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Pupil Number: CfE Higher Chemistry Unit 3 Chemistry in Society Chemical Industry Importance of the Chemical Industry the Chemical Industry is one of the largest British industries. its products are indispensable to many aspects of modern life and many are used for the benefit of society it is the only manufacturing industry to export more than it imports and so earns a trade balance surplus from these exports for Britain also invisible trade balance surplus from selling licenses to use British processes abroad the chemical industry involves the investment of large sums of money but employs relatively few people making it a capital intensive and not a labour intensive industry. Stages in the manufacture of a new product The manufacture of a new product is a step-wise process from its discovery. research and development laboratory process a new potentially useful chemical is prepared and patented. Some products are discovered by accident, but others as a result of long and expensive research. small scale to review the production route pilot study the product is now required in larger amounts and will be manufactured in a pilot study using the route identified by the research group but in kilogram quantities. Product quality, health hazards, and production costs will be discussed. scaling up planning the scaling up from lab quantities to full scale production will have been going on from the pilot study stage. Production plant design, planning considerations, commissioning and start up review this will occur at each stage. All processes are reviewed and modifications are made. Raw Materials and Feedstocks A feedstock is a chemical from which other chemicals are manufactured. Feedstocks are made from raw materials; the basic resources that the earth supplies to us. They are: Fossil fuels–coal, oil and natural gas metallic ores–e.g. aluminium extracted from bauxite(Al2O3) minerals–chlorine from sodium chloride water and air – water in hydration of ethene to ethanol and nitrogen in the Haber Process, oxygen in the catalytic oxidation of ammonia organic materials–of plant and animal or vegetable oils and starch Crude oil is a raw material from which naphtha is obtained by fractional distillation. Naphtha is a feedstock that can be cracked to produce ethene. 2 Batch and Continuous Processes In a batch process the chemicals are loaded into the reaction vessel. The reaction is monitored and at the end of the reaction the product is separated and the reaction vessel cleaned out ready for the next batch. In a continuous process the reactants are continuously loaded at one end of the reaction vessel and the products are removed at the other end. Each process has advantages and disadvantages. Batch Process v Continuous Process Process Batch Continuous Advantages Disadvantages suited to smaller scale production up to 100 tons per annum possibility of contamination from one batch to the next more versatile than continuous as they can be used form ore than one reaction more suited for multi step reactions or when reaction time is long filling and emptying takes time during which no product, and hence no money, is being made suited to large scale production >1000 tons per annum very much higher capital cost before any production can occur suitable for fast single step processes more easily automated using computer control not versatile, can make only one product not cost effective when run below full capacity smaller work force operates round the clock, 365 days per year tend to operate with relatively low volumes of reactants allowing easy removal of excess heat energy In general products that are made on a very large scale will use a continuous process eg. sulfuric acid, ammonia, iron, ethene, poly(ethene). Products made on a smaller scale or when a continuous process would be difficult to devise or operate will use a batch process eg. pharmaceuticals, dyes, copper refining by electrolysis. Factors Influencing the Choice of Synthetic Route - Cost - availability of feedstocks - Yield of the reaction – can unreacted starting materials be recycled, or sold? - Difficulty and cost of waste disposal - Energy consumption - Emissions to the atmosphere 3 Economic Aspects Operating Conditions The conditions under which a chemical process operates are chosen to maximise economic efficiency. We have considered these in other topics but examples are: Raising the temperature may increase the rate of a reaction but it will increase energy costs so may not be economic Increasing the pressure may shift equilibrium in favour of the product but will mean using stronger reaction vessels and more powerful compressors and may not be economic. Costs in the Chemical Industry Costs come under 3 main categories – capital, fixed and variable costs. Capital Costs These are incurred when building the plant. The life of a plant is assumed to be only about 10 years after which it is written off. The cost of this depreciation is recovered under fixed costs. Fixed Costs These are costs that