force of 0.7

is
volt, a very small quantity of hydrogen deposited at the cathode, and a very small quantity
of chlorine at the anode,
and current
will flow until the

i
concentrations of the
is
high enough
to
Pt H2 |HCl|Pt C 2 a counter electromotive force produce

gases in the cell
just equal to the applied 0.7 volt.

cell in
hydrogen-chlorine
which the gases have a pressure of i atmosphere has, according to the table on p. 135, a voltage of 1.35. At o. 7 volt we therefore have a H2 Cl2 cell in which the
concentration of the gases and therefore their solution pressure is much smaller than at atmospheric pressure These concentrations only become high (cf. p. 136).
enough to just balance the applied voltage. In order to produce this formation of H 2 and C1 2 current must flow on applying an electromotive force,
but
this
soon stops on account of the counter
electro-
motive force of the

If
-C1 2
cell
which
is
thus formed.
i
we now
gas,
increase the applied voltage to
current
more
appears, and the chlorine hydrogen cell also soon attains an electromotive lorce of i volt. This goes on until we
to
the
electrodes
volt a new become charged with
come
1.35 volts.
At
this voltage the electrodes are
charged with gas at atmospheric pressure. " This counter electromotive force is called polarization."
If
is
we now
increase the voltage to 1.5 the polarization
no longer able to bring the current down to zero, and above 1.35 volts we have a perceptible, continuous current. Above 1.35 is called the decomposition voltage of HC1.
1.35 volts the current follows the law,
153
E
where
= iw,
e
the applied voltage, motive force of polarization, and

is
the counter electrothe resistance of the
solution.
polarization increases very slightly above as the voltage and current rise, since the gases are 1.35 evolved under a pressure greater than that of the atmos-
The
phere, but since they are able to escape in gaseous form the polarization will never be as great as the applied
electromotive force.
Similar conditions also prevail when solid substances For instance when we electrolyze a are precipitated.
solution
of
CuCl 2 between Pt
electrodes,
chlorine
is
formed
at the
anode under a certain pressure, and at the

coating of such a density that the resulting
cathode a
cell
Cu
has the same electromotive force as the applied voltage.
The
known
small
amount
of electricity
which
is
necessary
to bring the
electrode into the polarized condition is " " of the electrode. as the polarization capacity
is
This capacity
the electrode
naturally dependent on the surface of
metal of which the electrode
and further depends on the nature of the is made. For equal surfaces
palladium has a higher polarization ^capacity when hydrogen is discharged on it than platinum, and platinum
a higher capacity than iron for the solubility of hydrogen is the greatest in palladium, and consequently a larger amount of hydrogen and therefore a larger amount
;
of current
required to bring the hydrogen dissolved in palladium up to the same pressure as that dissolved in platinum or iron.
is
154
If for
ELECTROCHEMISTRY.
any reason the substances which cause polareither by dissolving in the solution and diffusing away, or by chemical actions, we say " " occurs. This is the case when that depolarization we electrolyze a substance which gives soluble gases.
ization are removed,
Further, polarization is prevented when we have a reducing agent, as FeCl2 at the anode, for this prevents
the oxygen polarization by combining with oxygen to form a ferric salt (cf. p. 143). Such substances are
called
"
depolarizers."
FeCls
is
a cathodic
depolarizer^
is
since
to
it
prevents the hydrogen polarization and

.
reduced
FeCl 2
The
electrolysis of
of these facts.
If
we apply
water furnishes a good illustration i volt to two platinum elec-
trodes in water, the cathode becomes charged with hydrogen and the anode with oxygen until the electromotive
force of this gas-cell
is
i
volt,
when
the current should
The two gases C>2 and 2 however, are soluble stop. in water, and they consequently diffuse away from their
,
electrodes
and
either escape into the air or
recombine
at the electrodes to
form water.
The
electrodes therefore
are continually losing gas, and in order to make good this loss and keep up the electromotive force of i volt a
small current must continue to flow.

is
This small current

(Reststrom).
known
as
the residual
current
Such
substances as are easily oxidized at the anode and reduced at the cathode may maintain a much larger residual
current.
battery,
For instance
it
if
an iron
salt gets into the storage

salt
is
reduced to ferrous
at
the
cathode,
salt,
etc.
diffuses to the anode, diffuses
and
is
there oxidized to ferric
back
to the cathode,
and
is
again reduced,
Iron
salts
in the
storage battery therefore maintain a

residual current
.'55
which
air
is
useless for charging purposes

loss.
and causes a considerable

If
oxygen or
electrolysis
is
passed over the cathode during
this removes the hydrogen " and such an electrode is called unpolarpolarization, Those anodes are unpolarizable which are izable." In general an electrolytically dissolved, such as Cu. electrode is unpolarizable when no new substance is
the
of
water,
formed on
it during electrolysis. In order to determine the decomposition voltage of a salt, we put two Pt electrodes in the solution and connect
them with a source
of electricity
whose voltage may be
1.3
l.GT]
FIG. 17.
varied at
then gradually increase the voltage and observe the current at each voltage. The current
will.
We
first
rises
and then decreases almost

is
the
is
voltage
reached.
(cf
.
to zero every time the decomposition voltage raised, From this point on the current follows
until
Ohm's law
p. 78)
E
If
w.
the voltage
is
plotted as abscissa
and the current

In
as ordinate
we
obtain the curves shown in Fig. 17.
156
the case of
tically
is
ELECTROCHEMISTR Y.
AgNO 3
zero, above
this
the current below 0.7 volt it increases regularly.
is
prac-
0.7 volt
therefore the decomposition voltage of silver nitrate. The values in the following table were obtained by
his students.
Le Blanc and
DECOMPOSITION VOLTAGES.
Acids
Salts
4
H SO Nitric acid, HNO Phosphoric acid, H PO

Sulphuric acid,
2 3 3
i i
4
.
67
69
Zinc sulphate, Zinc bromide,
ZnSO 4
ZnBr2
2 .35
i
.
80
...
2
1.72
i
i i
Malonic
acid',
CH (COOH)
2
.69
.
Nickel sulphate, NiSO 4 Nickel chloride, NiCl 2
2.09
i
.85
Perchloric acid,
HC1O 4
HC1
65
Lead
Silver
nitrate,
Hydrochloric acid, Oxalic acid
.31
Pb(NO 3) 2 nitrate, AgNOs

nitrate,
1.52
95
Hydrobromic acid
Hydriodic acid
Bases
0.94 0.52
Cadmium Cadmium Cadmium
Cd(NOs) 2
sulphate,
chloride,
CdSO
CdCl 2
. .
4
.
0.70 i 98 2.03 i 88
. .
Cobalt sulphate, CoSO 4 ... 1.92 Cobalt chloride, CoCl 2 i 78

.
.
Sodium hydroxide,
NaOH
4
i i i
69 67
.
Potassium hydroxide,
KOH. Ammo'm hydroxide,NH OH.

Since
the
74
is
polarization
nothing
these
less
it
than a galfollow the

as
of
vanic
cell
resulting
from
electrolysis,
will
same laws and formulae
as
cells.
is
Just
the
electromotive force of a galvanic cell
made up
two
separate potentials (cf. p. 132) so the decomposition voltage of an electrolyte is composed of the two voltages Furthermore these necessary to discharge the ions.
"deposition voltages" must be exactly the same as the single potentials of the metals which are being deposited. They also follow Nernst's formula, i.e., the deposition
voltage is lower, and precipitation takes place easier when the concentration of the ions which are to be precipitated
is
high.
The decomposition
composed
of.
ride, 2.1 volts, is
voltage of zinc chlothe potential of zinc, 0.77,

table
and
that of
chlorine, 1.35
(cf.
on
p.
135).
The
157
deposition voltages may be measured by combining the electrode in question with one whose potential i constant and of known value. If a current is passed through the
;
combination
Pt|CuSO 4
so that
SO4 + Hg2SO 4 |Hg

it
Cu
is
precipitated,
is
found that the
electro-
motive force of the resulting
cell,
Cu|CuS0 4
is
S0 4 + Hg2 S0 4 |Hg,
is
0.315 volt.
Knowing
that the single potential of the
mercurous sulphate electrode
0.644
(cf.
p.
140)
we
-0.329, which is just the same as the single potential of Cu. There is still another kind of polarization, in which
the electrodes are not changed. electrodes in a solution of
find that the deposition voltage of
Cu
is
we have two silver and pass a current, AgNO a displacement of the concentration occurs, due to the different velocities with which the anion and cation move
If
3,
(cf. p.
108).
Consequently a concentration
cell
cell is
formed
whose electromotive force

voltage.
acts in opposition to the applied

like
all
This
also,
concentration
cells,
must follow Nernst's formula. Deposition and solution do not necessarily accompany Other reactions, as oxidation and reduction, electrolysis. take place, and these obey the laws which have may
been discussed in the preceding pages. Every reaction taking place at an electrode has its own particular voltage.
For
instance,
it
.
requires a definite potential to reduce
FeCl 3 to FeCl 2 In certain cases the gases do not

with Nernst's formula.
act in accordance
is
When
a gas
evolved at an
158
ELECTROCHEMISTRY.
electrode two separate reactions are to be distinguished: first, the discharge of the ions to form atoms, as
and secondly, the union

cules of the gas, as
of the
atoms
to
form the mole-
This reaction meets with a different resistance from the different metals used as electrodes, or, more correctly,
this
reaction has a great chemical resistance which is removed catalytically to a different extent by the different
metals.
Platinized platinum
is
the most effective cata-
is evolved on platinized lyzer for this purpose; hydrogen Iron is less effective at the potential o.o volt. platinum
and Hg, Pb, and Zn are the least. This " overvoltage," and we say that phenomenon is called evolved on zinc with an overvoltage of is hydrogen The following table shows the overvoltages 0.7 volt. necessary to evolve hydrogen and oxygen on the different
as a catalyzer
metals.
OVERVOLTAGE.
159
recognition of these facts was extremely important, for it explained a number of experimental discoveries which could not be theoretically accounted for.
The
In nearly
all
solutions there are several different ions
which
may be. discharged, and consequently several different reactions are possible at the electrodes. The
is
general rule
that
the
that
least
process
actually
takes
place
which
requires
if
expenditure of
energy.
,
For
instance,
we have
less
a solution containing ZnCl 2 CuCl2,
and HC1 no
motive force
voltage of
electrolysis will
be effected by any
for
electro-
than
is
i
volt,
the
i
decomposition
1.35 volts the only reaction at the cathode will be the deposition of Cu, since the decomposition voltage of HC1 is 1.35.
volt.
CuCl2
Between
and
Above
1.35 volts both
Cu and
H
will
may be
deposited, but
in reality that process will take place
which requires the

If the solution
lowest voltage, and only

as
is
it
Cu
be deposited as long
is
present in sufficient quantity.
electrolyzed with
in
the
immediate
all
becomes nearly
a condition
is
a high current, however, the Cu neighborhood of the cathode soon used up, its deposition voltage is
raised in accordance with Nernst's formula,
reached where hydrogen is easily discharged than copper. Finally, if the voltage is raised above 2.2 zinc may also be deposited, and this may be
and more
finally
brought about
by using a high-current density so that the solution around the cathode contains very little
copper.
By
deposited on the cathode on copper and zinc salts.
using a high-current density brass may be electrolyzing a mixture of
Now, hydrogen
and
ions are always present in some quantity, the fact that zinc may be deposited from a solution
160
ELECTROCHEMISTRY.
containing hydrogen ions can only be explained by the
phenomenon of overvoltage. If there were no overvoltage we could no more deposit zinc from a water As it is solution than we can aluminium or sodium.
zinc can only be precipitated
solution,
from a neutral or alkaline

containing
acids.
and
not
from
one
is
The
deposition voltage of zinc
0.77, that of hydrogen from
an acid solution, on account of the overvoltage, is raised from o.o to 0.70 as soon as the slightest trace of zinc In an acid solution the hydrogen will is deposited.
therefore be
solution,
deposited before the zinc. In a neutral however, when the concentration of the H-
ions
is
about io~ 7 the deposition voltage of hydrogen 7= 0.404 volt higher than raised, and is 0.0577 log io~
is
in
an acid solution
it is
raised
still
further in
an alkaline
lower.
is very much a neutral solution, therefore, hydrogen can be discharged electrolytically on zinc only at a potential
solution
where the H* ion concentration
From
of
0.4 + 0.7
= 1.1
volts,
and consequently from such a
solution the zinc will be deposited before the hydrogen. What is true of the deposition of ions is true of certain
other reactions:
lowest potential.
that one occurs

If
first
which requires the
we have
permanganate and
stances will be
first
chloric acid, that
a solution of potassium one of these sub-
reduced which has the highest oxis
idizing potential, for oxidizing potential than the effort of the substance to give
nothing
less
become reduced.
up oxygen and Such processes are really nothing less than a change of the charges on the ions. For instance, the reduction of FeCl 3 to FeCl 2 simply consists in
Fe'"
>Fe".
The
reduction of
'
salt consists in
MnO 4
Mn".
If
MnC>4 to a manganese we keep in mind this

transfer of charges,
161
we can
derive a formula similar to
Nernst's for
all
such reactions.
Using the method explained on p. 155 we can often obtain the deposition voltages of every kind of ion in In the the solution (Fig. 18).
anodic
curve
for
SO4 a
slight bend is noticed at 1.12 volts where the oxygen ions The change are discharged.
in
direction of
the
curve
is
slight, as Fig. 18 shows, because the concentration of the
J.1&
1.07
Volt*.
O"
ions
is
excessively small,
FIG. 18.
and when used up they are not immediately replaced by

of the water.
further
dissociation
On
further raising the voltage another
bend
noticed at 1.67 volts which probably corresponds Under suitable conto the discharge of the OH' ions.
is
ditions
1.9
where the
two other points are obtained with SO 4" ions are discharged and at
ions are discharged.
SO 4
at
2.6
where
the
HSO/
following deposition voltages not contained in the other table have been obtained by Nernst and his
The
students
Mg
Al
*O *OH
and
tion.
+1.482 +1.276 -i. 12
SO 4
HS0 4
NO
-1.9 -2.6 -1.88
-1.67
* These figures refer to solutions normal with respect to the H' ion; i.ia 1.67 are the deposition voltages of O" and OH' from a normal acid solu-
To
discharge
OH'
or
O"
ions
from a normal alkaline
solution requires 0.8 volt less than to discharge
them
62
ELECTROCHEMIS TR Y.
solution;
to
from a normal acid
discharge
volt
normal alkaline solution requires 0.8 from a normal acid solution.

