1ST YEAR LECTURE NOTES
HISTORY OF THE CHEMICAL
INDUSTRY
M A MORRIS
E-MAIL m.morris@ucc.ie
Rm: 108 Kane Building
Synopsis
 Start with initial use of chemicals and the






industrial revolution in the UK.
Importance of resources.
Inorganic chemicals and industry.
Look at advent of catalysis in bulk chemical
synthesis.
Petroleum industry and organics.
Start of the pharma-chem sector.
Materials market development.
Introduction
 Chemicals were known by the ancients
 Ancient Egyptians used ‘soap’
 Soda (sodium carbonates, natron in Egypt) plus
fats to wash corpses prior to during
mummification
 Cement dates back to Egyptians passed to
Romans and the Greeks (forgotten for 2000 yrs)
volcanic ash + rock + caustic soda (NaOH)
 500 yrs ago Mayan Indians used latex balls in
games and in clothing
Recipe for a mummy….












Four jars hold the liver, lungs, intestines, and stomach. The heart is
kept inside the body and the other internal body organs fried.
The brain is pulled thru the nose with a hook. Stuff the head with
tree resin and sawdust.
Soak the body in natron for 40 days. The body is put on a inclined
couch and the liquids and natron fall to the bottom into a pan.
Rub the body with olibanum oil to make the skin supple.
Pack the body to make it more lifelike (with spices or sawdust).
Use wax to seal any incisions.
Tear fine linen into strips 16 yards long and 2-8 inches wide.
Wrap the smaller extremities (toes and fingers) first.
Next, wrap the limbs, and finally, the torso.
Sing appropriate chants over each body part.
Secure linen with tree resin.
Tuck in an amulet after every few layers.
Modern Chemical Industry
 Began in UK around 1800
 Was sponsored by the industrial revolution
with demands for chemicals for other
industries.
 Soap manufacture (alkali + animal fat)
 Cotton – bleach
 Glassmaking – sand (SiO2) and soda
(sodium carbonate)
Some key chemicals needed to be
manufactured……..
 Sulphuric acid - oil of vitriol
 Soda – sodium carbonate
 Caustic soda – sodium hydroxide
Copperas
 Green vitriol (FeSO4.7H2O) was used extensively in the




textile and metallurgical industries and for a number of
other purposes.
Jabir-Ibn-Hayyan (721-815) distinguished between
green vitriol and blue vitriol, ferrous sulphate and copper
sulphate respectively
17th C manufacture copperas containing stones were
collected from the beach placed in oak vessels and
packed with chalk. After several years a liquor a mixture
of sulphuric acid (source of this for many years) and iron
sulphate solution was collected. Further iron was added
to bring it up to stoichiometery.
Sulphate crystals were collected by drying in sun. Twigs
etc were added to promote crystallisation processes.
Took place at Tankerton in Kent and in Dorset but soon
move to the NW of England
Sulphuric acid
 First chemical process on an industrial scale
 This source became green vitriol ( FeSO4.7H2O)





