A Chemistry Primer

An introduction for the non-chemist,using analog photography as an example

Chemistry is the scientific discipline involved with elements and scope of its subject, chemistry occupies an intermediate position
compounds composed of atoms, molecules and ions as well as between physics and biology. It is sometimes called the central
their composition,structure,properties,behavior and the changes science because, It provides a foundation for understanding both
fig.1 As of this writing, in 2019, there are they undergo during a reaction with other substances. In the basic and applied scientific disciplines at a fundamental level. For
118 elements known to exist, but only example, chemistry explains aspects of plant chemistry (botany),
a few of them find significant use in the formation of igneous rocks (geology), how atmospheric ozone
silver-based photography. Here, all is formed and how environmental pollutants are degraded (ecol-
are shown in the periodic table of ogy), the properties of the soil on the moon (astrophysics), how
elements,which some scientists refer medications work (pharmacology), and how to collect DNA
ionic
charge +1to as the
+2‘alphabet of the universe’. +1 +2 +3 +4 -3 -2 -1 0 evidence at a crime scene (forensics).

H
1

He
2
Periodic Table of Elements
1 The periodic table, or periodic table of elements or the ’alphabet of
Periodic Table of the Elements
hydrogen helium

Li Be
4

B
5

C
6

N
7

O
8

F
9

Ne
10
the universe’, as some scientists prefer to call it, is a tabular display
2 lithium beryllium boron carbon nitrogen oxygen fluorine neon
of all chemical elements, which are arranged by atomic number,
11 12 13 14 15 16 17 18

Na Mg Al Si P S Cl Ar electron configuration, and recurring chemical properties. The

3 sodium magnesium aluminum silicon phosphorus sulfur chlorine argon
structure of the table shows periodic trends. The seven rows of
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr the table, called periods, generally have metals on the left and
potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton
non-metals on the right. The columns, called groups, contain
5 Rb
37

Sr
38 39

Y
40

Zr Nb
41

Mo
42 43

Tc Ru
44

Rh
45

Pd
46

Ag
47

Cd
48 49

In Sn
50

Sb
51 52

Te
53

I Xe
54
elements with similar chemical behaviors. Six groups have ac-
cepted names as well as assigned numbers: for example, group 17
rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon

6 Cs
55

Ba
56 57-71 72

Hf
73

Ta W
74

Re
75

Os
76 77

Ir
78

Pt Au
79

Hg
80 81

Tl Pb
82

Bi
83

Po
84

At
85

Rn
86
elements are the halogens; and group 18 are the noble gases. Also
displayed are four simple rectangular areas or blocks associated
cesium barium lanthanides hafnium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon

87 88 89-103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr
francium
Ra
radium actinides
Rf
rutherfordium
Db
dubnium
Sg
seaborgium
Bh
bohrium
Hs
hassium
Mt
meitnerium
Ds
darmstadtium
Rg
roentgenium
Cn
copernicium
Uut Uuq Uup Uuh Uus Uuo
ununtrium ununquadium ununpentium ununhexium ununseptium ununoctium
with the filling of different atomic orbitals. The organization of
the periodic table can be used to derive relationships between
I II III IV V VI VII VIII the various element properties, and also to predict chemical
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
properties and behaviors of undiscovered or newly synthesized
La
lanthanum
Ce
cerium
Pr
praseodymium
Nd
neodymium
Pm
promethium
Sm
samarium
Eu
europium
Gd
gadolinium
Tb
terbium
Dy Ho Er Tm Yb Lu elements. Russian chemist Dmitri Mendeleev published the first
dysprosium holmium erbium thulium ytterbium lutetium

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

recognizable periodic table in 1869, developed mainly to illustrate
Ac
actinium
Th
thorium
Pa
protactinium
U
uranium
Np
neptunium
Pu
plutonium
Am
americium
Cmcurium
Bk
berkelium
Cf Es Fm Md No Lr periodic trends of the then-known elements. He also predicted
californium einsteinium fermium mendelevium nobelium lawrencium

some properties of unidentified elements that were expected to fill

Basic Chemistry259
 synthetic radionuclides of naturally occurring element oxide oxygen
e1- e1-
elements have also been produced in laboratories.
of metal of non-metal
Atomic Structure
e1-

e1-

e1-
e1 -
A simplified view of the basic atomic structure
(left)is that it looks very similar to a miniature
solar system. base water acid
p1+
n1±