Faraday's Law.
H from a more than
As we have already shown
(pp.
52,
82), equivalent
quantities of the ions of different substances are always
combined with the same amount of electricity, and this charge is 96 540 coulombs for every equivalent in grams. This amount of electricity is carried by 39.15
grams
of
the
positively
charged
univalent
potassium
ion, or by 35.5 grams of negatively charged univalent In general the ions of any substance chlorine ion.
carry 96 540 coulombs for every valence. If one equivalent of any substance passes through the cross-section of an electrolytic cell, it carries with
it
96 540 coulombs and the current strength is 96 540 ampere-seconds. When 108 grams of silver are de-
posited
on the cathode, 96 540 coulombs of positive If electricity pass from the solution to the electrode.
i coulomb, i.e., i ampere for i second, is passed through an electrolytic cell 0.01036 mg. equivalents are deposited. Faraday's law may therefore be stated: The amount of
electricity required
to
deposit, dissolve, or otherwise bring
into chemical action i

is
gram equivalent
of
any element or
in compound of the substance which is produced or destroyed grams may therefore be obtained by dividing the molecular weight (in the case of elements the atomic weight) by the valence, multiplying by the number of ampere-seconds and then by 0.00001036. The following table contains in the first column the elements, in the second the atomic
always p6 540 coulombs.
The weight
163
weights, in the third the milligrams per ampere-second, and in the fourth the grams per ampere-hour. All the
values except
those for H', Ag", and
Cu"
are approxi-
mate.
164
ELECTROCHEMISTRY.
quantity of any substance formed or destroyed is For instance, easily obtained with the help of this table. in the electrolysis of Na 2 SO4, 2 SO4 is formed at- the
The
anode and
the
per"
first
is
NaOH
i
;
at the -cathode.
The
equivalent of
= 49 = 0.507 J(i + +32 +64)
mg. of
H 2 SO4
ampere-second
= 40,
so that 0.414 mgr.
is 23 + 16 + 1 the equivalent of are formed per ampere-
NaOH
NaOH
second.
oxygen
is
At the same time 8X0.01036 = 0.0834 mgr. of liberated at the anode and 1.01X0.01036 =
0.0105 mgr. of hydrogen at the cathode.
Electrolysis.
We will now discuss briefly a few

reactions
of the
most important
which occur
at the electrodes.
all
metals which are discharged less easily than hydrogen, give off hydrogen at the cathode on electrolysis, and in the case of these salts the hydroxide
of the metal
is
Acids, and the salts of
also formed.
In a solution of NaCl the

Cl', since these
current
is
transported by the ions Na* and
are present in far greater quantities than the ions of

water,
H* and OH'.
The
passage of
is
electricity
from
of,
the solution to the cathode, however,
taken care
not by the Na" ions, but by the H' ions, since these have a much lower deposition voltage. At the cathode, therefore,
H'
ions disappear
and pass
is
off as
gaseous
2,
OH'
ions remain,
and Na'
ions are brought
up
by the current,
so that the result of electrolysis and gaseous 2 at the cathode.
the formation of
NaOH
The
as
concentration of the ions must always be considered

p.
is
on
156.
solution
deposition of nickel from an acid impossible, since from such a solution H' ions
The

are
165
more
easily
easily discharged than the Ni" ions, but Ni can be deposited from a neutral or alkaline solution.
The
deposition of zinc
of
is
only
zinc.
made
If
high overvoltage contains another metal such
on
possible by the the zinc solution
as
iron
which
is
easily
deposited and on which the overvoltage of hydrogen is not so high, the least trace of this metal on the cathode
an opportunity to be discharged, and no zinc can be deposited on the contrary, if any zinc has
gives the hydrogen
;
been precipitated
of hydrogen.
it
redissolves at once with the evolution
For similar reasons the presence of foreign metals

storage battery
is
in a
very
injurious.
The
reduction
if
of
PbSCU
at the cathode
would be impossible
lead showed
no overvoltage. As a matter of fact, when we try to reduce PbSC>4 on a Pt electrode no lead is formed, and we have simply an evolution of hydrogen. The same thing happens when a foreign metal such as copper gets into It is deposited on the cathode, and the storage battery.
when we attempt
to charge the battery, hydrogen is evolved on the traces of copper and no PbSC>4 is reduced. These facts are important in the analytical determina-
tion of the metals
by
electrolysis
(cf.
Book
II).
The
metals
can only be deposited when their deposition is below that of hydrogen, and we must give the voltage solution such a composition that this 'will be the case.
In determining nickel, for
niacal solution.
instance,
we
use an
ammo-
What
anode.
has been said also applies to the reaction at the An anion will only be discharged when this
reaction takes place easier than the discharge of the
O"
or
OH'
ions
which are always
present.
We
can never
66
ELECTROCHEM1S TR Y.
obtain fluorine by electrolyzing a water solution, but
we
can obtain bromine and iodine. When we electrolyze a " ions are not solution of Na 2 SO 4 the SO 4 discharged,
,
but rather the oxygen ions, and gaseous oxygen
is
evolved.
As
the oxygen ions disappear hydrogen ions remain in " the solution, and since SO 4 ions are brought up by the
current, this results in the formation of sulphuric acid at
the anode.*
Another
tunity to
class of reactions
may
occur
when
the ions
which have been brought up
anode find an opporenter into a reaction which requires a potential

to the
lower than that necessary for their discharge.

strongly acid solution of few O" ions, the reaction
easily
In a
Na 2 SO4 which contains very SO 4 + SO 4 = S 2 O 8 can be more

the evolution
little
brought
about
2S2
than
is
of
oxygen,
consequently
is
Os
formed and
or no oxygen
,
produced.
In an acid solution of
'
Na 2 SO 4
and
however,
it
OH' and
HSO 4
ions are also present,
is
very
probable that the formation of persulphuric acid is due to the direct union of two discharged 4 ions.
HSO
We
1.
have
When we
12 or a
consider the presence of OH' ions. electrolyze a solution with a voltage of about
still
to
little
higher,
O"
ions are discharged, but they
soon become so largely removed in the vicinity of the

*
It
should be noticed that

different
many
text -books explain these facts in a
somewhat
way, by assuming that the SO/' ions are actually discharged and then react with water according to the equation
S0 4 + H 2 0=H S0 + 0.
2 4
The
formation of
NaOH
at the
assumption that Na ions are react with the water, forming
first
is similarly explained on the discharged and then immediately and NaOH. It is evidently unneces-
cathode
sary to explain the facts in this roundabout way.
167
electrode that their deposition voltage is raised above Therefore in the electrolysis of that of the OH' ions.
NaOH
solution
we have
only a very
weak
current
between 1.12 and 1.67 volts. Above this last voltage, which is the deposition potential of the OH' ions, we
obtain a
stronger current. takes place at the electrodes is
much
The
reaction which
OH+OH=H 0+O.
2
reaction of this sort in which the ions are destroyed evidently not reversible (cf. p. 12 and 123), for the
is
OH
ions cannot be restored to the solution

current.
by reversing the
A
easily
chemical
reaction
may be
if
than by direct deposition
brought about more the ions have an oppor-
form a compound or alloy. For instance, if we electrolyze a sodium chloride solution, using a mercury
tunity to
cathode, two causes unite to lower the deposition voltage of the Na* ions below that of hydrogen: first, the discharge
is facilitated because it may unite with mercury form an amalgam, and secondly, the discharge of on mercury requires a high overvoltage. In this case
of
to
Na
Na' ions can be discharged before H*

facture of
ions,
and
this fact
forms the basis of a very important industry:
the
manu-
sodium amalgam and its subsequent conversion into pure sodium hydroxide. These primary reactions of deposition are to be diswhich
tinguished (Book III) from secondary reactions into the deposited substances may enter. In the of sodium chloride the chlorine set free at electrolysis
the anode dissolves in the solution, diffuses away,
and
68
ELBCTROCHEM1STR Y.
reacts with the
NaOH
which
is
formed at the cathode,
thus:
2
NaOH + C1 2 = NaOCl + NaCl + H 2 O
i.e., the hypochlorite is a secondary product of electrolysis. This reaction also has great technical importance, for the
electrolytic hypochlorite
solutions are largely
employed
for bleaching purposes.
If these bleaching solutions are

is
again electrolyzed the hypochlorite
oxidized to chlorate.
CHAPTER
VII.
THE ELECTRON THEORY.

RECENT
researches on the chemical effect of the silent
on the cathode and X-rays, and esthe discoveries in connection with radioactivity pecially have caused the revival of an old theory, according to which electricity is an actual chemical substance (formerly " must confine ourselves electric fluid "). called the " to a very brief outline of the development of the electron " and its application to electrochemical questions. theory The cathode rays discovered by Hittorf are rays sent
electric discharge,
We
out from the cathode of a
vacuum tube under
the in-
fluence of very high voltages.

electricity
They
consist of negative
which
high velocity. a certain weight, since a

force
to
from the cathode at a very These particles of electricity must possess

is
ejected
when
in
they are capable of exerting motion. At discharge potentials of
14 ooo volts their velocity ranges from 0.3 to o.yXio centimetres per second, i.e., is from TV to J of the velocity of light. When the rays enter an electric
3000
10
or magnetic field, their path becomes changed. From this deviation and from the velocity it has been calculated " " that the weight of the electric atom or electron is
about
ToW
tnat
tne hydrogen atom.

169
170
ELECTROCHEMISTRY.
rays emitted by radium and other radioactive substances are very similar to the cathode
rays, only their velocity
is
The Becquerel
(and consequently, their pene10
trating power) greater, being from 2.5 to 2.8Xio cms. per second, or nearly as high as the velocity of If the cathode rays consist of negative electrons, light.
we must assume
rays.
It
that the
same
is
true of the
radium
are
therefore follows
that negative
electrons
capable of existing in a free state

matter.
and not combined with
The same should be

it is
true of the positive electrons,
doubtful whether they have yet been isolated. although When electrons pass through air, they attach themselves
to
the gas molecules and form air ions, and the gas
becomes a conductor of electricity. The velocities of these ions have been measured, and it has also been found that they obey the ordinary laws of diffusion. The diffusion coefficients of the gas ions have been calculated
on the assumption that they are electrically univalent, i.e., contain only one positive or negative electron, and the calculated and experimental values
The conductivity imparted to air by agree very well. the electrons, and also their effect in causing the condensation of supersaturated vapors (which last may also be brought about by dust particles), forms an important test for the presence of electrons.
with a
at a high velocity collides broken up and new positive and negative electrons are formed. These may later on recombine and again form neutrons, according to the
When
"
an electron moving
neutron," the latter
is
equation
We
must assume the existence
of these neutrons
if
THE ELECTRON THEORY.
17*
accept the electron theory. Neutrons must be present everywhere like the ether, and are without mass, non-
we
conducting but capable of being polarized.*
The
from the
saturated
following electrochemical definitions would follow The electron acts chemically like theory.
It
an element.
combines with other elements
to
form
compounds, coulombs correspond to

the
which
i
are
of
mol
96 540 a univalent element;
the
ions.
unites with negative elements or radicals to form saturated compounds, as
O"
= SO 4",
can replace the metallic element in compounds, while combines with the positive elements and radicals and
is
capable of replacing the negative elements and radicals:
10
'fa
N H 4 +=NH4
If
=NH 4
-,
etc.
an electron can spring from one atom
to
another
as in the reaction
* For further details see Nernst, Theoretische Chemie, 4th edition,

D. 389
ff.
172
it
ELECTROCHEMISTRY.
existing in a free state for a certain
must be capable of
length of time, a conclusion which we have already from the conduct of the cathode rays.
drawn
The
electrons have a different affinity for the different
elements, just as the elements have a different affinity for one another. The positive electrons have a greater for the metals, and the order of this affinity is affinity
shown
in the table 'of potentials (p.
135);
the negative
electrons
radicals.
have an
affinity for the metalloids
and negative
for
The
affinity
of
the
positive
electron
any element or radical increases as the
affinity of the
list:
negative electron decreases, as in the following

F,
S0 4
Cl,
O, Br,
I,
Ag, Hg, Cu, Fe, Zn, Al, Na, Cs.
When
HC1
is
two ions unite, as H' + C1'=HC1, the molecule to be considered as a double salt of the form
into
its
HQC1, which decomposes dissolved in H O:

2
components on being
i.e., it
dissociates just as the
alums do when dissolved:
These " neutron double

their
salts
"
in
no way resemble
components, while the alloys, and compounds like PCla, BrCl, etc., which are not neutron double salts, retain some of the characteristics of the elements from
which they are made.
LITERATURE.
A.
BOOKS.
Verlag von Enke, Stuttgart.
W. NERNST.
1904.
Theoretische Chemie.
Theoretical Chemistry from the Standpoint of Avogadro's Rule, and Thermodynamics. Revised edition. 1904. W. OSTWALD. Lehrbuch der allgemeinen Chemie. Verlag von En-
1890-1904. gelmann, Leipzig Grundriss der allgemeinen Chemie.

