FERTILIZERS: Plants require compounds of more than a dozen different

elements for healthy growth .Nitrogen ,phosphorus and potassium and the big
three among them and are most vital .Calcium, magnesium and sulfur are the little
three which are essential but needed in smaller amounts .Several others needed in
traces are : iron ,manganese ,copper zinc boron and iodine.

Growing plants obtain most of these nutrients from the soil. Since the soil does not
contain an inexhaustible supply of these elements. We must add these nutrients to
the soil in the form of manures or fertilizers. Different types of manures are:

Requisite Qualities of a Fertilizers: requisite qualities of a good fertilizers are:

(i) It must provide the necessary constituents required for the plant growth.
(ii) Slightly basic soil (pH~7 to 8) is a must for the proper growth of plants.
A god fertilizer should, therefore, be basic and should not produce
acidity.
(iii) It must be soluble in soil moisture and get assimilated by plants.
(iv) It should not produce extra heat which may burn the plants.
(v) Its physical form should be such that it gets easily ad uniformly distribute
in the soil and keeps the soil loose. It should not be gummy and compact.
(vi) It must be stable so that the nutrient element present in it is available to
the plants over a long period. It should not be easily leached away from
the soil.

Symptoms of Deficiency: deficiency of various nutrient elements is indicated by

the following symptoms:

(i) Potassium deficiency: Appearance of white, yellow or reddish brown

spots on the leaves followed by the edges becoming brown, generally in
maize , cotton and tobacco plants.
(ii) Nitrogen deficiency: Leaf color becomes light green or yellowish green
ad leaves start yellowing and dying.
(iii) Phosphorus deficiency: It causes poor rot growth and purpling of leaves
generally seen in cotton, tobacco and potato crops. Plats growth is
stunted , ripening is delayed and fruiting is poor.
Classification of fertilizers
The term fertilizer is defined in the Act. No. 156/1998 Coll., as amended. Fertilizers
are considered substances containing nutrients for nutrition of crop plants and forest
trees, to maintain or improve soil fertility and positive influence on yield or quality of
production

Fertilizers are divided according to three basic aspects:

1. According to efficiency
1. straight fertilizers
2. auxiliary substances
2. According to origin
1. mineral fertilizers
2. manure
3. According to phase
1. solid fertilizers
2. liquid fertilizers

Staight fertilizers are substances that contain one or more plant nutrients, typically in
large amounts, either mineral or in organic form. They provide plants with macro- or
micronutrients, including mineral fertilizers and manure.

Auxiliary substances contain plant nutrients in larger quantities, thus not supply
nutrients to plants, but allow improving nutrition by editing environment or affecting
the metabolism of plants so that the plants can utilize larger quantities of nutrients to
yield formation.

Devided into:

1. Auxiliary soil substances – substances without effective amount of nutrients

which would biologically, chemically or physically affect the soil, improving
soil state or increasing the efficiency of fertilizers
2. plant preparations – substances without effective amount of nutrients which
otherwise favorably affect the development of cultivated plants or the quality of
plant products.

Mineral fertilizers include all fertilising substances manufactured outside the

agricultural plant. They are mainly chemical products, mining and construction
industries. The main representatives of this group are concentrated mineral fertilizers,
which are divided into
 1. one-component (straight) fertilizers – contain one nutrient as a major. They
may also comprise accompanying ions, respectively microelements. They are
divided into nitrogen, phosphoric acid, potassium, calcium and magnesium
fertilizers.
2. multi-component (compound) fertilizers – fertilizers containing at least two or
more major nutrients, may include accompanying ions and microelements..
According to the nutrient content they are divided into fertilizers – double ones
containing 2 major nutrients (NP, NK, PK), triple (full), fertilizers with
micronutrients and special group consists of fertilizers containing sulphur.