2 8 8 18 The center (nucleus) is formed by

positively-charged protons and nutreal
neutrons. The number of protons is equal to the
e1-

atomic number of the element;Typically,there

e1-

are as many neutrons as there are protons but,

e1-

in some cases,there are more or less neutrons;

e1-

salt
e1-

e1 -

The positively-charged nucleus is orbited by

negatively-charged electrons, and the
A simplified atomic structure with protons and neutrons in the center number of electrons is equal to the
forming the nucleus, orbited by electrons on several outer shells. number of protons; The Electrons or- fig.2 Chemical compounds can be divided
bit the nucleus on so-called shells;The into oxides, acids, bases and salts.
innermost shell can hold one or a
gaps within the table. Most of his forecasts proved to be correct. maximum of two electrons. The next orbit or
Mendeleev’s idea has been slowly expanded and refined with the shell is limited to eight electrons and so is the
discovery or synthesis of further new elements and the develop- third. However, the 4th shell can support up
ment of new theoretical models to explain chemical behavior. to 18 electrons to maintain a neutrally-charged
The modern periodic table now provides a useful framework for environment between nucleus and shells.
analyzing chemical reactions, and continues to be widely used
in chemistry, nuclear physics and other sciences. During photographic exposure, light is
The elements from atomic numbers 1 (hydrogen) through directed onto the emulsion, where its radiation
118 (oganesson) have been discovered or synthesized, completing affects light-sensitive silver salts and produces
seven full rows of the periodic table. The first 94 elements all a latent image. A chemical treatment, called
occur naturally, though some are found only in trace amounts ‘development’, turns the latent image into a
and a few were discovered in nature only after having first been visible image, by converting the silver salts that
synthesized. Elements 95 to 118 have only been synthesized in were affected by the exposure into metallic silver.
laboratories or nuclear reactors. The synthesis of elements having All remaining silver salts, not affected by the
higher atomic numbers is currently being pursued: these elements exposure and, consequently, not changed by
would begin an eighth row, and theoretical work has been done the developer, must subsequently be removed
to suggest possible candidates for this extension. Numerous to produce a permanent image. This is accom-
plished through another chemical treatment,

fig.3 The pH value is a measure of how

strong an acid or alkaline solution is.
260 The Polymath Handbook
Isotopes one electron one electron
Isotopes are variants of a particular chemical element which differ
in neutron number, and consequently in nucleon number. All
isotopes of a given element have the same number of protons but
different numbers of neutrons in each atom.
The term isotope is formed from the Greek roots ‘isos’(equal)
and ‘topos’place), meaning “the same place”; Thus, the meaning
behind the name is that different isotopes of a single element oc-
cupy the same position on the periodic table. It was coined by a
Scottish doctor and writer Margaret Todd in 1913 in a suggestion Protium 11H
to chemist Frederick Soddy.
The number of protons within the atom’s nucleus is identifies its
atomic number and is equal to the number of electrons in the
neutral (non-ionized) atom. Each atomic number identifies a
specific element, but not the isotope; An atom of a given element Deuterium 21H Tritium 32H
may have a wide range in its number of neutrons. The number
of nucleons (both protons and neutrons) in the nucleus is the
atom’s mass number, and each isotope of a given element has a radio-carbon dating
different mass number. Radiocarbon dating, (also referred to as carbon dating or car-
For example, carbon-12, carbon-13, and carbon-14 are three bon-14 dating) is a method for determining the age of an object
isotopes of the element carbon with mass numbers 12, 13, and containing organic material by us-
14, respectively. The atomic number of carbon is 6, which means ing the properties of radiocarbon,
that every carbon atom has 6 protons, so that the a radioactive isotope of carbon. The
neutron numbers of these isotopes are 6, 7, and 8, respectively. method was developed in the late
1940s by Willard Libby, who received
the Nobel Prize in Chemistry for
his work in 1960. It is based on the
fact that radiocarbon (Carbon-14)
is constantly being created in the Carbon-14/146C
atmosphere by the interaction of
cosmic rays with atmospheric ni-
trogen. The resulting Carbon-14
combines with atmospheric oxygen
to form radioactive carbon dioxide, Carbon-12/126C
which is incorporated into plants by
photosynthesis; animals then acquire
Carbon-14 by eating the plants.