Leipzig.
1899.
Verlag von Engelmann,
The
Scientific Foundations of Analytical Chemistry. 1899. Elektrochemie, ihre Geschichte und Lehre. Verlag von Veit
&
Co., Leipzig.
1896.
und R. LUTHER.
Engelmann, Leipzig.
Physico-chemische Messungen.
1902.
Verlag von
A Manual of Physical and Chemical Measurements. Macmillan & Co. 1902. Vorlesungen iiber theoretische und physikalische J. H. VAN'T HOFF. Chemie. Verlag von Vieweg & Sohn, Braunschweig. 1904. Lectures on Theoretical and Physical Chemistry. 3 vols. Longmans, Green & Co. Introduction to Physical Chemistry. Macmillan & Co., J. WALKER. New York. W. RAMSAY. Modern Chemistry. Macmillan & Cc. W. NERNST and A. SCHONFLIES. 2 vols. Einflihrung in die mathematische Behandlung der Naturwissenschaften. Verlag von Oldenbourg, Miinchen-Berlin.
F.
1904.
KOHLRAUSCH.
Lehrbuch der praktischen Physik.

1905.
Verlag von
173
Teubner, Leipzig.
174
A. A. NOYES.
Co.,
S.
LITERATURE.
General Principles of Physical Science.
York.
1902.
Henry Holt
&
New
ARRHENIUS.
Lehrbuch der Electrochemie.

Leipzig.
1901.
Verlag von Quandt
& Handel,
M. LE BLANC.
Leipzig.
Electrochemistry.
Longmans, Green, & Co. Lehrbuch der Electrochemie. Verlag von Leiner,
(A new edition preparing.)
1903.
Elements of Electrochemistry.
millan
F.
Mac-
&
Co.
HABER
Grundlage.
Grundriss der technischen Elektrochemie auf theoretischer Verlag von Oldenbourg, Miinchen. 1898.
R.
P.
LJBKE.
Berlin.
Grundz'jge
1903.
der
Elektrochemie.
Verlag
von
Springer,
TH. MULLER.
Cie, Paris.
Lois fondamentales de
Pelectrochimie.
Masson
&
A. HOLLARD.
Paris.
1903. La theorie des ions
et
Pelectrolyse.
Carre
&
Cie,
1900.
R. ABEGG.
Die Theorie der elecktrolytischen Dissociation. Verlag von Enke, Stuttgart. 1903. The Theory of Electrolytic Dissociation. Wiley & Sons. H. C. JONES. Theory of Electrolytic Dissociation. Macmillan & Co.,
New
F.
York.
B.
AHRENS.
Handbuch der Elektrochemie. Handbuch der Elektrochemie.

Hirzel,
Verlag von
Enke,
Stuttgart.
1903.
W. BORCHERS.
Halle.
Verlag von Knapp,

Leipzig.
1905.
(In preparation.)
Elektrometallurgie. Verlag v'on Electro Smelting. Lippincott Co.
H. DANNEEL.
Spezielle Elektrochemie.
Verlag von Knapp, Halle.
(In preparation.) Jahrbuch der Elektrochemie.

1905.
F.
Verlag von Knapp, Halle.
1902-
KOHLRAUSCH und
lyte.
L. HOLBORN.
Das Leitvermogen der Elektro-
Verlag von Teubner, Leipzig. 1898. Introduction to Physical Measurements.
F.
DOLEZALEK.
Macmillan & Co. Die Theorie des Bleiakkumulators. Verlag von
Knapp, Halle. 1901. The Theory of the Lead Accumulator. Wiley & Sons. Practical Methods of Electrochemistry. F. M. PERKIN. Longmans, Green & Co., New York and London. 1905. R. LORENZ. Elektrochemisches Praktikum. Verlag von Vandenhock und Ruprechht, Gottingen. 1901.
LITERATURE.
M. ROLOFF und P. BERKITZ.
Seminar.
Elektrotechnisches
175 und elektrochemisches

Verlag
Verlag von Enke, Stuttgart.

1894-1901.
1904.
W. NERNST und W. BORCHERS.

von Knapp, Halle.
Jahrbuch der Elektrochemie.
B.
PERIODICALS.
Organ der Bunsengesellschaft, Knapp,
Engelmann, Leipzig.
Voss,
Zeitschrift fiir Elektrochemie.
Halle.
Zeitschrift fur physikalische
Chemie. Chemie.
Zeitschrift fur anorganische
Hamburg.
Journal of Physical Chemistry. Ithaca, N. Y. Journal de chimie physique, Kundig, Genf; Gautiers-Villard, Paris.
Transactions of the American Electrochemical Society.
Published by
the Society, Philadelphia. Electrochemical Industry. Electrochemical Publishing Co., New York. Transactions of the Faraday Society. Published by the Society, London.
INDEX.
Absolute potential, 135 Absolute temperature, 10 Absolute velocities of the ions, 112 Absorption law, 136
Acceleration, 2
Boiling-point, rise of, 28, 47
molecular
rise of,
47
Carbon monoxide and oxygen, 38, 41 Carbon dioxide, dissociation of, 38,
41
Accumulator, 147
Acetic acid, dissociation of, 100 Acid-alkali cell, 72, 146
Calcium carbonate, dissociation

40
of,
Acids and bases, strength of, 97 Active mass, 36, 40 Additive properties of the ions, 74
Affinity of acids, 102
Calomel electrode, 141

Calorie, 4 Capacity, 117 of the storage battery, 148
Capillarity, 75 Catalyzers, 15
Air pressure, 16 Air ions, 170 Alcohols as solvents, 93 Alloys, potential of, 140
Catalysis
and
dissociation constant,
98
Cataphoresis, 119 Cathode rays, 169 Cation, 51
Cell, galvanic,
Amalgams,
Ammonia
potential of, 14 of, 167 as a solvent, 93 6 Ampere, 3, Analysis, electrolytic, 165 and the dissociation theory, 105 Anion, 51 Arrhenius, theory of, 56 Atmosphere, pressure of, 19 Atomic weights, table of, 163 Avogadro's Law, 18
formation
120
Chemical energy, 5, 6 Chemical equilibrium, 32

Chemical-force and reaction velocity,
14
Chemcial kinetics and statics, 35, 36 Chemical resistance, 15 Chemical work and osmotic pressure,
29 Chemistry, applications of the dissociation theory in, 61 Chlorates, 168 Chlorine electrode, 138
Bases, 64
Bases and acids, strength Becquerel rays, 1 70

Berthelot's Principle, 9
of,
97
Bleaching solutions, 168
Chlorine-hydrogen
cell,
152
177
78
INDEX.
Dyne, 2
Electric work, 3, 6
Electricity,
Chlorine potential of chlorides. 141 Clausius, theory of, 55 Complete reactions, 32 Compounds, potential of, 140 Concentration cells with respect to
Concentration
the electrodes, 137, 138 cells with respect to the electrolyte, 144
a chemical substance, 169 quantity of, 3 Electrochemistry, history of, 49 and work obtainable from reactions, 12
Conduction through
salts, 45 Conductivity, 77 of acetic acid, 100 Conductivity, metallic and electrolytic, 80 of the metals, 79
Electrodes, 51
of first
and second kind,
141, 142
Electrolysis, 164
of pure substances, 91 of solutions, 8 1

specific, 78 temperature coefficient of, of water, 73 Conservation of energy, 7 Contact electricity, 118
,
Electrolyte, 51 Electrolytic solution
pressure, 127 Electrolytic potential, 130 Electromotive force, calculation of,

79,
107
123
Electron, velocity theory, 169
and mass
of,
169
Copper, precipitation of by zinc, 126
Coulomb, 3, 78 and ion, 52

Current, production of, by chemical means, 115
Element, 120 Endosmosis, 119 Energy, chemical,

electric, 3,
free,
5,
heat, 4
kinds
Daniell
cell,
of, i,
n,
121, 126
Decomposition voltage, 152, 155, 156

Depolarization, 154 Deposition voltage of the ions, 156, 160, 161
Dielectric constant, 113 and dissociating power, 93, 94 Diffusion potential 145 Dilution law, Ostwald's, 101
kinetic, 7 law of the conservation of, 7 law of the transformation of,
mechanical, potential, 8
radiant, 5 table of equivalents, 5
Dissociating Dissociation Dissociation Dissociation sis, 68
power, 92
constant, 58, 99 constants, table of, 102
constant and hydroly-
Dissociation, electrolytic, 48 decrease of, 102
temperature coefficient of, 10 volume, 2 Energy equation of Gibbs-Helmholtz, 124 of van't Hoff, 31, 124 of Nernst, 127 Equilibrium, chemical, 32 and temperature, 41 Equilibrium, constant, 35
concentration, 125 Equivalent, 83
conductivity, 83, 86, 90
degree
of, 48, 57,

salts,
formula of
heat
of,
87 58
of gases, 38
67 pressure, 41
of salts, 96 stepwise, 63, 106
weights table of, 163 Ester formation, 32, 36
Expansion, work done

Faraday's law, 52, 162
in,
theory 45 of water, 73, 147

of,
Ferrocyanide of copper membrane, 24
INDEX.
Fluid, electric, 169 Force, 5 chemical, and reaction
179
velocity,
14 Free energy,
Hydrolysis, 68 and the dissociation constant, 71 Hydroxyl ions, deposition of, 167 Hypochlorites, 168
van't Hoff 's factor, table, 49 Incomplete reactions, 32, 33
I,
Freezing-point, lowering of, 27 molecular lowering of, 46 Friction, of the ions, 93

internal, 75 Frictional electricity, 119 Fugacity, 127
Insulators, conductivity of, 79 Inversion of sugar, 98

Ions,.-48, 52
Galvani's experiments, 120 Galvanic cell, 120 Gas-constant R, 18 value of, in different units, 5 Gas electrodes, 136 Gas laws, 16 Gas pressure, 16
additive properties of, 75 charges on, 49, 52 deposition voltage of, 156, 161 as electron compounds, 171
friction
160,
overcome by, 113
reactions of, 61
velocities of, 84 velocities of absolute, 112 Isohydric solutions, 103
Gases, dissociation
of,
37
16, 21
expansion
of, 2
Isosmotic and isotomic solutions, 23 158

Kinetics, law of chemical, 35 Kohlrausch, law of the independent wandering of the ions, 5 5 85 1 1 1
, ,
work obtainable from,

overvoltage
of,
Gay-Lussac's Law, 16 Gibbs-Helmholtz formula, 124
Gram
equivalent
and molecule.
18,
83 Grottnus, theory of, 53 Grove, theory of, 54 gas cell, 138, 144
Lead, deposition
of, 165 storage battery, 147 Light, absorption of, 75 Litre atmosphere, 2, 19 Liquids, contact potential of, 145
Heat energy,
4, 6 Heat, mechanical equivalent theory of, 7, 9 Heat and motion, 8 of reaction, 8, 43, 44
of,
Mass,
Mass
law
action, 36, 40
of,
35
and
of neutralization,
66
Maximum
dissociation, 57
Helmholtz's energy equation, 124 Henry's absorption law, 136 Heterogeneous systems, 39 H.ttorf's experiments on the transport number, 55
work, 6, 8 determination of, 12
Mechanical energy, 2 Mechanicat equivalent of heat, 4 Mercury, potential and surface

tension of, 135
Van't Hoff energy equation, 31 laws of solutions, 56 laws of dilution, 101 Homogeneous systems, 39 Hydrogen, deposition of, 160
,
normal electrode, 134 Metal solutions, potential
of,
140
of,
electrode, 133, 137 electrolytic potential, 133
Metals, specific conductivity Mixtures, potential of, 140 Mol, 18 Molecule, gaseous, 18
79
158 Hvdroiodic acid, formation

overvoltage
of,
Molecular concentration, 23 Molecular conductivity of the ions,

of,
37
85
i8o
Nernst's formula, 127 applications of, 146 Neutralization, 66 Neutralization cell, 146 Neutralization, heat of, 66
INDEX.
Potential, electrolytic, 130, 134 energy, 7
fall of,
116
of mixtures, 140 of reducing and oxidizing agents
Neutron, 170
Nitrogen, density of, 18 "Nobility" of the metals, 134 Normal electrodes, 134, 142
143
Pressure, 2 osmotic, and chemical work, 30 Principe du travail maximum, 9 Principles of thermodynamics, 6, 9,
Ohm's
law, 78, 117
10
Osmotic cells, 25 Osmotic work, 30 Osmotic pressure, 27

of salts, 49 of sugar (table), 26 and solution pressure, 128
R, the gas-constant, 18 Radium, 170 Reaction, complete and incomplete,

