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Chemistry for photographers.

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http://www.archive.org/details/cu31924031224060
CHEMISTRY FOR
PHOTOGRAPHERS.

CHAS. F. TOWNSEND, F.C.S., F.R.P.S.

ILLUSTRATED.

THIRD EDITION, REVISED.

LONDON:
DAWBARN & WARD, LIMITED,
6, Farringdon Avenue, E.C.

1902.
 Uniform with this Volume.

EARLY WORK
IN

PHOTOGRAPHY.
BY
W. ETHELBERT HENRY, O.E.

THIRD EDITION.

With Negative and Positive on Celluloid.

Is. net ;
post free, Is. 2d.
 CONTENTS.

HAP. PAaB
I. Introductory, 5

II. OHEMISTET OBKBRA.LLT, AND THE CHEMISTRY OF

THE Silver Salts in particular, ... 13

III. The Chemistry op the Photooraphic Image, . 36

IV. Developers, 63

v. Reversal, 79

VI. Reduction, Intensification, etc 83

VII. Printing in Silver, 88

VIII. Printing in Salts of Iron, . . . 102

IX. Printing in Platinum, . . ... 105

X. The Bichromate Printing Processes, . . . 109

XI. Orthochromatism 115

XII. Impurities and Substances that alter in the

Air, 118

XIII. Recovery of Residues 123

XIV. Cellulose . . 125

XV. Resins, Varnishes, etc., . . . . 129

CyoLOP.«Dic Index, 140

 CHEMISTRY FOR PHOTOGRAPHERS.

CHAPTEE I.

Intkoductory.

The first essentials to anyone studying chemistry

are accuracy and cleanliness. Most of thei surpris-
ing results obtained by students in their early days
are due to want of cleanliness. Another point I
should like to impress upon those just taking up the
subject is that learning "facts" in a more or less
mechanical way is not learning chemistry. It is
said that a good lawyer does not know much law,
but knows where to find his law. The same applies
to a good chemist. Above all, endeavour to get an
insight into the nature of things, and remember that
the proper place for a dictionary is not inside a
man's head, but on a shelf. If particular sets of
facts or figures are often required for reference,
don't try to learn them, but cut or copy them out,
give them a coat of varnish and paste them on the
b PRELIMINAET HINTS.

work-room door. There is still another point : never

take for granted any statement you read you pos-
if

sess the means of testing it and have five minutes

to spare. Even if the statement is correct, more
knowledge will be gained by merely seeiiig the thing

/\

¥ u
V

Fig. 1.

happen than by reading about it all day. Statements

in photographic and other scientific books are fre-
quently incorrect, having crept into an early text-
book by mistake and been copied religiously ever
since. Mistakes have a way of creeping into a book,
 MEASURING APPARATUS. 7

however carefully it is written, so test all statements

when an opportunity occurs.
As all chemical and photographic work is based
on measurement, it is important to have a rational
system of weights and measures. For this reason
it would be well if every photographer discarded the

Fig. 2.

system of the pharmacist, together with his measur-

ing apparatus, replacing ounces and minims by
grams and cubic centimetres, and conical graduates
by burettes and pipettes. The conical measures
now in use are bad in every way it is practically
:

impossible to measure accurately with them, and

they are very difiBcult to keep clean.
8 BURETTES AND PIPETTES.

The construction of a burette will readily be seen

from the figure (fig. 1). The instrument can be
purchased with a glass tap, or with a glass jet, a
piece of india-rubber tubing and a pinchcock, the
latter being quite as convenient and much cheaper.
For photographic purposes, burettes for the different
developing solutions should be suspended round the
sink as shown in the sketch (fig. 2), being fed from
stock bottles on a shelf above, when large quantities
of material are used. It is well to have an opal
glass plate at the back of the fixed burette, and to
read the level of the bottom of the black curve at
the top of the liquid when measuring. A float with
a line engraved on it is sometimes used for reading,
and has the advantage of keeping the solution from
the air as well as or better than a stopper. The
construction of a pipette will be seen from the
last part of figure 1. It is filled by drawing up the
liquid with the mouth : the finger is then placed
rapidly on the top, and the liquid is allowed to run
down to the mark. The pipette with its contents
is then transferred bodily to the vessel into which

it is required to run the liquid.

In the. metric system, the centimetre is the

measure of length, the cubic centimetre the measure
of capacity, and the weight of 1 cubic centimetre
of water at 15° C., or the gram, is the measure of
weight. How delightfully simple these are, com-
pared to the complicated and heterogeneous measures
of the pharmacist! An inch is about 2 J centi-
 — , '

WEIGHTS AND MEASURES. 9

metres, and an ounce about 28 grams, a fluid ounce

being 28 cubic centimetres. For larger measures
the litre containing 1000 c.c, and the kilogramme or
kilo, of 1000 grams, are used. For small measures
the decimals of the gram and the centimetre are
employed. Going up the scale, 10, 100, 1000, etc.,
grams and centimetres follow in order, and going
down the scale, jIq-, j^^, j^q of a gram or centi-
metre follow one another, the decimal system being
employed throughout. It is convenient to remember
that a litre is very nearly a pint'and three-quarters.
The following table gives the means of converting
English into metric equivalents, and vice versd.

TABLE I. Wbights and Measures in British and

Metric Systems.

APOTHECARIES' WEIGHT (by which FoRMULiE are made up).

20 grains = 1 scruple . . = 1 "296 grams.
.

3 scruples =1 drachm = 60 grains = 3*887 ,,

8 drachms = 1 ounce = 480 ,, = 31'1 ,,

12 ounces = 1 pound = 5760 ,, =373-2

AVOIRDUPOIS WEIGHT (by which Chemicals ake sold).

437^ grains = 1 ounce = 28 '4 grams.

. .

16 ounces = 1 pound = 7000 grains = 463 '59 ,

METRIC SYSTEM— WEIGHT.

10 milligrams = 1 centigram . = 1543
. . grain.
10 centigrams =1 decigram = 100 milligrams = 1'543 ,,

10 decigrams =1 gram = 100 centigrams = 15'432 ,,

10 grams =1 decagram . . . =164'323 ,,

10 decagrams =1 hectogram = 100 grams =3 ozs. 227 J grains.

10 hectograms = 1 kilogram =1000 grams . =35 ozs. 87i „
10 TEN PEE CENT. SOLUTIONS.

MEASURES OF LENGTH.
British.

3 barley-corns =1 inch = 2 54 cm.

. .

12 inches . =1 foot . =30-48 „.

3 feet =1 yard = 36 inches = 91 -44 „

.

Metric.
1 millimetres =1
centimetre = '3937 inch or Jf approx.
10 centimetres=l decimetre = 3'937 „
10 decimetres =1 metre =39 '37 ,,

FLUID MEASURE.
60 minims =1 drachm . . = 3 '5 . cubic centimetres.
8 drachms =1 ounce = 480 minims = 28 "4 „ „
12 ounces =1 pound =5760 ,, =340-8 „ „
20 ounces =1 pint* . . . =568'0 „ „
2 pints =1 quart = 40 ounces = 1-136 litres.
4 quarts =1 gallon = 160 „ = 4'544 ,,

METRIC SYSTEM— FLUID.

1 cubic centimetre (c.c.) . . . = 17 minims.
10 „ ,, =1 centilitre . .• =170 „
10 „ centilitres =1 decilitre = 100 c.c. =3'52 fl. oz.
10 „ decilitres = 1 litre =1000 c.c. =35-2 „
* The American pint is 1-6 ounces.

Many photographers have realised the con-

venience of a rational system, and in addition to
discarding the aboriginal system of weights and
measures, have adopted ten per cent, solutions for
all their work. From these any developer or other
dilute solution can be made up in a minimum of
time. In cases and one or two
of stock solutions
other instances it is convenient to have a fifty
per cent, solution, and in other cases five per
cent., or perhaps one per cent., solutions must be
employed, owing to the difficulty of dissolving a par-
 SCALES OF TEMPERATURE. 11

ticular substance, but solutions should always be

made up to contain so many parts per cent.
Some confusion in the reader's mind may be
saved by pointing out again that a cubic centimetre
of water weighs one gram, and a ten per cent, solu-
tion is understood to mean ten grams of the sub-
stance in one hundred of water, or one hundred
grams in a litre, i.e., ten grams dissolved in part qf
the water, and the whole made up to an even
hundred, not to a hundred and ten.
Temperature is measured in this country by
Fahrenheit's scale, on which the freezing point of
water is 32°, and the boiling point 212°, zero beiMg
32° below freezing point. In the Centigrade or
Celsius scale employed in scientific work, and in
general practice in some parts of the Continent, the
freezing poiut of water is zero and the boiling
point 100°. Table II. enables you to convert one
scale into the other.
The only mathematical signs used in the explana-
tions will be
+ added to
- subtracted from
X multiplied by
-r divided by.
= equals
and the signs for a proportion, aamely.
As is to so is to the figure required,
2 : 4 : : 3 : a;

that is to say,
4x8-7-2 = 6.
 —

12 COMPARISON OF THERMOMETERS.

TABLE 1 1. Theemombtkes. Comparison op

Fahrenheit and Centigrade (Celsius) Scales.

Cent.
 MBT. 13

CHAPTEE II.

Chemistry generally, and the Chemistry op the

Silver Salts in particular.

At the begmning of the book mention was made

of the importance of "Dirt" in a
cleanhness.
chemical sense is much more comprehensive than
is usually understood. To get any vessel chemically
clean is not an easy process, and a vessel, after
containing most chemicals, requires several careful
washings before it is fit for use again. The diffi-
culty about chemical dirt is that it is not always
visible to the eye, The porcelain dish used to con-
tain the "hypo." bath may look beautifully clean
after it has been washed out, yet the porcelain is

probably saturated with " hypo.," which will dissolve

into the next solution placed in the dish, if used
for anything but "hypo.," and spoil all the plates
and paper it comes into contact with. Three care-
ful washings are generally sufficient to cleanse an
article thoroughly, but in eases where very careful
cleansing is required, such as plates used for coating
in the wet plate process, a powerful mixture, such
as the following, must be employed, which burns up
 !

14 WASHING.

any dirt, Never allow the mixture to get on to

clothes or fingers

Potassium bichromate, . . 50 grams, . 1 oz.

Water, ....
Sulphuric acid (commercial), . 50 c.c,
1000 „
.

. 20
1 „
ozs.

Dissolve the bichromate in the water, and when

dissolved add the sulphuric acid in a thin stream,
stirring the while. For some purposes it is con-
venient to use much more sulphuric acid.
Einse well under the tap when clean. The solu-
tion, if no water is added to it, may be used over
and over again until exhausted.
Perhaps it will be well to define what is meant
by " In regard to utensils it is used in
washing."
the ordinary sense, but when employed in connection
with prints and negatives, a wrong impression is
often conveyed. When a photographer says " wash,"
he generally means " soak."
In a recently fixed
negative, for example, the " hypo." must be removed
from the film by soaking it out. A constant
diffusion goes on between the solution of "hypo."
in the film and the clean water in contact with it.
At first diffusion proceeds very rapidly, and
this
then more and more slowly as the " hypo." in the
film becomes dilute. 'No advantage is to be gained,
therefore,, by allowing the water to run furiously
over the surface of the plate, as force does not
assist the operation, and the water must be left in
contact with the film for a sufficient time to take up
 ATOMS. 15

its allowance of " hypo." Eunning water is a

distinct advantage, although frequent changes and
rocking of the dish do nearly as well ; but the water
may run as slowly as you please, and should flow
into the upper part of the whole contents of the
vessel,but out from the lower part. A syphon
should be used to remove the water from all deep
washing tanks.
Mention will be made
directly of atoms and
molecules, so that had better explain what is
I
meant by these terms, and by a chemical element.
If pure iron is ground up very small and acted upon

by the strongest forces that the chemist can bring

to bear upon it, nothing but iron can be obtained
from it. The substance cannot be split up into
two other materials, so that chemists call it and
all such substances " elements." If the powdered

iron that was spoken of just now be examined

under the microscope, it will be seen that the
particles would bear splitting up very much smaller.
Chemists have come to the conclusion, that if human
eyesight and fingers were keen enough to go on
splitting up these microscopic particles, a stage
would be reached when the particles could be made
no smaller. These ultimate particles are called
" atoms." All the atoms of iron, for instance, may
be considered as being exactly alike and of the
same size and weight. As it is not possible to
examine the actual atoms, equal quantities of the
different elements are compared with one another.
 —

16 CHEMICAL ELEMENTS.

In this way it is found that the iron atom is 56

times as heavy as the hydrogen atom, which, heing
the lightest, is called 1, and is used as the standard
of atomic weight. The silver atom is 108 times
as heavy as the hydrogen atom, so that the atomic
weight of silver is 108, and that of iron 56. These
atoms combine with one another to form " molecules,"
so that a molecule is compounded of atoms. The
iron atom, for instance, may combine with another
iron atom to form an iron molecule, or it may com-
bine with one or more atoms of some other element,
such as chlorine (see later), to form a molecule of
iron chloride. Now I want you to realise that
nothing ever happens by chance in chemistry.
Similar quantities same substances, acting
of the
in the same way, always produce the same result,
and the same quantity of it, as you will see directly.
For convenience, chemists employ a kind of
shorthand, using symbols for the different sub-
stances. H stands for hydrogen and for 1 gram or
ounce, or .whatever it may be, of hydrogen; Fe
(Latin,ferrum) stands for iron and for 56 grams,
or whatever it may be, of iron, and so on. The
following symbols for different elements will be
used in this chapter; particulars of the others will
be found in the index :

Atomic
Name. Symbol. Weight.
H
Hydrogen,
Oxygen,
Mtrogen,
...
. . .
.0
. N
1
16
14
 —

18 .
CAUSTIC SODA.

out half the hydrogen atoms from the water,

thus :

Water. Sodium. Caustic Soda. Hydrogen.

HOH + JSTa = NaOH + H escaping.
added to forms and

Instead of water there is now a weak solution of

caustic soda, which turns red litmus-paper blue,
changes acids into substances that are not acid but
neutral, and is called an alkali. If more sodium be
added to the solution, more hydrogen will be turned
out, the alkaline solution becoming stronger, forming
in the end a solid mass of caustic soda, which could
be run into moulds to make the familiar white
sticks.
It has been shown that a particle or molecule, as
chemists term it, of water (HOH) weighs 18.
In caustic soda (ISTaOH) there is an atom of
sodium (Na) occupying the place of one of the H's,
weighing 1. Now an atom of sodium is twenty-
three times as heavy as an atom of hydrogen, so
that caustic soda (NaOH) weighs 40 (23-)-16-f-l).
This means that if 23 grams, ounces, or lbs. of
sodium were cut up into small pieces and dropped
into 18 grams, ounces, or lbs. of water, 40 grams,,
ounces, or lbs. of caustic soda would be obtained,
than which nothing could be simpler. All chemical
formulae can be expressed in actual weights- in just
the same manner.
The formulae that appear so alarming are merely
this convenient and scientific kind of shorthand,
the key to which will be found on page 140.
 —

HYDROCHLOKIC ACID. 19

Chlorine is a yellowish-green, very irritating gas.

If the reader wishes to become aquainted with it,

let him warm ten drops of hydrochloric acid with

five drops of nitric acid in a test-tube or other glass
vessel, when fumes of chlorine will be freely given
off. This yellowish-green gas combines violently
with hydrogen to form hydrochloric acid (HCl), one
atom of the one combining with one atom of the
other. What is ordinarily called hydrochloric acid,
and purchased of a chemical dealer, is a solution of
hydrochloric acid gas; this solution will be found
to turn blue litmus red, to be intensely acid to the
taste (dilute), and to be exactly the opposite of the
alkaline caustic soda.
If caustic soda be mixed with hydrochloric acid
in proper proportions, a neutral liquid will be
obtained. A great deal of heat is given out, and the
experiment must be tried with dilute acid and
alkali. The resulting liquid is called " neutral,"
because it is neither acid nor alkaline, and has no

effect on litmus-paper it is, in fact, a solution of a

;

salt —
common salt or sodium chloride.
What has just happened is represented in chemi-
cal shorthand thus :

Hydrochloric Sodium
Acid, Caustic Soda. Chloride. Water.
HCl + NaOH = NaCl + HOH.
added to forms and

This is called an "equation," because there is an

equal quantity of material on both sides, but it is
20 EQUATIONS.

arranged differently. Whenever anything happens

in chemistry, there is the same quantity of material
at the end as there was at the beginning. Nothing
is ever destroyed ; the different parts are merely
rearranged.
Now take a solution of silver nitrate! If you
have the means of weighing and measuring accur-
ately, make up a 1 per cent, solution of silver

nitrate by dissolving 1 gram in 100 c.c. of distilled

water; fill a burette with the solutionand run
exactly 34 c.c. into a dish or gallipot of some kind.
Make up a 1 per cent, solution of sodium chloride
(1 gram in 100 put this in another burette,
c.c.) ;

and out of run 10 c.c. into the gallipot con-

this
taining the 34 c.c. of silver nitrate. A white
" precipitate " will form shake the vessel round
;

and allow the precipitate a few moments to settle

to the bottom. Then add a few more drops from
the sodium chloride burette. A fresh white pre-
cipitate will form and sink to the bottom. This
precipitate will go on forming until 117 c.c. alto-
gether of sodium chloride solution have been added.
If the solution be now allowed to stand until the
precipitate has settled, no more precipitate will form
when more sodium chloride is run in. If the
reader has not conveniences for measuring, he must
take a small quantity of silver nitrate solution, and
add solution of common salt in small quantities at
a time until no more precipitate thrown down. is

To explain what has been happening, it is necessary

 SILVER CHLORIDE. 21

to say a few words about silver nitrate. Nitric

acid contains one atom each of hydrogen and nitrogen
and three atoms of oxygen. As hydrochloric acid
isHCl, so nitric acid is HlSTOg. When silver (Ag)
is dissolved in nitric acid, the silver takes the place
of the hydrogen, producing silver nitrate (AgNOg).
When the run into the
sodium chloride was
silver nitrate in the experiment, the sodium and the
silver changed places.

Silver Nitrate. Sodium Chloride. Silver Chloride. Sodium Nitrate.

AgNOg + NaCl = AgCI + NaNOg.

The white precipitate was silver chloride, and the

sodium nitrate remained dissolved in the solution.
Further, it was seen from the experiment that 11-7
parts of sodium chloride were just sufficient to cause
all the silver in 34"0 parts of silver nitrate to pre-
cipitate as chloride. If the different parts of the
equation are calculated out, it will be seen that this
is the case.

Ag N O3 + Na CI = Ag CI + Na N O3
108 + 14 + 48 23 + 35-5 108 + 35-5 23 + 14 + 48

170 58-5 143-5 85

So that 170 AglSrOg requires 58-5 NaCl, or 340

requires 117. From this equation it will be seen
also that from 170 parts of silver nitrate 143;5
parts of silver chloride can be obtained. This
calculation, or similar calculations with bromide and
iodide instead of chloride, are being gone through
22 OHLOKIDE, BROMIDE, AND IODIDE.

constantly when making emulsions. Although

tables are given to save time, every photographer
should know how to work out the figures himself if

necessary.
Potassium (K) is a very similar metal to sodium,

and sometimes more convenient to use potassium

it is

salts, such as potassium bromide and potassium iodide,

instead of sodium salts, but the calculations are

exactly similar, using K
(39) in place of Na (23).
Bromine is a red liquid and iodine a brownish,
rather metallic looking, solid. They resemble
chlorine very closely, and silver bromide and iodide
are very like silver chloride. Take two gallipots
and place silver nitrate solution in each. Into one
run a solution of potassium bromide, and into the
other a solution of potassium iodide. A precipitate
will be formed in each case ; that with the bromide
being yellowish-white (silver bromide), and that
with the iodide being pale yellow (silver iodide).
These experiments can all be performed in test-tubes,
i.e., thin glass tubes closed at one end, or in beaker
flasks; the latter (fig. 3) are useful for many pur-
poses in the work-room.
As silver chloride, bromide, and iodide resemble
one another so closely in their chemical properties,
they can often be substituted for one another partly
or wholly without introducing any very great change
in the result. In making emulsions for dry plates,'
or in preparing collodion for wet plates, these salts
are introduced in varying proportions to suit the
 —

EQUIVALENT QUANTITIES. 23

subject. Accordingly it is important to know -what

quantity of chloride is equivalent to a certain
quantity of bromide or iodide, and vice versd. This
can be learned from chemical shorthand at once.
The formulae for the three compounds are AgCl,
AgBr, and Agl. An atom of bromine (Br) weighs
80 and iodine (I) weighs 126-5 so that ;

Silver chloride, AgCl, weighs 108+ 35-5 or 143-5

„ bromide, AgBr, „ 108+ 80 „ 188
„ iodide, Agl, „ 108 + 126-5 „ 234-5

From this it is clear that 143-5 parts of the

chloride are capable of doing the same work as 188
parts of bromide or 235 of iodide. The following
table gives equivalent quantities of these salts to
save calculations.