Basic Chemistry261
When the animal or plant dies, it stops exchang-
ing carbon with its environment, and from
that point onwards the amount of Carbon-14
itcontains begins to decrease as the Carbon-14
undergoes radioactive decay. Measuring the
amount of Carbon-14 in a sample from a dead
plant or animal such as a piece of wood or a
fragment of bone provides information that can
be used to calculate when the animal or plant
died. The older a sample is, the less Carbon-14
there is to be detected, and because the half-life
of Carbon-14 (the period of time after which
half of a given sample will have decayed) is about
5,730 years, the oldest dates that can be reliably
measured by this process date up to around
50,000 years ago, although special preparation
methods occasionally permitaccurate analysis
of older samples.
Research has been ongoing since the 1960s to
determine what the proportion of Carbon-14
in the atmosphere has been over the past fifty
thousand years. The resulting data, in the form
of a calibration curve, is now used to convert a
given measurement of radiocarbon in a sample
into an estimate of the sample’s calendar age.
Other corrections must be made to account for
the proportion of Carbon-14 in different types
of organisms (fractionation), and the varying
levels of Carbon-14 throughout the biosphere
(reservoir effects). Additional complications
come from the burning of fossil fuels such as coal
and oil, and from the above-ground nuclear tests
done in the 1950s and 1960s. Because the time it
takes to convert biological materialsto fossil fuels
is substantially longer than the time it takes for
its Carbon-14 to decay below detectable levels,
fossil fuels contain no Carbon-14.As a result,
262 The Polymath Handbook
there was a noticeable drop in the proportion of Carbon-14 in ions(+). The hydrochloric acid provides a ready supply of chloride
the atmosphere beginning in the late 19th century. Conversely, ions (−), which react with the gold ions to produce tetrachlorate
nuclear testing increased the amount of Carbon-14 in the atmo- anions, also in solution. The reaction with hydrochloric acid is an
sphere, which attained a maximum in about 1965 of almost twice equilibrium reaction that favors formation of chloroaurate anions
what it had been before the testing began. . This results in a removal of gold ions from solution and allows
further oxidation of gold to take place. The information iprovided
here is specific to a molar ratio of 1:3 between nitric acid and
hydrochloric acid . The relative concentrations of the two acids
in water often differ, values could be 65% w/v for nitric acid and
Aqua regia,aqua regis, Königswasser 35% w/v for hydrochloric acid — that is, the actual HNO3:HCl
Aqua regia is a mixture of nitric acid and hydrochloric acid, mass ratio is less than 1:2 and needs to be corrected.
optimally in a molar ratio of 1:3. Aqua regia is a yellow-orange heavy water
(sometimes red) fuming liquid,so named by alchemists because Heavy water (deuterium oxide or D2O) is a form of water that
it can dissolve some noble metals, such as gold and platinum, contains a larger than normal amount of the hydrogen isotope
although not all metals. Upon mixing of concentrated hydro- deuterium (2H or D, also known as heavy hydrogen), rather than
chloric acid and concentrated nitric acid, chemical reactions the common hydrogen-1 isotope (1H or H, also called protium;see
occur. These reactions result in the volatile products nitrosyl previous page) that makes up most of the hydrogen innormal water.
chloride and Chlorine gas as evidenced by the fuming nature and (H2O) Deuterium is a hydrogen isotope with anucleus containing
characteristic yellow color of aqua regia. As the volatile products a neutron and a proton; the nucleus of a protium (normal hydro-
escape from solution, aqua regia loses its potency. Aqua regia is gen) atom consists of just a proton. The additional neutron makes
primarily used to produce chloroauric acid, the electrolyte in the a deuterium atom roughly twice as heavy as a protium atom. The
process for refining gold and gold plating. Aqua regia is also used presence of deuterium gives the water different nuclear properties,
in etching and in specific analytic procedures. It is also used in and the increase of mass gives it slightly different physical and
some laboratories to clean glassware of organic compounds and chemical properties when compared to regular water.
metal particles. This method is preferred over the more traditional
chromic acid bath for cleaning NMR tubes, because no traces
chromium can remain. While chromic acid baths are discour-
aged because of the high toxicity ofchromium and the potential
for explosions, aqua regia is itself very corrosive and has been Don’t trust an atom; They make up
implicated in several explosions due to mishandling. Due to the everything.
reaction between its components resulting in its decomposition,
aqua regia quickly loses its effectiveness (yet remains a strong acid),
so its components are usually only mixed immediately before use.
Aqua regia dissolves gold, though neither constituent acid will
do so alone, because, in combination, each acid performs a dif-
ferent task. nitric acid is a powerful oxidizer, which will actually
dissolve a virtually undetectable amount of gold, forming gold
called ‘fixing’, which is followed by a final wash in plain water to
remove chemical residue. because they both have four electrons in the outermost shell. Electron Configurations
Chemistry and Photography Elements with similar chemical properties generally fall into the In addition, The row and column numbers of
Chemistry in Photography same group in the periodic table and elements in the same period the element in the periodic table also reveal the
A thorough understanding of chemistry is not required to effec- tend to have similar properties. Thus, itisrelativelyeasy to predict atomic electron configuration of the element in
tively operate a darkroom. You can successfully process film and the chemical properties of an element if one knows the properties question(see page112). It’s a fairly simple concept
paper, using commercially available photographic chemistry, by of the elements around it. but best explained by taking a closer look at a
simply following the instructions, without ever giving the underly- few examples:
ing chemical processes much thought. However, preparing your 1. Sodium (Na) has the atomic number’11’ and
own processing solutions according to a chemical formula, using is at the intersection of row’3’ and column
raw chemicals, makes you independent of commercial product ‘I’ or’1’; From this, we can ascertain that so-
availability and provides the opportunity for customized process dium has eleven protons at its nucleus and
optimizations. In dedicated literature, you will find a basic set of also eleven electrons orbiting on three shells;
formulae for developers, a stop bath, fixers and other processing Since , the first inner shell is limited to host-
chemicals. To better understand the purpose and function of ing two electrons and the second to hosting
their main ingredients, it will be beneficial to have a rudimentary eight, the eleventh electron is forced to orbit
understanding of photographic chemistry. on the third shell;The electron configuration
The periodic table of elements provides more information about is consequently written as 11Na 2,8,1.
each element than may be obvious at first glance: 2. Oxygen(O) has the atomic number’8 and
In the standard periodic table, the elements are listed in rows ,therefore,eight protons at its nucleus and
and columns in order of increasing atomic number z (the number eight electrons on two shells,According to its
of protons in the nucleus of an atom),which also equals the total placement in the periodic table, its electron
number of electrons on the shells. A new row (period) is started configuration must be 8O2,6.
when a new electron shell has its first electron. Columns (groups) 3. Silver(Ag) has 47 protons and electrons
are determined by the electron configuration of the atom; ele- configured as 47Ag2,8,8,18,11., Because being
ments with the same number of electrons on the outer-most shell listed on the 5th period, identifies it as hav-
fall into the same columns (e.g. oxygen and selenium are in the ing its electrons distributed over five shells
same column and,starting with the 4th shell,shells can
host up to 18 electrons;being listed in the
11th column reveals that its outer-most shell
I have never considered myself to be hosts eleven electrons.
technical. To me, adding bromide or
carbonate to a developer is about as Ions,Cations and Anions
technical as exposing for the shadows. An ion is an atom or molecule with a net electric
Every photographer should know that! charge due to the loss or gain of one or more
Steve Anchell electrons.

