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UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry
Equilibrium constant K
N2(g) + 3H2(g) H
2NH3(g)
m
= 92.4 kJ mol1
fig. 1.4.1 The effect of changing the temperature on the equilibrium constants for three different reactions.
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UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry
UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry Since the forward reaction is endothermic, high temperatures will move the equilibrium to the right producing more carbon monoxide and hydrogen. High temperatures will also, of course, speed up the reaction considerably. There is an increase in entropy in the forward reaction because there are more gaseous molecules on the right-hand side. Looking at table 1.2.3 in chapter 1.2 (page 45), an endothermic reaction with an increase in entropy is only spontaneous at high temperatures. This is consistent with our everyday experience that there is no reaction between coke and water at ordinary temperatures. The reaction can be carried out at normal pressure since attempting to use higher pressures will only push the equilibrium to the left, reducing the amount of products. Notice that there are 2 moles of gas on the right-hand side but only 1 mole of gas on the left-hand side. Synthesis gas is then mixed with hydrogen and then passed over a catalyst of copper, zinc oxide and alumina at 250 C and 50100 atmospheres. CO(g) + 2H2(g) CH3OH(g) H = 90 kJ mol1 Theoretically, the maximum yield of methanol would be obtained at low temperature (because the forward reaction is exothermic) and by high pressure (because there are 3 moles of gas on the left-hand side and only 1 mole on the right leading to a decrease in entropy). In practice, a sufficient yield is obtained by a moderately high temperature, high pressure and the use of a catalyst. Looking again at table 1.2.3, an exothermic reaction with a decrease in entropy suggests that this reaction is spontaneous only at low temperatures.
fig. 1.4.3 A bus in New York powered by methanol.
In a new process, methanol is produced from synthesis gas, comprising of hydrogen and carbon monoxide. The synthesis gas is passed through a liquid phase reactor containing a solid catalyst suspended in methanol. In this innovation, methanol acts both as a product and as a suspension medium for the catalyst. Doing the reaction this way gives a higher conversion to methanol. Questions
1 There are factors which affect both the equilibrium mixture of a reaction and the rate of the reaction. Why do these factors have to be considered very carefully in an industrial process? 2 If methane is used to make methanol, the first stage in producing synthesis gas is represented by:
It should be obvious as to how useful this last point is for enabling chemical industries to increase the yield of the substances they want to manufacture! Now you are going to consider how these general principles are applied in the manufacture of methanol. However, in an industrial setting it is not only the equilibrium mixture which is important. The rate at which the reaction takes place, and the economics of the process, have to be considered as well.
Methanol has a much higher octane rating than petrol and it has been used as a racing car fuel for decades. The methanol is usually mixed with petrol for example, M85 is 85% methanol mixed with petrol. However, there are problems with using methanol. A methanol molecule contains oxygen as well as carbon and hydrogen. One litre of methanol contains only about 53% of the energy of petrol. So fuel tanks would need to be larger and cars would be heavier. Methanol has a higher flash point (the temperature at which the vapour ignites) than petrol. This would need modifications to the ignition systems of vehicles to ignite the methanol. Methanol corrodes metal components and certain types of rubber. It is necessary to use stainless steel and methanolresistant rubbery materials. Methanol-fuelled vehicles produce less hydrocarbon, carbon monoxide and oxides of nitrogen emissions, but they do produce methanal emissions. A much more expensive exhaust system would be required.
CH4(g) + H2O(g) CO(g) + 3H2(g) H = +206 kJ mol1 The synthesis gas produced by this method contains more hydrogen from the same quantity of steam. If carbon dioxide is mixed with the synthesis gas made from methane, a secondary reaction takes place which also produces methanol. a Suggest, with reasoning, likely conditions for the reaction of methane with steam. b Write a balanced equation for the reaction of hydrogen with carbon dioxide. 3 a Write the rate equation, in terms of partial pressures, for the reaction of carbon monoxide and hydrogen to produce methanol. b At 671 K, the value of Kp is 12.07 MPa2. Would the value of Kp be higher, lower or the same at 771 K?
Manufacture of methanol
Today, methane (natural gas) or naphtha from the fractional distillation of crude oil are used to produce methanol. Alternatively coal could be used. Whichever method is used, the basic chemistry is the same. The first stage is the production of synthesis gas (a mixture of carbon monoxide and hydrogen). If coal is used, and there is reason to believe that this might be the best raw material in the future, the coal is first heated out of contact with air to produce coke. Then steam is passed over white-hot coke (at 8001200 C): C(s) + H2O(g) CO(g) + H2(g) H = +131 kJ mol1
Another way of using methanol in a vehicle is in a methanol fuel cell. Unfortunately these will not operate at room temperature but need a temperature of at least 50 C to operate.