32
heat
of,
and work, 20
Ostwald's dilution law, 101 Oxidation potential, 143 Oxygen electrode, 138 Oxygen, overvoltage of, 158 Oxygen and carbon monoxide, 38, 41 Oxygen-hydrogen cell, 138
Partial pressure, 17
34 work obtainable from, 12 Reaction velocity, 14, 35 Reduction potential, 143 Residual current, 154
reversible,
Resistance, chemical, 15 specific, of metals, 79 Reversibility, 12, 123

Saponification, 71, 99
Salt solution, osmotic pressure of, 47 Salts, dissociation of, 58
Perpetual motion, 7, 9 Persulphuric acid, 166 Plant cells, osmotic pressure of, 22, 24 Phosphorous chloride, formation of, 38
Physiological solutions, 76 Physiology and the theory of electrolytic dissociation, 75 Plasmolysis, 23 Platinum as semipermeable mem-
solution of, 40 Schlieren apparat, 28
Secondary reactions, 167 Secondary elements, 147 Semipermeable membranes, 22 of Cu 2 Fe(CN) c 24 of air, 28
,
brane, 25 Platinum black, catalytic action
of,
136 Poisonous action of the ions, 76

.
of ice, 27 of platinum, 25 Series of the elements according to their electrolytic solution pressure, 135 Silver analysis,
Polarization, 152 capacity, 153
and the
of,
dissociation
theory, 104
Polymerization power, 95
and
dissociating
Silver,
equivalent
3.
Cf. also
Faraday's law
Silver iodide, solubility of, 146 Silver ions, precipitation of, chlorine ions, 61
Potential, absolute, 135 of alloys, 140 of compounds, 140 at contact of solutions, 145 difference of, 2, 77, 116
electric,
by
116
Sodium acetate, hydrolysis of, 68 Sodium amalgam, 167 Solids, active mass of, 36, 40
INDEX.
Solubility, constant,
181
of water, 41
40
force,
Vapor pressure
146
from electromotive
Solubility product, 104 Solutions, conductivity of, 81 dilute and the gas laws, 20
isotonic, 23 of salts, osmotic pressure, 47 Solution pressure, electrolytic, 127,
lowering of, 27, 47 Velocity of the ions, 85 Volt, 4

Voltage,
3,
6
of,
measurement
Voltaic pile, 121
118
of decomposition, 152
128
Solvent, active
mass
of,
36
Walls, semipermeable, 22 Wandering of the ions, law of the
dissociating, 92 Specific conductivity of metals, 79 Statics, law of chemical, 35
Stepwise dissociation.
ciation
Cf.
Disso-
independent, 85 Water, conductivity of, 90 dissociating power of, 93

dissociation of, 65, 73, 147
electrolysis of, 154
Succinic acid, solution of, 44 Sugar, osmotic pressure of, 25 inversion of, 98
Sulphuric acid, specific conductivity of, 91 decomposition voltages of, 161
evaporation of, 32 vapor pressure of, 41 Watt second, 3, 6
Weight, 2 Williamson, theory

sure, 30
of,
55
pres-
Temperature, absolute, 10 and chemical equilibrium, 41 Temperature coefficient of capacity for work, 10
of conductivity, 79, 80, 107
Work, chemical, and osmotic

from expansion of gases,
16, 19
maximum,
Thomson's Rule, 9
Transformation of energy, 9 Transport number, 108
Valence, variable and dissociating power, 95
9 from natural processes, 6 osmotic, 19

7,
Zero, absolute, of temperature, 10 Zinc, deposition of, 160 Zinc amalgam, potential of, 139
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8vo, 8vo, 8vo, 8vo, 8vo,

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5 oo 3 oo> 3 50*
2
oo
Planning and Construction of High Office Buildings

Brigg's
Skeleton Construction in Buildings Modern American School Buildings 1
3 50 3 oo
4 oo
Carpenter's Heating and Ventilating of Buildings

Freitag's Architectural Engineering Fireproofing of Steel Buildings
!
'.
8vo, 8vo,
8vo,
French and Ives's Stereotomy 8vo, Gerhard's Guide to Sanitary House-inspection i6mo, Theatre Fires and Panics i2mo, i 50 *Greene's Structural Mechanics 8vo, 2 50 Holly's Carpenters' and Joiners' Handbook i8mo, 75 8vo, 2 oo Johnson's Statics by Algebraic and Graphic Methods Kidder's Architects' and Builders' Pocket-book. Rewritten Edition. i6mo,mor., 5 oo Merrill's Stones for Building and Decoration 8vo, 5 oo Non-metallic Minerals: Their Occurrence and Uses 8vo, 4 oo Monckton's Stair-building 4to, 4 oo Patton's Practical Treatise on Foundations 8vo, 5 oo 8vo, 7 50 Peabody's Naval Architecture Rice's Concrete -block Manufacture 8vo, 2 oo i6mo, mor., 4 oo Richey's Handbook for Superintendents of Construction * Building Mechanics' Ready Reference Book. Carpenters' and Woodworkers' Edition i6mo, morocco, i 50 Sabin's Industrial and Artistic Technology of Paints and Varnish 8vo, 3 oo Siebert and Biggin's Modern Stone-cutting and Masonry 8vo, i 50 Snow's Principal Species of Wood 8vo, 3 50 Sondericker's Graphic Statics with Applications to Trusses, Beams, and Arches. 8vo, 2 oo Towne's Locks and Builders' Hardware i8mo, morocco, 3 oo Wait's Engineering and Architectural Jurisprudence 8vo, 6 oo
Sheep,
4 oo 3 50 2 50 2 50 i oo
6 50
5 oo 5 50 3 oo
Law
of Operations Preliminary to Construction in Engineering
and Archi8vo, Sheep, 8vo,
tecture
Law
of Contracts
Wood's Rustless Coatings: Corrosion and Electrolysis of Iron and Steel. .8vo, 4 oo Woicester and Atkinson's Small Hospitals, Establishment and Maintenance,
Suggestions for Hospital Architecture, with Plans for a Small Hospital.
The World's Columbian Exposition
of 1893
i2mo, Large 4to,
i i
25
oo
ARMY AND
NAVY.
Bernadou's Smokeless Powder, Nitro-cellulose, and the Theory of the Cellulose Molecule i2mo, 2 50 * Bruff's Text-book Ordnance and Gunnery 8vo, 6 oo Chase's Screw Propellers and Marine Propulsion 8vo, 3 oo Cloke's Gunner's Examiner 8vo, i 50 4to, 3 50 Craig's Azimuth Crehore and Squier's Polarizing Photo-chronograph 8vo, 3 oo * Davis's Elements of Law 8vo, 2 50 * Treatise on the Military Law of United States 8vo, 7 oo
Sheep,
De Brack's Cavalry Outposts Duties. Dietz's Soldier's First Aid Handbook * Dredge's Modern French Artillery
*
(Carr.)
24mo, morocco, i6mo, morocco,

8vo,
7 50 2 oo
i
25
4to, half morocco, 15
Durand's Resistance and Propulsion of Ships

Dyer's
Eissler's
Handbook of Light Artillery Modern High Explosives

on Field
Fortification
iamo,
8vo,
* Fiebeger's Text-book
Hamilton's The Gunner's Catechism * Heff'B filnatatary Naval Tactics. ......................I.
Small 8vo, i8mo,

>
5 3 4 2
x
oo oo oo oo oo oo
,8vo,
50
Ingalls's
Handbook of Problems in Direct Fire * Ballistic Tables * Lyons's Treatise on Electromagnetic Phenomena. Vols. * Mahan's Permanent Fortifications. (Mercur.) Manual for Courts-martial
8vo,
I.
and
II.
8vo, .8vo, each,
4 oo I 50 6 oo
7 SO
8vo, half morocco,
* Mercur's Attack of Fortified Places * Elements of the Art of War 8vo, Metcalf's Cost of Manufactures And the Administration of Workshops. .8vo, * Ordnance and Gunnery. 2 vols I2mo, i8mo, paper, Murray's Infantry Drill Regulations
Nixon's Adjutants' Manual Peabody's Naval Architecture
Phelps's Practical Marine Surveying Powell's Army Officer's Examiner
*
241110,
i6mo, morocco, i2mo,
50 oo 4 oo 5 oo 5 oo
i
10
i
oo
8vo,
8vo, 12010,
7 50 2 50
Sharpe's Art of Subsisting Armies in War * Tupes and Poole's Manual of Bayonet Exercises and
i8mo, morocco, Musketry Fencing.

24010, leather,
4 oo i 50
* Walke's Lectures on Explosives Weaver's Military Explosives * Wheeler's Siege Operations and Military Mining Winthrop's Abridgment of Military Law Woodhull's Notes on Military Hygiene Young'* Simple Elements of Navigation
8vo,
8vo,
8vo,
50 4 co oo 3 2 oo
2
i
i2mo, i6mo, i6mo, morocco,
50 50 oo
ASSAYING.
Fletcher's Practical Instructions in Quantitative Assaying with the Blowpipe.
i2mo, morocco, 8vo, Furman's Manual of Practical Assaying Notes on Assaying and Metallurgical Laboratory Experiments. .8vo, Lodge's Low's Technical Methods of Ore Analysis 8vo, Miller's Manual of Assaying I2mo, Process i2mo, Cyanide Minet's Production of Aluminum and its Industrial Use. i2mo, (Waldo.) O'Driscoll's Notes on the Treatment of Gold Ores 8vo, Ricketts and Miller's Notes on Assaying 8vo, Robine and Lenglen's Cyanide Industry. (Le Clerc.) 8vo, Ulke's Modern Electrolytic Copper Refining. 8vo, Wilson's Cyanide Processes i2mo, Chlorination Process I2mo,
. .
50
3 oo 3 oo 3 oo
i
i
oo oo
50 oo oo 3 4 oo 3 oo
2
i i
50 50
ASTRONOMY.
Comstock's Field Astronomy for Engineers
Craig's
8vo,
4to,
2 50
Azimuth
on Practical Astronomy
3 50
Doolittle's Treatise
Gore's Elements of Geodesy Hayford's Text-book of Geodetic Astronomy Merriman's Elements of Precise Surveying and Geodesy
8vo, 8vo,
8vo, 8vo, 8vo,
12010,
4 oo 2 50 3 oo
2 50 3 oo 2 oo
* Michie and Harlow's Practical Astronomy * White's Elements of Theoretical and Descriptive Astronomy
BOTANY.
Davenport's Statistical Methods, with Special Reference to Biological Variation. i6mo, morocco, i 25 Thome and Bennett's Structural and Physiological Botany. i6mo, 2 25 Westerrraier's Compendium of General Botany. 8vo, 2 oo (Schneider.)
CHEMISTRY.
Adriance's Laboratory Calculations and Specific Gravity Tables Alexeyeff's General Principles of Organic Synthesis. (Matthews.) Allen's Tables for Iron Analysis
Arnold's Compendium of Chemistry. (Mandel.) Austen's Notes for Chemical Students
i2mo,
8vo, 8vo,
25
3 oo 3 oo
3 50
i
Small 8vo,
i2mo,
50
Bernadou's Smokeless Powder. Molecule
Nitro-cellulose,
and Theory
of the Cellulose
i2mo,
8vo, 8vo,
2
i
* Browning's Introduction to the Rarer Elements Brush and Penfield's Manual of Determinative Mineralogy
50 50
Claassen's Beet-sugar Manufacture. (Hall and Rolfe.) Classen's Quantitative Chemical Analysis by Electrolysis.
8vo,
(Eoltwcod.). .8vo,
4 oo 3 oo 3 co
2
Cohn's Indicators and Test-papers Tests and Reagents Crafts's Short Course in Qualitative Chemical Analysis. (Schaeffer.).
Dolezalek's Theory of the Lead Accumulator (Storage Battery).
i2mo,
8vo,
.
.
3
i
oo oo
50
Ende.)
Drechsel's Chemical Reactions.
(Merrill.)
i2mo, (Von i2mo, i2mo,

8vo, 8vo,
2
i
50
Duhem's Thermodynamics and Chemistry. (Burgess.) Eissler's Modern High Explosives Effront's Enzymes and their Applications. (Prescott.) Erdmann's Introduction to Chemical Preparations. (Dunlap.)
121110,
25 4 oo 4 oo
3
i
8vo,
oo
25
i2mo,
morocco,
Fletcher's Practical Instructions in Quantitative Assaying with the Blowpipe.