are the same whether 1 ton or 1000 tons of product are made. The effect of the fixed cost decreases as the amount of product increases. They include: - Depreciation of the plant - Labour - Land purchase - Variable Costs - These are directly related to output and include: - Raw materials and energy - Packaging - Waste disposal and effluent treatment Location of the Chemical Industry Many locations are for historical and practical reasons. They had to be near: Water supply Raw materials Good communications; near ports, roads and rail Reliable energy supplies Available skilled labour 4 Safety and the Environment The chemical industry is well aware of its environmental responsibilities and is acting accordingly. Power stations that burn fossil fuels must remove the sulfur dioxide from the gases before release to the atmosphere. The SO2 is converted to H2SO4 , which is sold. Waste used to be dumped in quarries, rivers, the sea or stored in containers from which it could leak into streams. These methods are no longer acceptable and are increasingly becoming illegal. Waste must be treated and discharged only when it is not harmful to the environment – it must meet requirements of pH and metal ion content. Water containing organic waste must not be discharged into rivers or canals if it will reduce significantly the oxygen content of the water, causing fish to die. Between 1990 and 1996 discharge of potentially harmful chemicals into UK rivers was reduced by 91%. Plants have reduced accidents by 50% in the last decade. Road and rail tankers that carry chemicals are constructed to withstand impact in accidents. Plants have their own fire fighting teams on site. Plants are designed with safety in mind. Chemicals are hazardous so the accident rate will never be zero but the aim is to learn from mistakes and reduce the rate to a minimum. It is essential at this stage to revise all of your National 5 calculations that were based on moles and equations. 5 Calculations Based on Equations A balanced equation is taken to give the relative number of moles of each reactant and product. Since the mass of one mole of any substance is expressed in grams, the masses involved can then be calculated as shown. Worked Example Calculate the mass of water produced on burning 1g of methane CH4 1 mole + 2O2 CO2 + 2H2O 2 moles It is not necessary to calculate the masses of carbon dioxide and oxygen – these substances are not included in the question. Step 1 Convert moles to mass for the substances involved CH4 2H2O 12 + (4 x 1) 16g Step 2 2 [ (2 x 1) + 16 ] 36g By proportion; determine the mass of water produced 16g 1g 36g 36 x 1 16g = 2.25g The Idea of Excess Reactants are needed for a chemical reaction to take place. When one of the reactants is used up the reaction will stop. Any reactant, which is left unreacted, is said to be “in excess”. Worked Example 1 8g of methane is mixed with 16g of oxygen. A spark is applied to the mixture to start the reaction. Calculate the mass of carbon dioxide produced. CH4 + 2O2 1 mole 2 moles Step 1 CO2 + 2H2O 1 mole Calculate the number of moles of each reactant No. moles CH4 = No. moles O2 mass = 8 gfm 16 = 0.5moles = mass = 16 = 0.5moles gfm 32 6 Step 2 Use the balanced equation to determine the quantity of each reactant used in the reaction. CH4 1 mole + 2O2 2 moles Therefore, for every 0.5 moles of methane 1 mole of oxygen would be required. Looking at the quantities of reactants from step 1 there is not enough oxygen to allow all of the methane to react therefore some methane will be left over at the end. The methane is said to be in excess and the oxygen will therefore determine the quantity of carbon dioxide produced. Step 3 Convert moles to mass and carry out a proportion calculation to determine the mass of carbon dioxide produced. CH4 + 2O2 1 mole 2 moles CO2 + 2H2O 1 mole 64g 16g 44g 16 x 44 64 = 11g Worked Example 2 What mass of hydrogen gas is produced when 2.45g of magnesium is added to 100cm 3 of dilute hydrochloric acid, concentration 1 moll-1? Mg + 2HCl 1 mole 2 moles Step 1 MgCl2 + H2 1 mole Calculate the number of moles of each reactant No. moles Mg = mass = gfm No. moles HCl = Step 2 So 2.45 24.5 = 0.1 moles Cx V 1 x 0.1 = 0.1 moles Use the balanced equation to determine the quantity of each reactant used in the reaction. Mg + 1 mole 0.1 moles requires 2HCl 2 moles 0.2 moles From step 1 it can be seen that there is not enough acid to allow all of the Mg to react hence the Mg will be in excess and the acid will control the mass of hydrogen produced. 7 Experiment 3.1—Excess Magnesium reacts with dilute sulphuric acid to produce hydrogen gas. Mg + H2SO4 (aq) H2 + MgSO4 If excess dilute sulphuric acid is used, the number of moles of unreacted acid can be found experimentally by titration with sodium hydroxide solution using an indicator. This can then be compared with the theoretical number of moles of unreacted acid. Experiment Accurately weigh out 0.4g of magnesium ribbon. Note the exact mass. Add the magnesium to a 250cm3 volumetric flask. Use a burette to add 50cm3 of dilute sulphuric acid, concentration 0.5 mol l -1 to the flask. When the fizzing has completely stopped, add water to the flask up to the 250cm 3 calibration point. Secure the lid and shake well. Titrate 25cm3 portions of this solution with sodium hydroxide solution, concentration 0.1 mol l -1, using phenolphthein as the indicator. Repeat until two concordant results are obtained (within 0.1cm3) Write Up Complete a full write up for this experiment including the all appropriate calculations. 