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UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry
UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry
The importance of a suitable catalyst was realised. Figure 1.4.5 shows the energy profiles for ammonia synthesis with and without an iron catalyst. The use of a catalyst lowers the activation energy, speeding up the reaction sufficiently to obtain ammonia under conditions where the equilibrium conversion is large enough to be useful.
0.9 0.8 0.7 0.6 0.5 50 10 3 1 500 600 700 800 Temperature/K 900
1/2 A E = 103 kJ mol1
P = 300 atm
200 100
without catalyst
Haber recognised that much higher pressures had to be used, which is in fact the real basis for the synthesis of ammonia. He also realised that significant yields of ammonia would not be made in a single pass of nitrogen and hydrogen over the catalyst. He developed the process of recycling unreacted nitrogen and hydrogen after condensation of the ammonia. Habers ideas represented a significant change from the previous static approach to industrial production and the development of a more dynamic approach. He was using reaction kinetics as well as thermodynamics. In 1909, Haber established a small-scale laboratory plant using the recycling process. This was capable of producing 80 g of ammonia every hour.
Energy
0.4
N2 + 3/2 H2
(a)
0.9 0.8 Ammonia/mol fraction 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 (b) 0 100
In 1910, construction work began on the first large factory, with an estimated annual output of 30 000 tons of ammonia. Scaling up the process was very much the responsibility of engineer Karl Bosch, whose company Badische Anilin- und Sodafabrik (BASF) had supported Habers research. Bosch solved some key problems, such as designing containers that could withstand a corrosive process over a period of time. It was, however, not easy and there were a number of explosions in the factories in the early days. A modern plant produces 10001500 tonnes of ammonia per day. The gases move through the plants at speeds of 10 00020 000 m3 per 1 m3 of catalyst per hour. This rapid movement of gas is important in getting a good yield. Improvement of the catalysts (e.g. the use of ruthenium) has enabled reductions to be made in the operating pressure to about 40 atmospheres. The atom economy of the modern Haber process is 100% because all of the reactants are successfully turned into the desired product.
The nitrogen and hydrogen molecules lose some of their freedom to move when bound to the catalyst surface. Haber experimented to find suitable catalysts. It was known that iron was suitable, but other transition metals were tried. He found that finely divided osmium could be used, as could uranium. However, these catalysts were too expensive and unstable to use for commercial production. Eventually, iron with a few per cent of alumina and a small amount of potassium was adopted.
300
46.1 kJ mol1
200 Pressure/atm
The equilibrium constant for this reaction is: Kp = p(NH3) / p(N2) p(H2)/ This information shows that the formation of ammonia is an exothermic process and that it is accompanied by a reduction in entropy as there are more moles of gas on the left-hand side. Looking at table 1.2.3 on page 45, it should be clear that this process is likely to be spontaneous only at low temperatures. It was also clear that the yield of ammonia increased as pressure increased. This was supported by experiments carried out by Haber and his team. They examined the equilibrium under different conditions of pressure (at constant temperature) and temperature (at constant pressure). They also calculated Kp values to four decimal places. The results are shown in fig. 1.4.4.
fig. 1.4.4 The mole fraction of ammonia at equilibrium from an initial mixture of nitrogen and hydrogen in a 1 : 3 ratio (a) at different temperatures at a constant pressure; (b) at different pressures at a constant temperature.
Questions
1 In the contact process for manufacturing sulfuric acid, the key reaction is: SO2(g) + O2(g) SO3(g)
O H = 98 kJ mol1
e What does this suggest about the most suitable temperature for the process? f What problems does this cause? Suggest how they are overcome.
In fact, equilibrium conditions are only part of the story. They dont give any indication about the rate of the reaction. The reaction does not take place at low temperatures because a great deal of energy is required to break the bonds required to turn nitrogen and hydrogen molecules into atoms. A temperature of about 3000 C is required to break nitrogen molecules, and about 1000 C to break hydrogen molecules. Unfortunately, raising the temperature to break these bonds will push the equilibrium to the left.
a Write down the expression for Kp. b Is there an increase or decrease in entropy in the forward reaction? Explain your answer. c Is this reaction exothermic or endothermic?
The process is carried out using slightly more oxygen than the 2 : 1 ratio suggested by the equation. g What is the benefit of this? Why is a much greater concentration of oxygen not used? h The conversion of SO2 to SO3 is efficient even with relatively low pressures. What does this mean for the process on an industrial scale?