According to the process of manufacture we distinguish multi-component mixed

fertilizers (manufactured by mechanical mixing of one-component fertilizers and are
either in powder or granulated form) and combined (manufactured by chemical
processes of the original raw material)

Livestock manure are fertilizers which are characterized by a large volume, are
produced in agricultural production and are divided into:

1. Stable
1. farmyard manure,
2. manure
3. slurry
4. dung water
2. Other
1. compost
2. green fertilization
3. straw for fertilization
4. other organic matter

Solid fertilizers –mineral fertilizers straight or compound, which are divided

according to particle size:

1. Powder (prevalent particles smaller than 1 mm)

2. Granular (particles typically 1-4 mm) and according to the method of
manufacture may be crystalline or granulated

Liquid Fertilizers can again be straight or compound, are produced as clear solutions
or suspensions and may be subdivided into inorganic fertilizers liquid - pressure-free,
high and low pressure.

Similarly, it is possible to conduct distribution of manure into solid (manure) and

liquid (liquid manure, dung water, slurry)
Nitrogenous Fertilizers

Mineral and organic substances used as a source of nitrogen nutrition for plants. Th
ey aredivided into organic fertilizers (manure, peat, compost) containing other nutr
ients besidesnitrogen; manufactured mineral fertilizers; and green fertilizers (lupin
e, serradella).
Nitrogenous fertilizers were used in very ancient times. Manure was extensively us
ed inancient Rus’. Green fertilization has long been known in the irrigated agricult
ure of Middle Asia.Mineral fertilizers came into use much later. The first was sodi
um nitrate, obtained since themiddle of the 19th century from natural deposits in C
hile (South America); its consumption in1900 was about 300,000 tons (converted i
nto nitrogen). In the next years industry began toproduce ammonium sulfate, calciu
m cyanamide, and calcium nitrate.
By 1913 world production of nitrogenous fertilizers was almost 700,000 tons (conv
erted tonitrogen). Synthesizing ammonia from atmospheric nitrogen and hydrogen
on an industrialscale (1914–
1918) made a sharp boost in world production of nitrogenous fertilizers possible;pr
oduction rose in 1966 to 19,200,000 tons (converted to nitrogen), including 6,400,0
00 in theUnited States, 1,449,000 in the Federal Republic of Germany, 1,082,000 i
n France, 462,000 inPoland, and 343,000 in the German Democratic Republic.
Russia produced 3,000 tons (converted to nitrogen) in 1913. A large nitrogenous fe
rtilizerindustry came into being during the first five-
year plan. Agriculture was supplied withnitrogenous fertilizers (converted to nitrog
en) as follows: 2,000 tons in 1928, 199,000 tons in1940, 75,000 tons in 1945, 307,
000 tons in 1950, 1,003,000 tons in 1960, 2,712,000 tons in1965, 3,188,000 tons in
1966, 3,753,000 tons in 1967, and 4,177,000 tons in 1968. Mineralnitrogenous fert
ilizers may contain nitrogen in ammonia (NH3), ammonium nitrate (NH3 andNO3),
nitrate (NO3), and amide (NH2) forms.
Ammonia fertilizers Ammonia fertilizers include ammonium sulfate, ammonium c
hloride,ammonium bicarbonate, and liquid nitrogenous fertilizers. Ammonium sulf
ate and ammoniumchloride are most effective on base-
saturated soils (chernozems, calcareous serozems,chestnut) which can neutralize th
eir acidifying effect. Systematic fertilization with ammoniumsulfate or ammonium
chloride increases soil acidity, which can be corrected by liming.Ammonia nitroge
n is less susceptible to leaching than nitrate nitrogen; thus, ammoniafertilizers can
be added in the fall, before planting. They are less suitable for surface (assuppleme
ntary feeding for winter crops) and local (in rows or by cluster sowing) application.
Excessive chlorine in ammonium chloride has an adverse effect on the size and qua
lity of theyield of many crops, including potatoes, flax, oil
producing plants, tobacco, and grapes.Ammonium bicarbonate, still produced only
in limited quantities for experimental purposes, hasan alkaline reaction, but it unde
rgoes nitrification in soil. Among the ammonia forms, liquidfertilizers—
liquid anhydrous ammonia, aqua ammonia, and ammoniates—
are the mostimportant.
Ammonium nitrate fertilizers Ammonium nitrate fertilizers include ammonium nit
rate andammonium nitrosulfate (leuna saltpeter, ammonium sulfate-
nitrate). Ammonium nitrate isproduced chiefly in pellet form; it acidifies the soil sl
ightly. Ammonium nitrosulfate has acomparatively high acidifying capacity.
Nitrate fertilizers Nitrate fertilizers include sodium nitrate (Chilean saltpeter), calci
um nitrate(lime saltpeter, Norwegian saltpeter), and potassium nitrate. Sodium nitr
ate is physiologicallyalkaline and is therefore best applied to acid soils, especially
when sugar beets, wheat, barley,and other acid-
sensitive crops are grown. Calcium nitrate is put up in pellets usually admixedwith
ammonium nitrate; it, too, alkalizes the soil. Potassium nitrate contains potassium a
s wellas nitrogen and is a source of nitrogen-
potassium nutrition for plants. It is applied to chlorine-