TABLE III. Equivalent Quantities of Silver Salts.

Silver
(Metallic).
 24 EXPERIMENTS.

of ammonia solution; the silver chloride will dis-

solve completely. To this solution add a few drops
of acid to neutralise the ammonia
the white silver
;

bromide will reappear, showing that, although it is

soluble in ammonia, it is insoluble in acids. To
the bromide precipitate add a solution of what is
generally known as hyposulphite of soda; the pre-
cipitate will dissolve completely. The other pre-

IFig. 3.

cipitate may be treated with potassium cyanide, with

a like result.
Now to go back to the first experiment, when
metallic sodium was added to water, so that an
atom of sodium took the place of an atom of hydro-
gen, formiiig NaOH instead of HOH. If the ex-
cess of water be driven off by heating the solution,
or if enough sodium be added to combine with all
the water, a solid mass of sodium hydrate (caustic
Soda, NaOH) will be formed. If more sodium^ be
added to this and the mixture be warmed, the other
 —

OXIDES. 25

hydrogen atom will be turned out by the sodium,

thus:
HOH, then NaOH, then NaO:!Sra.

This substance, 'Nafi, is called " oxide " of sodium,

and much resembles the hydrate or caustic soda in
appearance.
Now add some caustic soda solution to a little

silver nitrate solution by — a " little " is meant from

half an inch to an inch of liquid in a small test-tube
or measuring glass. A light brown precipitate will
sink to the bottom. This light brown substance is

oxide of silver, or AggO, and is put together in exactly

the same way as oxide of sodium.

H.O.H
26 FERROUS AND FERRIC.

of hydrogen from water, or replacing two atoms of

silver, ortwo atoms of sodium,' etc. The white pre-
cipitate was ferrous hydrate. As iron is capable of
taking the place of two atoms of sodium, you have

„ f OH . , , , NaOH
FeJQjjmsteadofj^^Qjj

so that ferrous hydrate is Fe(0H)2.

When this hydrate is dried and heated, a particle
or molecule of water sphts off, leaving the oxide,
FeO, thus:—
Water
Ferrous oxide

In actual practice, however, you have seen that

the white precipitate turned green and then brown.
The ferrous hydrate was using the oxygen of the
air to convert itself into another hydrate containing
more OH, viz., Fe(0H)3. From this you see that
iron can combine with either two or three OH's, i.e.,
can take the place of either two or three atoms of
hydrogen or silver or sodium, etc. Consequently,
ferrous iron is always hungry until it has got hold
of the third OH, whatever it may be. It is im-
or
portant that you should understand this thoroughly,
as it is the basis of the development of negatives.
In the solution, after the addition of the caustic soda
to the ferrous sulphate, you had essentially (neglecting
the sodium and the sulphate) water, oxygen from the
 —

OXIDIZING AND EBDUOING. 27

air dissolved in the water, —

and a substance ferrous
hydrate —ready up any OH that might be
to pick
available. The oxygen is anxious to combine with
hydrogen to form water, so that you have ferrous
hydrate and oxygen with a particle of water between,
like a duck and a hen over a worm. The water
comes in half, as the metaphorical worm would do ;

the iron gets its OH (hydroxyl), and the oxygen

gets its hydrogen, and everybody is satisfied,
thus :

re(OH), HO
Fe(0H)2
 — ;

28 COMBINING PROPOETIONS.

metallic silver, whilst the ferrous iron appropriates

the NO3 to raise itself to the ferric state.
It is quite clear, then, that an oxidizing agent is

a substance that is anxious to take up hydrogen, and,

vice versd, a reducing agent is a substance that is

hungering after oxygen. Hydrogen itself is a very

powerful reducing agent. With metallic salts,

oxidation raises them further from

, the metallic
state; reduction robs them of whatever other sub-
stance, such as chlorine or nitric acid (nitrate), they
are combined with, and brings them back wholly
or partly to the simple metallic condition.
From the talk about ferrous and ferric salts, you
have seen that chemical elements may combine in
other proportions than one to one. Silver chloride
contains one of silver to one of chlorine ferrous iron
;

takes two of chlorine ferric iron, three of chlorine

;

in platinic chloride there is one of platinum to four

of- chlorine, and there are other compounds with a

higher proportion of chlorine still. For convenience

in chemical shorthand, the number of atoms of
hydrogen an element is capable of replacing is de-
noted by dashes, thus:

Ag'Cr, Silver chloride.

Fe'Cig, Ferrous ,,

Fe"'Clg, Ferric
Pt'^Cl^, Platinic „

Sulphuric acid has the composition represented in

chemical shorthand as HjSO^, so that, as ferrous
iron can replace two H's, the composition of ferrous
 "WATER OF OEYSTALLIZATION. 29

sulphate is FeSO^. The green

that you crystals
buy, ot that would be obtained you evaporated a if

solution of ferrous sulphate to a thick syrup and

allowed it to crystallize, contain water, as do most
crystals. In assuming the solid condition, many
substances crystallize in two or three different forms
according to the amount of water their particles
entangle. Ferrous sulphate carries down with it

seven molecules of water, so that the formula for the

green crystals is reSO^,?!!^©. This is important,
as, in making up percentage or other solutions, this
water has to be taken into account. For instance,
suppose a ten per cent, solution of ferrous sulphate
is required. Then
FeS04(56 + 32 + 64) = 152
7H2O ( 2 + 16) =126
278

So that 278 parts of the crystals only contain

152 parts of ferrous sulphate. To calculate how
much FeSO^ must actually be used, you make the
proportion sum,
is to as is to tbe amount required.
152 : 278 : : 10 : x.

278 X 10 H- 152 = 18'3 parts as nearly as possible.

multiplied divided gives
by ,
by

A f«w words now about acids Several, different !

acids have been mentionecj, but they possess one

feature in common ;> they all contain hydrogen.
Acids are salts of hydrogen. Hydrochloric acid
 —

30 ACIDS.

(HCl) is hydrogen chloride just as AgCl is silver

chloride; being hydrogen sulphate.
sulphuric acid
The last named acid contains two atoms of hydrogen,
both of which can be replaced by k metal, and there
are other acids, such as phosphoric acid (H3POJ,
which contain more than two atoms of hydrogen.
In the carbon or organic acids, such as citric or
acetic acids, there are atoms of hydrogen that are
not replaceable, and their formulae are liable to
confuse the reader, but in the last chapter (which
see) the hydrogens that can be displaced by iron or
sodium of silver, etc., to form salts are shown quite
clearly.
With hydrochloric acid, where there is only one
hydrogen, the latter must be displaced entirely, but
with sulphuric acid, where there are two hydrogens,
you may have either one or both atoms replaced by
a metal. For instance, there are two sodium sul-
phates, thus :

H2SO4, Sulphuric acid.

NaHSO^, Acid sodium sulphate.
NagSO^, Neutral or normal sodium sulphate.
The salt in which only one of the hydrogens has
been displaced has an acid character, as you would
expect, and is called " acid
sodium sulphate." You
will understand from this that an "acid" salt
means a salt in which the hydrogen is only partly
displaced by metal. The term " hi " is used fre-
quently instead of " acid," so that ISTaHSO^ is gener-
ally called sodium bi-sulphate.
 SULPHATE AND SULPHITE. 31

In salts that are derived from acids containing

oxygen there is a possibility of reducing that oxy-
gen. Sulphuric acid or a sulphate, for example,
may be deprived of one or two atoms of oxygen,
producing
HgSD^, Sulphuric acid.
H2SO3, Sulphurous acid.
HjSOg, Hyposulphurous acid.

Their sodium salts are

NajSO^, Sodium sulphate.
, NagSOg, „ sulphite.
NajSOj, „ hyposulphite.

'
This last salt is true sodium hyposulphite; the
photographer's "hypo." is not hyposulphite of
sodium, correctly speaking, but sodium thiosulphate,
Na^S^Oj.
From all this the reader will gather some idea of
the way in which chemical compounds are named.
The termination "-ide" signifies a salt consisting of

a metal united with another element, such as silver

chloride ; "-ate " signifies a salt containing oxygen
as well; "-ite" contains less oxygen than "-ate."
If "hypo" is put in front of the word, it means
that the salt is below the "-ite " stage. The prefix
" per " or " hyper " means above, so that a per-
sulphate of sodium is richer in oxygen than sulphate

of sodium.
Having said so much about acids, it is necessary

to devote a paragraph to alkalies. You have seen

at the beginning of the chapter that caustic soda or
32 ALKALIES.

sodium hydrate is water in which one atom of

hydrogen has been replaced by one of sodium.
Caustic potash, or potassium hydrate, is exactly
similar,potassium (K) taking the place of sodium.
Caustic potash and caustic soda dissolved in water
possess a peculiar " alkaline " taste, turn litmus-
paper blue, and neutralize acids to form salts. An
alkali, therefore, is a soluble hydrate. Nearly all

hydrates and oxides, although not soluble in water,

have an alkaline tendency, and possess some of .the
properties enumerated above.
Ammonia, properly speaking, is a gas, not a
liquid. formed of one atom of the element
It is
nitrogen, which constitutes four-fifths of the atmos-
phere, combined with three atoms of hydrogen.
This NH3 dissolves in water with avidity, forming
NH3H2O or NH^OH. Eather curiously this is a
powerful alkali, and closely resembles caustic potash
or soda in its action. So much is this so that NH^
is called by one word, " ammonium," and ISTH^OH is
ammonium hydrate. The liquid ammonia of the
druggist, then, is a strong solution of ammonium
hydrate. This " ammonium " forms salts exactly
like sodium or potassium, producing ammonium
chloride, NH^Ol, ammonium sulphate (NH^)2S0^,
etc.

As caustic potash, soda, and ammonia are such

strong alkalies, when they unite with a weak acid
their salts are alkaline. Carbonic acid is a weak
acid, and sodium carbonate is strongly alkaline!
 OAKBONATBS. 33

The bicarbonate, although it is theoretically an acid

salt, is faintly alkaline. Carbonic acid, by the way,
is formed whenever carbon (coke or charcoal) or any
substance containing carbon is burnt in the air.
Carbon (C) unites with two oxygens to make COg,
and when this gas dissolves in water carbonic acid
is formed. The term " carbonic acid " is from
long usage generally applied to the COj gas, but
all the carbonates are formed from COg dissolved in

water, thus,

HjOjCOj or HjCOg, Carbonic acid.

NaHCOg, Sodium bicarbonate.
Na^COo, „ carbonate.

Sodium carbonate is the compound used as an

alkali in photography. It can be obtained perfectly
dry, but the most convenient form is washing
soda. The crystals of this material contain water
in the same way that ferrous sulphate crystals
contain water, the formula for washing soda being
]Sra2CO3,10H2O. Now Na^COg adds up to 106
(46 + 12 + 48),
and 10 of water make 180; so that,
adding the two together, 286 of washing soda are
equivalent to 106 of, dry sodium carbonate, and this
fact must be borne in mind when making up
solutions.
This is a convenient place to say a few words
about electro-chemistry. When two metals, such
as zinc and copper, are joined together and placed
in a liquid that condxicts electricity, such as dilute
3
 ;

34 ELECTRO-CHEMISTRY.

sulphuric acid, an electrical currentis produced and

flows from the copper or positive metal through

the wire, or whatever it is that joins them, to the
zinc or negative metal, then through the acid back
to the copper again, completing the circuit. -This
arrangement is called an electric battery various ;

other combinations of metals are used in different

batteries, but the principle is the same. It is not
necessary to use two metals to produce an electric
current, a metal and a solution of a metallic salt,
or even two solutions separated by a porous parti-
tion, being sufficient ,to cause a current. It is

evident that nearly every chemical change must

produce an electric current, or vice versd, and it is
difficult, if not impossible, to separate one from the

other.
Now try this experiment : Make a little electric
battery of a strip of zinc and a strip of some other
metal, dipping in dilute acid in a jam-pot or some-
thing of the kind connect the copper strip by a
;

wire to another smaller strip of copper, and the

zinc in a similar way to another little strip of zinc
allow the two latter strips to dip into a solution
of sulphate of copper in a beaker or glass of some
kind, so that you can see what is going on. In a
few minutes, the zinc strip will have become coated
with copper, and if you had weighed the copper
strip before the experiment, you would find that
.

some of it had dissolved. This is the principle of

electro-typing, electro-plating, electro-gilding, and
 "

ELECTKO-DEPOSITION. 35

SO on. If you had had a convenient solution of

silver instead of the sulphate of copper, silver would
have heen deposited on the zinc.
As you will see in the next chapter, much of
what goes on during development resembles electro-
plating. In the solution a kind of " ladies' -chain
is taking place, the atoms of metal travelling in the

direction of the current, to he deposited finally on

the negative electrode or terminal of the wire con-
nected with the zinc of the battery or whait corre-
sponds to it. In developing, it is very possible that
each particle of reduced silver in the latent image
acts as the terminal of a tiny electric battery or
" couple," as it is called, and the silver from the sur-
rounding silver salts is deposited on it to build up
the visible image.
36 PHOTO-SALTS.

CHAPTEE III.

The Chemistry ok the Photogkaphig Image.

The chemistry of the different processes for pro-

ducing and developing a latent image are so inter-
woven that it is convenient to talk about them to-
gether ; the composition of the different plates and
developing materials will be considered separately
afterwards. First of all, however, it will be
necessary to say a few words about the photo-
chloridesand kindred salts of silver.
The photo-chlorides of silver, which Carey Lea
did so much to investigate, are the compounds pro-
duced by the action of light or reducing agents, such
as ferrous sulphate, on silver chloride. They con-
tain less chlorine than silver chloride, and may be
regarded as stepping-stones between silver chloride
and metallic silver. There seems to be a consider-
able number of them, and they vary in colour from
white, through fiesh-colour, pink, rose, copper-red,
reddish-purple and chocolate, to black. They appear
to be permanent if kept in the dark, but change
rapidly in the light. More about these interesting
 THERMOGRAPHIC IMAGES. 37

compounds and about some curious and beautiful

forms of metallic silver, which are soluble in water,
will be found in Chapter VII.
The photo-bromides and photo-iodides resemble
the photo-chlorides very' closely. In all cases the
presence of soluble chlorides, bromides or iodides,
such as sodium chloride or potassium bromide,' etc.,

in solution hinders the formation of the photo-salts,

an acid having the same effect, whilst an alkali or
reduced silver hastens their formation.
To pick up the thread where it was dropped at
the end of the last chapter. Hunt found, in the early
days of photography, that invisible images could be
produced by heat, and that these could be developed
subsequently. If a hot coin be held close to a piece
of clean glass, the image of the coin can often be
reproduced by breathing on the glass. The action
is properly electrical, but in any case there is a

selective action, so that the moisture sticks to one

part and not to another. Hunt used polished metal,
and developed his images with mercury vapour, the
principle being the same.
In Daguerre's process a polished silver plate was
exposed to iodiae vapour, so as to form a thin film
of silver iodide on the surface. This plate was then
exposed in the camera, and developed with mercury
vapour. In this ease the result was very different
from the heat or "thermographic" images. The
light in the bright parts of the image thrown by
the lens had reduced the silver iodide in the thin
38 DAGDEEEEOTYPB.

film on the surface, and the liberated iodine probably

acted on the metallic silver just behind to form
more photo-iodide, thus intensifying the effect of the
light. The mercury vapour combined chemically
with the reduced parts of the plate, so that a visible
image was formed. This was fixed and toned with
gold salts.

So far you have seen, first, a mechanical effect

caused by heat, and developed mechanically secondly, ;

mechanical effect caused by light, ending in chemical

action, and extended or developed by chemical action.
In the former case the invisible or latent image was
due probably to different electrical conditions on
In the latter case,
different parts of the surface.
you have every reason to suppose that the latent
image was composed of reduced silver iodide or
photo-iodide. I should like to take the opportunity
here of impressing on the reader's mind the fact
that photographic action is not yet thoroughly
understood. Even in such a comparatively simple
affair as a Daguerreotype
plate, the latent image
cannot be taken out and examined. In wet plates,
and more especially dry plates, the conditions are
much more complicated, so that the difficulty in
finding out what happens is greatly increased.
Consequently, scientific guesswork has to be brought
to the aid of the investigator; the guesswork is of
a very shrewd order, but it is guesswork none the
less. When you consider that in a wet plate, for
example, you have an almost microscopically thin,
 THE LATENT IMAGE. 39

and by no means simple, film to start with, and that

only the outermost particles of this thin film appear
to be affected directly by the light, you will see
down the law as to what
that, it is not easy to lay
happens in the film.
A wet plate after exposure consists essentially of
a film of collodion containing silver iodide, a part of
which has been acted upon by the hght, and this is
covered with a layer of silver nitrate. The developer,
made up of a solution of ferrous sulphate containing
a little acid —generally acetic acid — is poured over
this. Ferrous sulphate alone would reduce the
silver nitrate at once, covering the plate with a black
deposit of metallic silver; but the presence of the
acid hinders this action, so that the reduction only
proceeds slowly. Probably the first action of the
developer is to reduce to the metallic state the
photo-iodide that has already been acted upon by
the light. This forms a nucleus for the deposit of
silver from the reduced nitrate, in a similar manner
to the- selective action in the thermographic image,
and this reduced silver is built up on the latent
image forming the visible image of the wet plate.
As development proceeds, the ferrous sulphate
becomes oxidized (see p. 27) and loses its reducing
power, so that the formation of the image progresses
more and more slowly, or, in photographic language,
the developer becomes more and more restrained.
It is obvious that if any substance be present that
will absorb the acid given off by the silver on reduc-
40 poitevin's experiment.

tion, the formation of the image will go on more

rapidly. In 1866 Poitevin tried the experiment of
squeezing a collodion film containing silver iodide,
free from excess of nitrate, on to a silver plate, and
treating a glass plate in a similar manner. Both
were exposed to light and developed. The film on
the silver plate showed a considerable image, being
very mnch denser than that on the glass plate, but
the latter did show a slight image. From this it is
clear that an image of reduced silver can be formed
even when there is nothing to absorb the iodine or
whatever it may be that is given off. It is con-
jectured that in such a case a compound must be
produced similar to —
KI3 the dark substance
obtained on dissolving iodine in potassium iodide.
The statement that an absorbent of iodine, chlorine,
or acids, such as metallic silver, hastens development,
however,is amply proved by this experiment:

In making a wet plate for use, collodion (see

Chap. XIV.) is iodized by dissolving soluble iodides,
or even iodine itself, in the collodion. Except for
process work, usual to employ bromide as well
it is

as iodide. The latter alone gives a hard negative,

and bromide alone a flat detailed negative; the
proportion of the two can be varied to suit the
subject. The bromides and iodides of cadmium
and ammonium are those generally used.
The glass plates to be coated must be carefully
cleaned and polished with tripoli, whiting, or rouge,
or better, by soaking in sulphuric acid and bi-
 PEEPAEING WET PLATES. 41

chromate of potash (see p. 14); then edged with

india-rubber solution and given a first coat or sub-
stratum of albumin or gelatin to which a few drops
of ammonia have been added. This preliminary
edging and coating is to prevent the collodion
slipping or coming away from the glass. The
iodized collodion is 'poured on to the plate and
distributed by rocking, the excess being
evenly
drained off at In subsequent opera-
one corner.
tions this corner should always be kept at the
bottom. The plate is then immersed in a bath
of silver nitrate, which is generally made faintly acid
with nitric acid. The silver nitrate is converted into
bromide and iodide (see p. 22), and the plate is ready
for use. As this iodide is soluble in silver nitrate,
the silver bath is saturated with iodide before use
by adding a few grains of potassium iodide, and
filtering off any undissolved precipitate of silver
iodide.
After exposure the plate is developed by pouring
over it a solution of ferrous sulphate made acid
with acetic Ammonio-ferrous sulphate and
acid.
copper sulphate are used sometimes in the de-
veloper the former replaces part of the ferrous
;

sulphate, acting more slowly, and the latter acts

as a restrainer.
The positives on glass, made by the wet plate
process, are really negatives which receive a less
exposure in the camera than is required for the
ordinary negative, and are coated on the film side
 —

42 FORMULAE FOR WET PLATES.

with black varnish after development. Conse-

quently the black of the varnish shows through
the transparent parts of the plate, and the silver
deposit shows white by reflection, so that the nega-
tive is turned into a positive.
The various formulae for producing a finished
wet plate negative are as follows, those marked
with an asterisk being employed at the Bolt Court
Process School :

The Substratum*

Sheet gelatin, . 2 '5 grams, . 22 grs.

Ammonia "880, . 4 c.c, . 40 minims.
Water (distilled), . 1000 „ . 20 fl. ozs.