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UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry
UNIT 4 General principles of chemistry I Rates, equilibria and further organic chemistry
Controlling reactions for safety, yield, cost and Controlling reactions for safety, yield, cost and atom economy atom economy [4.6c, d]
In any industrial process, the aim is to achieve the maximum yield for the minimum cost. As a result, reaction conditions are balanced to give the best equilibrium position that can be achieved under conditions that are not too expensive to maintain. High pressure needs expensive reaction vessels. High temperatures use a lot of energy and are expensive. So, whenever possible, catalysts are used to increase reaction rates and products are removed to push the equilibrium position towards the desired yield. Safety is another important issue. It is important for many reasons that an industrial chemical process is as safe as possible, and this is another reason why very high temperatures and pressures are avoided if there is a good alternative route. Finally, for all industrial reactions economy is the bottom line. If a process does not make money, it wont succeed. This is where the concept of the atom economy of an industrial process is so important: atom economy (%) = mass of atoms in desired product 100% mass of atoms in reactants A reaction with a good atom economy is very efficient at turning reactants into the desired products with very little waste. In pages 31, 206 and 2445 of Edexcel AS Chemistry, you discovered the importance of this concept and how it was developed. There are a number of ways in which the atom economy of a process can be improved they include capturing and recycling any unused reactants, and using more efficient alternative reactions in the process where possible, e.g. the alternative methods of producing synthesis gas for the production of methanol. The Haber process takes account of both thermodynamic and kinetic factors as well as recycling unreacted reactants. These ideas can be applied to other industrial processes always be on the lookout for them.
heat
CO2
NH3
Step 2: Purification The major impurities in the mixture at this stage are water, produced during the reaction, and any unused reactants ammonia, carbon dioxide and ammonium carbamate.
Recovery cooling
Synthesis urea, excess NH3, ammonium carbamate, H2O Decomposition urea, H2O heat Concentration urea Granulation H2O H 2O
NH3, CO2
The purification is carried out in three stages to reduce the formation of undesirable products. The pressure is reduced to 17 atmospheres and the solution is heated. This causes any ammonium carbamate to decompose into ammonia and carbon dioxide. Excess ammonia and carbon dioxide escape from the solution. Then the pressure is reduced and more carbon dioxide and ammonia escape. Finally, the pressure is reduced to less than 1 atmosphere. Again more carbon dioxide and ammonia escape from the solution. Any ammonia and carbon dioxide remaining are recycled.
Urea granules
The formation of biuret reduces the yield of urea. Whats more, if it is mixed with the urea used as fertiliser, it will burn the leaves. Another unwanted reaction that can occur during the process is the hydrolysis of urea: NH2CONH2(s) + H2O(l) 2NH3(g) + CO2(g)
Step 3: Concentration
75% of the urea solution is heated under vacuum, which evaporates some of the water, increasing the urea concentration. Some urea crystallises. After evaporating some more water, a concentrated solution of urea is produced.
Step 1: Synthesis
This involves two reactor vessels. A mixture of carbon dioxide and ammonia is compressed to 240 atmospheres. An exothermic reaction takes place, and a heat exchanger removes heat and uses it to turn water to steam. About 78% of the carbon dioxide is converted into urea and the liquid is then purified. The gas from the first reactor and recycled gases go into the second reactor where the pressure is about 50 atmospheres. Here, about 60% of the remaining CO2 is converted to urea. The solution is then purified in the same way as the liquid from the first reactor.
Step 4: Granulation
Urea is sold as a fertiliser in the form of small granules. These can be formed by spraying the concentrated solution or molten urea onto seed granules. All dust and air from the granulator is removed by a fan into a dust scrubber.
Questions
1 Explain how these reactions maximise the yield while keeping the cost of the process to a minimum and maintaining safety standards. 2 a Which steps of this reaction will help to increase the atom economy of the process? b Try to find out figures for the atom economy of the manufacture of urea. c How does the atom economy step in the manufacture of urea compare to the Haber process and why? 3 Urea dust can irritate the skin, eyes and nose. What precautions are taken in the factory to prevent anyone suffering from these effects? 4 Draw the displayed formulae for a ammonium carbamate; b urea; c biuret. 5 Suggest why a sudden reduction of the pressure is not carried out during the purification.
Figure 1.4.6 shows the flow diagram for urea production. The process is designed to maximise the yield from these two reactions and stop the formation of an unwanted compound, biuret: 2NH2CONH2(s) NH2CONHCONH2(s) + NH3(g)
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