sensitive crops. All the nitrate forms of nitrogen are not absorbed by the soil. In reg
ions withexcess moisture, nitrate fertilizers are leached out of light soils with weak
water-
retentioncapacity. It is best, therefore, to use ammonia fertilizers as the main fertili
zers.
Amide fertilizers Amide fertilizers include urea (carbamide), calcium cyanamide, a
nd urea-
formaldehyde. Urea is the most valuable. In soil it readily changes into ammonium
carbonate; itfirst slightly alkalizes the soil and then weakly acidifies it. It is recom
mended that urea beadded early. It is also used as a protein supplement for ruminan
ts. Calcium cyanamide is ableto reduce soil acidity.
 Table 1. Properties of the main mineral nitrogenous fertilizers
Chemi Averagenitro Fertilizerm Drillabilityafter stora Tende Hygr
calfor gencontent(i ass byvolum ge ncyto oscop
3
mula npercent) e(kg/m ) cake icity
Ammoni (NH1)2 20.5–21.5 800 good (withmoistureco slight very
umsulfat S04 ntentslightveryweakno weak
e..... morethan 2%)
Ammoni NH2C 26.0 600 satisfactory moder slight
umchlori L at
de . . .
Anhydro NH3 82.3 620 — — —
usammo
nia ...
Aquaam NH3 + 20.0 910 — — —
monia.... H2O
....
Ammonium nitrate
granulat NH1 N 34.7–35.0 820 good slight very
ed.......... O3 stron
g
crystalli NH1N 34.7–35.0 840 poor strong very
ne .......... O3 stron
g
Sodiumn NaNO 16.0 1,100–1,400 satisfactory slight mode
itrate...... 3 rate
..
Calcium Ca(N 17.0 900–1,100 satisfactory strong very
nitrate.... O3)2• 2 stron
.. H20 g
Urea
granulat (NH2)2 46.0 650 good does n very
ed.......... CO otcake weak
crystalli (NH2)2 46.0 650 poor slight very
ne .......... CO weak
If applied in the fall, it is effective on mellow neutral soils rich in organic matter. It
is unsuitablefor local application. Calcium cyanamide is also used as a defoliant to
remove leaves fromcotton before it is harvested. Urea-
formaldehyde fertilizers are not leached out of the soil andare especially effective i
n regions of excess moisture and irrigated agriculture. The use of largeamounts pro
vide crops with enough nitrogen to last several years. The characteristics ofmineral
nitrogenous fertilizers are given in the table.
Nitrogenous fertilizers are an effective means of increasing crop productivity, espe
cially in thenonchernozem zone, humid regions of the forest steppe, and the zone o
f irrigated agriculturewhere the soils do not contain enough nitrogen. The fertilizati
on rates vary with soil conditions,biological characteristics of the crops, and availa
ble supply of manure or other organicfertilizers. The approximate rates of nitrogen
ous fertilizers (in kg per ha converted intonitrogen) are 40–
60 for winter grains sown after an occupied fallow and 30–
40 after a cleanfallow; 40–60 for spring grains; 60–
120 for silage corn and for grain in the nonchernozem zoneand northern part of the
forest-steppe zone, 45–60 on rich chernozems of the forest steppe,and 120–
150 in irrigated regions; 45–
60 for sugar beets on chernozems of the forest steppe,80–
120 on gray forest soils, podzolized chernozems of the forest steppe, and in thenon
chernozem zone, and 100–150 in irrigated regions; 120–140 for cotton; 40–
60 for fiber flax;45–90 for hemp; 45–90 for potatoes; 90–120 for cabbage; 60–
90 for tomatoes and cucumbers;60–100 for fruits and berries.
Smaller amounts are applied to soils richer in natural nitrogen or when manure or o
thernitrogen-
containing organic fertilizers are used at the same time. If nitrogenous fertilizers ar
e inample supply, the rates can be increased in humid regions; this generally increa
ses the yieldand improves the quality of the crops. For example, good nitrogen nutr
ition favors theformation of gluten in wheat grain and increases the protein content
of fodder crops.
Nitrogenous fertilizers are used as the base fertilizer and as supplementary feeding.
They areadded to winter crops which were sown after a clean fallow only as early
spring supplements (30-
40 kg of nitrogen per ha) on semithawed soil (on the ground’s ice “crust”). In all zo
nes ofthe USSR, it is useful to add nitrogenous fertilizers at the full rates to spring
crops beforesowing and, if the crops are to be irrigated, in stages before irrigation.
Cotton is fertilized threetimes: before sowing, at the start of budding, and at the sta
rt of flowering (one-third of the rateat a time).
 Phosphatic fertilisers:
The nutrient phosphorus present in phosphate fertilizers are usually expressed in
terms of phosphoric anhydride or simply as phosphorus pentaoxide, P 2O5. The
availability of phosphorus in which it is present. The amount of phosphorus
available to the plants depends upon the extent to which the fertilizer supplies
HPO4----or H2PO4 –ions. According to the solubilities, the phosphatic fertilizers are
divided in following groups.
a. Water soluble phosphatic fertilizers: These fertilizers contain phosphorus in
available form in neutral soils, which can be readily absorbed by young
plants. In acid, soils and free iron, aluminium hydroxy phosphates but in
alkaline and calcareous soils, water soluble phosphorous is converted into
insoluble calcium phosphate. The common examples of these fertilizers are:

Sr. No. Fertiliser % P2O5

i Single Superphosphate (CaH2PO4)16 18% P2O5

ii Double superphosphate CaH4(PO4) 2 32% P2O5

iii Triple superphosphate Ca(H2 PO4) 2 46 to 48% P2O5

iv Ammonium phosphate 20% P2O5

 b. Citric acid soluble Phosphatic Fertilizers: The citric soluble fertilizers are
suitable for acidic soils because at low pH citrate soluble phosphorus is
converted to monocalcium phosphate not as water soluble phosphate and
therefore, phosphorus is not fixed as iron and aluminium phosphate.

Sr. No. Fertiliser % P2O5

i Dicalcium phosphate, CaHPO4 14% P2O5 extract soluble

ii Basic slag (CaO) 5P2 O5. SiO2 17 20% P2 O5 extract soluble

iii Calcium metaphosphate Ca (PO3) 2 60 to 64%P2 O5 extract soluble

a. Water and citrate insoluble phosphatic fertilizers: These mineral fertilizers

contain phosphorus, which is insoluble in water as well as in citric acid.
They are suitable in strongly acid soils or organic soils. These fertilizers are
given in green manured fields. The phosphorus is very slowly released by
microbes at action and remains in soil for long time.

Sr. No. Fertiliser % P2O5

i Rock Phosphate Ca3 (PO4)2CaF2 20 to 30% P2O5extract soluble

ii Bone meal (Ca(PO4) 2) 3 CaF2 21 to 25% P2O5 extract soluble

(d) Other phosphatic fertilizers: Following are the other phosphatic fertilisers.