Basic Chemistry263
 A cation is a positively charged ion, i.e. one that would be at-
element oxide oxygen
tracted to the cathode in electrolysis. t(he opposite of an anion). A Note on Mixing Chemicals
An anion is a negatively charged ion, i.e. one that would be at- The sequence in which chemical
of metal of non-metal
tracted to the anode in electrolysis. (the opposite of a cation). compounds are listed in photo-
graphic formulae is not accidental.
Elements and Compounds Always add them one after the other,
An element is a substance containing only one kind of atom; according to the list.
a compound contains two or more different kinds of elements.
base water acid
For much of its history, chemistry was a relatively simple a. weigh out dry chemicals onto
science with all matter divided into just four elementary ma- separate pieces of small paper
terials: air, water, earth and fire. This changed in 1661 when b. arrange chemicals in order and
Robert Boyle summarized a better understanding of matter and add them one after the other
proposed that there is a difference between elements and com- c. slowly sift chemicals into water
pounds. Since then, an element is defined as the simplest form while steadily stirring it
salt of matter (atom), indivisible and with individual characteristics, d. make sure it is completely dis-
but, combined with each other, elements can create a number of solved before adding the next
compounds (molecules) with distinctively different properties.
mixing solutions
to mix two solutions of different concentra-
tions, use the criss-cross diagram on the right.
to just dilute a hihly-concentrated stock solu- % strength of solution
fig.4a The crisscross method is a simple technique
tion to a lesser-concentrated working solution
to be diluted
of mixing two compatible liquids into a
with water, it might beeasier to use the general a x = c-b target solution of desired strength. It can
formula: be used to create a working solution from
c1*V1=c2*V2 to get % strength desired c mix x parts of ‘a’ with y parts of ‘b’ two existing stock solutions, or it may help
where ‘c’ stands for the concentration and to determine how a stock solution must be
‘V’ ‘ stands for the volume of ‘1’ and ‘2’, which b y = a-c diluted to create the working solution.
are the stock and working solutions respectively. % strength of diluting
solution
We can rearange the formula above to solve
for any of the variables.
assuming, we want to dilute a 25% acid 50% acetic acid
fig.4b In this example, 50% acetic acid is mixed
stock soution and need 1,000ml of 2% working 50 28 = 28-0 with water (0%) at a ratio of 28/22 to create
solution(V2). solving forV1(volume of concentrate), 28% acetic acid, by subtracting the working
we get: to get 28% acetic acid 28
mix 28 parts of acid
with 22 parts of water
strength (c=28) from the stock strength (a=50)
V1=(c2*V2)/c1 and: and the diluting strength (b=0) from the
V1=(0.02*1,000ml/0.25) 0 22 = 50-28
working strength (c=28) and knowing how
=80ml of acidstock and the rest, 920ml, of many parts of each are required for the mixture.
water (0%)
plain water.