8 Molar Volume The molar volume is the volume of which one mole of a gas occupies. Worked Example 1 The volume of 8g of oxygen is 5.5 litres. Calculate the volume of 3 mol of oxygen. gfm O2 = 2 x 16 = 32g 8g 96g 5.5 5.5 x 96 8 = 66 litres Worked Example 2 Calculate the volume of 0.14g of nitrogen. (Assume the molar volume of the gas is 23 litres mol -1) gfm N2 = 2 x 14 = 28g 28g 0.14g 23 23 x 0.14 28 = 0.115 litres or 115 cm3 Worked example 3 Calculate the volume of hydrogen produced when 0.2g of zinc reacts with excess sulfuric acid. (Take the molar volume to be 22.2 litres mol-1) Zn + 1 mole H2SO4 1mole Zn 0.2 x 1 65 =0.003moles ZnSO4 65g 0.2g + H2 1 mole Therefore, we have 0.003 moles of H 2 1 mole 22.2 Litres 0.003moles 0.003 x 22.2 1 = 0.068 Litres Reacting Volumes 1 mole of any gas occupies roughly the same volume (at the same temperature and pressure). This means that equal volumes of gases contain the same number of moles. = = 1 litre of O2 1 litre of H2 1 litre of CO2 We already equation gives the same number of moles of reactants and products. N2(g) + 3H2(g) 1 mole 3 moles So.. 1 litre + 3 litres 9 2NH3(g) 2 moles 2 litres know that a balanced NOTE: liquid or solid reactants and products are not included in this calculation! C(s) + 1mole O2(g) 1mole CO2(g) 1mole So.. not a gas 1 litre 1 litre Worked Example 1 30cm3 of methane is completely burned in 100cm3 of oxygen. What is the volume and composition of the gas at the end of the experiment? (All volumes are measured at atmospheric pressure and room temperature) CH4(g) 1mole + 2O2(g) 2moles CO2(g) + 2H2O(l) 1mole Step 1: from the balanced equation determine which reactant is in excess 1 mole CH4 reacts with 2 moles of O2 30cm3 60cm3 Since there is 100cm3 of O2, O2 is in excess by 40cm3 Step 2: since the oxygen is in excess the methane will be used up first and hence will control the volume of product. CH4(g) 1mole 30cm3 + 2O2(g) CO2(g) + 2H2O(l) 1mole 30cm3 So the total volume and composition of gas at the end of the experiment is: Total Volume at the end will be: 70cm3 40cm of O2 left unreacted and 30cm3 of CO2 produced 3 NOTE: since the water is a liquid it is not considered. 10 Experiment 3.2—Synthesising sodium citrate—Percentage Yield Calculation. Sodium citrate is also known as food additive E331. It is often used as an acidity regulator in drinks, and as an emulsifier for oils when making cheese. It allows the cheeses to melt without becoming greasy. Sodium citrate is also the main ingredient in over the counter cystitis medication. You are going to synthesis sodium citrate and calculate the percentage yield and atom economy achieved. Experiment Weigh out 3.5g of citric acid crystals, add to a beaker Measure out 50cm3 of 1.0 mol l-1 sodium hydroxide and add to the crystals Stir the mixture until all the crystals have dissolved Evaporate the sodium citrate solution in an evaporating basin Weigh dried powder with an accurate balance and calculate the percentage yield. Write up Complete a full write up for this experiment. The calculation involving percentage yield can only be completed once the next page is completed. 11 Percentage Yield Calculations The yield in a chemical reaction is the quantity of product obtained. The actual yield can be compared, as a percentage, with the theoretical. Worked Example 1 5g of methanol reacts with excess ethanoic acid to produce 9.6g of methyl ethanoate. Calculate the percentage yield. Step 1: determine the theoretical yield (the quantity expected from the balanced equation) CH3OH + CH3COOH CH3OOCCH3 + 2 H20 1 mol 74g 74 x 5 32 1 mol 32g 5g = 11.56g Theoretical Yield Step 2: = 11.56g The actual yield is always given in the question. Actual yield = 9.6g Step 3: Percentage yield = = 9.6 x 100 11.56 83% The percentage yield is a very important consideration for industrial chemists. They must take account of cost of raw materials, plant-running costs etc. If the yield of product is not sufficient enough to cover the costs of production then the process would not be considered to be economically viable. Atom Economy Atom economy is a measure of the proportion of reactant atoms which are incorporated into the desired product of a chemical reaction. Calculation of atom economy therefore also gives an indication of the proportion of reactant atoms forming waste products. % atom economy = Mass of desired product(s) x 100 Total mass of reactants In developing an atom economical reaction pathway the industrial chemist may well prefer rearrangement and addition reactions over less environmental friendly substitution and elimination reactions. 