Sr. No. Fertiliser % P2O5

i Kotka phosphate 26% P2O5

ii Rhenmia phosphate 26 to 28% P2O5

iii Thermophos 18.3% P2O5

iv Pelophos 18% P2O5

v Coronat phosphate 21% P2O5

MATCH INDUTRY
Early matches
A note in the text Cho Keng Lu, written in 1366, describes a sulfur match, small
sticks of pinewood impregnated with sulfur, used in China by "impoverished court
ladies" in AD 577 during the conquest of Northern Qi. During the Five Dynasties
and Ten Kingdoms (AD 907–960), a book called the Records of the Unworldly and
the Strange written by Chinese author Tao Gu in about 950 stated:
If there occurs an emergency at night it may take some time to make a light to light
a lamp. But an ingenious man devised the system of impregnating little sticks of
pinewood with sulfur and storing them ready for use. At the slightest touch of fire
they burst into flame. One gets a little flame like an ear of corn. This marvellous
thing was formerly called a "light-bringing slave", but afterwards when it became
an article of commerce its name was changed to 'fire inch-stick'.
Another text, Wu Lin Chiu Shih, dated from 1270 AD, lists sulphur matches as
something that was sold in the markets of Hangzhou, around the time of Marco
Polo's visit. The matches were known as fa chu or tshui erh.
Chemical matches

The Alchemist in Search of the Philosophers Stone (1771) by Joseph

Wright depicting Hennig Brandt discovering phosphorus.
Prior to the use of matches, fires were sometimes lit using a burning glass (a lens)
to focus the sun on tinder, a method that could only work on sunny days. Another,
more common method was igniting tinder with sparks produced by
striking flint and steel, or by sharply increasing air pressure in a fire piston. Early
work had been done by alchemist Hennig Brandt, who discovered the flammable
nature of phosphorus in 1669. Others, including Robert Boyle and his
assistant, Ambrose Godfrey, continued these experiments in the 1680s with
phosphorus and sulfur, but their efforts did not produce practical and inexpensive
methods for generating fires.
A number of different ways were employed in order to light smoking tobacco: One
was the use of a spill, a thin object something like a straw, rolled paper, or a thin
candle, which would be lit from a nearby, already existing flame and then used to
light the pipe or cigar - most often kept near the fireplace in a spill vase. Another
method saw the use of a striker, a tool that looked like scissors, but with flint on
one "blade" and steel on the other. These would then be rubbed together, ultimately
producing sparks. If neither of these two was available, one could also use ember
tongs to pick up a coal from a fire and light the tobacco directly.
The first modern, self-igniting match was invented in 1805 by Jean Chancel,
assistant to Professor Louis Jacques Thénard of Paris. The head of the match
consisted of a mixture of potassium chlorate, sulfur, sugar, and rubber. The match
was ignited by dipping its tip in a small asbestos bottle filled with sulfuric
acid.[3] This kind of match was quite expensive, however, and its use was also
relatively very dangerous, so Chancel's matches never really became widely
adopted or in commonplace use.
This approach to match making was further refined in the proceeding decades,
culminating with the 'Promethean Match' that was patented by Samuel Jones of
London in 1828. His match consisted of a small glass capsule containing a
chemical composition of sulfuric acid colored with indigo and coated on the
exterior with potassium chlorate, all of which was wrapped up in rolls of paper.
The immediate ignition of this particular form of a match was achieved by
crushing the capsule with a pair of pliers, mixing and releasing the ingredients in
order for it to become alight.