i
50
Fowler's Sewage Works Analyses i2mo, 2 oo Fresenius's Manual of Qualitative Chemical Analysis. (Wells.) 8vo, 5 oo Manual of Qualitative Chemical Analysis. Part I. Descriptive. (Wells.) 8vo, 3 oo (Cohn.) System of Instruction in Quantitative Chemical Analysis. 2 vols 8vo, 12 50 Fuertes's Water and Public Health i2mo, i 50 Furman's Manual of Practical Assaying 8vo, 3 oo * Getman's Exercises in i2mo, 2 oo Physical Chemistry Gill's Gas and Fuel Analysis for Engineers i2mo, i 25
Grotenfelt's Principles of Modern Dairy Practice. (Woll.). Groth's Introduction to Chemical Crystallography (Marshall)
.
i2mo, i2mo,
oo
125
4 oo
i
Hammarsten's Text-book of Physiological Chemistry. (Mandel.) 8vo, Helm's Principles of Mathematical Chemistry. (Morgan.) .i2mo, i6mo, morocco, Bering's Ready Reference Tables (Conversion Factors)
Hind's Inorganic Chemistry * Laboratory Manual for Students Holleman's Text-book of Inorganic Chemistry. (Cooper.) Text-book of Organic Chemistry. (Walker and Mott.) * Laboratory Manual of Organic Chemistry. (Walker.)
8vo,
50
50
3 o~
i
i2mo,
8vo, 8vo,
oo 50
oo
2 50
i
i2mo,
8vo, 3 oo Hopkins's Oil-chemists' Handbook Jackson's Directions for Laboratory Work in Physiological Chemistry. .8vo, i 25 8vo, 2 50 Keep's Cast Iron Ladd's Manual of Quantitative Chemical Analysis i2mo, i oo 8vo, 3 oo Landauer's Spectrum Analysis. (Tingle.) * Langworthy and Austen. The Occurrence of Aluminium in Vegetable 8vo, 2 oo Products, Animal Products, and Natural Waters i2mo, i oo Lassar-Cohn's Practical Urinary Analysis. (Lorenz.) Application of Some General Reactions to Investigations in Organic i2mo, i oo Chemistry. (Tingle.) Leach's The Inspection and Analysis of Food with Special Reference to State
Control.
8vo,
8vo, 8vo, 8vo.
7 50
(Lorenz.) Lob's Electrochemistry of Organic Compounds. Lodge's Notes on Assaying and Metallurgical Laboratory Experiments Low's Technical Method of Ore Analysis
3 oo 3 oo 3 oo
i
Lunge's Tech.no-chemical Analysis.
(Cohn.)
i2mo
oo
* McKay and Larsen's Principles and Practice of Butter-making 8vo Mandel's Handbook for Bio-chemical Laboratory I2mo, * Martin's Laboratory Guide to Qualitative Analysis with the Blowpipe i2mo, Mason's Water-supply. (Considered Principally from a Sanitary Standpoint.) Rewritten 8vo, 3d Edition, Examination of Water. (Chemical and Bacteriological.) 12010, The Textile Fibres Matthew's 8vo, Meyer's Determination of Radicles in Carbon Compounds. (Tingle.). I2mo,
.
.
i
i
50
50 60
Miller's
Cyanide Process Minet's Production of Aluminum and its Industrial Use. Mixter's Elementary Text-book of Chemistry
I2mo, i2mo, I2mo, (Waldo.) i2mo, i2mo, Morgan's An Outline of the Theory of Solutions and its Results Elements of Physical Chemistry I2mo, * Physical Chemistry for Electrical Engineers i2mo, Morse's Calculations used in Cane-sugar Factories i6mo, morocco, Mulliken's General Method for the Identification of Pure Organic Compounds. Vol. I Large 8vo, 8vo, O'Brine's Laboratory Guide in Chemical Analysis 8vo, O'Driscoll's Notes on the Treatment of Gold Ores i2mo, Ostwald's Conversations on Chemistry. Part One. (Ramsey.) " " " " Part Two. i2mo, (Turnbull.) * Penfield's Notes on Determinative Mineralogy and Record of Mineral Tests.
of
Manual
Assaying
4 oo i 25 3 50 i oo i oo i oo 2 50 i 50
i
3
i
i
oo oo 50 50
5 oo 2 oo
2
i
oo 50
200
50
5 oo
i
Pictet's
The Alkaloids and
their
Chemical Constitution.
(Austen.)
(Biddle.)
8vo, paper, 8vo,
Pinner's Introduction to Organic Chemistry. Poole's Calorific Power of Fuels

Prescott and Winslow's Elements of
I2mo
Water
8vo, Bacteriology, with Special Refer-
50 oo
ence to Sanitary Water Analysis i2mo, i * Reisig's Guide to Piece-dyeing 8vo, 25 2 Richards and Woodman's Air.Water and Food from a Sanitary Standpoint. .8vo Ricketts and Russell's Skeleton Notes upon Inorganic Chemistry. (Part I. Non-metallic Elements.) 8vo, morocco, Ricketts and Miller's Notes on Assaying .8vo, 3 Rideal's Sewage and the Bacterial Purification of Sewage 8vo, 3 Disinfection and the Preservation of Food 8vo, 4
,
2$ oo
oo>
75
oo50-
'.
oo25,
Riggs's Elementary
Rostoski's
Manual
for the
Chemical Laboratory
(Le Clerc.)
Robine and Lenglen's Cyanide Industry.
8vo, 8vo,
4 oo>
i
Serum Diagnosis.
in
(Bolduan.)
I2mo,
8vo,
oo-
Ruddiman's Incompatibilities in Prescriptions

*
2 oc
i
Whys
Pharmacy
and Varnish
(Orndorff.)
I2mo,
8vo,
8vo,
oo,
Sabin's Industrial and Artistic Technology of Paints
Salkowski's Physiological and Pathological Chemistry. Schimpf's Text-book of Volumetric Analysis Essentials of Volumetric Analysis f
Qualitative Chemical Analysis Smith's Lecture Notes on Chemistry for Dental Students Spencer's Handbook for Chemists of Beet-sugar Houses
*
3 oo> 2 502 50*

i
i
I2mo, i2mo,
8vo,
8vo,
25
25.
Handbook for Cane Sugar Manufacturers Stockbridge's Rocks and Soils

* Tillman's Elementary Lessons in Heat * Descriptive General Chemistry
i6mo, morocco, i6mo, morocco,

8vo,
8vo,
2 503 ou>
3 oo
2 so>
i
50-
Treadwell's Qualitative Analysis.
(Hall.)
(Hall.) Quantitative Analysis. Turneaure and Russell's Public Water-supplies
8vo, 8vo, 8vo,

.8vo,
3 oa3 oo-
4 oo5 oo>
i
Van
Deventer's Physical Chemistry for Beginners. * Walke's Lectures on Explosives
(Boltwood.)
I2mo,
8vo,
so>
Ware's Beet-sugar Manufacture and Refining Washington's Manual of the Chemical Analysis of Rocks 5
Small 8vo, cloth,

8vo,
4 oo4 oo>
2 oo>
\Vassermann's
Immune
Sera
Haemolysins, Cytotoxins, and Precipitins.

'
'
'
'
(Bol-
'
'
'
"Weaver's Military Explosives ............ ...... '.'.'.'. .gvo,' 3 oo "Wehrenfennig's Analysis and Softening of Boiler Feed- Water .8vo. t. oo Wells's Laboratory Guide in Qualitative Chemical Analysis ........ i~ 50 .8vo, Short Course in Inorganic Qualitative Chemical Analysis for Engineering Students .............................................. i 2 mo, i 50 Text-book of Chemical Arithmetic ........................... 12010, i 25 Whipple's Microscopy of Drinking-water ............................ 8vo, 3 50 Wilson's Cyanide Processes ...................................... i 2 mo,' i 50 Chlorination Process ........................................ I2mo, i 50 Winton's Microscopy of Vegetable Foods ............................ 8vo, 7 =;o V/ulling's Elementary Course in Inorganic, Pharmaceutical, and Medical
,
'. '.
'.
'.
'.
'.
'.
Chemistry .............................................. iamo
2 oo
CIVIL ENGINEERING.
BRIDGES AND ROOFS.
HYDRAULICS.
RAILWAY ENGINEERING.
MATERIALS OF ENGINEERING.
3 oo
Baker's Engineers' Surveying Instruments i2mo, Bixby's Graphical Computing Table Paper ig X 24! inches. ** Burr's Ancient and Modern Engineering and the Isthmian Cana (Postage, 27 cents additional.) 8vo,
..
25
3 50 2 50 i oo
i i
Comstock's Field Astronomy for Engineers Davis's Elevation and Stadia Tables
-
8vo, 8vo,
""
Engineering for Land Drainage Practical Farm Drainage *Fiebeger's Treatise on Civil Engineering Flemer's Phototopographic Methods and Instruments Folwell's Sewerage. (Designing and Maintenance.) 2d Edition, Rewritten Freitag's Architectural Engineering. ^French and Ives's Stereotomy
Elliott's
I2mo, i2mo,
8vo, 8vo, 8vo, 8vo, 8vo,
50 oo
5 oo 5 oo 3 oo 3 50
Goodhue's Municipal Improvements Goodrich's Economic Disposal of Towns' Refuse -Gore's Elements of Geodesy Hayford's Text-book of Geodetic Astronomy
i2mo,
8vo, 8vo, 8vo,
50 75 3 50 2 50 3 oo
i
i6mo, morocco, Bering's Ready Reference Tables (Conversion Factors) ^Howe's Retaining Walls for Earth i2rno, * Ives's Adjustments of the Engineer's Transit and Level. i6mo, Bds. Ives and Hilts's Problems in Surveying i6mo, morocco, Small 8vo, Johnson's (J. B.) Theory and Practice of Surveying 8vo, .Johnson's (L. J.) Statics by Algebraic and Graphic Methods Laplace's Philosophical Essay on Probabilities. (Truscott and Emory.) i2mo, JMahan's Treatise on Civil Engineering. (1873.) (Wood.) 8vo,
.
2 50
i
25
25 50
4 oo 2 oo 2 oo
5 oo
Descriptive Geometry ."Merriman's Elements of Precise Surveying and Geodesy Merriman and Brooks's Handbook for Surveyors
INugent's Plane Surveying
8vo, 8vo,
i6mo, morocco,
8vo,
50 50 2 oo
i
3
2
5<>
Ogden's Sewer Design

Parsons's Disposal of Municipal Refuse Patton's Treatise on Civil Engineering
"Reed's Topographical Drawing and Sketching Hideal's Sewage and the Bacterial Purification of
,
i2mo,
8vo,
oo 2 oo
7 50 5 oo
8vo half leather,

4to,
Siebert and Biggin's
Sewage Modern Stone-cutting and Masonry
8vo, 8vo,
3 50
i
8vo, Smith's Manual of Topographical Drawing. (McMillan.) Sondericker's Graphic Statics, with Applications to Trusses, Beams, and Arches.
8vo,
50 50
oo
Taylor and Thompson's Treatise on Concrete, Plain and Reinforced 8vo, * Trautwine's Civil Engineer's Pocket-book i6mo, morocco, Venable's Garbage Crematories in America 8vo, Wait's Engineering and Architectural Jurisprudence 8vo, Sheep, Law of Operations Preliminary to Construction in Engineering and Archi8vo, Sheep, Law of Contracts 8vo, Warren's Stereotomy Problems in Stone-cutting 8vo, Webb's Problems in the Use and Adjustment of Engineering Instruments.
tecture
5 oo 5 oo
2 oo>
6 6
5 5
2
i
oo 50
oo
50
50
25
3 oo-
i6mo, morocco,
Wilson's Topographic Surveying
8vo,
50
BRIDGES AND ROOFS.