recovered from mineral pyrites and was first material that
Joshua Parr attempted to make at Mynydd Parys (1795).
FeS2(s) + 11O2 → 2Fe2O3(s) + 8SO2(g)
Eventually sulphide/S mines in N. Wales sent material to
Liverpool (Garston sulphuric Acid Co.). Start of the NW
chemical industry.
S (as pyrite also) was oxidised in air to give SO2.
Saltpeter (KNO3) was used as catalyst releasing NOx
Water in reaction chamber absorbed gases
Reactions took place in small glass lined vessels but
scale of production was increased by Roebuck and
Gardner (1746) using large lead lined chambers.
Sulphuric acid improvements
 Gay-Lussac towers (1837)– introduced oxygen
to form SO3 in increased amounts and
recovered NOx reducing requirement for the
KNO3. Improved by Glover (UK) and towers
common in 1870s
 1880s saw further increases. Phillips (UK
vinegar merchant) patented Pt catalysed
oxidation of SO2 to SO3. Was not used until
catalyst reactor built in Germany in 1875. But
technology widely used by 1890.
 In the 20C Pt replaced by vanadium oxides
Soda ash manufacture
 Based on the synthesis of H2SO4
 Leblanc process: 2NaCl + H2SO4 → Na2SO4 + 2HCl
 Na2SO4 + CaCO3 + 2C → Na2CO3 + CaS + 2CO2
 The salt came from the Cheshire salt plain
NaOH manufacture
 From the sodium carbonate:
 Na2CO3 + Ca(OH)2 → 2NaOH + CaCO3
 The HCl was a major problem. James Muspratt
(the most important figure in developing the NW
chemical industry). The fumes were so dense
that visibility in the area was <90m.
 Led to the Alkali Act in 1863 first legislation to
limit air pollution.
Solvay process
 John Hutchison – pioneered NW chemical
industry recognising efficiency of scale
 1847 founded chemical works (Halton –
Runcorn)
 Three key recruits:
Towers – analysis; Brunner – manager; and Mond
from Germany as scientific officer
In 1872 formed Brunner-Mond (part of the giant
ICI)
1874 introduced the Solvay process
Solvay process
 Ernst Solvay Belgium 1838-1922
 Several similar processed but difficult on large
scale (Muspratt had almost gone bankrupt).
Used to much NH4 which was not widely
available
 Advantages of Solvay were:- use of brine, less
waste (low volume CaCl2 vs high vol CaSO4),
CO2/NH3 recovered, costs some 70% less.
However, plant cost was greater
 1890 Solvay was 90% of market
 Process centred on iron towers where rising CO2
was mixed with brine spray
Solvay process
 NH3 + H2O + CO2 → NH4HCO3
 NaCl + NH4HCO3 → NaHCO3 + NH4Cl
 CO2 and NH3 could be recovered
 2NaHCO3 → Na2CO3 + H2O + CO2
 NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 + 2H2O
Ammonia production
 Vital chemical in several industries
 Dyes, cotton treatments, plastics, fertilizer
and Solvay process
 It was difficult to make – hydrogen is
expensive and the N2/H2 reaction was very
high temperature
 Before 1800s from distallation of natural
products
Ammonia production
 1800s Distillation of coal became primary source




for organics and ammonia and town gas. All
towns had a gas works.
1880s Solvay designed his own coke ovens
(source of C for iron).
Coal was heated at very high temperatures in
reducing atmospheres (coal hydrocarbons)
In this very reducing atmosphere significant
quantities of ammonia were produced.
First fertilizer was ammonia sulphate from
reaction of NH4Cl plus sulphuric acid
Cement and lime
 Lime (limestone CaCO3, lime CaO and
slaked lime) were central to most chemical
processes in the 1800s
 Also central to cement – Portland cement
was the first advanced materials.
 Joseph Aspdin (Leeds bricklayer) patented
Portland cement in 1824
 Limestone came originally from S Coast of
UK
Cement
 Most common preparation is mixture of
limestone, clay and sand heated (1500C) in a
Kiln to produce klinker pellets, a mixture of
calcium silicates, calcium aluminates and
calcium aluminosilicates
 CaCO3 = CaO + CO2
 These are ground to a fine powder with gypsum
and iron oxides.
 Used to seal and rebuild the Thames tunnel
Chlorine
 Is a strong bleaching agent and disinfectant used in




textiles and medical application. Was originally used as
chlorine water.
Charles Tennant (Glasgow) opened a factory there in
1799 that produced bleaching powder which was much
less harmful than the bleach based on chlorine in an
aqueous solution
At the time Cl2 was produced by reaction of salt with
sulphuric acid and manganese dioxide
In the 1860's two industrial chemists, Walter Weldon and
Henry Deacon, devised a way of recovering chlorine
from the waste hydrochloric acid produced by the
Leblanc soda factories.
MnO2 + 4HCl → Cl2 + MnCl2 + 2H2O
Chlorine
 The MnO2 could be recovered. The manganese chloride
was treated with milk of lime (a thin cream of slaked lime
and water) to make ‘Weldon Mud’ (a mixture of calcium
manganite CaO.2MnO2 and manganese manganite
MnO.MnO2).This was separated from the CaCl2 solution
and used again in the chlorine production process.
 1870 Deacon developed the process
2HCl + 1/2O2 → H2O + Cl2 used copper as a catalyst
 Gaskell, Deacon & Company based at Widnes exploited
this technology
 Eventually all of the Leblanc companies merged to form
United Alkali Company who later where one of the
companies merged to form ICI
Chlorine
 All of the chlorine technologies were dirty
 Electrochemistry would be cleaner and
first observed by Cruikshank in 1800
 First patent based on a porous diaphram
was 1851 to Watt
 However, the lack of domestic electricity
supplies limited technology
 United alkali company operated first
membrane cell in 1890
Cell technologies
 Membranes were required for efficient
production of Cl2 and NaOH from salt
solution.
 Anode: NaCl → Na+ + Cl-; Cl- → Cl. + e
 2Cl. → Cl2