Rubber Solution for Edging*

Pure rubber cut into small pieces, 1 gram, 20 grs.

Benzole, . . . 100 c.c, . 5 ozs.

Silver Bath for Sensitizing*

Silver nitrate, . . 68 grams, . 600 grains.
Water (distilled), . 1000 c.c, . 20 fl. ozs.
Pot. iodide (10% solution), 1 „ .60 minims.
Sodium carbonate cryst., 3"5 „ . 30 grs.

Dissolve the silver nitrate in one-quarter of the

total water, then add the potassium iodide, and
shake; when
the precipitate has dissolved, add the
sodium carbonate dissolved in part of the water,
shake, and add the rest of the water. Acidify
with a few drops of 10°/„ nitric acid.
 COLLODION FOEMULiE. 43

Collodion*

Plain collodion, . . 750 c.c, . 15 ozs.

lodizer (B solution), . 250 „ . 5 „

lodizer (B. Solution).

Iodine, . -45 gram,

.

Alcohol (ethyl), 100 c.c,

... . .
2 grs.
1 oz.

The iodizer must be mixed with the collodion

in the proportion given, at least 24 hours before
use. Store in a cool place, and do not disturb the
sediment.

Collodion (another Formula).

Plain collodion, 100 c.c,

. . . 1 oz.
Cadmium iodide, -1 gram,
. .
J grain.
Ammonium iodide, '7 „ .3 grains.
Ammonium bromide,
.

4 „ .
If „
The iodides and bromide may be dissolved in
the collodion, which is then suitable for general

purposes. The proportions can be varied to suit

the subject in accordance with the following tables,
remembering that cadmium has a tendency to
make the coUodion granular. The table of chlorides
is added for convenience.
 —

44 BROMIDE AND IODIDE EQUIVALENTS.

TABLE IV. Equivalent Quantities of Dipfbeent

Bromides.

Bromine.
 —

WET PLATE DEVBLOPEES. 45

TABLE VI. Equivalent Quantities op Different

Chlobidbs.

Chlorine.
 —

46 DRY PLATES.

B.
Water, ....
Sodium thiosulphate 200 grams,
(hypo.),
1000 c.c,
Either A. or B. may be used.
4 ozs.
20 „ .

For intensification and reduction see Chap. VI.

Further information about the wet plate process
will be found in Wet Collodion Photography, by
Charles W. Gamble.
The dry plate differs from the wet plate in many
important respects. Silver bromide and a little
iodide, or rather the materials to produce these
silver nitrate and potassium or ammonium bromide
—
and iodide are incorporated in an emulsion of
gelatin, which is spread on glass plates or some
other stiff material, such as celluloid, and allowed
to dry. Collodion is sometimes employed instead
of gelatin the first dry plates having been made of
;

collodion emulsion before gelatin was thought of.

Before coating the plates, all excess of potassium
and ammonium bromides and iodides, etc., are
removed from the emulsion by prolonged soaking
in water, the sensitiveness of the plate depending
to a large extent on the thorough removal of these
salts.

After exposure to light in the camera quite a

different state of things exists to that on the wet
plate. The silver salt (bromide mostly) is im-
bedded in gelatin, and is, therefore, much less open
to attack by the developer, and there no silver is

nitrate present. Two consequences from this: arise

The silver image cannot be built up above the
 ACTION OF THE GELATIN. 47

latent image, as, in the absence of silver nitrate,

there no material to build from, so that the
is

image must be formed from the silver bromide in

the emulsion moreover, the silver image is sunk
;

downwards into the film instead of being built up

above the latent image. Secondly, as no easily
reducible silver salt is present, much more powerful
developers or reducing agents can be used than
sulphate of iron or other ferrous salts.

Although a further reference will be made to

gelatin in the chapter on developers, in connection
with pyrogallic acid, etc., a few words here about
the complications introduced by the gelatin will
not be amiss. In the first place, gelatin is a most
complicated body itself, containing carbon, hydro-
gen, nitrogen, and oxygen, and its chemical structure
is not known, so that when other substances, such

as silver bromide, are mixed with it, complicating

matters still further, it is not easy to find out
exactly what happens. Either the silver bromide,
before exposure, may lie perfectly inert, like so
much shot in the gelatin, or may combine bodily
it

with the gelatin, or some interchange may take

place between them; the combination, if it exists,
is probably a loose one. In any case the ultimate
effect is to allow the silver bromide to present a
large surface to the action of the light. The pro-
cess of stewing the emulsion or mixing ammonia
with it, both of which have such a strong effect

in adding to the sensitiveness of the plate, probably

48 THE BUILDING OF THE IMAGE.

act by causing a most intimate mixture of silver

bromide and gelatin. When the plate is exposed, and
still more when it is developed, the gelatin probably
increases the sensitiveness by absorbing the free
bromine when the bromide is reduced, in the same way
that the metallic silver acted in Poitevin's experiment.
It is a doubtful point whether the silver bromide
that been touched by the light, as, for
has not
example, the deeper parts of the film in an under-
exposed plate, can be reduced by the developer, so as
to help in building up the image. As the reader prob-
ably knows from bitter experience, the shadows and
detail in the half-tones of a badly under-exposed
plate remain absolutely unreduced, even after pro-
longed development. On the other hand, Abney
tried theexperiment of exposing a gelatino -bromide
plate in the camera, and then covering it with a
coUodio-bromide emulsion. On development, the
two were separated, and it was found that
films
each contained an image, so that, whilst the image
was developing downwards in the ordinary way in
the gelatino-bromide film, it was being added to
from above by the silver bromide in the superposed
film that had never seen the light. This result
was confirmed by an experiment of Eder's, who suc-
ceeded in developing the image completely through
a very thick and opaque film. When something is
known with certainty about the nature of the latent
image, it will be possible perhaps to say what is the
correct view,
 —

COLLODION DKY PLATES. 49

A collodion dry plate is made as follows :

A,
 — —

50 GELATINO-BROMIDE EMULSION.

thiosulphate (hypo.), as given for wet plates, prefer-

ably the former. The plates should be under-
developed, as compared with gelatin dry plates, and
then intensified (see Chap. VI.).
There are numerous formulae for making gelatin
dry plates, and the proportions of bromide and
iodide vary according to the object for which the
plates are intended to be used. The following
formula/ due to E. Child Bayley, may be taken as
an example of a gelatin bromo-iodide emulsion :

A. Potassium bromide, . 43 grams, 1^ ozs.

Distilled water up to . 300 c.c, 10 . ,,

B. Silver nitrate, re-crystallized, 52 grams, If ,,

Distilled water up to . 360 c.c., 13 . ,,

C. Potassium iodide, . . 1'6 grams, 25 grains.

Distilled water up to . 60 c.c, . 2 ozs.

The proportions in these stock solutions are

suf&cient to make twelve batches of emulsion of
half-a-pint each. Solution B should be rendered
faintly acid to litmus-paper by adding two or three
drops —not more— of acetic or nitric acid.
For use take
A. 75 c.c. (If ozs.) containing 10-75 grams of
potassium bromide.
B. 90 c.c. (3| ozs.) containing 13 grams of silver
nitrate.
C. 15 c.c (5 drams) containing 0'4 grams of
potassium iodide.
* A full account of emulsion making, from which this formula is
taken, will be found in Vol. II. of The Photogram, p. 15%, Other
formula;, varied to suit the most exacting tastes, will be found in
the different year books of the photographic journals.
 MAKING THE EMULSION. 51

A is placed in a large (20 oz.) flask, B in a

smaller flask. Two grams of hard (Heinrich's)
gelatin are weighed out and allowed to soak for an
houi" in the cold bromide solution in the larger
flask. Both flasks are brought to 160° F. by placing
in a saucepan half full of hot water, and testing
with a thermometer. The contents of the smaller
flask are then added in small quantities at a time
to the gelatin and bromide in the larger flask,
shaking the while. When the whole mixture is
made, C is added, and the emulsion is placed in a
covered earthenware jar to stew in the saucepan for
an hour or so. The jar is supported by passing
through a tin plate on the top of the saucepan, so
that the bottom of the jar is about an inch from the
bottom of the saucepan. At this point the emulsion
should be tested by placing a drop on a piece of
clean glass, taking it out of the dark room, where
all the operations except the weighing and making

up of the stock solutions are conducted, and looking

through it at a candle flame. The emulsion should
not appear gritty or strongly coloured.
After stewing in water, boiling gently for an hour
or so, until it appears almost blue on examining a
drop by the candle flame, the emulsion is allowed to
cool, 10 grams more gelatin, which have been soaking
in cold water for an hour, are added, and the whole
well stirred until dissolved, when it is allowed to
set. The cold emulsion is washed to soak out any
soluble bromide, iodide, and nitrates, by squeezing it
 —

52 COATING THE PLATE.

many times through net or canvas under water.

The emulsion is then warmed to 120° F., when the
following is added, a few drops at a time, and the
whole filtered through calico or chamois leather :

Chrome alum (1 per cent, solution), 10 c.c, 3 drams.

Alcohol, 40 CO., IJ ozs.

The plates to be coated must be cleaned thor-

oughly by washing with strong soda, rinsing well,
and allowing to dry. It does not pay, as a rule, to
re-coatold negative glass. The coating may be
performed with emulsion warmed up again to 105°
F., in a somewhat similar manner to that described

under wet plates. More material, however, must be

run on to the plate, and very little need be drained
off. The plate is rocked for some time, and then
placed on a carefully levelled piece of glass to set.
Drying must be performed in a dark room or well-
ventilated cupboard as free as possible from dust.
—
Note. Never pack plates in newspaper under any
circumstances, as the print will be reproduced on
development. Grooved cardboard boxes form the
best packing. Turpentine, drying oils, varnishes and
many other substances act upon an undeveloped dry
plate, and care must be taken not to use these
materials in the camera or double-back, or to pack
plates in boxes containing them.
 STANDARD IKON DEVELOPER. 53

CHAPTEE IV.

Developers.

By this time the reader understands a good deal

about the general principles of development. So
far, however, acid iron developers only have been

talked about. In a gelatin dry plate there is no

easily reducible silver nitrate present, and the silver
bromide itself is protected to some extent by the
gelatin, so thatmuch more powerful developers can
be used than with wet plates, and alkalies can be
introduced, which adds greatly to the rapidity of
the plates.
The acid iron developer is very suitable for
gelatin plates, giving very vigorous negatives, al-
though it is necessary for the exposure to be cor-
rectly made. This developer is used in most
standard work, as it causes no stain in the film.
The following is the standard formula used in speed-
testingon the Hurter and Driffield system, which
will be referred to again directly. The formula,
which works excellently, is due to Mr Oadett
 ;

54 STANDARD IRON DEVELOPER.

Ferrous oxalate is the iron salt used as a reducing

agent; instead of the oxalate itself, however, the
materials for making the oxalate, namely ferrous
sulphate and potassium oxalate, are employed.

Ferrous Potassium Ferrous Potassium

Sulphate. Oxalate. Oxalate. Sulphate.
FeSO^ + KgCgO^ = FeCsO^ + KsSO^.

The potassium sulphate produced does not inter-

fere with the development.

Ferrous Oxalate Formula.

A. Keutral oxalate of potassium, 200 grams, 1 part.

Distilled water, 800 c.c,
'.
4 parts.
. .

B. Sulphate of iron, 100 grams, 1 part.

Citric acid. I gram, ^^-^
„
Distilled water, 300 c.c, 3 parts. .

. C. Potassium bromide, 1 gram,

. 1 part!
Distilled water. 100 cc, 100 parts.

For test use take A, 100 parts ; B, . 25 parts

C, 10 parts, in the order named. Make the devel-
oper up to a temperature of 65° F. and develop for
fiveminutes then, without washing, fix in a bath
;

of sodium thiosulphate (hypo.) made up of 1 part

to 3 parts of water; then, after thorough washing,
place the plate in a 2°l^ solution of hydrochloric
acid to remove lime or other stains, and finally wash
well.
The addition of a few drops of 1% sodium thio-
 INFLUENCE OF TEMPERATURE. 55

sulphate (hypo.) solution to each ounce accelerates

the development of under-exposed plates when using
a ferrous oxalate developer. The exact action is

not known.
When using the above formula for ordinary
studio or landscape work, it is a convenient, plan
to commence development with an old developer
This contains bromide from the reduction of the
silver bromide in the film, so that there is no
occasion to add bromide when working with an old
developer. Many photographers stand the bottle
containing the old developer in the sun to re-
generate it, the light reducing the ferric oxalate to
ferrous oxalate, which can be used over again.

Ferric oxalate Ferrous oxalate. Carbojiic acid.

¥62(020^)3 + light =. 2FeC20^ + 2CO.3.

In the directions given above for using the ferrous

oxalate developer, the correct temperature for
development was stated to be 65° F. For standard
work, such as testing the speed of plates, it is
necessary to have the temperature as uniform as
possible, and even in ordinary work, although ex-
cessive accuracy need not be observed, it is well
to always develop as far as possible at the same
temperature. Many photographers know the im-
portance of employing a thermometer, but many
others fail to realise the marked effect increase of
temperature produces in hastening development.
56 KESTKAINEES.

In some experiments made recently by the author, a

difference of 15°— from 55° to 70° F.— caused an
increase in the density of about one-third. From
'

this it is clear that an under-exposed plate should

be developed with a warm developer at, say, 70° F.,
and an over-exposed plate with a cold developer at,
say, 45° to 55° F.
This is a convenient stage to talk about restrainers.
It was seen (p. 37) that all soluble haloid salts
(chlorides, bromides,and iodides) had a tendency to
hinder the reduction of the bromide and kindred
salts of silver. As any soluble haloid can be used,
common salt may be used as a restrainer in the
absence of potassium bromide. The reason why acids
act as restrainers was explained on page 40. It is
advisable to always work with some bromide in the
developer, as otherwise the image comes up mvich too
quickly, and the silver is apt to be reduced to a
greater or lesser extent over the whole pliate, causing
"fog" and obscuring the finer detail.
All the organic developers in general use bear
a close chemical resemblance. Phenol (carbolic
acid) is the base of them all, and phenol itself is
benzene in which one hydroxyl (OH) has taken
the place of one atom of hydrogen. Benzene, CgHg,
is always represented in chemistry like this,—
 C H H C H H

PYEOCATECHIN, EESORCIN, HYDROQUINONE. 57

H H

H— C /\ C— H— C /\ C— OH
phenol being I

H—C H—C C—
I

C—
I |

c ,
c

Pyl'ocatechin, resorcin, and hydroquinone are di-

phenols, i.e., they contain two OH's,

OH OH OH
I I I

G C C

H—
H—
II0—
COG
/\C-OH

\/
H
Pyrooatechin.
1-2
I

'
•
H-C
H-C
II
/\0—H

\/
H
I

Resorcin.
1-3
'

H— C
C— OH H—
/\ 0—
IIC—
\/
OH
I

Hydroquinone.
1-4

the difference being that the atoms are arranged

differently, all three compounds having the formula
CeH,(OH),.
Pyrogallic acid is a tri-phenol, having the formula
CgH3(OH)3, and is still the most extensively used
of all developers. It is very soluble in water,
58 ACTION OF SULPHITES.

forming a 40 per cent, solution when saturated. It

is soluble also in alcohol, ether, and glycerin.
Like phenol (carbolic acid), it is not a true acid, such
as sulphuric acid, and its proper chemical name is
pyrogallol. It does form a combination with alkalies,
however, and in this condition is a very powerful
reducing agent. If left exposed to the air, it

absorbs oxygen rapidly, turning first yellow, then

brown, and finally black. The exact nature of the
oxidation compounds formed are not accurately
known. These brown products have a strong staining
action on the gelatin, so that under-exposed negatives
are much more liable to be stained, as not only are
they in the developer for a much longer time, but
the pyrogallate (i.e., the compound of the pyrogallic
acid with the alkali) is much more highly oxidized

through contact with the air all the while. It has

been found that a sulphite has the power of pre-
venting this staining to a large 'extent. Sulphite of
soda, NajSjOg, is generally employed, but sometimes
the metabisulphite of potassium (KgS^Og) takes its

place. The drawback to the last-named is that it

renders the solution very acid after a short time.

Only one quarter the amount of metabisulphite is

required, as compared with the crystallized sulphite.

As regards the influence of the quantity of sul-
phite in the developer on the resulting negative,
sulphite has a distinct restraining action on the
actual deposit of silver, and if a very large propor-
tion of sulphite be present, the developer almost
 PYRO-STAIN. 59

stops working. The diminution of the yellow stain

in the negative, however, very marked as the
is

sulphite is increased. The reduction in the quantity

of sulphite from 5 to 2^ grains to the fluid ounce of
developer, in some recent experiments by the author,
doubled the yellow stain in the dense part of the
experimental plate, and increased it by about four
times in the lighter portions. The entire absence
of sulphite in another part of the same plate caused
three times the stain in the denser parts, and about
five times in the lighter parts, as compared with
that portion of the plate developed with 5 grains to
the ounce. Alfred Watkins and others have shown
that this " pyro-stain "
has an important influence on
the printing value of the negative, so that it is
better to use suflBicient sulphite, say 4 grams to the
100 c.c. or 20 grains to the ounce, to practically elim-
inate the staining altogether. Some photographers
have an affection for the yellow stain, and think
it improves the " quality " of the negative. This
may be true in cases of hard negatives, but the
photographer should have complete command of his :

plate ill the same way that the engine-driver has of

the various levers that control the engine. If stain-
ing is allowed to creep in, the result becomes largely
a matter of chance. For the same reason, the phobog-
rapher should understand the effect of, and have
under his command, each separate constituent of his
developer, for these are the levers, so to speak, that
control the photographic negative.
60 ALKALIES IN DEVELOPMENT.

Ammonia solution or the carbonates of sodium

and potassium are the alkalies employed in develop-
ing with pyrogallic acid. Ammonia, although it is
still largely used, especially by professional portrait
photographers, seems unsatisfactory, because the
ammonia evaporates from the solution during
development, so that the developer grows continually
weaker in alkali the original concentrated solution
;

itself is always varying in strength. Besides this, it

must be a very bad thing for other plates or
sensitive material to be in a room reeking with
fumes of ammonia, which combine with any acid
fumes that may be about, and deposit over every-
thing in minute crystals. '.

Potassium carbonate possesses no- advantage over

sodium except that it is much more
carbonate,
soluble, which an advantage in making up- vei;y
is

strong solutions, but has the drawbacks that it is

much dearer, is more difficult to obtain, and more of
it is required in the developer. - :

Sodium carbonate is the most convenient alkali

to use. Ordinary washing soda is the form generally
employed, but there are two other forms that can
be used equally well, namely, -the monohydrated
sodium carbonate and dry powdered sodium
carbonate. The former of these, two has recently
been introduced commercially, so that it is well to
includeit. The latter is, or should be^ pure sodium
carbonate, N'a2G0g. The following table gives the
equivalence of the three carbonates to one another
 —

CARBONATES OF SODA. 61

and to sodium hydrate (caustic soda),. which may be

useful with other developers.

TABLE VII. Equivalence between CAtrsTio Soda

AND CaBBONATBS OF SoDA.

. Dry Sodium
Carbonate.
 —

62 VARYING THE PTEOGALLOL.

remaining the same, gave less than half the density

in the high lights of the negative, and only one-
fifth or one-sixth in the shadows. When the pyro.
was increased by a half {i.e., to 3 grains) there was
a distinct falling-off in the density, as compared
with the rightly proportioned developer, to three-
quarters in the high lights, and about the same in
the shadows. When the pyro. was doubled {i.e., 4
grains to the ounce) without change in the .alkali,

the result was practically the same as if one grain

to the ounce had been used, showing the strong

restraining action of the pyrogallic acid. As the
shadows were restrained more in proportion than
the high lights, a considerable excess of " pyro." over
alkali is clearly an advantage in developing an over-
exposed plate. The effect of bromide in this
direction, however, is almost the same. With these
experiments in varying the quantity of pyrogallic
acid in the developer, it was found that the yellow-
stain did not increase with the " pyro." by any
means, appearing to bear little relation to it, but
followed the density of the silver deposit very closely.
As regards the composition of the developer,
every photographer must be a law unto himself.
The developer must be handled according to the
exposure of the plate and the result the worker
desires to obtain. The formulae given by plate
makers are, as a rule, needlessly complicated. The
following is a good, sensible formula, which will
work well with any plate :
. 2
 —

64 STOCK SOLUTIONS.

Ten per cent, solutions may be used as recom-

mended in the previous formula. When large
quantities are required, the sulphite and the pyro-
gallic acid may be incorporated into one stock
solution in the proportion of

Pyrogallic acid, 50 grams, .