Boiler's Practical Treatise * Thames River Bridge
on the Construction
of Iron
Highway
Bridges. .8vo,
4to, paper,
oo
5 oo
3 3
5
Burr's Course on the Stresses in Bridges and Roof Trusses, Arched Ribs, and
Suspension Bridges 8vo, Burr and Falk's Influence Lines for Bridge and Roof Computations 8vo, and Construction of Metallic Bridges Design 8vo, Email 4to, Du Bois's Mechanics of Engineering. Vol. II Foster's Treatise on Wooden Trestle Bridges 4to, Fowler's Ordinary Foundations 8vo, Roof Trusses Greene's 8vo,
50 oo
10
5 3 50i
oa oo oo
25
8vo, 2 50 Bridge Trusses Arches in Wood, Iron, and Stone 8vo, 2 50 Howe's Treatise on Arches 8vo, 4 oo 8vo, 2 oo> Design of Simple Roof-trusses in Wood and Steel 8vo, 2 50 Symmetrical Masonry Arches Johnson, Bryan, and Turneaure's Theory and Practice in the Designing of Small 4to, 10 oo Modern Framed Structures Merriman and Jacoby's Text-book on Roofs and Bridges: Part
Part
I.
Stresses in Simple Trusses
8vo,
50
8vo, 2 50 Graphic Statics Part III. Bridge Design 8vo, 2 50Part IV. Higher Structures 8vo, 2 50 Morison's Memphis Bridge 4to, 10 oo Waddell's De Pontibus, a Pocket-book for Bridge Engineers. i6rro, morocco, 2 oo * i2mo, 50 Specifications for Steel Bridges 8vo, 3 50 Wright's Designing of Draw-spans. Two parts in one volume
II.
.
HYDRAULICS.
Barnes's Ice Formation
8vo, Bazin's Experiments upon the Contraction of the Liquid Vein Issuing from an Orifice. (Trautwine.) 8vo, 8vo, Bovey's Treatise on Hydraulics
3 oa
2 oo>
Church's Mechanics of Engineering
8vo,
5 oo? 6 ooi
Diagrams of Mean Velocity
of
Water
in
Open Channels
paper,
Hydraulic Motors Coffin's Graphical Solution of Hydraulic Problems

Flather's
8vo,
2 2
50 oo
50
i6mo, morocco,
Dynamometers, and the Measurement

Water-power
7
of
Power
:
I2rco,
Folwell's Water-supply Engineering

Frizell's
8vo, 8vo,
oo 4 oo
3
oo
, .121110, Fuertes's Water and Public Health Water-filtration Works i2mo, Ganguillet and Kutter's General Formula for the Uniform Flow of Water in Rivers and Other Channels. (Hering and Trau twine.) 8vo, Hazen's Filtration of Public Water-supply: 8vo,
50
2 50
4 oo 3 oo
2 50 2 oo
Hazlehurst's Towers and Tanks for Water-works 8vo, Herschel's 115 Experiments on the Carrying Capacity of Large, Riveted, Metal 8vo. Conduits Mason's Water-supply. (Considered Principally from a Sanitary Standpoint.) 8vo,
Merriman's Treatise on Hydraulics 8vo, * Michie's Elements of 8vo, Analytical Mechanics Schuyler's Reservoirs for Irrigation, Water-power, and Domestic Watersupply
4 oo 5 oo 4 oo
5 oo
Large 8vo,
** Thomas and Watt's Improvement of Rivers (Post., 44c. additional. ) 4to, 6 oo Turneaure and Russell's Public Water-supplies 8vo, 5 oo 4to, 5 oo Wegmann's Design and Construction of Dams Water-supply of the City of New York from 1658 to 1895 4to, 10 oo "Williams and Hazen's Hydraulic Tables 8vo, i 50
Wilson's Irrigation Engineering Wolff's Windmill as a Prime Mover Wood's Turbines
Small 8vo,
8vo,
4 oo 3 oo
2
'.
8vo,
8vo,
50
Elements of Analytical Mechanics
3 oo
MATERIALS OF ENGINEERING.
Baker's Treatise on Masonry Construction
8vo,
Roads and Pavements
8vo,
Black's United States Public Works Oblong 4to, * Bovey's Strength of Materials and Theory of Structures 8vo, Burr's Elasticity and Resistance of the Materials of Engineering 8vo, 8vo, Byrne's Highway Construction Inspection of the Materials and Workmanship Employed in Construction.
5 oo 5 oo 5 oo 7 50
7 50
5 oo
i6mo,
Church's Mechanics of Engineering Du Bois's Mechanics of Engineering. Vol. =*Eckel's Cements, Limes, and Plasters
,
8vo,
I
3 oo 6 oo
7 50
Small 4to,
8vo,
Johnson's Materials of Construction

'Fowler's Ordinary Foundations
Large 8vo,
8vo,
6 oo 6 oo
3 50 4 oo 2 50 2 50 7 50 7 50 4 oo 5 oo 5 oo i oo 2 oo 5 oo 3 oo 4 oc 5 oo
i 25 3 oo
Graves's Forest Mensuration * Greene's Structural Mechanics Keep's Cast Iron Lanza's Applied Mechanics Marten's Handbook on Testing Materials. (Henning.) Maurer's Technical Mechanics Merrill's Stones for Building and Decqration Merriman's Mechanics of Materials Strength of Materials
Metcalf's Steel.
8vo, 8vo, 8vo,

8vo,
2 vols
.'
8vo, 8vo, 8vo, 8vo,
A Manual
for Steel-users
i2mo, i2mo,
8vo,
Patton's Practical Treatise on Foundations
Richardson's Modern Asphalt Pavements 8vo, Richey's Handbook for Superintendents of Construction i6mo, mor., * Ries's Clays: Their Occurrence, Properties, and Uses 8vo, Rockwell's Roads and Pavements in France i2mo, Sabin's Industrial and Artistic Technology of Paints and Varnish 8vo, Smith's Materials of Machines 12010, -Snow's Principal Species of Wood 8vo,
oo
3 50
Spalding's Hydsaulic
Cement
....
Text-book on Roads and Pavements Taylor and Thompson's Treatise on Concrete. Plain and Reinforced
Thurston's Materials of Engineering. 3 Parts Part I. Non-metallic Materials of Engineering and Metallurgy Iron and Steel Part II
i2mo, i2mo,
8vo, 8vo, 8vo,
oo oo 5 oo 8 oo
2 oo
8vo,
3 50
2 50
Part
Treatise on Brasses, Bronzes, and Other Alloys Constituents

III.
and
their
8vo,
8vo,
Thurston's Text-book of the Materials of Construction Tillson's Street Pavements and Paving Materials WaddelFs De Pontibus (A Pocket-book for Bridge Engineers.)Specifications for Steel Bridges.
5 oo
8vo,
4 oo
2 oo
i
i6mo, mor., i2mo, ... Wood's (De V.) Treatise on the Resistance of Materials, and an Appendix on the Preservation of Timber 8vo, Wood's (De V.) Elements of Analytical Mechanics 8vo, Wood's (M. P.) Rustless Coatings; Corrosion and Electrolysis of Iron and
Steel
25
2 oo
3 oo
8vo,
4 oo
RAILWAY ENGINEERING.
Andrew's Handbook for Street Railway Engineers. .. .3x5 inches, morocco, Berg's Buildings and Structures of American Railroads 4to, Brook's Handbook of Street Railroad Location i6mo, morocco Butt's Civil Engineer's Field-book i6mo, morocco, Crandall's Transition Curve i6mo, morocco, Railway and Other Earthwork Tables 8vo, Dawson's "Engineering" and Electric Traction Pocket-book i6mo, morocco,
.
25
50
5 oo
i
2 50
50 50 5 oo
i
i
Paper, 5 oo Dredge's History of the Pennsylvania Railroad: (1870) * Drinker's Tunnelling, Explosive Compounds, and Rock Drills. 4to, half mor., 25 oo Fisher's Table of Cubic Yards Cardboard, 25 Godwin's Railroad Engineers' Field-book and Explorers' Guide. i6mo, mor., 2 50 Howard's Transition Curve Field-book i6mo, morocco, i 50 Hudson's Tables for Calculating the Cubic Contents of Excavations and Embankments 8vo, i oo Molitor and Beard's Manual for Resident Engineers. i6mo, i oo i6mo, morocco, 3 oo Nagle's Field Manual for Railroad Engineers Philbrick's Field Manual for Engineers. i6mo, morocco, 3 oo Searles's Field Engineering i6mo, morocco, 3 oo
. .
Railroad Spiral
i6mo, morocco,
8vo, Taylor's Prismoidal Formulae and Earthwork * Trautwine's Method ot Calculating the Cube Contents of Excavations and
50 50 oo
Embankments by
The Field Practice
of
the Aid of Diagrams Laying Out Circular Cyrves for Railroads.
8vo,
i2ino, morocco,
Cross-section Sheet
Paper,
Webb's Railroad Construction Economics of Railroad Construction Wellington's Economic Theory of the Location
of
Railways
i6mo, morocco, Large i2tno, Small 8vo-
50 25 5 oo 2 50 5 oo
DRAWING.
Barr's Kinematics of Machinery * Bartlett's Mechanical Drawing " " "
8vo
8vo,
2 50
3 oo
Abridged Ed
8vo, 8vo, paper,
150
i
Coolidge's
Manual
of
Drawing
9
oo
Coolidge and Freeman's Elements of General Drafting for Mechanical Engineers Oblong 4to,
Durley's Kinematics of Machines Emch's Introduction to Projective Geometry and
Hill's
its
2
2
50 50
50
Applications
8vo, 8vo,
4 oo
2 oo 2
Text-book on Shades and Shadows, and Perspective Jamison's Elements of Mechanical Drawing Advanced Mechanical Drawing
Jones's Machine Design:
8vo,
8vo,
8vo,
oo 50
of Machinery 8vo, Form, Strength, and Proportions of Parts 8vo, MacCord's Elements of Descriptive Geometry 8vo, Kinematics; or, Practical Mechanism 8vo, Mechanical Drawing 4to, Velocity Diagrams 8vo, MacLeod's Descriptive Geometry Small 8vo, * Mahan's Descriptive Geometry and Stone-cutting 8vo, Industrial Drawing. (Thompson.) 8vo, Moyer's Descriptive Geometry 8vo, Reed's Topographical Drawing and Sketching 4to, Reid's Course in Mechanical Drawing 8vo, Text-book of Mechanical Drawing and Elementary Machine Design. 8vo, Robinson's Principles of Mechanism 8vo, Schwamb and Merrill's Elements of Mechanism 8vo, Smith's (R. S.) Manual of Topographical Drawing. (McMillan.) 8vo, T Smith (A. W.) and Marx's i achine Design 8vo, * Titsworth's Elements of Mechanical Drawing -.Oblong 8vo, Warren's Elements of Plane and Solid Free-hand Geometrical Drawing. 12 mo, i2mo, Drafting Instruments and Operations Manual of Elementary Projection Drawing i2mo, Manual of Elementary Problems in the Linear Perspective of Form and Shadow i2mo, Plane Problems in Elementary Geometry i2mo, i2mo, Primary Geometry Elements of Descriptive Geometry, Shadows, and Perspective 8vo, General Problems of Shades and Shadows 8vo, Elements of Machine Construction and Drawing 8vo, 8vo, Problems, Theorems, and Examples in Descriptive Geometry (Hermann and Weisbach's Kinematics and Power of Transmission.
I.
Part Part
Kinematics
II.
3 oo 3 oo 5 oo
.*
4 oo i 50 i 50 i 50
3 50 2 oo
5 oo
2
oo
3 3
3
2
oo oo
oo
50
25 oo
3 oo
i
i
i
25
50
oo
25,
75
3 50 3 00
7 50 2 50
Klein.)
Whelpley's Practical Instruction in the Art of Letter Engraving Wilson's (H. M.) Topographic Surveying; Wilson's (V. T.) Free-hand Perspective Wilson's (V. T.) Free-hand Lettering Woolf's Elementary Course in Descriptive Geometry
8vo, 12 mo, 8vo, 8vo, 8vo, Large 8vo,
5 oo
2
oo
3 50
2
i
50 00
3 oc.
ELECTRICITY AND PHYSICS.

Small 8vo, Anthony and Brackett's Text-book of Physics. (Magie.) i2mo, Anthony's Lecture-notes on the Theory of Electrical Measurements.
.
3
i
oo
oo
Benjamin's History of Electricity

Voltaic Cell Classen's Quantitative Chemical Analysis
* Collins's
8vo,
3 oo
3 oo
by
Electrolysis.
8vo, (Boltwood.).8vo,
3 oo
2
Manual
of
Wireless Telegraphy
i2mo, Morocco,
8vo, Crehore and Squier's Polarizing Photo-chronograph Dawson's "Engineering" and Electric Traction Pocket-book. i6mo, morocco, 10
50 oo oo 3
i
5 oo
Dolezalek's
Theory
of
the
Lead Accumulator (Storage Battery).
Ende.)
(Von i2mo,
8vo,
Jtt
Duhem's Thermodynamics and Chemistry. (Burgess.) Flather's Dynamometers, and the Measurement of Power Gilbert's De Magnete. (Mottelay.)
o^
-
i2mo,
8vo,
Hanchett's Alternating Currents Explained i2mo> i6mo, morocco, Bering's Ready Reference Tables (Conversion Factors) Holman's Precision of Measurements 8vo, .Large 8vo, Telescopic Mirror-scale Method, Adjustments, and Tests. Kinzbrunner's Testing of Continuous-current Machines 8vo, Landauer's Spectrum Analysis. (Tingle.) 8vo,
.
.
3 oo* 2 50 i oo
2
2 50,
Le Chatelier's High-temperature Measurements. (Boudouard Burgess.) i2mo, 3 Lob's Electrochemistry of Organic Compounds. 8vo, 3 (Lorenz.) * Lyons's Treatise on Electromagnetic Phenomena. Vols. I. and II. 8vo, each, 6 * Michie's Elements of Wave Motion Relating to Sound and Light 8vo, 4 Niaudet's Elementary Treatise on Electric Batteries. (Fishback.) i2mo, 2 * Parshall and Hobart's Electric Machine Design 4to, half morocco, 12 50 * (Haldane Gee Kinzbrunner.). .8vo, i 50 Rosenberg's Electrical Engineering. 8vo, 2 50 Ryan, Norris, and Hoxie's Electrical Machinery. Vol. 1 Thurston's Stationary Steam-engines 8vo, 2 50* Tillman's Elementary Lessons in Heat 8vo, i so Small 8vo, 2 oa Tory and Pitcher's Manual of Laboratory Physics Ulke's Modern Electrolytic Copper Refining 8vo, 3 oa
.
oo 75 oo oo oo oo oo oo 50
LAW.
* Davis's Elements of Law * Treatise on the Military
*
8vo,
2 50.. 7
Law
of
United States
8vo,
oo
Sheep,
7
i
50
50
Manual
for Courts-martial Wait's Engineering and Architectural Jurisprudence
i6mo, morocco,
8vo,
Sheep,
6 oo 6 50
5 oo 5 50 3 oo 2 50
Law
of Operations Preliminary to Construction in
Engineering and ArchiSvo, Sheep, 8vo,
tecture
Law
of Contracts
Winthrop's Abridgment of Military
Law
i2mo,
MANUFACTURES.
Bernadou's Smokeless Powder Molecule Bolland's Iron Founder
Nltro-oelluiose
and Theory
of the Cellulose
The Iron Founder," Supplement Encyclopedia of Founding and Dictionary of Foundry Terms Used in the
Practice of Moulding
i2mo, I2mo, i2mo,

i2mo,
8vo,
a $<&*
a so> 2 50...
3 oo3 00* 6 oo
Claassen's Beet-sugar Manufacture. (Hall and Rolfe.) * Eckel's Cements, Limes, and Plasters
Eissler's
Modern High Explosives Effront's Enzymes and their Applications.

