1ST YEAR LECTURE NOTES

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Published on February 22, 2008

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1ST YEAR LECTURE NOTES HISTORY OF THE CHEMICAL INDUSTRY :  1ST YEAR LECTURE NOTES HISTORY OF THE CHEMICAL INDUSTRY M A MORRIS E-MAIL m.morris@ucc.ie Rm: 108 Kane Building Synopsis:  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:  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….:  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:  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……..:  Some key chemicals needed to be manufactured…….. Sulphuric acid - oil of vitriol Soda – sodium carbonate Caustic soda – sodium hydroxide Copperas:  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:  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:  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:  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:  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:  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:  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:  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:  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:  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:  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:  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:  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:  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:  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:  Cell technologies Membranes were required for efficient production of Cl2 and NaOH from salt solution. Anode: NaCl → Na+ + Cl-; Cl- → Cl. + e 2Cl. → Cl2

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