 OXYGEN TRAPS. 65

same proportions as used in the developer; this

arrangement will last for a year or more without
being renewed. If the oxygen trap, etc., is not
available, do not put the whole stock into one
stoppered bottle, as is generally recommended; but

Fig. 5.

fill a number of small corked bottles with the

solution, cork them tightly, melt up some paraffin
candle ends in an iron ladle or something of the
kind, aiid dip the tops of the bottles in the melted
paraffin to render them air-tight. Stock solution
treated like this will keep indefinitely, and no
preservative, such as citric acid, is required, as
there is no large air space above the solution to
make it go wrong.
5
 —

66 HYDEOQUINONE.

Hydroquinone works more slowly than^pyrogallic

acid. For that reason there is less tendency to
fog the plate during the prolonged development
necessary for under-exposed plates, for which hydro-
quinone developer is very suitable. Although an
excellent developer, there, does not seem to be so
much control over the plate as with pyrogallic acid.
The following is a good formula, giving a choice
of either sodiuni hydrate or carbonate ; the former
is to be Except in cases
preferred. of over-ex-
posure, for which hydroquinone is not satisfactory,
the bromide may be left out.

Hydroquinone, . . . .
•8
'8 gram, .
'
4 grains.
Sodium sulphite (crystals),
Citric acid, .

Potassium bromide,
( Caustic soda,

y .or
( Sodium carbonate (crystals),
Water up to

Caustic soda is an inconvenient material to weigh

out in small quantities, so that it will be better to
make up a stock of 10% solution. The rest of the
materials can be made up into a solution double
the strength in the formula, thus :

A. Hydroquinone, ;
. 16 grams, . 160 grains.
Sodium sulphite, 70 ,, . i^ ozs.
Citric acid, . . 1 ,, .20 grains.
Potassium bromide, 4 ,, 40 „
Water up to 1000 c.c, . 20 ozs.
 — , —

EIKONOGEN. 67

B. Caustic soda 10% solution, 80 c.c, If ozs.

or
Sodium carbonate 10% sol., 600 ,, 13^ ,,
Water up to . . . 1000 „ 20 „

For use take equal parts A and B. The same

quantity of water may be added with advantage
if the plate is not under-exposed. The strong
alkali used in this developer is liable to cause
frilling.

The best formula for the use of pyrocatechin is as

follows :

A. Pyrocatechin, . . 5 grams, . 10 grains.

Sodium sulphite, . 25 „ . 50 ,,

Water, . . . 250 c.c, . 1 oz.

B. Sodium phosphate, . 47 grams, 100 grains.

Caustic soda 10% sol., 50 c.c, . 1| drams.
'
Water, . '. . 200 „ .
f oz.

Use one part each of A and B and one part of

water.
Eikonogen is a complicated organic sodium salt
(see index). It is not a convenient developer
to use, as it dissolves in water with difficulty
and deteriorates rapidly when it has dissolved.
Its action is very powerful, however, and many
workers use it for developing snap-shots, lantern
slides, and badly under-exposed plates. The foUow-
ing' formula is recommended :

A. Eikonogen, . . .5 grams, 24 grains.

Sodium sulphite, . . 20 „ 96 ,,

Potassium bromide, . '5 ,, 2 ,,

Water up to . . 300 c.c, 3 ozs.

 ——

68 METOL.

B. 8odium carbonate (crystals), 15 grams, 70 grains.

Water up to . . 100 c.c, 1 oz.

For use take 3 of A to 1 of B immediately

before developing. It is not advisable to make up
more than is required for immediate use. For
very under^e'xposed plates, the following may be used
instead of B :

Caustic soda 10%, . . . 50 c.c, J oz.

Water up to . . . 100 ,, 1 ,,

Metol* possesses a marked effect in bringing out

detail in under-exposed plates, and a mixture of
this with hydroquinone is advantageous, because
tiydroquinone gives density, whilst metol brings out
the detail.
Metol is an excellent developer, being preferred by
many people to pryogallic acid. The following is a
good formula :

Metol, . . . . '8 grams, . 4

Sodium sulphite (crystals), . 5'5 „
Sodium carbonate (crystals), 4"5 ,,

Potassium bromide, . . "2 ,,

Water up to . . . 100 c.c.

It is well to dissolve the metol first and thpii

add the other constituents. Some people are very
sensitive to the action of metol, which sets up
violent inflammation in their hands.
Amidol is, chemically speaking, di-amido-phenol
or pyrogallic acid in which two of the OH's are
replaced by NHg. This- last is derived from
* For chemii'al formula see index.
 AMIDOL. 69

ammonia, NHg, in the same way that OH is derived

from water, OHg, and plays a very important part
in organic chemistry.

Pyrogallic acid. Di-amido-phenol (amidol).

I
UH ( NH.,

( OH ( OH"
lb is a powerful reducing agent, and has the
peculiarityof working without an alkali. The
image comes up very quickly when using amidol,
and care must be taken to leave the plate in the
developer until it has attained sufficient density.
Amidol more readily in a solution of sul-
dissolves
phite than in water, and sulphite has an accelerating
action with this developer. Amidol keeps very
badly, and it is advisable to make up. fresh solution
for each batch of plates. It is not easy to restrain
this developer, as bromides do not seem very effectual
with it. The presence of a small quantity of
bromide, however (say 1 drop of a 10% solution
to each ounce of developer), prevents any tendency
to fog.

Amidol, . . . . '5 grams . 2^ grains.

Sodium sulphite (crystals), 3'0 „ . 15 ,,

Water up to . . . 100 c.c. . 1 oz.

In case of underexposure, add 1 c.c. to each 100

c.c, or 5 or 6 drops to each ounce of a lO"/,, solution
of sodium carbonate crystals, and the same quantity
of potassium bromide.
Another material, called di-amido-resorcin, which
 ———

70 EODINAL, GLYCIN.

is very similar to amidol, has been proposed recently

as a developer. The following is the formula recom-
mended for use :

Diamido-resorcin hydrochloiate, . . 1 part.

Water, ....
Sulphite of soda (crystals), .

.
6 parts.
100 „

Paramido-phenol is hydroquinone in which one

OH has been replaced by NH^.
Hydroquinone. Paramido-phenol.

Its hydrochloride, or compound with hydrochloric

acid (CgH^.OH.NHg.HCl), is usually employed, and
is sold in solution which keeps
as " Kodinal,"
excellently. Those who use it speak very highly'
of it as an all round developer, and the author has
'

obtained good results with it in radiography. It

is convenient to make up a strong solution, similar

to rodinal, and dilute it when required.

Strong solution
Paramido-phenol hydrochloride, '5 grains, 25 grains.
Sodium sulphite, . . .9 ,, 1 oz.
Sodium carbonate (crystals), .9 ,, 1 „
Water \ip to . . . 100 c.c, . 10 ozs.

For use, take

Strong solution (Rodinal), . . 10 c.c, 1 oz.

Potassium bromide 10°/„ solution, . 2 ,,
^ ,,

Water up to . . . . 100 „ 10 „

Glycin* can be made to give hard, sharp negatives.

* For chemical formula see index.
 —

HYDEOXYLAMINE. 71

It is useful, therefore, in copying line drawings and

similar subjects, and works well with kinematograph
films. G-lycin is rather insoluble by itself, but
dissolves readily in alkali and sulphite. The follow-
ing is a good formula :

Glycin, ....
Sodium sulphite (crj'stals), 2
'8 grains,

,,
.

.
4 grains.
10 „
Sodium carbonate (crystals), 3 ,, .15 ,,

Water up to . 100
. c.c, . 1 oz.

For convenience, it may be made up four times

this strengthand diluted for use.
As regards the majority of these developers, it

is difficult to say that one is better or worse than

another. The best developer is undoubtedly the
developer that suits the photographer's particular
method of exposing, developing, and printing. The
same dictum applies to the various formulae, which
must not be taken as absolute, but merely as gene-
ral guides, to be varied according to circumstances.
Before closing the subject of development, atten-
tionmust be paid for a few moments to the work of
Hurter and Driffield, whose results are quite easy to
understand. In a perfect negative, containing only
black and white and no yellow stain, you have minute
black spots on a transparent ground. Supposing
you had a small plate, say one inch each way, and
you divided it by cross lines into ten thousand equal
squares, and then stopped up nine thousand so that
no light could come thrdugh these particular squares,
you would have something that would represent
72 HURTER AND DRIFFIELD.

roughly a photographic negative. If you put this

in a printing frame against the light, only one-tenth

on the plate would come through.
of the light falling
Supposing another similar plate were placed behind
the first plate, it would pass one-tenth of the light
that had filtered through the first plate, i.e., one-
tenth of one-tenth of the original light. The light
coming through a third similar plate would be one-
tenth of one-tenth of one-tenth of the original, and
so on. That is to say, the light comipg through each
of the three plates would be ^loth, xJq^^j T^Vo^^'
etc., of the original, or taking it the reverse way, the
ratios between the lights would be 10, 100, 1000;
etc. Now the logarithmis of 10, 100, 1000, etc., are
1, 2, and so on so that the logarithm of the
3, ;

light stopped by one screen or one density is 1, by

two screens, 2, by three screens, 3, etc. Supposing
you want to photograph a scale of tones so graded
that they are in the order 1, 2, 3, 4. A correct
result will only be obtained if the printing values of
the different parts of the negative are 1, 2, 3, 4 ; that
is to say, " each density must be proportional to the
logarithm of the light intensity that produced it."

By experiment Hurter and Driffield found that for

every plate there was a particular exposure, within
the limits of which this law held good above and ;

below these limits the ratios were false. More than

this, they found that the gradation in a negative,

developed with ferrous oxalate, could not be altered

by any amount of development, supposing no fog
 SPEED" MEASUREMENT. 73

was introduced, but depended entirely on the ex-

posure.
On this was based the H
and D system of deter-
mining the sensitiveness of plates.
The plate receives exposures from a standard light
graduated from 2^, 5, 10, 20, 40 to 160 sees., the first
portion of it, called the " fog strip,'' receiving no ex-

KfiVBR
mmnmm

mmmi
Fig. 6. —Speed readings of two plates—A, ordiuarf ; B, rapid.

posure at all. This plate is developed in the standard

developer for a standard time at a standard tempera-
ture (see p. 54), and the densities of the different
strips are read on a photometer, and recorded in the
manner shown above (fig. 6). The bottom line of
the chart represents the logarithms of the exposures,
and the upright line the densities read on the photo-
74 INFLUENCE OF PYKO-STAIN.

meter, the density of the fog strip being subtracted

from each one. It will be noticed that several of
the dots are in a straight line ; this is the period of
correct exposure. The straight line is prolonged to
meet the base line, and the number read off, which
gives the "inertia" of the plate, or the exposure
required before the commences to register
plate
correctly. To obtain the H and D. speed number,
the figure where the straight line cuts the base is
read off, and this divided into 34 gives the speed
number required.
The important points brought out by Hurter and
Driffield, in addition to the accurate method of
determining the speed of plates, are first, that the
gradation in a negative cannot be altered during
development, unless fog or stainis introduced; and

pyro-ammonia is a very uncertain de-

secondly, that
veloper. Another point arises out of the former one,
namely, that sensitiveness of the plate is as much-
a matter of the developer used as of the state of
the emulsion itself, the speed number of the plate
developed with pyro-soda being nauch higher than
when develofted with ferroiTS oxalate, and the speed
number with metol, for instance, is higher still.
The Hurter and Driffield system, as has been
pointed out, takes no account of the yellow stain
produced by development with pyrogallic acid and
other organic developers. Alfred Watkins and
others have given considerable attention to this
matter, and have shown that the " pyro-stain " has
 —

TANNING OF GELATIN. . 75

an important inliuence on the printing value of the

negative. This pyro-stain is something more than
a mere stain, for if the silver be dissolved out of the
plate with nitric acid, a faint yellow image remains.
Light, oxidizing agents, tannin, and other agents
cause gelatin to become insoluble. This is probably
the explanation of the pyro-image. Various agents
are present, such as the oxidized pyrogallic acid
which resembles tannin in some respects, and the
nascent compounds set free when the silver bromide
is reduced, whilst the action of the light itself on the
gelatin, and other known causes, are at work to
little
" Wherever the gelatin becomes
tan " the gelatin.
insoluble, —
and this is most likely to happen where
the chemical action of building up the silver image
is taking place, —
it fixes some of the highly coloured

products of the oxidation of the pyrogallic acid or

other phenolic developer.
As regards the " tanning " of the gelatin, or
rendering it insoluble, formaldehyde (see p. 76) has
a strong action, and is used to prevent plates frilling
in hot weather. Plates washed with formaldehyde
may be dried by means of heat, that could not be
applied in the ordinary way without melting the
gelatin. Formaldehyde is supplied commercially in
40 per cent, solution. This should be diluted as
follows,and the plate should be immersed for ten
minutes, being well washed afterwards:

"Water, ......
Formaldehyde (407„ solution), . . 1

3 parts.
part.
 —

76 KOBMALDEHYDE, ACETONE.

Following up the work of Schwartz and Merckliii,

and of Hellheim, Messrs Lumiere and Seyewitz
have found that formaldehyde is not the only -alde-
hyde capable of tanning gelatin. Aldehydes add to
the reducing power of the developer, but only in
the presence of sulphite. Acetone has a similar
effect to aldehydes, and can be used advantageously
to take the place of the alkali. "With pyrogallic
acid,development is effected rapidly with hydro- ;

quinone, the development is not so rapid, but the

results are as vigorous as with alkaline carbonates.
Lumiere and Seyewitz find that the addition of
formaldehyde (formalin) to the developer causes
strong staining of the film, with the exception of
paramido-phenol (rodinal) and metol developers. The
following are the formulae recommended for develop-
ment with acetone and sulphite in place of an
alkali :

Water, ....
A. Pyrogallic acid, 1 gram,
100 c.o.,
5 grains.
1 oz.
Sulphite of soda (crystals), 10 grams, 50 grains.
Acetone, . . c.c, .10
50 minims.

B. Hydroquiuone, . . 3 grams, 15 grains.

Sulphite of soda, . . 20 „ 100 „
Acetone, . . .10 c.c, 50 minims.
Water . . • 100 „ 1 oz.

When the plate has been developed to the right

density, it is washed carefully under the tap, and

allowed to soak for a few minutes in water then it ;

is fixed, i.e., the unaltered silver salts are dissolved

 FIXING. 77

out of the film, so as to leave no material sensitive

to light on the plate. The principal, and practically
the only, substances used fdr this purpose are
potassium cyanide and sodium thiosulphate (" hypo.").
The action of the two solvents is very similar : the
first action of the cyanide form insoluble silver
is to
cyanide by double decomposition with the silver
bromide, and then to make a double silver potassium
cyanide, which is soluble in water.

Potassium
 —

78 ACID THIOSULPHATB.

Acids decompose sodium thiosulphate into sul-

phurous anhydride (sulphurous, acid gas, or burnt
sulphur) and free sulphur. The reader should try
the experiment of adding a little hydrochloric acid
to a little solution of sodium thiosulphate.
In a
few moments he will be able to smell the burnt
sulphur, and will see the liquid turn milky with
free sulphur, thus

Sodium Hydrochloric Sodium -^ .

^''
thiosulphate. acid. chloride. *
NagSjOg + 2HC1 = 2N"aCl + HgO +
Sulphurous c , ,

anhydride ^"'P'^'^^-

SO2 + S.

Sulphurous acid has a very strong bleaching action,

and the sulphur is liable to cause stains. Acid or
alum, which contains free acid, should never be
added to the fixing bath.
As soon as the fixing bath begins to work slowly,
it should be thrown out and a fresh lot made up.

Exposure to the air gradually oxidizes the thio-

sulphate and sets up decomposition. Old baths full
of dirt and pyro-stains should not be used, as they
are almost certain to bleach or discolour the negative
or print.
As regards the washing of negatives free from
thiosulphate after fixing, the reader is referred to
page 14.
 POSITIVE AND NEGATIVE. 79

CHAPTEE V.

Eeveksal.

In one sense it is largely accidental that a

" produced by the ordinary method of
negative " is

exposure and development. If a piece of paper be

coated with ferric oxalate and exposed in the
camera, the reduced image will be lighter than the
unreduced —that is to say, a positive 5*ill be produced.
If this be washed over with ferricyanide of
potassium, the positive will be converted into a
negative ; if ferrocyanide had been used, the positive
would have remained positive.
All chemical reactions are reversible, given proper
conditions. In a mixture of substances such as
exists in the film of a sensitive plate, where there
is no outlet for the products of decomposition^the
excess of bromide or other halogen set free on
reduction in this case —a state of equilibrium is

reached at a certain point. If decomposition is

carriedbeyond this point, reversal sets in, which

may go the whole way until the original compounds
are re-formed.
 —

80 EEVERSAL.

This occurs in actual practice in photography.

When a plate is over-exposed, the high lights are
thin after development i.e.-, partial reversal has
taken place. By great over-exposure, reversal can
be carried to such an extent that a positive is
obtained instead of a negative. This process is
actually employed for copying negatives without
going to the trouble of making a transparency and
printing from that again. The resulting negative is
reversed as regards right and left, which is a draw-
backMf needed for ordinary photographic printing,
though it is an advantage in many " process " applica-
tions.

The actual method of accomplishing this, due to

T. Bolas, is as follows :
—Soak a gelatino4)romide dry
plate for five minutes in a 4 per cent, solution of
bichromate of potassium, rinse once or twice, and
then dip into a bath of equal parts of methylated
spirit and water. Blot off the superfluous moisture
and allow the plate to dry, all these operations
being conducted in the dark room. Then expose
the plate in a printing frame behind the original
negative, and expose to direct sunlight for three or
four minutes. On removal from the frame in the
dark room a faint image will be seen on the plate,
which is developed and fixed as usual. A chloride
plate must not be used for this purpose, as the re-
duction of silver chloride cannot be reversed in the
same way as silver bromide.
Several chemicals have the power of reversing a
 —

HALATION. SI

plate in a similar manner to light. Sodium hypo-

phosphite has this peculiarity. The organic substance
thiosinamine and the organic salts known as thiocar-
bamides, when added to the developer, have this
effect. Colonel J. Waterhouse recommends for this
purpose the following developer :

A. Lithium carbonate saturated

solution, ,
. . 100 c.c, . 1 oz.
Eikonogen, . 1 gram, . 5 grains.
Sodium sulphite, . 1 „ . 5 ,,

Dissolve the two latter in the first just before using,

and add a few drops of

B. Ammonium bromide, . part.

. .1
Thiocarbamide, . . parts.
. .3
Dissolved in water (quantity not stated).

" Solarization " is the word usually employed to

denote the local reversals that sometimes occur on
plates containing very strong contrasts. " Halation,"
or the veiling or blurring of the edges of the high
lights, such as the sky-lines of houses or the
branches of trees taken against the light, is a species

of partial reversal, generally/ attributed to reflection

from the back of the plate. To prevent this it is
usual tp " back " the plate with some non-actinic
medium, such as caramel and burnt sienna. The
following formula, due to J. S. Teape, is a good
one :—
Boil 1 lb. of white lump sugar in a saucepan large
enough to hold twice the bulk, for one hour after it has
6
 —

82 BACKING PLATES.

melted, stirring with a wooden rod the whole time.

Allow the liquid to cool slightly, then add, in small
quantities at a time, 4 ounces of boiling water, and stir

between each addition.

Of this caramel take . 1| . . ozs.
Saturated solution of gum tragacanth, 1 oz.
Powdered burnt sienna, 2 . . ozs.
Methylated spirit, . . . 2 ,,

Add the spirit after the other ingredients are well

mixed. Apply thinly to back of plate by dabbing with
flat hog's-hair brush.

Instead of making the caramel from the sugar, it

can be purchased the dry powdered form is the
;

best.
Some recent work of the author's seems to show
that the caramel alone is sufficient to stop halation,
and that the following formula is satisfactory :

White starch or flour, .

 FERRIC YANIDE REDUCTION. 83

CHAPTEK VI.

Eeduction, Intensification, etc.

If the image in the negative is too dense, it is

sometimes necessary to reduce its intensity. Any

perchloride, such as perchloride of iron, or similar
have the effect of converting the silver of
salt, will

the image into chloride. This must be associated

with an agent, such as thiosulphate of soda, which is
capable of dissolving the silver chloride as it is

produced, otherwise it would be difficult to know

when the reduction had proceeded far enough.
The method generally used in practice is that of
Howard Parmer, in which a mixture of potassium
ferricyanide and sodium thiosulphate is employed.
The action is very simple, silver ferricyanide being
produced, which dissolves in the thiosulphate.
The reducing mixture should be made up in small
quantities at a time, as the thiosulphate slowly
redvices the ferricyanide, rendering the mixture
useless. The negative should be soaked in water
for ten minutes, and then be placed in a 15i%
solution of sodium thiosulphate to which a certain
84 INTENSIFICATION.

quantity of 10% solution of potassium ferricyanide

has been added ; the amount can be regulated
according to the rapidity of reducing action re-
quired. All the liypochlorites act on the silver
image, and can be used to reduce its density.