264 The Polymath Handbook

As of this writing, there are 118 known elements (fig.1),which
some scientists refer to as the ‘alphabet of the universe’ but, only
the first 94 elements occur naturally on earth. The rest are mainly
short-lived by-products of nuclear reactions. The number of pos-
sible compounds, on the other hand, seems to be endless.
Compounds, created by chemical reaction, often have prop-
erties quite different from the elements they are made of. For
example, the elements sodium and chlorine are both extremely
Typical Metric Units
(use in photographic formulae)
1 kg = 1,000 g
1 g = 1,000 mg
1 l = 1,000 ml or cm3
1 ml = 20 drops
A Note on Safety
As with all other chemicals, there are risks
associated with contact, inhalation and
ingestion of darkroom chemicals. We
strongly advise that you study the material
safety data sheet (MSDS) of each chemical
before using it. In general, one must always
observe the following practices while
handling darkroom chemicals.
a. don’t smoke in darkroom
b. don’t eat or drink in darkroom
c. wear goggles
d. wear an apron
e. wear a face mask
f. wear rubber or latex gloves
g. ensure good ventilation
h. never inhale chemical dust
i. label chemical bottles clearly
dangerous, but when combined chemically, they produce harm- pH
less sodium chloride, which we know as ordinary table salt. The The ‘power of hydrogen’, or pH, is a measure
chemical equation for this reaction is written as: of strength for an acid or alkaline solution (see
page116), and measured pH values typically
Na + Cl = NaCl range from 1 to 14. Roughly speaking, the pH
sodium + chlorine = sodium chloride value is the negative logarithm of the hydrogen
ion concentration, but it is more important to
Types of Compounds remember that acids have pH values < 7 and
Elements can be roughly divided into two groups: metals and bases have pH values > 7. Distilled water is said
non-metals. Compounds can be classified as being organic or to be neutral with a pH of 7.
inorganic. Organic compounds are mainly composed of hydro- Precise pH measurements require sophisticat-
gen, carbon, nitrogen, oxygen and sulfur. Inorganic compounds ed pH meters, but sufficiently accurate pH values
usually contain metallic elements. Another useful classification can be obtained with a litmus test. Litmus is a
of compounds (fig.2) differentiates four groups: water-soluble dye that changes its color depend-
ing on the pH value of the solution with which
Oxides are compounds of oxygen and other elements. Ex- it comes into contact. Test papers, containing
amples are sulfur dioxide (S + O2 = SO2) and sodium oxide litmus, turn bright red in acid solution and deep
(4Na + O2 = 2Na 2O). Many oxides are soluble in water, blue in alkaline solutions. The actual pH value
and, depending on the type of element combined with the can be estimated by comparing the resulting
oxygen, this results in either an acid or a base. color to a calibrated color chart.
Acids are formed when the oxides of non-metallic elements A pH test is useful for darkroom workers, be-
are dissolved in water. For example, sulfur dioxide dissolved cause the pH value of a photographic solution is
in water produces sulfurous acid (SO2 + H2O = H2SO3). often an indicator of its freshness or activity. For
Acids are sour and have a pH value < 7. example, a fresh acid stop bath has a pH value of
Bases are formed when oxides of metallic elements are 4 or less, but when in use, it will be continuously
dissolved in water. For example, sodium oxide dissolved in contaminated with alkaline developers. The
water produces sodium hydroxide (Na2O + H2O = 2NaOH). alkali carry-over raises the pH value of the stop
Bases are alkaline and have a pH > 7. bath, and by the time it approaches a pH value
Salts are typically combinations of acids and bases. For of 6, the stop bath has lost most of its usefulness
example, when sulfurous acid reacts with sodium hy- and must be replaced. In another example, the
droxide, sodium sulfite is formed (H 2 SO3 + 2NaOH = pH value of a developer can be an indicator of
Na 2SO3 + 2H2O). Sodium sulfite is found in many photo- its activity. A changing pH value, due to age or
graphic formulae. usage, will lead to process inconsistencies, which
can be predicted and controlled, after the actual
pH value has been determined.
Basic Chemistry265
Chemistry kickstarting Photography During the exposure, light energy is absorbed by the silver- Stop Bath
In 1727, Johann Heinrich Schulze experimented halide crystals, which produces a chemical reaction within the Once the desired degree of development has been reached, the
with several compounds of silver and noticed salts. This creates a latent image, which is made visible through process must be stopped quickly to avoid overdevelopment. This