Sulphur-head matches, 1828, lit by dipping into a bottle of phosphorus

In London, similar matches meant for lighting cigars were introduced in 1849 by
Heurtner who had a shop called the Lighthouse in the Strand. One version that he
sold was called "Euperion" (sometimes "Empyrion") which was popular for
kitchen use and nicknamed as "Hugh Perry", while another meant for outdoor use
was called a "Vesuvian" or "flamer". The head was large and
contained niter, charcoal and wood dust, and had a phosphorus tip. The handle was
large and made of hardwood so as to burn vigorously and last for a while. Some
even had glass stems.[10] Both Vesuvians and Prometheans had a bulb of sulfuric
acid at the tip which had to be broken to start the reaction.
Samuel Jones introduced fuzees for lighting cigars and pipes in 1832. A similar
invention was patented in 1839 by John Hucks Stevens in America.
In 1832, William Newton patented the "wax vesta" in England. It consisted of a
wax stem that embedded cotton threads and had a tip of phosphorus. Variants
known as "candle matches" were made by Savaresse and Merckel in 1836. John
Hucks Stevens also patented a safety version of the friction match in 1839.
Friction matches

A tin "Congreves" matchbox (1827), produced by John Walker, inventor of the

friction match.
Chemical matches were unable to make the leap into mass production, due to the
expense, their cumbersome nature and inherent danger. An alternative method was
to produce the ignition through friction produced by rubbing two rough surfaces
together. An early example was made by François Derosne in 1816. His crude
match was called a briquet phosphorique and it used a sulfur-tipped match to
scrape inside a tube coated internally with phosphorus. It was both inconvenient
and unsafe.
The first successful friction match was invented in 1826 by English chemist John
Walker, a chemist and druggist from Stockton-on-Tees, County Durham. He
developed a keen interest in trying to find a means of obtaining fireeasily. Several
chemical mixtures were already known which would ignite by a sudden explosion,
but it had not been found possible to transmit the flame to a slow-burning
substance like wood. While Walker was preparing a lighting mixture on one
occasion, a match which had been dipped in it took fire by an accidental friction
upon the hearth. He at once appreciated the practical value of the discovery, and
started making friction matches. They consisted of wooden splints or sticks of
cardboard coated with sulphur and tipped with a mixture of sulphide of
antimony, chlorate of potash, and gum. The treatment with sulphur helped the
splints to catch fire, and the odor was improved by the addition of camphor.
The price of a box of 50 matches was one shilling. With each box was supplied a
piece of sandpaper, folded double, through which the match had to be drawn to
ignite it. He named the matches "Congreves" in honour of the inventor
and rocket pioneer, Sir William Congreve. He did not divulge the exact
composition of his matches. Between 1827 and 1829, Walker made about 168
sales of his matches. It was however dangerous and flaming balls sometimes fell to
the floor burning carpets and dresses, leading to their ban in France and
Germany. Walker either did not consider his invention important enough to patent
or neglected it.
In 1829, Scots inventor Sir Isaac Holden invented an improved version of Walker's
match and demonstrated it to his class at Castle Academy in Reading, Berkshire.
Holden did not patent his invention and claimed that one of his pupils wrote to his
father Samuel Jones, a chemist in London who commercialised his process. A
version of Holden's match was patented by Samuel Jones, and these were sold
as lucifer matches. These early matches had a number of problems - an initial
violent reaction, an unsteady flame and unpleasant odor and fumes. Lucifers could
ignite explosively, sometimes throwing sparks a considerable distance. Lucifers
were manufactured in the United States by Ezekial Byam. The term "lucifer"
persisted as slang in the 20th century (for example in the First World
War song Pack Up Your Troubles) and matches are still called lucifers in Dutch.

Packing girls at the Bryant & Mayfactory.