Eeeently ammonium persulphate has come into

use for reducing the density of negatives. Owing to
the chemical reactions that take place in the. upper
layer of the film, the persulphate is said to act
only on the deeper portions, so that the dense
portions are reduced more in proportion than the
half-tones. The persulphate must not be used in
stronger solution than 5% otherwise it acts upon
;

the gelatin.
Intensification is very commonly employed,
especially inwet plate negatives. All the methods
employed have for theix object the conversion of
the particles of silver into some compound that
will increase the printing value. With the ex-
ception of a few cases, the image is first bleached
with mercuric chloride, which converts the black
silver image into a white double silver-mercurous
chloride. This must be washed carefully before
proceeding to the next stage, and it is absolately
necessary to success in intensification that the
film be thoroughly cleansed from "hypo." Mr
Chapman Jones has done a great deal of valuable
work on intensification.* He finds that the old

* See Moyal Photographic Society's Journal, June 1897, and

earlier issues.
 VARIOUS INTBNSIFIERS. 85

method with ferrous

of treating the bleached plate
oxalate developer is by
most reliable
far the
method. The plate is first of all treated to a bath
of dilute hydrochloric acid containing one part in
one hundred, and is then soaked in

Perchloride of mercury, . . 2 paits

Water, 100 „

until thoroughly bleached. After well washing,

the plate is placed in a bath of ordinary ferrous
oxalate developer (which see) until quite black,
when it is again washed. If not sufficiently
intensified, whole operation may be repeated
the
a second, and
even a third time, the chemical
effect being to form an amalgam of silver and
mercury, which, through the protection afforded by
the gelatin, is permanent.
A very common method is to treat the bleached
plate 'with very dilute ammonia. The action in
this case is very complicated, as the black intensi-
fied image consists principally of uncertain com-
pounds of ammonia and .mercury, the silver being
largely dissolved out. Consequently, the effect on
the plate is by no means uniform, the thinner parts
being actually reduced by the solvent action just
referred to. If employed, the ammonia solution
should contain about ten drops of liquor ammonia
880 to the ounce.
Sulphite of soda can be used after bleaching with
mercury, but the intensifying action, is not very
 —

86 SILVER AND LEAD INTENSIFIEES.

strong or certain. The chemical effect is to reduce

part of the silver and mercury to the metallic state,
and to dissolve part as sulphites.
A of potassium iodide and potassium
mixture
cyanide, sometimes applied to the bleached plate.
is

It is uncertain in its action, and changes take

place on storing, as they do with plates blackened
by ammonia. The same applies to a mixture of
silver nitrate and potassium cyanide sometimes
employed.
Wet plates are frequently intensified by silver
nitrate mixed with an acid developer, such as pyro-
gallic acid containing citric acid, the following being
employed at the Bolt Court Process School :

A. Silver nitrate, 22'8 grams, . 200 grains.

Water distilled, 1000 CO., . 20 ozs.

B. Pyrogallic acid. 11 "4 grams, . 100 grains.

Citric acid. 28-5 „ . 250 „
Water distilled. 1000 CO., , 20 ozs.

Feri'icyanides of uranium and lead are occasion-

ally used, the action being to form an insoluble
ferrocyanide. It is therefore very important that
in making the solution the crystal of ferricyanide of
potassium be washed free from any adhering ferro-
cyanide. The uranium ferrocyanide is red in colour,
and very opaque to the rays causing photographic
is

action, so that care must be taken not to over-

intensify. The lead ferrocyanide is white, and must
be treated with ammonium sulphide, which turns it
 LEAD AND URANIUM. 87

into black sulphide ol lead. Instead of the ferri-

cyanides of lead or uranium, a mixture of potassium
ferricyanide and lead or uranium nitrate is used.

Lead Intensifier.

Lead nitrate, . . 4 grams, . 20 grains.

Potassium ferricyanide, 6 ,, . 30 ,,

Acetic acid (glacial), . 2 c.c, . 10 minims.

Distilled water up to 100 „ . 1 oz.

Uranium Intensifier.

Uranium nitrate, . 1 gram, 5 grains.

Potassium ferricyanide, 1 „ 5 „
Acetic acid (glacial). 2 grams, 10 „
Distilled water up to 100 c.c, 1 oz.

Mr Charles W. G-amble has pointed out an

interesting point in connection with intensification
of half-tone negatives by lead. If the mixture of
lead and silver ferricyanides is treated with fresh
ammonium sulphide, the dots in the negative come
out sharp and black, but if the ammonium sulphide
has been made up several days, each dot is sur-
rounded by a grey margin instead of being sharp.
The explanation of this is, that, on exposure to the
air, ammonium sulphide is oxidized to a mixture of

thiosulphate and polysulphides which have a solvent

action on the silver, which is first dissolved and
then re-precipitated as a blurred margin round the
djt,
88 PHOTO-SALTS.

CHAPTEE VII.

Feinting in Siltbe.

From the short account given on page 36, the reader

will have learnt something about the photo-chlorides
of silver. These intermediate compounds between
ordinary silver chloride and metallic silver are of
most varied colours, ranging from white through
shades of red and purple to black. They are per-
manent in the dark, but are altered by light. Besides
these coloured photo-chlorides and other photo-salts
of silver, there are several coloured varieties of
metallic silver, which in this state more resembles a
colloid substance (see p. 113), and possesses the re-
markable property of dissolving in water. In addition
to the ordinary white form of metallic silver, there
seem to be at least four other modifications. The
first, which we may call A, is soluble, forming a deep

red solution in water. When concentrated, or if

nitrate of ammonium is added to the solution, it forms

a precipitate, which may be either matt black, blue or
green, whilst moist. As soon as it is dry, however,
it acquires a brilliant metallic surface, having a
 SOLUBLE SILVER. 89

bluish-green tint. Modification B is insoluble, and

isproduced from the foregoing it is dark reddish- ;

brown when moist, but resembles A when dry.

The third form, C, is of a dark bronze hue when
moist, but like burnished gold when dry. No
soluble modification of this exists, but a copper-
coloured variety is formed under certain conditions.
All the varieties have the remarkable property of
drying with their particles in optical contact, pro-
ducing perfect mirrors if spread out on paper and
allowed to dry. Unfortunately, like the photo-
chlorides, these forms of metallic silver are affected
by light A and B become brown after some hours,
;

and the coppery modification of C becomes bright

yellow. In spite of this, several occasions can be
imagined on which they would be serviceable for
making a large mirror for immediate use in the
studio, or where a large reflecting surface is required.
C has the property of changing into ordinary silver
of great beauty in presence of moisture, and immedi-
ately, on being subjected to friction in any part, the
action spreading to the rest of the film. The reader
has probably seen a good many of these photo-
chlorides and varieties of metallic silver in the
ordinary silver printing papers after exposure behind
the negative.
The old process of sensitizing albumen paper
with silver nitrate is still' the most largely used of
any printing process in spite of numerous drawbacks.
In preparing the paper on a large scale, the eggs
 —

90 ALBUMENIZBD PAPEE.

are broken separately, the whites separated from the

yolks and run into drums. This albumen is then
run into churns driven by steam and " frothed,"

being allowed to stand until quite limpid, when

it is decanted from the embryos and stringy
off
portions of the white of egg, and run into tall glass
jars to ferment. After this it is filtered and again
treated to the frothing process and allowed to settle,
the stringy portionsnow finally removed.
being
Ammonium added to the albumen, and
chloride is

Eives or Saxe paper is coated by floating the sheets

on the surface of the liquid. The paper is hung up
to drain, stored for some time and re-albumenized,
being hung up to drain the reverse way. This pro-
cedure equalizes the quantity of albumen on the
surface.
From this description of work on the large scale,
the reader will see how to proceed in the small way
if ever he finds it necessary to do so, the following
quantities of materials being used, and a whisk
being employed instead of a churn :

Albumen,
Ammonium
.....
chloride, . . .60
G ozs.
grams.
Rectified spirit, . . .96 minims.
Distilled water, . . . -If ozs.

The paper is sensitized just before use by floating

on a solution of silver nitrate containing 50 grs. to
the oz., or 10 grams in 100 c.c.
The action of the sensitizing bath is to convert
 PRINTIKG AND WASHING. 91

the silver nitrate into chloride, which is entangled

in the albumen by interaction with the ammonium
chloride. Besides this, however, the silver nitrate
has an important action on the albumen, forming
an albumenate of silver, which is insoluble in
water, so that the albumen does not dissolve off
the paper. Consequently, the stronger the sensi-
tizing bath, the longer will the paper have to be
floated, as the silver nitrate penetrates more slowly
through the insoluble albumenate.
In printing on this paper the action is probably
very complicated, as the albumenate of silver takes
part in the reduction as well as the chloride. The
ready sensitized paper, used so largely by amateurs,
contains citric acid in addition to the other con-
stituents, which still further complicates matters.
When printed, the paper is washed in water con-
taining one part of common salt and toned
in 40,
with gold or other more or less permanent reducible
metal, in order to counteract the objectionable red
tones of the silver print. In washing the print
before toning, the reason that the water turns milky
is that the soluble silver salts react with the salt in
the water to form chloride.
Of the numerous toning baths, the acetate is that
most usually employed. The gold chloride generally
piurchased is a double chloride of gold and sodium,
and is frequently acid. It is important, therefore,
to neutralize the gold chloride solution by shaking
it up with a little powdered chalk. For use it is
92 TONING WITH GOLD.

convenient to dissolve the contents of the 15-grain

tube in If ounces of water, making approximately
1 grain to 1 dram or a 2 per cent, solution; or it

dissolved in 50 c.c. of water, a practically 2 per cent,

solution of the commercial salt, or a 1 per cent,
solution of gold, is obtained. The following Table
shows a few of the various formulae recommended by
different workers for toning sensitized paper with
gold.

TABLE VIII.— Gold Toning Baths.

Each to be made up to 10 ounces with water.

 ;
:

CHEMISTRY OF TONING. 93

these conditions, sulphiir combines with the silver,

forming silver sulphide, and the toning is due to the
sulphur instead of to the gold such prints fade very
;

rapidly, and the whites soon turn yellow. For

this reason combined toning and fixing baths can-
not be too strongly condemned. Consequently,
the fixing bath should be made alkaline by the
addition of ammonia, or, better, bicarbonate of soda
in the proportion of 5 grains to- each ounce of
" hypo." Always with litmus-paper before use
test
if acid, i.e., if the litmus-paper turns red, add more

bicarbonate. Toning baths should be made alkaline

with bicarbonate in the same way, if on the acid
side, as it is essential that the bath be alkaline.
After toning, it is well to immerse the prints in salt
and water before fixing. They may be left there
until all the batch has been toned, so as to avoid
contamination of the fingers with the fixing bath
whilst toning is in -progress.
The chemistry toning process is as follows
of the
In the alkaline solution the gold chloride is reduced
first of all from auric chloride (AuClg) to aureus

chloride (AuCl) ; then an atom of gold is deposited,

an atom of silver taking its place, thus,

Aureus chloride. Silver. Silver chloride. Gold.

AuCl + Ag = AgCl -I- Au.
From this it is clear that other metals can be
used for toning instead of gold. With a platinum
toning bath, for instance, platinum is deposited in
the place of the silver, and with a lead toning bath,
 — — ;

94 GELATINO-CHLORIDE PAPER.

lead is exchanged for the silver in the print. The

following platinum toning bath is recommended by
Liesegang :

Potassium chloroplatinite,
Nitric acid,
Water, .
...
. .
.

.
-1

100
gram,
-5 c.e.,

„
.

.
2
1
| grain.
minims.
oz.

Gelatino-chloride and coUodio-chloride papers are

emulsions of silver chloride and an organic salt with
gelatin in the one case and with collodion in the
other. These papers are generally known as
" printing-out " papers.

W. K. Burton's formula for gelatino-chloride

emulsions is as follows:

A. Ammonium chloride, 3'5 grams, . 53 grains.

Gelatin, . . . 27 „ 420
Distilled water, . 850 c.c, . 30 ozs.

Soak the gelatin and ammonia chloride in the

water for an hour and dissolve in a water-bath
then add
Silver nitrate, . . 9 '7 grams, 150 grains.
Distilled water, . 14 c.c, ^ oz.

B. Sodium citrate, . 2 grams, 30 grains.

Gelatin, . . . 6'3 ,, 100 „
Distilled water, . 100 c.c, 3^ ozs.

Allow to soak for an hour and dissolve in the

water-bath; then add
Silver nitrate, . . 3 grams, . 45 grains.
Citric acid, . . 5 „ . 80 „
Distilled water, . 14 c.c, .
^ oz.
 — —

COLLODIO-CHLOEIDE PAPER. 95

Mix A and B ; wash as directed in dry-plate

emulsions, and after keeping for three or four days,
coat the paper by floating.
Geldmacher's formula for eoUodio-chloride emul-
sion is as follows:

A. Pyroxylin, .22-75 grams,

. . 6| drams.
Ether (not methylated), 425 c.c, 15 ozs.
Alcohol (not methylated), 425 „ 15 „
Castor oil, . 3'5 ,, . . , 1 dram.
B. Silver nitrate, 20 grams. . . 308 grains.
Distilled water, 21-5 c.c, . . . 6 drams.
Alcohol (not methylated), 42-5 „ IJ ozs.

C. Citric acid,
Alcohol,
...
. . .
5 grams,
70 c.c, .
75
2^
grains.
ozs.

D. Strontium chloride, . 5 grams, 75 grains.

Alcohol, . . . 70 c.c, 2J ozs.

Mix C and D and add to A, shaking vigorously.

In the dark room, add B to the mixture in small
portions at a time, shaking constantly. The emul-
sion ready for use after standing for an hour.
is

Alpha paper is essentially a gelatin emulsion

of silver citrate. The following is Wellington's
formula :

Silver nitrate, .

B.
 —

96 TONING PRINTING-OUT PAPERS.

Both solutions are to be heated to 66° C. A is

then added to B, and 1600 grains (10 '4 grms.) of
gelatin, previously swollen and melted, is added to
the mixture, which is run into a dish and allowed
to set. It is then broken up, washed and re-melted
before coating the paper, which is best developed
with the hydroquinone formula given below (p. 99)
and toned.
As regards toning, the coUodio- and gelatino-
chloride papers may be treated alike. The same
baths may be used as for ordinary sensitized paper,
but these papers work better in a bath composed of
ammonium sulphocyanide and gold chloride than
in any other. The quantity of sulphocyanide may
vary considerably, but as it has a tendency to dis-
solve gelatin, it is not advisable to use more than
is recommended in the formula. These printing-
out papers require to be toned somewhat more deeply
than ordinary sensitized paper. The gelatin paper
should not be touched with the fingers, as the gelatin
is apt to soften* with the warmth and retain the
marks ; for the same reason, all solutions should be
kept cold. To prevent uneven toning, it is well to
give the prints a thorough washing, preferably in
salt and water (see p. 87), before toning. Tlie
following bath can be recommended:

Gold chloride (2% solution), . 6 c.c, 1 dram.

Ammonium sulphocyanide (10%
solution), . . . 30 „ 5 drams.
Water, . . . . 100 „ 16 ozs.
 —

TONING AND FIXING BATHS. 97

Ammonium sulphocyanide is very deliquescent,

and should be dissolved in water at once to form a
10°/^ solution. In making up the bath, always mix
the sulphocyanide with the water first, and then add
the solution of gold chloride.
In toning, it should always be borne in mind ,that

the number of prints that can be toned with a given

quantity of gold depends quite as much upon the
nature of the prints as upon their size. A dark
print with heavy shadows may require three or four
times as much gold as a light print of, say, a cloud
effect. It is important, when economy of gold is

desired, to trim thQ prints before toning.

The following formula has been strongly recom-
mended by printers:
Gold chloride (2% solution), r5 c.c, . 3 drams.
Ammonium sulphocyanide
(10% solution), . . 20 „ .2 ozs.
Sodium thiosulphate, . 1 gram, . .5 grains.
Water up to . . . 100 c.c, . 10 ozs.

Numerous otherformulae are in existence, and

will be found in the various year books and other
books of reference, but exigencies of space forbid
their inclusion here.
Some photographers use and recommend the
combined toning and fixing baths. These may be
all very well for routine work in careful and
experienced hands, but they are wrong in principle,
and the least carelessness may produce disaster.
The author never uses them himself, and gives the
7
 — —

98 PRINTING-OUT PAPERS.

following formula, which is due to Dr Liesegang,

under protest, so to speak:

Ammonium sulphooyanide
(10%
Common
Alum,
...
solution),

....
salt,
. 10 e.c,
. 10 drams.
4 grams, 240 grains.
2 „ 120 „
Sodium thiosulphate (hypo.), 15 „ 2 ozs.
Distilled water up to 100 e.c,
. 12 „

To 60 parts of this solution, add 7 parts of a 27^

solution of gold chloride, diluted with an equal bulk
of water. When the mixture has been made, add
40 parts of old, used, combined bath.
Printing-out papers can be developed after a
short exposure, and can then be toned and fixed in
the usual way. Only a faint image is required to
and it
start with, is advisable not to print beyond the
point where the details just begin to show in the
half-tones. It is well to follow the excellent sug-
gestion ofMr Wilson of the Paget Prize Plate Co.
and immerse the prints in a 10°/„ solution of potas-
sium bromide bfefore developing, thus changing the
silver chloride into silver bromide. After soaking
in this solution for from 10 to 20 minutes, passing a
clean camel-hair brush over the surface of the paper
to ensure the absence of bubbles, the paper should
be thoroughly washed for about 10 minutes in run-
ning water to remove excess of potassium bromide,
which would render the development too slow.
Then develop with the following:
 —

BROMIDE PAPER. 99

A. Hydroquinone, 2 grams, 10 grains.

Sodium sulphite, 2 „ 10 „
Sulphurous acid, 1 c.c, 5 minims.
Water up to . 100 „ 1 oz.

B. Sodium carbonate
(washing soda), 5 grams, ioz.
Water up to . 100 C.C., 10 ozs.

For use, take one part each of A and B, and one

part of water.
The papers can be toned with platinum; for
formula see p. 94.
Bromide paper is coated with a gelatino-bromide

of silver emulsion similar to that used for dry

plates, but generally much less rapid. The follow-
ing is Dr Eder's formula for an emulsion suitable
for coating paper :

A. Ammonium bromide. 20 parts.

Gelatin, . 50-80 „
Distilled water, . 400 „

Soak the gelatin in the water for 12 hours, then

dissolve in the water-bath at 50-60°
C, and add
the bromide. Take the emulsion into the dark
room, and add, with constant shaking,

Silver nitrate, 30 parts.

Distilled water, 400 „

After standing for about an hour, pour out into a

dish to set, squeeze through muslin, and wash in the
manner described on page 52. The above formula
gives black tones. If brown tones are required,
 —

100 BROMIDE PAPER.

replace two parts of the ammonium bromide by two

parts of potassium iodide.
Bromide paper may be developed with ferrous
oxalate or with most of the dry plate developers,
except pyrogallic acid. The author much prefers
ferrous oxalate. The following is a good formula :

A. Neutral oxalate of potash, 23 grams, 1 lb. avoir.

Distilled or boiled water, 100 c.c, 3J pints,

B. Ferrous sulphate, . . 30 grams, 1 lb. avoir.

Sulphuric acid, . . 5 c.c, 15 minims.
Distilled or boiled water, 100 ,, 54 ozs.

For use, add one part of B to six parts of A, not

the reverse, or a precipitate of ferrous oxalate would
be formed. A few drops of 10°/^ potassium bromide
solution may be added as a restrainer.
If, after development, the prints were to be put
direct into water, a precipitate of ferric hydrate
would be formed in the paper. To avoid this, the

paper is placed in dilute sulphuric acid (say ^ oz. in a

pint, or 25 c.c. in 1000 c.c.) which dissolves out any

iron from the paper.

As regards development with agents other than
ferrous oxalate, the combinations that can be made
are almost unlimited. For practical purposes, any
of the formulee used for dry plate development may
be employed, but the strength must be only one-
third of that given in the formulae for dry plates.
The proportion of sulphite in each ounce or 100 c.c.
of developer, however, may remain the game or be
 . :

TONING BR6MIDE PRINTS. 101

only s%htly reduced, so as to ensure absence of

stain.
Bromide prints are frec[uently toned with platinum
or uranium salts. In the former case, the platinum
replaces the silver to a greater or less extent.
Uranium, although it changes the tone to a reddish-
brown, acts principally as an intensifier, and can be
applied beneficially to weak prints. It is important
that every trace of " hypo." be removed by thorough
soaking, otherwise toning will be uneven. Selle's
formula for uranium toning is essentially as follows

Uranium nitrate, .
5 gram,
Potassium f erricyanide,
Acetic acid (glacial),.
Water up to

After toning, the print should be washed in dilute

acetic acid (say 1 to 30) for twenty minutes or
longer.
102 BLUB PRINTS.