that silver salts darkened under the influence development. can be achieved through a simple water rinse, but an acid stop
of light. In 1802, Thomas Wedgwood and bath is more effective in neutralizing the alkaline activators and
Humphrey Davy coated paper with a silver-salt Developer stopping development almost instantaneously.
solution and exposed it in a camera obscura to Developers are able to differentiate between exposed and unex- A dilute solution of acetic or citric acid makes for a powerful
produce an image, which could only be seen posed silver halides. They liberate exposed silver halides from their stop bath. However, with developers containing sodium carbonate,
for a limited time. In 1834, William Henry salts and reduce them to metallic silver, but unexposed halides the acid concentration must be kept sufficiently low to avoid the
Fox Talbot suggested that a developer could remain untouched. The chemical process of development is rather formation of carbon-dioxide gas bubbles in the emulsion, because
amplify a weak exposure of silver salts, turn- complex, and an exact equation cannot be given, but in simple this may lead to ‘pinholes’ in the emulsion.
ing a latent image into a visible image, and in terms, the following reaction takes place:
1837, two years prior to the official invention of Fixer
photography, John Herschel proposed sodium AgCl After the stop bath has successfully terminated the development
thiosulfate as a solvent for unexposed silver salts AgBr > exposure > development = Ag of exposed silver halides, all unexposed halides still remain in the
to create a permanent image. AgI emulsion, because they are not soluble in water. This is of great
benefit during the development process, but during fixing, they
Emulsion Developer solutions contain a number of ingredients, which can must be removed completely, or they will eventually darken upon
A photographic emulsion is a thin layer of be divided into four groups: further exposure to light, and the image will not be permanent.
light-sensitive material suspended in photogra- This requires a fixing bath with a number of ingredients:
phy-grade gelatin. The gelatin makes it possible Developing Agents are relatively complex organic compounds,
for the emulsion to be coated onto a substrate which provide the electrons required to reduce silver ions to Fixation Agents must dissolve all remaining silver halides
of glass, plastic film or paper. Three silver salts metallic silver. The most commonly used developing agents and convert them into water-soluble compounds. Only two
have been found to be particularly sensitive to are metol, hydroquinone and phenidone. chemicals, sodium and ammonium thiosulfate, are known to
light: silver chloride (AgCl), silver bromide (AgBr) Accelerators increase the alkalinity of the developer and do that without negatively affecting the silver image or the
and silver iodide (AgI), and as a group, they are provide additional ions to create metallic silver. In general, gelatin layer. Since ammonium thiosulfate dissolves silver
often referred to as silver halides. the higher the pH value of the developer, the more active it halides more rapidly than sodium thiosulfate, it is commonly
Typical emulsions contain a mixture of two is. Typical accelerators are sodium hydroxide, sodium carbonate known as ‘rapid fixer’.
or three silver halides, because they differ in and borax. Acids are optional fixer ingredients, separating fixers into acid
light and color sensitivity. But, even as a group, Preservatives are added to developer solutions to protect and alkali solutions. Acid fixers have the benefit of neutral-
they are mostly blue-sensitive and not able to developing agents against oxidation. A frequently used pre- izing any residual developer solution and preventing emulsion
record the entire visible spectrum. To make silver servative is sodium sulfite. swelling in the wash. Often, a combination of acetic and boric
halides responsive to all wavelengths of light, Restrainers suppress the formation of chemical fog, which is acid is used. Acid-free fixers produce a less objectionable odor
complex organic chemicals, so-called optical an unwanted silver production on unexposed silver halides. A and are easier to wash out of the emulsion.
sensitizers, are added to the emulsion. They act minute amount of potassium bromide effectively reduces fog, Preservatives are used with acid fixers to prevent an accumu-
as an internal color filter, extending the color but larger amounts affect the rate of normal development. lation of sulfur, due to a reaction of thiosulfate with acids. This
sensitivity from blue into green and red.