Fitzgerald's Boston Machinist Ford's Boiler Making for Boiler
(Prescott.)
8vo, 8vo, 8vo,
Makers
I2mo, i8mo,
.
4 oo~ 3 oo i oo
i
oo
Hopkin's Oil-chemists' Handbook Keep's Cast Iron
.8vo,
8vo,
3 oo a 50.
11
Xeach's The Inspection and Analysis of Food with Special Reference to State Control Large 8vo, * McKay and Larsen's Principles and Practice of Butter-making 8vo, Matthews's The Textile Fibres 8vo, Metcalf s Steel. A Manual for Steel-users i2mo, Mstcalfe's Cost of Manufactures And the Administration of Workshops. 8 vo, 4to, Meyer's Modern Locomotive Construction Morse's Calculations used in Cane-sugar Factories i6mo, morocco, * Reisig's Guide to Piece-dyeing 8vo, -8vo, Rice's Concrete-block Manufacture 8vo, Sabin's Industrial and Artistic Technology of Paints and Varnish 8vo, Smith's Press-working of Metals I2mo, Spalding's Hydraulic Cement i6mo, morocco, Spencer's Handbook for Chemists of Beet-sugar Houses Handbook for Cane Sugar Manufacturers *6mo, morocco, 8vo, Taylor and Thompson's Treatise on Concrete, Plain and Reinforced
Thurston's Manual of Steam-boilers, their Designs, Construction and Operation
7 50
i
50
3 50
2 oo
5 oo 10 oo
i 50 25 oo 2 oo 3 oo 3 oo 2 oo 3 oo 3 oo 5 oo
8vo,
* Walke's Lectures on Explosives 8vo, Small 8vo, Ware's Beet-sugar Manufacture and Refining 8vo, Weaver's Military Explosives i2mo, West's American Foundry Practice Moulder's Text-book i2mo, 8vo, Wolff's Windmill as a Prime Mover Wood's Rustless Coatings: Corrosion and Electrolysis of Iron and Steel. .8vo,
5 oo 4 oo 4 oo 3 oo
2 50 2 50
3 oo
4 oo
MATHEMATICS.
Baker's Elliptic Functions * Bass's Elements of Differential Calculus Briggs's Elements of Plane Analytic Geometry
8vo,
Compton's Manual of Logarithmic Computations

Davis's Introduction to the Logic of Algebra
i2mo, i2mo, i2mo,

8vo,
i 50 4 oo oo
* Dickson's College Algebra Large i2mo, * Introduction to the Theory of Algebraic Equations Large i2mo, to Projective Geometry and its Applications 8vo, Emch's Introduction 8vo, Halsted's Elements of Geometry 8vo, Elementary Synthetic Geometry i2mo, Rational Geometry
* Johnson's
"*
50 50 50
25 50 75 50 75
15 5 oo
(J.
B.) Three-place Logarithmic Tables: Vest-pocket size. paper, too copies for
Mounted on heavy cardboard,
8X 10
inches,
25
2 oo 3 oo
i i
10 copies for Johnson's (W W.) Elementary Treatise on Differential Calculus. .Small 8vo, Small 8vo, Elementary Treatise on the Integral Calculus i2mo, Johnson's (W. W.) Curve Tracing in Cartesian Co-ordinates
50 oo
Johnson's
(W W.)
Treatise on Ordinary
and Partial
Differential Equations.
Small 8vo, Johnson's (W. W.) Theory of Errors and the Method of Least Squares. i2mo, * Johnson's (W W.) Theoretical Mechanics I2mo, Laplace's Philosophical Essay on Probabilities. (Truscott and Emory.) i2mo, * Ludlow and Bass. Elements of Trigonometry and Logarithmic and Other 8vo, Tables Each, Trigonometry and Tables published separately * Ludlow's Logarithmic and Trigonometric Tables 8vo. Manning's Irrational Numbers and their Representation by Sequences and Series
.
3 50
i
50
3 oo 2 oo 3 oo 2 oo
i
oo
25
T2mo
1Q
Mathematical Monographs.
S.
Edited by Mansfield Merriman and Robert Octavo, each No. i. History of Modern Mathematics, by David Eugene Smith. No. 2. Synthetic Projective Geometry, by George Bruce Halsted. No. 3. Determinants, by Laenas Gifford Weld. No. 4. HyperNo. 5. Harmonic Funcbolic Functions, by James McMahon. No. 6. Grassmann's Space Analysis, tions, by William E. Byerly. by Edward W. Hyde. No. 7. Probability and Theory of Errors, by Robert S. Woodward. No. 8. Vector Analysis and Quaternions, by Alexander Macfarlane. No. 9. Differential Equations, by William Woolsey Johnson. No. 10. The Solution of Equations, by Mansfield Merriman. No. n. Functions of a Complex Variable,
Woodward
oo
by Thomas
S. Fiske.
Maurer's Technical Mechanics .8vo, Merriman's Method of Least Squares 8vo, Rice and Johnson's Elementary Treatise on the Differential Calculus. Sm. 8vo, 2 vols. in one Small 8vo, Differential and Integral Calculus. Wood's Elements of Co-ordinate Geometry 8vo,
.
4 oo 2 oo 3 oo
2 50
2 oo
i
Trigonometry: Analytical, Plane, and Spherical
i2mo,
oo
MECHANICAL ENGINEERING.
MATERIALS OF ENGINEERING, STEAM-ENGINES AND BOILERS.
"Bacon's Forge Practice
Baldwin's Steam Heating for Buildings

Barr's Kinematics of Machinery
* Bartlett's
i2mo, i2mo,
8vo, 8vo,
Abridged Ed Benjamin's Wrinkles and Recipes Carpenter's Experimental Engineering Heating and Ventilating Buildings Cary's Smoke Suppression in Plants using Bituminous Coal.
tion.)
"
Mechanical Drawing
"
"
8vo,
i2mo,
8vo, 8vo,
(In Prepara-
50 50 50 3 oo i 50 2 oo 6 oo 4 oo
i
2
2
Gas and Oil Engine Manual of Drawing Coolidge and Freeman's Elements
Clerk's
Small 8vo,
8vo, paper,
of General Drafting for
Coolidge's
4 oo i oo
2 50
Mechanical En-
gineers Cromwell's Treatise
on Toothed Gearing Treatise on Belts and Pulleys Durley's Kinematics of Machines Fiather's Dynamometers and the Measurement Rope Driving Gill's Gas and Fuel Analysis for Engineers
Hall's Car Lubrication
Oblong 4to, I2mo, I2mo,

8vo,
of Power.
*
.-
Bering's Ready Reference Tables (Conversion Factors)
i2mo, i2mo, i2mo, i2mo, i6mo, morocco,

'.
50 50 4 oo 3 oo 2 oo
i
25 oo
2 50
5 oo 2 50
i
Button's The Gas Engine Jamison's Mechanical Drawing

Jones's Machine Design: Part I. Kinematics of Machinery Part II. Form, Strength, and Proportions of Parts
8vo, 8vo, 8vo, 8vo,
50
Kent's Mechanical Engineers' Pocket-book i6mo, morocco, Kerr's Power and Power Transmission 8vo, Leonard's Machine Shop, Tools, and Methods 8vo, * Lorenz's Modern 8vo, Refrigerating Machinery. (Pope, Haven, and Dean.) MacCord's Kinematics; or Practical Mechanism 8vo,
.
.
3 oo 5 oo
2 oo 4 oo 4 oo 5 oo 4 oo
i
Mechanical Drawing
Velocity Diagrams
'.
4to 8vo,
.
50
13
MacFarland's Standard Reduction Factors for Gases Mahan's Industrial Drawing. (Thompson.)
Poole's Calorific Power of Fuels Reid's Course in Mechanical Drawing
'
8vo, 8vo, 8vo, 8vo,
50
3 50 3 oo
2
oo
Text-book of Mechanical Drawing and Elementary Machine Design. 8vo, Richard's Compressed Air i2mo, Robinson's Principles of Mechanism 8vo, Schwamb and Merrill's Elements of Mechanism. 8vo,
Smith's (O.) Press-working of Metals
3 oo
i
50
3 oo
3 oo
3 oo 3 oo
Smith (A. W.) and Marx's Machine Design Thurston's Treatise on Friction and Lost Work in Machinery and Mill Work.. 8vo, Animal as a Machine and Prime Motor, and the Laws of Energetics 12 mo, Warren's Elements of Machine Construction and Drawing 8vo, Weisbach's Kinematics and the Power of Transmission. (Herrmann
.
8vo, 8vo,
3 co>
i
oa 5^
Klein.).
8vo,
5 oa
5
Machinery of Transmission and Governors. Wolff's Windmill as a Prime Mover
(Herrmann
Klein.). .8vo,
oo
8vo,
Wood's Turbines
8vo,
3 oo 2 50
MATERIALS OP ENGINEERING.
and Theory of Structures Burr's Elasticity and Resistance of the Materials of Engineering. Reset
*,Bovey's Strength of Materials
8vo, 6th Edition.
8vo, 8vo,
7
50
Church's Mechanics of Engineering * Greene's Structural Mechanics Johnson's Materials of Construction Keep's Cast Iron Lanza's Applied Mechanics Martens's Handbook on Testing Materials. Maurer's Technical Mechanics Merriman's Mechanics of Materials
Strength of Materials
Metcalf's Steel.
7 50 6 oo
2
8vo,
8vo, 8vo, 8vo, 8vo, 8vo, 8vo,
50
6 oo
2 50.
7 50. 7 so> 4 oa
(Henning.)
"
A manual
for Steel-users
i2mo, i2mo,
of Paints
and Artistic Technology Smith's Materials of Machines

Sabin's Industrial
and Varnish.
8vo,
i2mo,
Thurston's Materials of Engineering 3 vols., 8vo, Part II. Iron and Steel 8vo, Part III. A Treatise on Brasses, Bronzes, and Other Alloys and their Constituents 8vo, Text-book of the Materials of Construction 8vo, Wood's (De V.) Treatise on the Resistance of Materials and an Appendix on
the Preservation of Timber
oo oa 2 oa 3 oa i oa 8 oa 3 50
5
i
2 50*
5 oo>
2 oo-
Elements
of Analytical
Mechanics
Corrosion and
Electrolysis of Iron
Svo, Svo,
oo
Wood's (M.
P.) Rustless Coatings: Steel.,
and
8vo,
400.
STEAM-ENGINES AND BOILERS.

i2mo, Berry's Temperature-entropy Diagram ..i2mo, Carnot's Reflections on the Motive Power of Heat. (Thurston.). , .i6mo mor., Dawson's "Engineering" and Electric Traction Pocket-book.
.
. .
Ford's Boiler Making for Boiler Makers Goss's Locomotive Sparks Hemenway's Indicator Practice and Steam-engine
i8mo,
8vo,
Economy
i2mo,
25 50 5 oo i oo 2 oo 2 oo
i i
Button's Mechanical Engineering of Power Plants. Heat and Heat-engines Kent's Steam boiler Economy Kneass's Practice and Theory of the Injector MacCord's Slide-valves Meyer's Modern Locomotive Construction
'
8vo, 8vo,
oo
5 oo
Peabody's Manual of the Steam-engine Indicator Tables of the Properties of Saturated Steam and Other Vapors Thermodynamics of the Steam-engine and Other Heat-engines.
Valve-gears for Steam-engines
4 oo i 50 2 oo 4to, 10 oo famo, i 50
8vo, 8vo, 8vo,
8vo, 8vo,
8vo,
i
oo
5 oo 2 50
8vo, Peabody and Miller's Steam-boilers Large 8vo, Pray's Twenty Years with the Indicator Pupin's Thermodynamics of Reversible Cycles in Gases and Saturated Vapors. (Osterberg.) i2mo, i2mo, Reagan's Locomotives: Simple Compound, and Electric Rontgen's Principles of Thermodynamics. (Du Bois.) 8vo, Sinclair's Locomotive Engine Running and Management I2mo, Smart's Handbook of Engineering Laboratory Practice i2mo, Snow's Steam-boiler Practice. 8vo,
4 oo 2 50
i
25
ot>
2 50
5
2 2
oo 50
3 oo
Spangler's Valve-gears
8vo,
-
Notes on Thermodynamics Spangler, Greene, and Marshall's Elements of Steam-engineering Thomas's Steam-turbines Thurston's Handy Tables
i2mo,
8vo, 8vo,
8vo,
2 vols., 8vo, Steam-engine Part I. History, Structure, and Theory 8vo, Part II. Design, Construction, and Operation 8vo, Handbook of Engine and Boiler Trials, and the Use of the Indicator and the Prony Brake 8vo, Stationary Steam-engines 8vo, Steam-boiler Explosions in Theory and in Practice I2mo, Manual of Steam-boilers, their Designs, Construction, and Operation 8vo, Wehrenfenning's Analysis and Softening of Boiler Feed-water (Patterson) 8vo, Weisbach's Heat, Steam, and Steam-engines. (Du Bois.) 8vo, Whitham's Steam-engine Design 8vo, Wood's Thermodynamics, Heat Motors, and Refrigerating Machines. .8vo,
.
Manual
of the
50 oo 3 oo 3 50 i 50 10 oo
i
6 ,00 6 oo
5 oo 2 50
i
50
5 oo
4 5 5 4
oo oo oo
oo
MECHANICS AND MACHINERY.