CHAPTEE VIII.

Pjrinting in Salts of Ikon.

Pkactically the whole of the processes for printing

in salts of iron depend upon the fact that ferric
salts are reduced to the ferrous state by the action
of light, ferric oxalate, Fe"'2(C204)g, becoming ferrous
oxalate, Fe"C20^. Potassium ferricyanide converts
the reduced salt into insoluble Prussian blue, the
unreduced ferric salt being nearly colourless and
soluble. If /erroeyanide of potassium be used as
a developer instead of /erricyanide, the reduced
portions remain colourless, whilst the unreduced
parts are turned blue.
The paper usually employed for reproducing
engineering plans, and for making blue prints from
negatives, is coated with a mixture of ammonio-
ferrous citrate, better known as ammonio-citrate or
citrate of iron, potassium ferricyanide and gum
arabic in water. The process was first employed by
 —

PRINTING IN IKON SALTS. 103

Sir John Herschell in 1842. The following is

Rockwood's formula :

A. Potassium ferricyanide, . 10 grams, . 1 oz.

Water, . . . .100 c.c, . 10 ozs.

B. Ammonio-citrate of iron, . 30 grams, . 3 „

Gum arable, . . . 5 „ . |^ oz.
Water, . . . .100 c.c, . 10 ozs.

Equal parts of A and B to be taken, and after

standing for a few minutes until quite clear, the
paper should be coated by means of a stiff brush.
The paper should be dried quickly and kept dry.
It is fixed by washing in water until the whites are
quite clear. If over-printed, a little carbonate of
soda may be added to the water. If under-printed,
fuller density may be obtained by adding a little
ferric salt to the first wash water and allowing it
to remain until sufficient depth is obtained. This
is the same principle as re-developing a gelatino-
bromide plate. Spots can be bleached by a weak
solution of potassium oxalate.
This paper can be toned with various substances.
Strong tea containing a little sodium carbonate
changes the blue to black, the iron forming an ink
with the tannin. The colour can be altered by
difi'erent reagents, sulphocyaii^de turning it red, and
so on.
If the paper be coated with the iron solution (B)
only, without the ferricyanide, it can be developed
with this solution, or with gold chloride.
The process of making a paper for subsequent
 — —

104 DEVELOPING BLUE PRINTS.

devBlopment with ferrocyanide Of potassium, whereby

the whites of the negative come out white, is as
follows, using Pizzighelli's formula :

A. Gum arahic, 20 grams, . 2 ozs,

Water, lOOcc, . 10

B. Ammonio-citrate of iron, 50 grams, . 5

Water, 100 CO., . 10

C. Ferric chloride. 50 grams, . 5

Water, 100 c.e., . 10

For use, add 20 parts of A to 8 parts of B, and

the whole to 5 parts of C. Allow to stand until
clear and then coat the paper. As the reduced
ferrous is lighter than the ferric salt, the image
appears lighter than the background.
Develop with.

Potassium ferrocyanide, . 20 grams, . 2 ozs.

Water, . . . . 100 „ . 10 „

Paste the developer on the surface of the print

with a brush; as soon as dark enough, wash, and
fix in a 10°/„ solution of hydrochloric acid until the
whites show clear.
Those who want further information about ferric
printing processes will find all they require in an
excellent little work by G. E. Brown, F.I.C., entitled
" Ferric and Heliographic Processes."
 PLATINUM PRINTING. 105

CHAPTEE IX.

PuiNTiNts IN Platinum.

Platinum printing is not a direct process; it is

really an iron printing process, but instead of bring-
ing out the reduced ferrous image with ferricyanide,
a platinum salt is used, the platinum being reduced
by the ferrous image to form a permanent print.
The platinum salt can be incorporated in the sensi-
tizing solution that is applied to the paper, as in the
cold process, or the iron image can be obtained first

by printing on paper coated by ferrous oxalate, and

treating this afterwards with a solution containing
platinum, as in. the hot-bath process. Platinic
chloride, PtCl^, can be used, but the effect is not
good, as the salt has to be reduced such a long way,
so that the lower or platinous chloride gives better
results. This salt is nearly insoluble in water,
but a double chloride of platinum and potassium
is very soluble, so that the latter or potassium
chloroplatinite, as it is generally called, is the actual
salt employed.
By the -addition of mercuric or palladium salts

to the sensitizing solution, " sepia- " toned images

 — —

106 PREPARING THE PAPER.

can be secured.The sepia tone does not appear

any admixture of a mercury or palla*
to be due to
dium compound, but, as V. Hubl has shown, to a
peculiar condition of the platinum itself.

W. WiUis and Captain Pizzighelli are the two

best-known workers on platinum printing, the hot-
bath process of the former inventor being still
the most reliable printing method, and that most
generally used. Eives paper, 'No. 74, is sized with
arrowroot and gelatin, in some such proportion as
the following
.....
:

Arrowroot,
Nelson's gelatin,
Alum, .
.... . . . .
500
180
110
grains.
,,

,,

Water up to . . . . 120 ozs.

The gelatin is allowed to swell and then dissolved

at about 80° F. ; the arrowroot, being made into a
thin cream with a little of the cold water, is then
poured in. The paper is sized on this for about-
three minutes by floating, and after being hung up
to dry, is sensitized by coating with the following
solution :

I. Ferric oxalate, 24 grams, 120 grains.

. .

(Carefully prepared and kept away from the light, so .

as to ensure absence of ferrous salt.)

Oxalic acid, IJ grams,
. 8 grains.
. .

DistUled water, . 100 c.c, . 1 oz.

II. Potassium chloro-platinite solution In. .

(80 grs. to 1 oz. of water) . .

^
j
No. 1 solution, . . . . 22 „
Distilled water, . . . . 4 „
 —

DEVELOPING PLATINUM PRINTS. 107

The addition of a few drops of 1°/^ solution of

potassium chlorate produces contrast, and should be
used in case of a weak negative, or where a brilliant
print is desired.

Coat the paper in a room heated to 70° F., the

atmosphere being kept moist. The paper should
be allowed to get surface dry, and should then be
dried completely on an iron plate in front of a fire,

taking care not to overheat. To keep the paper

dry, it should be stored in a tin having a lid at
each end, the bottom lid containing asbestos fibre
soaked in strong calcium chloride, and dried bone dry
by heating on an iron plate. A perforated zinc grat-
ing should cover the calcium chloride and asbestos to
prevent any contact with the paper.
It is important to keep the paper as dry as
possible whilst printing, and for this purpose sheets
of india-rubber are placed behind the paper in the
printing frames. Printing is allowed to continue
until a faint iron image is visible, when it is de-
veloped with a solution of oxalate of potash at a
temperature not lower than 100° F. The solution
of oxalate of potash contains

Potassium oxalate (neutral), . .16 parts.

Water, 60 „

Hard negatives or under-exposed prints require a

. hotter oxalate bath, as it tends to soften and flatten
the detail.
 —

108 TONING WITH CATECHU.

When developed sufficiently, the prints are fixed

without washing in a bath containing

Hydrochloric acid, . . . .1 part.

Water, 60 parts.

The solution is poured away after a few minutes,

and fresh poured on, this being again repeated. The
object is to dissolve out every trace of iron and
unreduced platinum salt. The paper must be washed
to remove the acid.
Paper is made for developing in the cold, but this
paper gives very brilliant results in the hot bath.
By adding mercuric or cupric chloride to the de-
veloping solution, a sepia tone is produced. Various
substances can be used to tone or intensify platinum
prints, but with the exception of catechu, they are
not to be recommended. The toning-bath is prepared
by boiling 7 grams of powdered Bombay catechu
with 150 c.c. of water for ten minutes, cooling,
adding 30 c.c. of alcohol, and filtering. Of this con-
centrated solution 5 c.c. are taken and made up to
500 c.c. at 60° F. As the catechu-tannic acid in the
catechu combines to form an inky compound with
iron, it is important that every trace of the latter
be removed from the paper before toning.
 THE CARBON PROCESS. 109

CHAPTEE X.

The Bichromate Printing Processes.

All that can be told about the chemistry of the

bichromate processes, so far as it is known, can be
said in a very few words, the subsequent applica-
tions of this knowledge being purely mechanical.
There are two chromates of potassium, the normal
yellow chromate (KgCrOJ, and the acid orange
chromate (KgCr^O^). When the latter is mixed
with a colloid organic substance (see p. 114) and
exposed to light under a negative, two important
changes are noticed the organic matter is rendered
:

comparatively insoluble where the light has acted,

and the material has lost its power of absorbing
water and becoming sticky, or " tacky." On these
facts the whole of the bichromate processes depend.
In the carbon process, carbon, Bartolozzi red, or
some other colouring matter is incorporated with
gelatin, and made into thin sheets of " tissue," which,
about twelve hours before use, are sensitized by
immersing in a 5 per cent, solution of potassium
bichromate for three minutes in winter and two in
 —

110 CAKBON TISSUE.

summer, at 60° F. They are then hung up to dry

in the dark. The exposure is made under a nega-
tive, the time required being judged by means of
an aetinometer. After exposure, the tissue is trans-

ferred from its own paper to another paper prepared

specially beforehand by coating with

Nelson's No.
Water,
1 gelatin, ... J
10
oz.
ozs.

Allow the gelatin to soak for an hour in the

cold water, and then dissolve in a water-bath.
When dissolved, stir in half a dram of formalin.
Brush well over the surface of the paper, and allow
to dry. The object of this is to make sure that the
tissue will stick fast when squeegeed on to the
paper.
The transfer paper is soaked in water for a time,
which varies according to the thickness of the
paper. The tissue is then placed in the same water
with the prepared paper, and when the tissue
begins to flatten, the two are lifted from the water
together, being then squeegeed into close contact by
means of a flat squeegee. After being pressed be-
tween blotting boards, the whole is immersed in
hot water at about 110° F. As soon as the gelatin
begins to soften round the edges, the original sup-
porting paper is removed.
The back of the sensitive gelatin film is now
uppermost, the surface on which the light has
fallen being beneath. Where the light has acted
 —

SINGLE AND DOUBLE TEANSFER. Ill

strongly, the gelatin is insoluble nearly right through,

but in the parts corresponding to the black parts of
the negative only a thin film is insoluble. By
washing the film from the back, which is now
uppermost, the soluble portions wiU be washed
away, leaving a sort of raised map, the hills corre-

sponding to the light parts of the negative, and the

dales to the dark portions. Where the gelatin be-
comes insoluble, it entangles and fixes the colouring
matter, so that a print in monochrome with all the
gradations of the original is produced.
The method just described is that of single trans-
fer, the right and left of the original subject being
reversed. In some cases this is objectionable, so
the tissue isdeveloped on a temporary support, con-
sisting generally of opal glass, coated with the fol-

lowing :

Pure bee's wax, . . .2 drams

Yellow resin,
Turpentine, ...
. . . . . 6 ,,

.1 pint,
any excess being removed by polishing with a
cloth paper coated with a film of partially soluble
;

gelatin to be used as a final support. Before use,

a sheet is soaked for half-an-hour in a 2 per cent,
solution of alum,and then placed in water with the
supported which should be transferred iu the
tissue,
manner described under single transfer.
In both cases the development should be carried
out with warm water, the temperature of which
can be varied according to the correctness of the
112 ARTIGUE PAPEK.

exposure, higher temperature being employed for

under-exposed prints. After development, the prints
should receive a final wash with cold water, and
should then be soaked in a 5 per cent, solution of
alum until all bichromate stain has been removed,
when a final rinse with cold water is given. The
development should be carried out as soon as pos-
sible after printing, as the action once started by
the light continues automatically in the dark. It is

advisable to "safe edge" the print before exposing,

by protecting the margin of the negative from the
lightby means of black paper. All who are inter-
ested in carbon printing should read J. A. Sinclair's
excellent monograph, which appeared, together with
other valuable and interesting papers on the
bichromate processes, in the Jov/rnal of the Royal
Photographic Society for May 1896, the set of papers
being subsequently published by Dawbarn & Ward,
Ltd.
A very beautiful process for carbon printing
without transfer has been revived recently, and is

known as the Artigue or bichromate gum process, an

account of which will be found in Mr Sinclair's paper.
Instead of gelatin, a warm
black pigment is worked
up with gum, and coated on paper. This is sensi-
tized in a 2 per cent, solution of bichromate of
potash, and exposed under the negative without a
" safe edge," an actinometer being employed as in

the ordinary carbon process. In development, the

paper is first treated with warm water, and then
 HALF-TONE AND COLLOTYPE. 113

with a mixture of warm water and fine sawdust.

After development is complete, the paper is soaked
in a 5 per cent, solution of alum, and then washed
in cold water.
The Grum-Bichromate process, which has been the
subject of so much controversy, is somewhat similar
to the Artigue process.
In the half-tone process of reproducing photo-
grams and tone drawings, a copper, or sometimes a
zinc, plate receives a coating of gelatin or other
colloid, which is sensitized with bichromate. This
is exposed under a negative made from the original

through a cross line or other screen which breaks

up the tones into dots. After printing, the plate
is developed by washing, and etched with ferric
chloride or an acid. There are various modifica-
tions of this process, all depending on the action of
light causing the gelatin to become insoluble. For
details of these processes other works should be
consulted.
In collotype, advantage is taken of the fact, pre-

viously mentioned, that when bichromatized gelatin

is acted upon by light, it loses its tendency to absorb
water and become tacky. After printing under
the negative, the sheet of gelatin is fixed on the
press and kept moist. Where the light has acted,
the surface takes bhe ink in proportion to the
amount of light that has fallen upon it. Several
other processes depend upon this selective action of
the gelatin as regards greasy ink.
8
 —

114 ASPHALTUM.

G-lue, fish-glue, size, and isinglass are all forms of

gelatin. They are colloids i.e., they will absorb
water to an indefinite extent, but do not pass
through animal membranes, such as bladder, as a
solution of salt, sugar, or other crystalloid substances
would do. For photographic purposes, gelatin
should contain ash —
little not more than about 3
per cent. — should take up from five to ten times its

weight of water when soaked in the cold, and suf-

ficient to dissolve it on warming to 85° F.

In the common line-engraving process, asphaltum
is generally used as the sensitive substance. This
asphaltum or bitumen is obtained from deposits of
pitch in different parts of the world. In has a pecu-
liar smell,and resembles the heavier portion of gas
tar. It is partly soluble in alcohol and ether, more
so in benzene and essential oils, and dissolves com-
pletely in chloroform, carbon bisulphide, and mineral
oils. Caustic alkalies dissolve it ; hot sulphuric
acid dissolves and decomposes it, but nitric acid is

without action upon it. Asphaltum is sensitive to

and is obtained in best condition by exhausting
light,

with ether, the insoluble portion being dissolved in

benzene. A plate is coated with a varnish of this
material, and exposed under a negative or
to light
transparency, being developedwith a mixture of
benzene and turpentine, which dissolves off the
bitumen that has not been rendered insoluble by
light. The plate is then etched and treated in
various ways.
 LISHT FILTERS. 115

CHAPTER XL
Gkthoohkomatism.

Light 'does not affect an ordinary gelatino-bromide

emulsion in the same manner as it does the eye.
The latter is most sensitive to the yellow of the
spectrum in the neighbourhood of the sodium or D
line, but the violet and ultra-violet part of the

spectrum has the greatest effect on a gelatino-

bromide film. To remedy this defect, yellow or
yellow-orange light-filters are introduced, either in
front of the lens, or between the lens and the
plate. The effect of this is to cut off the violet
end of the spectrum to a greater or less extent.
The author has investigated a large number of these
filters, and has found considerable variations in their

absorptive powers. As a general rule, the gelatin

or collodion filters should be avoided, as the colour-
ing matter in this form has a great tendency to
fade. The filter should consist of a cell filled with a
standard coloured solution, which should be renewed
from time -to time. The question of what filter to
employ is a very difficult one, as the action depends
116 SENSITIZERS FOE DIFFERENT EATS.

SO largely on the strength of the light. It is un-

fortunate that no standard light-filters have yet been
fixed upon for iso-chromatic work, although several
dry-plate makers have introduced light-filters which
are eminently satisfactory.
In addition to this means of modifying the light
before reachiag the plate, it has been found that
certain organic dyes have an important influence
on the absorptive power of the silver salt for
the different parts of the spectrum. The undyed
gelatino-bromide plate is most affected by the
blue rays, the action of the green and red on the
plate being very small in comparison. In a
plate dyed with ammoniacal eosin, the action,
although stni greatest in the blue and about the
same in the violet, extends right up to the yellow-
green, falling away rapidly, however, at this point.
Ammoniacal erythrosin renders the action com-
paratively uniform from the green-blue to the end
of the visible violet. In the green-blue there is a
rapid falling-off, as is the case with eosin, followed
by a rise in the green, the maximum action being
reached in the yellow instead of the yellow-green
as with eosin, and the action extends with lessen-
ing effect right through the orange. Ammoniacal
rose Bengal gives a very similar effect, but the
maximum is in the yellow-orange and extends
further into the red. Ammoniacal cyanin has its

maximum effect in the red.

Speaking generally, rose Bengal is the best sen-
 COLOUE SENSITIZERS. llY

sitizer for the yellow-green, and cyanin for the red.

A solution of one part of the dye in ten thousand
of water is a convenient strength to use, one part
of ammonia being added to each hundred parts of
water or alcohol. After soaking the plates for two
minutes in the solution of the dye, they are washed
to remove the excess of dye, and dried before
exposure. As a rule, orthochromatic plates lose
their sensitiveness and go wrong more rapidly than
ordinary plates, and should be used as soon as
possible after manufacture. They tend also to fog
if forced in development. These drawbacks, how-
ever, are, as a rule, insignificant compared with the
advantages gained in colour correctness, and it is
only under trying conditions, such as long storage,
that these defects interfere seriously with the use of
the plates. The brands of colour-sensitized plates
now in the market have reached great perfection and
possess better keeping properties than the early
orthochromatic plates.
Goerulein, alizarin blue, and other dyes are used
as sensitizers for the red, besides those mentioned.
118 CHEMICAL PURITY.

CHAPTER XII.

Impurities and Substances that Alter in the Air.

It is extremely probable that no substance has ever

been obtained chemically pure. No one who has not
occupied himself in chemical research, or read the
memoirs of those who have done so, can have any idea
of the almost insuperable difficulties to be encountered
in obtaining a substance in a state of purity. In fact,

the word " pure " as applied to chemicals is entirely

comparative. It is impossible to obtain pure water,
for instance, in glass vessels and in the air, as the
water attacks and dissolves out the alkali from the
glass on the one hand, and dissolves air on the other.
Distillation in platinum vessels in a vacuum is the
only method of obtaining water in the pure state,
and then the purity is probably far from absol-.
ute. Consequently, "pure" in a chemical dealer's
list means freedom from any gross impurity. For
many purposes the ." commercial " variety of chemi-
cal answers quite as well for photographic pur-
poses as the "pure," but there are instances in
which it is necessary to guard against some par-
 ;

IMPURITIES IN WATEE. 119

ticular impurity, and these cases are indicated

below.
Water, as ordinarily supplied from the tap or the
well, is avery impure material. Apart from actual
suspended matter, well or spring water contains
varying quantities of carbonate and sulphate of lime
and magnesia, phosphates, nitrates, chlorides —
generally of sodium —
and a certain quantity of
ammonia. Surface water usually contains more
ammonia, not much lime and magnesia, but a certain
quantity of peaty matter. Eain water is fairly pure
unless the roof from which it is collected is
particularly dirty. Occasionally a water contains
iron, and there are rarer impurities which need not
be considered here. The worst impurity from a
photographic point of view is chloride, whicii reacts
with silver nitrate to form insoluble silver chloride
excess of lime or magnesia is often objectionable,
particularly where oxalates are used, as insoluble
oxalates of lime and magnesia are formed ; ircjn is, of

course, fatal, but does not often occur ;

peaty matter
is objectionable, as it stains printing papers.
All
these impurities maybe removed by distilling the
water, rejecting the first pint that comes over, as it
contains nearly all the ammonia. Boiling is sufficient

to precipitate the carbonates of lime and magnesia,

or temporary hardness; but the sulphates, or per-
manent hardness, still remain.
Commercial sulphuric acid contains lead and
other impurities. Acid of good quality is so cheap
 — !

120 IMPUEITIBS IN ACIDS AND ALKALIES.

that it should be used for all photographic purposes.