266 The Polymath Handbook

 is achieved by adding sodium sulfite, which quickly reacts with research has shown that minute amounts of thiosulfate actually
colloidal sulfur and creates fresh sodium thiosulfate. protect the silver image against environmental attack.
Hardeners can be added to prevent excessive swelling of the An alternative to using sodium sulfite alone is using it together
emulsion during washing and protect against physical damage. with sodium bisulfite, which is done in commercial washing
The most widely used hardener is potassium alum. Hardeners aids. This constitutes a compromise, as lower pH values reduce
impede washing and are not recommended for normal process- emulsion swelling in the wash, but lowering the alkalinity also
ing, but they find use in special application. reduces the rate of thiosulfate elimination. To prevent calcium
Buffers such as sodium sulfite and sodium carbonate are used to precipitation and ‘print scum’, some sodium hexametaphosphate,
stabilize the pH value of acid and alkali fixers. If alkali fixers also known as Photo Calgon, may be added to the washing aid
are preceded by an acid stop bath, sodium carbonate must be as a sequestering agent.
substituted with sodium metaborate or balanced alkali to avoid
the formation of carbon-dioxide gas bubbles. Toner
Unprotected metallic image silver is subjected to constant at-
Washing Aid tacks by reducing and oxidizing agents in our environment. The
After fixing, emulsion and film or print substrate contain a con- mechanisms of image protection are not entirely understood,
siderable amount of thiosulfate, which must be removed so not but the positive influence of sulfide and selenium on silver image
to adversely affect later processing operations and to optimize permanence is certain. Toning baths, containing sodium sulfide,
image longevity. Washing is a combination of displacement and polysulfide or selenium, convert the image forming metallic silver
diffusion, and consequently not a chemical but a physical process. into more stable silver compounds, such as silver sulfide and
However, certain chemicals can positively affect the rate of wash- silver selenide, and sodium carbonate buffers the pH value in
ing and its efficiency. polysulfide toners.
According to Modern Photographic Processing by Grant Haist,
a salt bath prior to washing was suggested as early as 1889, and The information presented in this chapter was not designed to
washing in seawater has been known to speed up the rate of wash- withstand scientific scrutiny. Instead, it was purposely oversim-
ing since 1903. On a global average, seawater contains roughly plified to provide a brief overview and basic understanding of
3.5% salt, mainly sodium chloride. Unfortunately, seawater chemistry and photographic processes, while trying to avoid
cannot be left in the emulsion, because the remaining salts cause getting hopelessly lost in scientific detail. I trust this will make
a fading of the silver image under storage conditions of high some more comfortable and confident with chemistry and in-
humidity and temperature. stigate others to deepen their studies. Much of what has been
The modern alternative to seawater is a washing aid, containing presented here can be found in far more detail in an excellent
up to 2% of sodium sulfite. Applying a washing-aid bath prior to book, called Photographic Chemistry by George T. Eaton, which
the final wash is standard practice with fiber-base print processing, is unfortunately out of print. I highly recommend finding a sec-
and is also recommended for film processing. It makes residual ondhand copy of this book to anybody interested in the subject
fixer and its by-products more soluble and reduces the washing of photographic chemistry.
time significantly. Washing aids are not to be confused with hypo
eliminators, which are no longer recommended, since recent