Barr's Kinematics of Machinery * Bovey's Strength of Materials and Theory of Structures Chase's The Art of Pattern-making
:
8vo, 8vo,
2 50
i2mo,
8vo, 8vo,
7 50 2 50
i2mo, i2mo, I2mo, Treatise on Belts and Pulleys i2mo, Dana's Text-book of Elementary Mechanics for Colleges and Schools. i2mo, Dingey's Machinery Pattern Making i2mo, Dredge's Record of the Transportation Exhibits Building of the World's Columbian Exposition of 1893 4to half morocco, u Bois's Elementary Principles of MechanicsVol. I. Kinematics 8vo,
. .
.
Church's Mechanics of Engineering Notes and Examples in Mechanics. Compton's First Lessons in Metal-working. Compton and De Groodt's The Speed Lathe Cromwell's Treatise on Toothed Gearing.
. ,
6 oo
2
.*
oo 50
50 50 50 50 oo
5 oo
3 50
Vol.
II.
Statics
8vo,
Vol.
I.
,
400
4 oo
Mechanics of Engineering.
-Durley's Kinematics of Machines
Vol. II.
Small 4to, 7 50 Small 4to, 10 oo

8vo,
15
Fitzgerald's Boston Machinist Flather's Dynamometers, and the
Measurement
^
of
Power
16010, 12 mo,
oo
oo oo oo
3 oo
2
Rope Driving
Goss's Locomotive Sparks * Greene's Structural Mechanics
Hall's Car Lubrication
i2mo,
8vo.
8vo,
2 50
i
Holly's Art of
Saw
Filing
i2mo, i8mo,
75
2
James's Kinematics of a Point and the Rational Mechanics of a Particle. Small 8vo, * Johnson's (W. W.) Theoretical Mechanics i2mo,
Johnson's (L.
J.) Statics
oo
by Graphic and Algebraic Methods

,
.8vo,
3 o* 2 oo
Jones's Machine Design:
Part I. Kinematics of Machinery .8vo, i Part II. Form, Strength, and Proportions of Parts. 8vo, 3 Kerr's Power and Power Transmission 8vo, 2 Lanza's Applied Mechanics 8vo, 7 Leonard's Machine Shop, Tools, and Methods 8vo, 4 * Lorenz's Modern Refrigerating Machinery. (Pope, Haven, and Dean.). 8vo, 4 MacCord's Kinematics; or. Practical Mechanism 8vo, 5 i 8vo Velocity Diagrams. * Martin's Text Book on Mechanics, Vol. I, Statics i2mo, i Maurer's Technical Mechanics 8vo, 4 Merriman's Mechanics of Materials 8vo, 5 * Elements of Mechanics i2mo, i * Michie's Elements of Analytical Mechanics 8vo, 4 * Parshall and Hobart's Electric Machine Design 4to, half morocco, 12
.
.
50 oo oo
50
oo oo oo
50
25
oo
oo
oo oo
i2rno, Reagan's Locomotives Simple, Compound, and Electric Reid's Course in Mechanical Drawing 8vo, Text-book of Mechanical Drawing and Elementary Machine Design. 8vo, Richards's Compressed Air i2mo, Robinson's Principles of Mechanism 8vo, 8vo, Ryan, Norris, and Hoxie's Electrical Machinery. Vol. 1 Sanborn's Mechanics: Problems .Large i2mo, Schwamb and Merrill's Elements of Mechanism. 8vo, Sinclair's Locomotive-engine Running and Management I2mo, Smith's (O.) Press-working of Metals 8vo, Smith's (A. W.) Materials of Machines i2mo, Smith (A. W.) and Marx's Machine Design 8vo, 8vo, Spangler, Greene, and Marshall's Elements of Steam-engineering Thurston's Treatise on Friction and Lost Work in Machinery and Mill
. ,
2
2
50 50 oo
3
i
oo
50
3 oo 2 50
i
50
3 oo
oo oo i oo 3 oo 3 oo
2
Work
8vo,
Animal as a Machine and Prime Motor, and the Laws of Energetics. i2mo, i Warren's Elements of Machine Construction and Drawing 8vo, 7 Weisbach's Kinematics and Power of Transmission. (Herrmann Klein.). 8vo, 5 (Herrmann K ein.).8vo, 5 Machinery of Transmission and Governors. Wood's Elements of Analytical Mechanics 8vo, 3
!
oo oo
50 oo oo oo 25 50 oo
Principles of Elementary Mechanics
I2mo,
8vo,
4to,
Turbines The World's Columbian Exposition of 1893
2
i
METALLURGY.
Egleston's Metallurgy of Silver, Gold, and Mercury.Vol.
I.
Silver
Gold and Mercury A Reference Book Goesel's Minerals and Metals: ** Iles's Lead-smelting. (Postage 9 cents additional.).
Vol.
II.
8vo, 8vo,
t
50
7 50
3 oo 2 50 2 50
i6mo, mor. i2mo,

8vo,
Keep's Cast Iron
16
Kunhardt's Practice of Ore Dressing in Europe. . , Le Chatelier's High-temperature Measurements. (Boudouard

Metcalf' s Steel.
Miller's
8vo,
;Burgess.)i2mo.
12010,
50
Manual
for Steel-users
3 oo 2 oo
i
i2mo, Cyanide Process (Waldo.). .. i2mo, Minet's Production of Aluminum and its Industrial Use. Robine and Lenglen's Cyanide Industry. (Le Clerc.) 8vo, I2mo, Smith's Materials of Machines 8vo, Thurston's Materials of Engineering. In Three Parts 8vo, Part II. Iron and Steel Part III. A Treatise on Brasses, Bronzes, and Other Alloys and their
Constituents
Ulke's
oo
50 oo
4 oo
i
8 oo
3 50
2
Modern
Electrolytic Copper Refining,,
8vo, 8vo,
50
3 oo
MINERALOGY.
Barringer's Description of Minerals of Commercial Value. Boyd's Resources of Southwest Virginia
Oblong, morocco,
8vo,
2
3 2
50
oo
Southwest Virignia Map Brush's Manual of Determinative Mineralogy. Chester's Catalogue of Minerals
of
Pocket-book form.
(Penfield.)
oo
oo
8vo,
4 oo
i
25 8vo 3 So Dictionary of the Names of Minerals. Dana's System of Mineralogy Large 8vo, half leather 12 50 " First Appendix to Dana's New Large 8vo, i oo System of Mineralogy." 8vo, 4^00 Text-book of Mineralogy i2mo, i 50 Minerals and How to Study Them Large 8vo, i oo Catalogue of American Localities of Minerals i2mo, 2 oo Manual of Mineralogy and Petrography i2mo, i oo Douglas's Untechnical Addresses on Technical Subjects 8vo, i 25 Eakle's Mineral Tables 8vo, 2 50 Egleston's Catalogue of Minerals and Synonyms A Reference Book Goesel's Minerals and Metals i6mo,mor.. 3 oo i2mo, i 25 Groth's Introduction to Chemical Crystallography (Marshall) Hussak's The Determination of Rock-forming Minerals. ( Smith.). Small 8vo, 2 oo Merrill's Non-metallic Minerals- Their Occurrence and Uses 8vo, 4 oo * Penfield's Notes on Determinative Mineralogy and Record of Mineral Tests.
i
:
8vo, paper, Cloth,
8vo, paper,
50
5 oo
2 oo.
Rosenbusch's Microscopical Physiography of the Rock-making Minerals.

(Iddings.) * Tillman's Text-book of Important Minerals
*.
and Rocks
8vo, 8vo,
MINING.
Beard's Ventilation of Mines
I2mo,
,
2 50
8vo, 3 Boyd's Resources of Southwest Virginia Pocket-book form, 2 Map of Southwest Virginia. i2mo, i Douglas's Untechnical Addresses on Technical Subjects * Drinker's Tunneling, Explosive Compounds, and Rock Drills. .4to,hf. rnor. 25 8--> Eissler's Modern High Explosives 4 A Reference Book Goesel's Minerals and Metals i6mo, mor. 3 i2mo, 2 Goodyear's Coal-mines of the Western Coast of the United States
y
. .
oo
oo oo oo
"o
Ihlseng's
Manual
of
Mining
.
8vo,
oo 50 5 oo
2 50
i i
Lead-smelting. (Postage o,c. additional.) Kunhardt's Practice of Ore Dressing in Europe. Miller's Cyanide Process
Iles's
**
i2mo,
. . .
.8vo,
50
i2mo,
oo
17
'
-O'Driscoll's Notes
on the Treatment of Gold Ores Robine and Lenglen's Cyanide Industry. (Le Clerc.) * Walke's Lectures on Explosives Weaver's Military Explosives
Wilson's Cyanide Processes Chlorination Process
Hydraulic and Placer Mining.'
Treatise
Svo,
8vo, 8vo, 8vo,
oo 4 oo 4 oo 3 oo
50 50 2 oo
i i
on Practical and Theoretical Mine Ventilation
i2mo, i2mo, i2mo, T2mo,
125
SANITARY SCIENCE.
fiashore's Sanitation of a Country House * Outlines of Practical Sanitation
i2mo, I2mo,
8vo, 8vo,
oo
Folwell's Sewerage.
(Designing, Construction, and Maintenance.)
25 3 oo
i
Water-supply Engineering
Fowler's Sewage Works Analyses Fuertes's Water and Public Health
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Electrochemistry Heinrich Daniel

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LIBRARY

THEORETICAL ELECTROCHEMISTRY AND ITS PHYSICO-CHEMICAL FOUNDATIONS

TRANSLATED FROM THE SAMMLUNG GOSCHEN

Associate Professor of Chemistry in Marietta College, Ohio

ROBERT DRUMMONI), PRINTER, NEW YORK

science of electrochemistry has

far wider range of application than formerly.

utilization of chemical affinity for

electrochemistry has given rise

theories, the theory

has been of immense value.

magnesium, calcium carbide,

which can only be

go over some of the

physical and physico-chemical

and give such

illustrations as are nec-

be contained in the second volume.

third will be devoted to the technical applications.

Gas Laws, and

Pressure and van't Hoff's Equation.

THEORY OF ELECTROLYTIC DISSOCIATION

Faraday, Grotthus, Clausius,

Hittorf, van't Hoff, Arrhenius.

ELECTROMOTIVE FORCE AND THE GALVANIC CURRENT

Galvani, Volta, Daniell.

Calculation of Electromotive Forces.

Compounds. Oxidation and Reduction

Applications of Nernst's ForNeutralization Cells. Secondary Elements,

and the Accumulator.

Atomic and Equivalent Weights.

WORK, CURRENT, AND VOLTAGE.

certain reaction can do, for instance

and the temperature

that this reaction,

the oxidation of carbon monoxide,

practically impossible, although mechanical

be completely transformed into

is the erg the unit of the

which a kilogram can do in

falling a distance of i metre.

a pressure on the walls of the vessel enclosing

expands, the weight of the atmosphere above

WORK, CURRENT, AND VOLTAGE.

to the number of The expanding gas

work against the pressure of the atmosphere.

Such a column of mercury weighs 1.0333 kilograms,

kilograms are raised

033 ooo cms.

ergs; the value

013 200000 ergs.

ordinary unit of electric

the electric charge

precipitate this quantity of

flows through a conductor

and a watt-second is is able to do when flowing for of i ohm. A watt-second

voltXi ampere (a power), the work which a current of i ampere

second through a resistance therefore io8 Xio~ 1 = io7

necessary to raise the

equivalent of heat has been determined

we will use the value adopted by The meaning of this number is as

just sufficient to raise the temperature

in use, there are the