It should not be exposed to the air, as it absorbs
water rapidly and in diluting, the strong acid should
;

always be added to the water instead of vice versd,

as great heat is developed.
Commercial hydrochloric acid or muriatic acid
invariably contains iron. Photographers should avoid
an acid that shows any trace of yellow.
Alkalies, whether caustic or carbonate, contain
various impurities. It is well to filter the solutions,
when making up concentrated developers, etc.,

through a plug of asbestos or glass wool, or to allow

the solution to stand and decant off the clear portion.
Alkalies act strongly on the glass of the bottles con-
taining them, and a clear solution generally has a
deposit at the bottom after awhile. Alkalies should
never be kept in stoppered bottles, as the stoppers"
become hopelessly fixed after a short time.
Cyanide of potassium deteriorates somewhat
,

rapidly owing to the carbonic acid of the air turning

out the prussic (hydrocyanic) acid. Old cyanide
should never be used, as it probably contains
nothing but carbonate. See that the cyanide you
buy has not been in the shop for a long time
Sulphocyanide is very hygroscopic i.e., it absorbs
water from the air. For this reason it is best to
convert it into, say, a 10°/^, solution as soon as
possible after purchasing.
Sulphites and bisulphites should be kept in
stoppered or well-corked bottles, which should not
 IMPURITIES IN IRON SALTS. 121

have a large air space above the crystals, as the air

oxidizes them rapidly to sulphates, in which condition
they are useless to the photographer.
Thiosulphate ("hypo.") as usually sold is pure
enough for the photographer's purposes. When
making up a solution, care should be taken to
neutralize any acidity with a little ammonia or
sodium bicarbonate. Thiosulphate solutions oxidize
readily in the air, and fixing baths become acid on
keeping. (See also p. 73.)
Ferrous sulphate contains more or less ferric salt,
due to oxidation, and any crystals that show a
yellow or brownish tinge should be picked out and
thrown away. Some chemists keep pieces of
metallic iron at the bottom of fheir solutions of
ferrous sulphate, but a better plan is to fill a number
of small bottles quite full, cork them, melt up some
parafBn candle ends, and dip the tops of the bottles
into the paraffin for a few moments. In this con-
dition the contents of the bottles can be kept from
the air until required. If the ferrous sulphate
solution be put into a large bottle, air is admitted
every time the stopper is taken out, and the air
space above the solution gets larger as the material
is used, so that deterioration goes on at an
increasingly rapid pace.
Ferric chloride nearly always contains free
hydrochloric acid, and sometimes ferrous chloride,
but this is not usual. For etching purposes the
presence of free hydrochloric acid is an advantage,
 —

122 IMPURITIES IN SILVER AND GOLD.

SO long as there is not too much of it. Neutral or

nearly neutral ferric chloride has a tendency to
deposit basic salts i.e., compounds of oxide and
chloride —and this should be guarded against. If too
acid, the resist may come away from the plate when
etching. Only experience can tell the etcher when
his bath is in the right condition. If it shows a
tendency to deposit, a little hydrochloric acid should
be added if too acid,
; it is well to add a little ferric

hydrate, kept for the purpose and made by adding

ammonia to ferric chloride solution, allowing the jelly
to settle as far as it will, decanting off the clear
portion, adding hot water, and again decanting.
Silver nitrate is generally pure, but does occasion-
ally contain copper, which can be detected by the
colour of the solution. It is necessary to keep all
silver salts from the light, as they darken and spoil.
G-old chloride, as obtained commercially, contains
hydrochloric acid, which requires to be neutralized
with a little chalk or whitening. Instead of the
pure salt, the double chlorides of gold with sodium
or potassium are often sold. These are quite as
convenient for photographic purposes as the pure
chloride, and so long as the photographer gets his
proper quantity of metallic gold, it is of no conse-
quence whether it is in the form of pure chloride
or not.
 —

RECOVERING SILVER. 123

CHAPTEE XIII.

Recovery of Residues.

The waste gold, silver, and platinum salts contained

in used up fixing- and toning-baths, spoilt sensitized
paper, etc., are often saved and treated for the
recovery of the metals. It is rarely worth the
while of an amateur to trouble about saving his
residues unless he works on a very large scale, but
it is a matter that should not be neglected by the
professional photographer. The fixing-baths, satu-
rated with the double thiosulphate of and silver
sodium, are most worth Every five
attention.
ounces of " hypo." is capable of taking up about two
ounces of silver, and although the saturation point is
never reached ia ordinary practice, yet fixing-baths
that have had a large number of plates and papers
passed through them do contain a considerable pro-
portion of silver. The old fixing-baths are thrown
into a tub with a solution of " liver of sulphur "
a complicated mixture of sulphides and other things
obtained by fusing sulphur writh potassium carbonate
—which precipitates the silver as sulphide. When
the tub is nearly full, a sample should be taken in
a test-tube" or small vessel, and a few drops of liver
of sulphur solution should be added to it. If no
 ;

124 SILVIR AND GOLD RESIDUES.

precipitate forms, all the silver has been deposited

if the liquid turns brown, more liver of sulphur must
be added to the tub. When' the deposit has quite
settled, the clear portion of , the liquid should be
drawn off through a tap in the side about a foot
from the bottom. In time the sludge of silver
sulphide will reach the level of the tap, when
the cask should be emptied by running it out
through a hole at the bottom, closed in the ordinary
way by a wooden plug. Underneath the hole at
the bottom of the cask, a large glass funnel con-
taining a rag or filter should be placed, and the
sludge shoilld be run on to this the liquid portion
:

filters through, leaving the solid silver sulphide on

the filter. It should be allowed to dry and then be

labelled " sUver sulphide," and sent to a refinery to
be reduced.
Scraps of sensitized paper, gelatino-chloride,
bromide, and other papers should be burnt to an
ash, and forwarded to the refiner.
Toning-baths are treated with solution of ferrous
sulphate, which reduces the gold to' the metallic
state.
The reduction of the silver is performed at the
refiner's by fusing the sulphide, etc., with red lead,
etc. ; the resulting button of lead contains all the
silver. The button is heated on a cupel or dish of
bone-ash in a current of air. The lead is oxidized
to litharge (PbO), which sinks into the cupel, leaving
the silver behind.
 CELLULOSE AND VISCOSE. 125

GHAPTEK XIV.

Cellulose.

Cellulose is the essential constituent of all the

hard parts of plants, and its usefulness to mankjnd
in general, and to the photographer in particular, is
almost unlimited. Jute, hemp, paper, linen, cotton,
etc., are more or less pure forms of cellulose.
all

Schleicher and SchuU's filter-paper is pure cellulose,

whilst cotton-wool and ordinary blotting-paper con-
tain very little foreign matter. Pyroxylin, or gun
cotton, is a nitrate of cellulose, and collodion is made
by dissolving this in suitable solvents. Cellulose
belongs to a large family, which, besides several
closely allied forms of cellulose itself, iiicludes starch,
cane-sugar, grape-sugar, dextrin, and other bodies.
They are all known in chemistry as carbo-hydrates,
because they contain carbon and
hydrogen and
oxygen in the proportion form water. Although
to
their percentage composition has been known
accurately enough for some time, the actual way in
which they are built up is still being worked out, and
although the materials out of which they are built
126 WILLESDEN PAPER.

are so simple, the actual structure is very com-

plicated. Cellulose, for example, is generally
written (CgH^„Og) which means that chemists do
not yet know how many CgHi^Og's go to make up a
complete molecule of cellulose. The same is true of
starch and dextrin.
Cellulose is soluble in strong sulphuric acid, being
converted into glucose or grape sugar, but if paper
be passed through dilute sulphuric acid of specific
gravity, 1'5, it is parchmentized. Copper sulphate
precipitated as hydrate of copper by ammonia solu-
tion, and dissolved in excess of the latter, forms the
usual solvent for cellulose. Advantage is taken of
this solubility incuprammonia solution in the manu-
facture of "Willesden" paper. Thick paper is
treated with the solution, which gelatinizes the
surface, rendering it more resistent and waterproof.
For roofing and similar purposes, two or three sheets
of the paper are cemented together by the solution.
Strong alkalies and zinc chloride disintegrate cellulose
after a short time, but alkali of moderate strength,
such as 15 per cent, solution of caustic soda, com-
bines to form alkali-cellulose, adding considerably to
the strength of the material.
This treatment with 15 per cent, alkali is known
as " mercerizing." About seven years ago, Messrs
Cross and Bevan discovered that if this mercerized
cellulose be treated with carbon bisulphide, a
soluble xanthate of cellulose is produced. This
compound, which the inventors term " viscose," has
 PYROXYLIN. 127

almost endless applications, many of which are of

great interest to photographers, the important point
about it being that from its solution in water, the
cellulose can be recovered almost chemically pure.
The solid "viscoid," made by coagulating viscose,
closely resembles " celluloid " (see below), and can
replace it for many purposes, having the advantage
of being practically uninflammable.
By treating cotton-wool with nitric acid, various
nitrates are formed. To secure good results it is

necessary to have the nitric acid perfectly dry. As

this is difficult to obtain in practice, a mixture of
nitric and sulphuric acids is used, which produces
the same effect as if perfectly dry nitric acid alone
were employed. Three fluid ounces of nitric acid
(sp. 1429) are mixed with two fluid ounces of
gr.

water in a large beaker-flask, and nine fluid ounces

of strong sulphuric acid (sp. gr. 1839) are run into
the mixture with constant shaking round. One
hundred grains of dry cotton-wool divided into
about ten pieces are dropped into the solution when
its temperature has fallen to 150° F., and allowed to

remain for 7 or 8 minutes, when the acid is drained

off, the cotton being squeezed with a glass rod to

squeeze out as much acid as possible. It is necessary

to wash the cotton thoroughly remove every trace
to
of acid, when it may be dried in the air. This gun
cotton, or pyroxylin as it is often called, is soluble
in a mixture of alcohol and ether, but they
must neither of them be methylated. The follow-
 —

128 CELLULOID.

ing are convenient proportions for making plain

collodion :

Pyroxylin,
 COLOPHONY AND LAC RESINS. 129

CHAPTER XV.

EESINS, VARNISHES, ETC.

The resins form a large class of complicated organic

substances, found principally as exudations from
trees in nearly all parts of the world. They are
soluble as a rule in alcohol, ether, and benzene, but
are insoluble in water.Photographers use them in
making varnishes and in laying a dust ground
in photogravure. The resins of most importance in
this connection are colophony or common resin, lac,
mastic, dammar, sandarac, dragon's blood, anime,
copal, amber, caoutchouc, and gutta-percha.
Colophony varies in colour from pale yellow to
dark red-brown, and is soluble in nearly all organic
solvents and in hot linseed oil. Heated with caustic
soda or potash it forms a resinate, which is an.
important constituent of yellow soap. Specific
gravity, 1'07.
Lac resin owes its red colour to the insects whose
bite causes the resin toexude from the tree. The
most convenient variety to use is "shellac."
9
 -

130 MASTIC.

The specific gravity of the resin is about 1'12,

and it is soluble in all the usual solvents, and in
dilute hydrochloric and acetic acids, and in caustic
alkalies. By treatment with chlorine, bleached lac is

made. After bleaching, it should be kept under

water, being dried shortly before use, as exposure
to the air soon renders it insoluble. The fieshly
bleached lac forms a nearly colourless solution in
alcohol, and is soluble in a hot solution of borax
and in sodium carbonate. In a mixture of the last
two solvents, it forms a water varuish, sometimes
used for negatives, etc. An excellent waterproof
ink can be made by rubbing up Indian ink with a
solution of lac in borax (water, 1 oz. borax, 130 ;

grains; freshly bleachedlac, 100 grains; sodium

carbonate, 6 grains). Ordinary alcohol contains at
least 5 per cent, of water, and as the alcohol
evaporates in the cold faster than the water, the
latter is left behind, dulling the surface of the lac.

If heat be applied, however, the alcohol and water

are driven off together, leaving a bright surface.
This difficulty is not met with if the lac or other
resin be dissolved in chloroform or benzene, which
can be used cold.
Mastic occurs in pale yellow, transparent " tears," is

and sweet-smelling, melting at about 226°

brittle F.
Alcohol or warm acetone dissolves it freely, and it

is partly soluble in hot linseed oil, precipitating

slightly on cooling. Specific gravity, 1-07.
Sandarac somewhat resembles mastic. It has a
 VAEIOUS EESINS. 131

specific gravity of 1'04, and dissolves readily in the

usual solvents, including hot linseed oil.

Dragon's blood. — It dissolves in most of the usual

solvents and in caustic soda and glacial acetic acid,
but is in petroleum ether (benzine or
insoluble
benzoline), and but sparingly in ether or oil of
turpentine. There is a good deal of variation,
however, in its constitution and properties. It
melts at about 250° F., and has a specific gravity of
1 197. In photography it is used as a resist when
etching metal.
Elemi contains a large proportion (12^ per cent.)
of volatileoil, is pale yellow in colour, and of various

origin. It is very fusible, and is used to give tough-

ness to lacquers and varnishes. Elemi is often
adulterated, or a factitious product, consisting of
colophony, Canada balsam, and essential oils, is

substituted for it. The fraud may be detected by

heating, when, after a short time, the turpentiny
smell of the common resin is unmistakable.
Dammar is not very soluble in alcohol, more so
in ether, and completely so in j)il of turpentine,
petroleum ether, etc. ; it dissolves also, in hot or
cold solutions sodium carbonate.
of Its specific
gravity is about 1-05. Kauri gum is another form
of dammara resin.
Anime and copal are obtained from various
sources, some of them fossil, the latter being highly
'

prized. Hard copal is light-brown in colour and

makes excellent varnish. Its- specific gravity is
132 RESINS, BALSAMS, AND INDIA-EUBBEE.

generally between 1'06 and 1'07. Before being

heated, copal is insoluble in alcohol, and only slightly
soluble- in ether or oil of turpentine. On heating,
however, gases are given off, and the residue dissolves
readily in ether and oil of turpentine.
Amber is insoluble in alcohol, essential oils, and
in acids, with the exception of sulphuric acid. The
specific gravity of amber varies from 1:05 to I'lO, and
its melting-point is 550° F. Like copal, it is changed
by heat, and is then soluble in alcohol and turpentiue
oil.

The balsams are resins containing varying pro-

portions of essential oils and similar substances.
Jkaong these oleo-resins, Canada balsam is of
importance to photographers. It is a pale yellow,
transparent material, which forms a beautifully
jclear^ glassy varnish. Canada balsam dissolves in
benzol or chloroform, and is much used in this state
as a medium mounting microscopic objects.
for
Caoutchouc, or india-rubber and gutta-percha, are
pfteu; but they are quite different sub-
confused,
stances. Caoutchouc is a complicated body containing
several different chemical substances, and varies a good
deal in its properties according to its place of origin.
It is soluble in coal-tar naphtha, ether, chloroform,
bisulphide of carbon, benzene, and oil of turpentine.
Its principal use in photography, besides india-rubber
tubing, vulcanite dishes, etc, is for safe edging
pla.tes. , , combines with caoutchouc, the
Sulphur .

product-r-vulcariite— being insoluble in any solvent,

 OILS AND SOAPS. 133"

not affected by heat or cold, much more elastic than

caoutchouc, and generally more permanent.
As this is a somewhat miscellaneous chapterv it is,

convenient here to say a few words about oils and

solvents. Gils may be divided into mineral oils,

fixed oils, and essential oils. Essential oils nearly'

all possess the formula Cj^Hjg; they are very
volatile and possess strong odours, which are some-
times due, however, to the preseuee of other volatile
materials, such as cinnamic aldehyde in oil of
cassia, benzoic aldehyde in oil of almonds, etc; Oils
of turpentine, lavender, cloves,- peppermfint, etc., are
examples of essential oils. They possess strong
solvent powers, especially on resins;
The fixed oils are of -vegetable and animal origin,
and consist principally of mixtures in varying pro-
portions of oleic, palmitic, stearic, and similar acids
combined with glycerin. Alkalies combine with
the acids, setting free the glycerin, and this is what
happens when soap is made, soap being oledte';

palmitate, stearate, etc., of soda or potash.

The drying oils contain linolic and linoleic acids,
which are acted upon rapidly by oxygen if exposed
to the air, a skin being formed which acts as an
excellent waterproof varnish. Advantage of this
property of drying oils is taken in mixing paints;
it is not the colouring matter of the paint but the
drying oil that aiffords the protecting- surface:
Lead salts assist this drying action, and a white or
red lead paint dries very rapidly and forms an
134 SOLVENTS.

excellent protection against weather. The principal

drying oil is linseed ; the following oils, however,
possess drying properties to a less extent: hemp,
walnut, poppy, and sunflower.
Castile soap should be. made from pure olive oil.

Once upon a time Marseilles soap was made from

olive oil, and some of it may be still, but the greater
portion of the Marseilles soap in the market is made
from all kinds of oils.

Beeswax is the principal wax employed, but it is

adulterated with paraffin, Carnauba wax, and Japan

wax. Paraf&n is used largely as an adulterant,
and may be detected by treating the wax with oil
of turpentine, which dissolves the beeswax and
leaves the paraffin.
As regards solvents,, two of importance are fre-
quently confused : benzene and heuzine are quite
different bodies. The
latter is light petroleum oil,
sometimes called petroleum ether, whilst the former
is the active constituent of coal-tar naphtha. Crude
paraffin or petroleum oil contains a whole series of
bodies known as paraffins, the lowest of which are
gases —marsh gas (CHJ, ethane (C^Hg), propane
(CgHg), butane (C^Hj^) —
then come volatile liquids,
beginning with pentane (C5HJ2), each member of the
paraffin series differing from the- next by CHj, then
the burning oils, then the heavy oils solar distil-
, —
lates, used for enriching water gas then the —
vaselines, then the lubricating oils, and at last solid
paraffins or paraffin wax. Benzine or benzolLae
 ALCOHOL AND ETHER. 135

consists of the paraffins following and including

pen tans; all the liquid paraffins, however, possess
strong solvent powers for grease, resins, and many
other substances.
Benzene is obtained by refining light coal-tar oil,
and is perhaps the most important compound known
to chemists. It contains six atoms of hydrogen
united to six atoms of carbon, and acts in all its
properties and derivatives as if it were joined into
a six-sided ring, as shown on page 57. It is some-
times called benzole.
may be considered as marsh gas (CH^)
Chloroform
in which 3 H's have been replaced by 3 Cl's, its
formula being CHClg. It possesses great solvent
powers, especially for fats.

By meant ethyl alcohol. The alcohols

alcohol is
form a series in the same way as do the paraffins,
being derivatives of the paraffins. For example,
ethane, by a round-about chemical process, can be
converted into ethylic alcohol, thus:
Ethane. Ethylic iodide. Ethylio alcohol.
CHs.CHg CH3.CH2I CH3.UH2OH.
From ethylic alcohol, ethylic ether or " ether " can
be obtained by removing a molecule of water with
sulphuric acid,

Ethylic alcohol.
 —

136 SOLVENTS AND VARNISHES.

By oxidation, alcohol is converted into aldehyde

(CH3.COH), and by further oxidation into acetic acid
(CH3.COOH).
From acetic acid another solvent, acetone
(CH3.CO.CH3) is obtained. It is a powerful solvent
of most organic substances.
Methylated spirit has crude wood spirit added to
it for the purpose of making it undrinkable, so that
the material, as sold, contains ethylic and methylic
alcohols, besides acetone and various resinous
materials.
It is interesting to note that pure methylic
alcohol is the lowest of the series, being based on
marsh gas (CH^) in the same way that ethylic
alcohol is based on the next member of the series,
ethane. By similar treatment to that given above,
methylic alcohol, methylic aldehyde, or formic alde^
hyde as it is usually called, and formic acid are
obtained.
Carbon bisulphide is a compound of carbon and
sulphur (CSj). It is used principally as a solvent
for india-rubber.
The following are useful formulae for varnishes :

Amber Varnish iAhney).

Fused amber (powdered), . . 1 part.

Chloroform, . . . . .16 parts.

May be used cold for plates or prints."

 . —

VARNISHES. 137

Collodion Varnish, {Gamble).

Pyroxylin, ...
Ether (methylated), .
2 grains,
50 c.c, .
100
5 ozs.
grains.

Alcohol (methylated), . 50 ,, . 5 „
Castor oil, . . . 0'3 „ . 16 minims.

Dammar,
Benzole,
.....
Varnish for Collodion Lantern Plates (Pliotogram).

..... 20
1 part.
parts.
This varnish can be used cold.

Lac Varnish (Cooley).

Seed Lac or Shellac,

Kectified spirit, .
...
. . . 20
4 parts.
,,

Clear Mastic, Varnish (Photogram).

Mastic, . . . . . .14 ozs.
Canada balsam, . . . . 2 ,,

Sandarac, . . . . . 6 ,,

Oil of turpentine, . . . . 44 „
Shake, and stand till clear ; filter.

The mastic, sandarac, and turpentine oil must be

dry. The longer it is left before use the better.

Gold- Coloured Lac Varnish {Cooley).