Basic Chemistry267
alchemy
is the medieval forerunner of chemistry, based
on the supposed transformation of matter. It was
concerned particularly with attempts to convert
base metals into gold or to find a universal elixir
Alchemyis also an ancient branch of natural
philosophy, a philosophical and protoscien-
tific tradition that was historically practiced in
China, India, the Muslim world, and Europe.
In its Western form, alchemy is first attested
in a number of pseudepigraphical texts written
in Greco-Roman Egypt during the first few
centuries AD. Alchemists attempted to purify,
mature, and perfect certain materials. Com-
mon aims were chrysopoeia, the transmutation
of “base metals” (e.g., lead) into “noble metals”
(particularly gold); the creation of an elixir of
immortality; and the creation of panaceas able
to cure any disease. The perfection of the human
body and soul was thought to result from the
alchemical magnum opus (“Great Work”). The
concept of creating the philosophers’ stone was
variously connected with all of these projects.
Islamic and European alchemists developed
a basic set of laboratory techniques, theories,
and terms, some of which are still in use today.
They did not abandon the Ancient Greek philo-
sophical idea that everything is composed of four
elements, and they tended to guard their work in
secrecy, often making use of cyphers and cryptic
symbolism. In Europe, the 12th-century transla-
tions of medieval Islamic works on science and
the rediscovery of Aristotelian philosophy gave
birth to a flourishing tradition of Latin alchemy.
This late medieval tradition of alchemy would go
268 The Polymath Handbook
on to play a significant role in the development of early modern
science (particularly chemistry and medicine).
philosophers’ stone
is a mythic alchemical substance capable of turning base
metals such as mercury into gold or silver. It is also called
the elixir of life, useful for rejuvenation and for achieving
immortality; for many centuries, it was the most sought-
after goal in alchemy. The philosopher’s stone was the central
symbol of the mystical terminology of alchemy, symbolizing
perfection at its finest, enlightenment, and heavenly bliss. Efforts
to discover the philosopher’s stone were known as the Magnum
Opus (“Great Work”).
The temperature of a mix of similar liquids
To simplify the calculation a few assumptions are made: fig.5 (below)with the aid of a simple spreadsheet
1. The two liquids have a similar heat and the equation above,the resulting mixing
capacity such as two aqueous temperature of two aqueous liquid solutions
solutions. Table 1 of any temperature can easily be determined.
2. The two solutions are in the same solution1 solution2 mixture
state of matter such as liquid. mass[ml] 100 300 400
temperature 16 22 20.5
3. The influence of all liquid ves- heat energy 1,600 6,600
sels and ambient temperature is
ignored.
Furthermore we can take for grant-
ed that the heat energy of the entire
mix is equal to the sum of the heat
energies stored in the two solutions.
The equation to the top-right reflects
these assumption. Solving it for Tmix
will allow to calculate a temperature
for the mixture.Mmix is, of course
the sum of the two solutions m1+m2.