Lucifers were, however, quickly replaced after 1830 by matches made according to
the process devised by Frenchman Charles Sauria, who substituted white
phosphorus for the antimony sulfide. These new phosphorus matches had to be
kept in airtight metal boxes but became popular. In England, these phosphorus
matches were called "Congreves" after Sir William Congreve; they went by the
name of loco foco in the United States. The earliest American patent for the
phosphorus friction match was granted in 1836 to Alonzo Dwight Phillips
of Springfield, Massachusetts.
From 1830 to 1890, the composition of these matches remained largely unchanged,
although some improvements were made. In 1843 William Ashgard replaced the
sulfur with beeswax, reducing the pungency of the fumes. This was replaced
by paraffin in 1862 by Charles W. Smith, resulting in what were called "parlor
matches". From 1870 the end of the splint was fireproofed by impregnation with
fire-retardant chemicals such as alum, sodium silicate, and other salts resulting in
what was commonly called a "drunkard's match" that prevented the accidental
burning of the user's fingers. Other advances were made for the mass manufacture
of matches. Early matches were made from blocks of woods with cuts separating
the splints but leaving their bases attached. Later versions were made in the form
of thin combs. The splints would be broken away from the comb when required.
A noiseless match was invented in 1836 by the Hungarian János Irinyi, who was a
student of chemistry. An unsuccessful experiment by his professor, Meissner, gave
Irinyi the idea to replace potassium chlorate with lead dioxide in the head of the
phosphorus match. He liquefied phosphorus in warm water and shook it in a glass
vial, until it became granulated. He mixed the phosphorus with lead and gum
arabic, poured the paste-like mass into a jar, and dipped the pine sticks into the
mixture and let them dry. When he tried them that evening, all of them lit evenly.
He sold the invention and production rights for these noiseless matches to István
Rómer, a Hungarian pharmacist living in Vienna, for 60 forints (about 22.5 oz t of
silver). As a match manufacturer, Rómer became rich, and Irinyi went on to
publish articles and a textbook on chemistry, and founded several match factories.
Replacement of white phosphorus

The London matchgirls strike of 1888 campaigned against the use of white
phosphorus in match making, which led to bone disorders such as phossy jaw.
Those involved in the manufacture of the new phosphorus matches were afflicted
with phossy jaw and other bone disorders, and there was enough white phosphorus
in one pack to kill a person. Deaths and suicides from eating the heads of matches
became frequent. The earliest report of phosphorus necrosis was made in 1845 by
Lorinser in Vienna, and a New York surgeon published a pamphlet with notes on
nine cases.
The conditions of working class women at the Bryant & May factories led to
the London matchgirls strike of 1888. The strike was focused on the severe health
complications of working with white phosphorus, such as phossy jaw. Social
activist Annie Besant published an article in her halfpenny weekly paper The
Link on 23 June 1888. A strike fund was set up and some newspapers collected
donations from readers. The women and girls also solicited contributions.
Members of the Fabian Society, including George Bernard Shaw, Sidney Webb,
and Graham Wallas, were involved in the distribution of the cash collected. The
strike and negative publicity led to changes being made to limit the health effects
of the inhalation of white phosphorus.
Attempts were made to reduce the ill-effects on workers through the introduction
of inspections and regulations. Anton Schrötter von Kristelli discovered in 1850
that heating white phosphorus at 250 °C in an inert atmosphere produced a red
allotropic form, which did not fume in contact with air. It was suggested that this
would make a suitable substitute in match manufacture although it was slightly
more expensive. Two French chemists, Henri Savene and Emile David Cahen,
proved in 1898 that the addition of phosphorus sesquisulfide meant that the
substance was not poisonous, that it could be used in a "strike-anywhere" match,
and that the match heads were not explosive.

New York Times report dated January 29, 1911

British company Albright and Wilson, was the first company to produce
phosphorus sesquisulfide matches commercially. The company developed a safe
means of making commercial quantities of phosphorus sesquisulfide in 1899 and
started selling it to match manufacturers. White phosphorus however continued to
be used, and its serious effects led many countries to ban its use. Finland
prohibited the use of white phosphorus in 1872, followed by Denmark in 1874,
France in 1897, Switzerland in 1898, and the Netherlands in 1901. An agreement,
the Berne Convention, was reached at Bern, Switzerland, in September 1906,
which banned the use of white phosphorus in matches. This required each country
to pass laws prohibiting the use of white phosphorus in matches. The United
Kingdom passed a law in 1908 prohibiting its use in matches after 31 December
1910. The United States did not pass a law, but instead placed a "punitive tax" in
1913 on white phosphorus–based matches, one so high as to render their
manufacture financially impractical, and Canada banned them in
1914. India and Japan banned them in 1919; China followed, banning them in
1925.
In 1901 Albright and Wilson started making phosphorus sesquisulfide at
their Niagara Falls, New York plant for the US market, but American
manufacturers continued to use white phosphorus matches. The Niagara Falls plant
made them until 1910, when the United States Congress forbade the shipment of
white phosphorus matches in interstate commerce.
Safety matches

Jönköpings safety match industry 1872.