Ground turmeric, . . . . |^ lb.

Eectified spirit, . . . .1 gall.

Macerate for a week, strain, and squeeze off, and add

Gamboge,,
Pale shellac,
Sandarac,
.....-If
.

.
.

. .
. .

•
.

6
f oz.
ozs.
lbs.

When dissolved, strain, and add further of turpentine

mastic varniah (last formula), 1 -pint.
 —

138 VARNISHES.

This varnish is suitable for picture frames, brass

and other metal work. The colour can be altered
as desired by varying the constituents. By substi-
tuting dragon's blood for gamboge, a deep gold-
coloured varnish is obtained. It is a good plan to
keep the colouring matters separate in concentrated
solutions, and add them as required.
By using annotta instead of turmeric, and dragon's
blood instead of gamboge, a red varnish, suitable
for wood, is obtained.

Ordinary Spirit Varnishes {Thorpe).

Brown hard
I.

Sandarac,
Pale shellac,
.....
. . . . .
3
2
lbs.
„
Methylated spirit, . . . . 2 galls.

Dissolve and add 1 quart turpentine mastic varnish.

Agitate well, strain through gauze, and after one month
decant off clear portion.

White hard—
II.

Sandarac, ......2 5 lbs.

Camphor,
Pounded glass,
Methylated spirit,
.

...
.

...
. .

.3
.7
ozs.
lbs.
quarts.

Dissolve, and, when strained, add 1 quart pale Canada

balsam.

All the above are "spirit" varnishes. An "oil

varnish" contains a drying oil in addition to the
 —

VARNISHES. . 139

resin and other constituents. The following is a

good oil varnish suitable for wood-work, etc.

Pale hard copal, . . . .2 lbs.

Fuse and add-

Hot- boiled linseed oil, . . . l«piiit.

Boil until stringy, and thin with about 3 pints oil of

turpentine.
 t

140 CYCLOPEDIC INDEX.

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 CYCLOPEDIC- INDEX. 141

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 "

142 CYCLOPEDIC INDEX.

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 CYCLOP^.DIO INDEX. 143

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144 CYCLOPAEDIC INDEX.

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146 CYCLOPAEDIC INDEX.

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 CYCLOPEDIC INDEX. 147

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150 CYCLOP^CDIC INDEX.

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152 CYCLOPAEDIC INDEX.

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 ;

CYCLOPEDIC INDEX. . 153

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154 CYCLOPAEDIC INDEX.

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 CYCLOPAEDIC INDEX. 155

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156 CYCLOPEDIC INDEX.

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 GYGhOPMmC INDEX. 157

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158 CYCLOP JiDIC INDEX.

1
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1
1
WRATTEN &
WAINWRIGHT'S
L0NB0N"
PLATES.
SINCE 1877 the "LONDON" Plates have been known through-
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: for the
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WRITTEN & WHINWRIGHT,

CROYDON, SURREY.
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Commercial Photography. (No. 48 Photo-Miniature Series), Postage 2d. 6

HISTORY, CHEMISTRY, OPTICS.

Photography; Its History. Processes, Apparatus and Materials.
By A. Brothers. New Edition. Postoge6d ... 21
Ohamlstry for Photographers. By Charles F. Townsend, F.C.S.,
F.R.P.S. Illustrated. CONTENTS — Introduction— Chemistry
generally and the Chemistry of the Silver Salts in particular Chemis- —
try of the Photographic Image— Developers Reversal— Reduction, —
—
Intensification, etc.—Printing in Silver Printing in Salts of Iron-
Printing in Platinum—The Bichromate Printing Processes— Ortho-
—
ohromatism Impurities and Substances that Alter in the Air Reco- —
— —
very of Residues Cellulose Resins, Varnishes, etc.- Cyclopaedic
Index. 3rd Edition. Cloth. Postage 3d. ... ... ... 1
Ution of Light In Photography. By Capt. Abney. Illustrated.
Postage 3d. ... ... ... ... ... ... 3 6
First Book of the Lens. By C. Welborne Piper. Postage 3d. ... 2 8
The Lens. A Practical Guide to the Choice, Use, and Testing of Photo-
graphic Objectives. Edited by Geo, E. Brown, F.I.C. (Joint Editor.
of The Piuitogram), and with a chapter by Thomas Bolas, F.I.C.
Postage 3d.; ... ... ... ... ... ... 2 6
Lons Work for Amateurs. By Henry Orford. Profusely illustrated.
Cloth. Postage 3d. ... ... ... ..; 3
Photographic Lenses. Hon to Choose and Hon to Use. By John
A. Hodges. Illustrated. . Cloth, Postage 2jd. ... ... ... 2
Photographic Lenses. A simple treatise by Conrad Beck and Herbert
Andrews. 2nd Edition. Postage 3d. ... ... ... 1
Photographic Optics. By Qtto Lummer. Translated by Silvanus P.
Thompson. Postage 4a. ... ... ... ... ... 6
Photographic Optics, a Treatise on. By R. S. Cole. Illustrated.
Cloth. Postage 4d. ... ... ... ... ... 6
The Optics of Photography and Photographic Lenses. By J. Traill
Taylor. Many Diagrams. Cloth. Postage 3d. ... ... 3 6
Optics for Photographers. By W. K. Burton. Illustrated. Postage 2d. 1
Blomentary Telephotography. By Ernest Marriage. Illustrated.
Postage 4d. ... ... ... ... ... ... 3 6
Tables of Conjugate Foci. For the Users of Photographic Lenses.
Compiled and Explained by J. R. Gotz, F.R.P.S. 2nd Edition.
Postage id. ... ... ... ... ... ... 6
The Camera and ItsAppurtenances. By H. J. Masse. Postage id. 6
Btenopalc or Pinhole Photography. With exposures and other
Tables. By Frederick Wm. Mills, F.R.M.S., and Archibald C.
Ponton. Illustrated. Cloth, 1/6. Postage 2d. Paper ... ... I Q
The Photogram Lens-Testing Chart. Large Size (20 by 30) on heavy
surfaced paper. An invaluable test-object for anyone who wishes to
compare the performance of various Lenses. This Chart is four
times the size of the one given with the January (1897) issue of the
("kotogmmf and is on superior paper, Post free, m Roll, 1/3 •••
t
 12

eXPOSURB. LANDSCAPE WORK, 8NAP-

SHOTTINQ, ARCHITECTURE, PORTRAITURE.&O,
The Photographer's Exposure Book and Tables. Compiled by F.
W. Mills. 2nd Edition. With Pencil. Postage id.
The Photographer's Systematic Exposure Book. Postage id.

Wheeler's Exposure Register and Tables. i6th Edition. Postage id.

The Amateur Photographer's Ready Reckoner. Being Exposure
Tables by Vi». Second Edition. Postage id. ...
Peerless Exposure Notebook. Edited by George E. Brown, F.I.C,
(Joint Editor of The Photogram.) Postage id. ...
Photography by Rule. ByJ. Sterry. Postage 2d.
Picture Making by Photography. By H. P. Robinson, Cloth.
Postage 3d.
Art Photography. By H. P. Robinson. Full page plates. Cloth.
Postage 2d.
Practical Essays on Art. By John Burnet, i. Composition. 2.
Light and Shade. 3. The Education of the Eye. Profusely Illus-
trated. Cloth. Postage 4d.
Pictorial EfTect in Photography. By H. P. Robinson. Illustrated,
Cloth. Postage 3d,
Letters on Landscape Photography. By H. P. Robinson, Illustrated.
Postage id.
Studies in Photography. By John Andrews, B.A. Collotype Illustra-
tions, Cloth. Postage 3d,,,.

Practical Pictorial Photography. Part I, By A. Horsley Hinton.

Illustrated, Postage 2d,
Do. do. do. Part II, Postage 2d, ...

Do. do. do. The two

Hand- parts combined, in
some Cloth, Gilt lettered. Postage 3d, .,. ... ,„

Photography Outdoors. No, 4 Photo-Miniature Series, Postage ijd.

Hand Camera Photography. By Walter Kilbey. Fully illustrated.
Cloth 2s, Postage 2d.
The Hand Camera and How to Use it. By W, D. Welford. Postage id.
Hand Camera Work. (No, 3 Photo-Miniature Series), Postage ijd. ,.,

Drop Shutter Photography. By F. W. Filditch. Illustrated, Postage id,

Instantaneous Photography. By Capt, W. de W, Abney. Illustrated.
Postage 2d, .,. ,., ... ,,. .„

Photography* and Architecture. By E. MacDowel Kosgrove, M,D„

F R.C.P.S, Postage id. ...

Exterior and Interior Photography. By Frederick Wm. Mills,

F.R.M.S. CONTENTS— Apparatus— Light and Colour— Exposures
— —
of Interiors Exposures of Exteriors Development Intensifioatio'a —
of Negatives, etc—The Platinotype Processes Bromide Printing- —
Autotype Printing— Printing on Gelatino-Chloride Paper Mountmg —
Prints—Appendix, Illustrated. Postage 3d. ... ... ,., 3 g
Architectural Photography. By C. A, T, Middleton. Postage 2d, ... j
Indoor Photography. By Bertha M. Lothrop. Postage id. .,. g g
The Studio and What to Do in It. By H. P. Robmson. Cloth,
Illustrated. Postage 3d. .,. ... .„ ,„ ,„ j g
The Photographic Studio. A guide to its construction, etc. By T,
Bolas. Postage 3d. ... ' ... ... ... ,„ 2 g
 18

Tha Uiktlni in Phototrapblc Btndloi. By P. C, Duchochois. Re-

vised, withadditianalmatterbyW.EthelbertHenry,C.E. Postageip. 1

lltiltio Lighting. By James Inglis. Postage 2d.... ... ... 2 6

Tbe Foie in Portialtare. No 2 Photo Miniature. Postage id. ... 6
Photography at Home. No 8 Plioto Miniature Series. Postage ijd. ... Q 6
Home Portraltnra. By Ricliard Penlake. Postage 3d. ... ... 2 8
Klomenti o( Btereouoplo Photography. ByC. F, Seymour Rotliwell.
Postage id. ... ... ... ... ... ... 6
tereoiooplo Photography, No s Photo Miniature Series. Postage ijd. 8
taraoieope and Btereoiooplo Photography. From the French of F,
Dtouui. Fully illustrated. Cloth. Postage 3d. ... ... 2
Praotioal Photo-Hlcrography. By Andrew Pringle. New Edition.
Postage 4d. ... ... ... ... ... ... 3 g
Photo-Hlorography. ByJ. H. Jennings. With a chapter on preparing
Bacteria, by Dr. R. L. Maddox. Postage 3d. ... ... ...
3
The A.B.C. of Photo-Hlcrography, A practical handbook for beginners.
By W. H. Wamsley, F.R.M.S., F.A.A.A.S. 135 pages. Illustrated,
Postage 3d. ... ... ^. ... ... ... 5
Hanlpniatloni of the HlcroBCope, By Edward Bausch. Postage 3d. 4 g

THE NEQATIVE.
DeTelopari and Development. By Geo. E. Brown, F.l.C. (Joint
Eihot oi Tht Photogmm). Cloth. Postage 2d. ... ... 1 Q
Daveloperi and Development. No. 11 Photo Miniature. Postage ijd. Q 6
Hegatlve Haklng. By Capt. W. de W. Abney, F.R.S. Postage 3d. ... t
Photography with Emulsions. By Capt, W. de W. Abney, F.R.S.
Postage 3d. ... ... ... ... ... ... 3
Orthoohromatlo Photography, No. 6 Photo Miniature. Postage ijd. 6
The Dark Room, and Its Equipment. By H. J. Masse. Postage id. 6
Finishing the Negative, A handbook of Processes coming between
developing and printing. It treats with great clearness on the drying,
clearing and hardening of negatives what to do with negatives whicti
:

are too thin or too dense, or which are under or over exposed how :

to make hard negatives print soft, and vice versa: how to varnish
ncgetiTM and films how to strip tliem from glass or paper, and
:

transfer them to other supports how to re-touch portrait negatives

:
;

how to improve printing quality technically and artistically: how to

spot and block out negatives :. how to repair cracks or- fractures how ;

to title negatives. A most valuable and complete book explaining

many difficulties, and emphasising its precept and practice in many
illustrations. Edited by George E. Brown (Joint Editor of The
Photogram). 160 pages. Demy 8vo. Cloth. Postage 3d. ... 2 8
Tha Perfeot Negative. By-Rev. F. C. Lambert. Postage 2d. ... 1 g
Wet Collodion Photography. By Chas. W. Gamble. Illustrated.
Postage 2d. ... ... ... ... ... ... |

Art of Retouching Negatives, and Finishing and Colouring Photo-

grams. By Robert Johnson. 11 Plates. Postage 4d. ... - 2
Art Of Retouching. ByJ. Hubert. Cloth. Postage 2d. ... ... f g
Practical Retouching. Including directions for the After-treatment of
the Negative generally. By Drinkwater Butt, F.R.P.S, Illustrated.
Postage 2d. .. ... ... ... ... ... -10
Katouching Negatives and Prints. No. 12 Photo Miniature. Postage
ijd. Q q
 14

PftlNTlNQ FROM THE NEGATIVE.

4rt and Practice of Silver Printing. By H. P. Robinson aud Capt.
W. de W. Abney. Illustrated. Postage 2d; .u ... •>. 2 6
Platinotype : its Preparation and Manipulation. By Capt, Abney
and Lyonel Clark. Postage 3d. ... ... ••• ••• 2 6
Platinum Toning. By Lyonel Clark. Clotb, Postage 2d. ... ... 1

Platinotype Printing. By A. Horsley Hinton. Cloth, Postage 2d. ... 1

Platinotype Processes. No. 7 Photo Miniature. Postage ijd, ... 6

Tlie Gum Bichromate Process. By W. J. Warren. Illustrated.
Postage 2d, ... ... ... ... ... ... 1

Photo-Aquatint, or Gum-Bichromate Process. By A- Maskell and

R. Demachy. Postage 2d. ... ... ... ... ... 1

A.BiC. Guide to Autotype Permanent Photography. By J. R. Sawyer.

With Autotype Frontispiece. Cloth. Postage 3d. ... ... 2 6
Carbon Printing. By E. J. Wall, F.R.P.S. Illustrated. Postage 2d. ... 1 Q
Bromide Printing. By F. C. Lambert, M,A, Postage 2d, ... ,„ 1 Q
Ferric and Heliographic Processes. By G. E. Brown, F.I.C. (Joint
Editor of The Photogram), A handbook of printing with iron salts
for photo^apbers and engineers. How to reproduce tracings and
—
drawings in white lines on blue ground blue lines, black lines, or
brown lines on a white ground. Arranging a blue printing house.
Making the sensitive papers. Six actual specimens are included,
No other book handles this subject so thoroughly and practically,
Postage 3d. 2
Photographic Reprodufstion Processes. By
P. C. Duchochois. A
treatise on Photographic Impressions without silver salts. Postage 3d.
The Blue Print with Variations. No. 10 Photo Miniature Series,
Postage ijd.
Popular Photographic Printing Processes. By Hector Maclean.
Illustrated. Cloth Bound. Postage 3d.
Art of Photographic Painting. By A. H. Bool. Cloth. Postage ijd.
Enamelling and Retouching. By P. Piqueppe, Cloth. Postage 2d,
Kallitype Process, (No. 47 Photo-Miniature Series). Postage lid. ...

Photographlo Colourlst. By J. W. Neville. Cloth. Postage id.

Photo-Ceramlos. Photography appUed io the decoration of Plaques,
Pottery, and other Ceraimc and Metallic Surfaces. Practical direc-
tions for a very fascinating department of photographic work. By
W. Ethelbert Henry, C.E., and H. Snowden Ward. Cloth is. 6d,
Postage 2d. Paper ... ... ... .„ ,„ '|
g

LANTERN HANDBOOKS.
How to Make Lantern Slides. Second Edition. By S. L. Couithurst,
With Additional Matter by Geo, E. Brown (Joint Editor of Tht
Photogram), This book contains full and complete instructions for
the maldng of Lantern Slides by contact or reduction. The printing
in of clouds, intensification, reduction, and the after-treatment 01
slides is fiilly dealt with. Simply expressed and thoroughly practical,
the directions given by the author can be strongly recommended.
Illustrated. Postage 2d. ... ...
.
... ... ... .|
g
Lantern Slide Making. By Rev. F. C. Lambert. Cloth. Postage 2d. \
Lantern Slides: Their Production and Use. By J. Pike. Postage id.
8
Lantern Slides. By A. R, Dresser. Revised by S. Herbert Fry
Postage Id. ... ... ... ... ... ..'
g g
Lantern Slldeil. No, 9 Pboto Miniature Series, Postafp ru - ,
2
 —
16

Hklf-Tone Proceii on the Amerioan Baili. By Wm. Cronenberg,

Postage Sid. ... ... ... ... ." — 2
Photo<raphlo and Photo-Hechanloal Printing Prooeaaei. By W.
K. Burton. Cloth. Postage 4d. ... ... ... ... 4
Zincography. By Josef Bock. Postage 2d. ... ... . 2 6
The Proceii Tear Book, Illustrated. Postage sd. Foreign lod. ... 3 g
A Handbook of Illnitratlon. By A. Horsley Hiaton. With Repro-
ductions from Photqgrams and Sketches by the Author and other
Artists. CONTENTS—Introduction—A Neglected Field—Theory
and Principles of Illustration— Diflerent kinds of Illustration— Repro-
duction by Half-tone Process— Preparation of Originals for Reproduo-^
tlon by Half-tone— Line Process- Methods of Line Reproduction-
—
Materials for Simple Line Drawing Comparison of Line Processes
—Other Methods for Line Reproduction—The Material required
Mechanical and Drawing. Cloth. Postage 4d. ... ... ... 3
Hlnti on Drawing for Process Reproduction. By Charles J. Vine.
Illustrated. Postage id. ... ... ... ... ... I

Photo-Lltbography. By George Fritz, Vici^President o) State Printing

Works, Vienna. Translated by E. J. Wall, Author of "The Dictionary
of Photography,'^ '* Carbon Printing," etc. With a series of examples
of "scraper-boards" and seven- fine and expensive examples of
Photo-Lithography, printed by the State Printing Office, Vienna.
Cloth. Postage 3d. ... ... ... ... ...
3 6
Praotloal Collotype. By A. W, Fithian. Postage 3d. ... ... 2 6
Photo-Hechanloal Prooesaea. By W. T. Wilkinson. Cloth. Postage
3d. ... ... ... ... ... ... ... 6
k Treatise on Photogravnre In Intaglio. By the Talbot Klic Process.
By Herbert Denison, F.R.P.S. Illustrated. Postage 4d. ... ... 4 g
Photogravure. By W. T. Wilkinson. Second Edition. Postage id. ... 1 g

THE PHOTO-MINIATURB.
i Berloa of Practical Handbooks on the varloua branchea of Photo-
graphy. Price Sd. each net, post free 7id.

I, Modern Lenses 2. The Pose In Portraiture

; 3. Hand Camera Work ;
4
Photography Outdoors; 5. Stereoscopic Photography; 6. Orthochrom'atio
Photography; 7. Platinotype Processes; 8. Photography at Home; 0. Lan-
tern Slides; 10. The Blue Print with Variations; 11. Developeisiuid Develop-
ment; IS. Retouching Negatives and Prints; 13; Photogra^ine Flowers an^
Trees; 14. Street Photography; 15. Intensincation and Reduction- 16 Bro-
mide Printing and Enlarging; 17. The Carbon Process; 18. Chemical Notions •

ig. Photographing Children so. Trimming, Mounting and Framing

;
ai! ;

Albumen and Plain Paper Printing; ss. Gum Bichromate Printing; 23.
Photographic Manipulations; S4. Photographing Clouds; 25. Landscape
Photography; 36. Telephotography; 27. Pinhole (Lensless) Photography
S8. Seashore Photography; 29. Flashlight Photography; 30. PhotograpHo
Interiors; 31. Photography at Night 32. Defects in Negatives 33. The Dark
; ;

Room; 34. More about Development; 35. Enlarging Negatives; 36. Lens
Facts and Helps 37. Film Photography 38. Color Photography 39. Photo-
; ;
;
graphing Animals; 40. Platinotype Modifications; 41. Copying Methods' 43
Genre Photography 43. Photograriiic Chemicals 44. Coloring Photographs'.
; ;

45. More About Orthochromatic Photography 46. Development Printine ;

Papers; 47. Kallitype Process; 48. Commercial Photography;

49. Dark Room
Dodges. (Others in Preparation).

MISCELLANEOUS.
Photography for Artists. By Hector MacLean, F.R.S P , FGCS
lUusixated, Postage 3d. ... ... ,.,
'
'' • • • •

vaning Work for Amateur Photographers. By T. c. Henworth

"'
Cloth. Postage 4d. .„ „, ,„ ,