The dangers of white phosphorus in the manufacture of matches led to the
development of the "hygienic" or safety match. The major innovation in its
development was the use of red phosphorus, not on the head of the match but
instead on a specially designed striking surface.
Arthur Albright developed the industrial process for large-scale manufacture of red
phosphorus after Schrötter’s discoveries became known. By 1851, his company
was producing the substance by heating white phosphorus in a sealed pot at a
specific temperature. He exhibited his red phosphorus in 1851, at The Great
Exhibition in London.
The idea of creating a specially designed striking surface was developed in 1844
by the Swede Gustaf Erik Pasch. Pasch patented the use of red phosphorus in the
striking surface. He found that this could ignite heads that did not need to contain
white phosphorus. Johan Edvard and his younger brother Carl Frans Lundström
(1823–1917) started a large-scale match industry in Jönköping, Sweden around
1847, but the improved safety match was not introduced until around 1850–55.
The Lundström brothers had obtained a sample of red phosphorus matches
from Arthur Albright at The Great Exhibition, held at The Crystal Palace in
1851, but had misplaced it and therefore they did not try the matches until just
before the Paris Exhibition of 1855 when they found that the matches were still
usable. In 1858 their company produced around 12 million matchboxes.
Super Deportistas matches from mid 20th century Mexico, part of the permanent
collection of the Museo del Objeto del Objeto in Mexico City.
The safety of true "safety matches" is derived from the separation of the reactive
ingredients between a match head on the end of a paraffin-impregnated splint and
the special striking surface (in addition to the safety aspect of replacing the white
phosphorus with red phosphorus). The idea for separating the chemicals had been
introduced in 1859 in the form of two-headed matches known in France
as Allumettes Androgynes. These were sticks with one end made of potassium
chlorate and the other of red phosphorus. They had to be broken and the heads
rubbed together. There was however a risk of the heads rubbing each other
accidentally in their box. Such dangers were removed when the striking surface
was moved to the outside of the box. The development of a
specialized matchbook with both matches and a striking surface occurred in the
1890s with the American Joshua Pusey, who sold his patent to the Diamond Match
Company.
A match at the beginning of the combustion process
The striking surface on modern matchboxes is typically composed of 25%
powdered glass or other abrasive material, 50% red phosphorus, 5% neutralizer,
4% carbon black, and 16% binder; and the match head is typically composed of
45–55% potassium chlorate, with a little sulfur and starch, a neutralizer (ZnO
or CaCO
3), 20–40% of siliceous filler, diatomite, and glue. Some heads
contain antimony(III) sulfide to make them burn more vigorously. Safety matches
ignite due to the extreme reactivity of phosphorus with the potassium chlorate in
the match head. When the match is struck the phosphorus and chlorate mix in a
small amount forming something akin to the explosive Armstrong's mixture which
ignites due to the friction.
The Swedes long held a virtual worldwide monopoly on safety matches, with the
industry mainly situated in Jönköping, by 1903 called Jönköpings & Vulcans
Tändsticksfabriks AB. In France, they sold the rights to their safety match patent to
Coigent Père & Fils of Lyon, but Coigent contested the payment in the French
courts, on the basis that the invention was known in Vienna before the Lundström
brothers patented it. The British match manufacturer Bryant and May visited
Jönköping in 1858 to try to obtain a supply of safety matches, but it was
unsuccessful. In 1862 it established its own factory and bought the rights for the
British safety match patent from the Lundström brothers.