12 Example 1: Addition reaction – halogenation of an alkene H H C Br + C H3C H Br2 CH3 Br C C H3C H CH3 (Z)-but-2-ene C4H8 1mol (12 x 4) + (8 x 1) Bromine Br2 1mol 2 x 79.9 2,3-dibromobutane C4H8Br2 1mol (12 x 4) + (8 x 1) + (79.9 x 2) = 56g = 159.8g = 215.8g Total mass of reactants = 56 g + 159.8 g = 215.8 g (Note: Product mass is also 215.8 g) Mass of desired product (2,3-dibromobutane) = 215.8 g % atom economy = Mass of desired product(s) x 100 Total mass HofHreactants 2 HO C C Cl H % atom economy = Ca(OH)2 + H 215.8 2-chloroethanol x 100 = 100% 215.8 C2H5OCl 2mol 2[(12 x 2) + (5 x 1) + 16 + 35.5] Calcium hydroxide Ca(OH)2 1mol 40 + 2(16 +1) = 74g This process is 100% atom efficient, with all the reactant = 161g atoms included within the desired product. Example 2: Elimination reaction Desired Product H H 2 HO C H C Cl + Ca(OH)2 2 H 2-chloroethanol C2H5OCl 2mol 2[(12 x 2) + (5 x 1) + 16 + 35.5] = 161g Desired Product O C H H C + CaCl2 + 2H2O H Calcium hydroxide Ca(OH)2 1mol 40 + 2(16 +1) ethylene oxide C2H4O 2mol 2[(12 x 2) + (4 x 1) + 16] Calcium chloride CaCl2 1mol 40 + (2 x 35.5) Water H2O 2mol 2 [(2 x 1) + 16] = 74g = 88g = 111g = 36g Waste Products Total Omass of reactants = 161 g + 74 g = 235 +g CaCl2 H H + 2 (Note: product mass = 235 g) C Total C H H Waste Products 2H2atom O % economy = Mass of desired product(s) x 100 Total Mass of reactants H Mass of desired product ethylene oxide = 88 g ethylene oxide C2H4O 2mol 2[(12 x 2) + (4 x 1) + 16] Calcium chloride CaCl2 1mol 40 + (2 x 35.5) Water H2O % atom economy 2mol 2 [(2 x 1) + 16] = 88 235 x 100 = 37.4% This elimination reaction is therefore = 36g efficient, with the remaining 62.6% in the = 111g only 37.4% atom form of unwanted waste products (calcium chloride and water). = 88g 13 Equilibria Reversible Reaction Many reactions are reversible. A reversible reaction can reach equilibrium in a closed system. A reaction reaches equilibrium when the rate of the forward reaction equals the rate of the reverse reaction. reactants ⇌ products At equilibrium, the concentration of the products and the reactants will remain constant. The concentration of reactants will probably not equal the concentration of the products. Where an industrial process produces an equilibrium, costly reactants may not be completely converted into products; chemists try to manipulate the equilibrium to achieve the best possible conversion rate. Catalysts increase the rate at which an equilibrium is formed but do not affect the equilibrium position. The Position of Equilibrium The position of equilibrium means the extent to which the reaction has taken place. The equilibrium in this case lies well to the right hand side. There is 80% conversion of A into B. Sometimes this is indicated by the size of the arrows. In this example, equilibrium would be said to lie to the left. Can you explain what happens in the case of water? Le Chateliers Principle An equilibrium will move to undo any change imposed upon it by temporarily favouring either the forward or backward reaction until a new equilibrium position is reached. reactants ⇌ products If the forward reaction is favoured we say the equilibrium has moved to the right. If the reverse reaction is favoured we say the equilibrium has moved to the left 14 Products of an Equilibrium Reaction with Time At the start of the reaction there will be 100% reactants. However, as the reaction proceeds the reactants will be used up and the products will be formed. Eventually the reaction will reach equilibrium. At this stage the concentration of both the reactants and products will remain constant. 100 100 75% % % 50 50 25% 0 0 Time Time 100 75% % 50 25% 0 Time In a reversible reaction when the curve levels off this indicates that the reaction has reached equilibrium. (it does not indicate that the reaction has stopped). Shifting the Position of Equilibrium If, once an equilibrium has been established the reaction conditions are changed then the position of equilibrium will be altered. If a new equilibrium is established where there is an increase in products we say the equilibrium has shifted to the right. If the new equilibrium results in an increased amount of reactants then we say the equilibrium has shifted to the left. Changing reaction conditions such as concentration, temperature and pressure will cause a shift in equilibrium position. Changing Concentration Increasing the concentration of the reactants, or decreasing the concentration of the products shifts the position of equilibrium to the right hand side Decreasing the concentration of the reactants or increasing the concentration of the products shifts the position of equilibrium to the left. 15 Changing Temperature Increasing the temperature favours the endothermic reaction. Decreasing the temperature favours the exothermic reaction. Changing Pressure In the gaseous state molecules have high energies and are fast moving. Pressure is the result of gas molecules bombarding the walls of the vessel in which the gas is contained. The greater the number of molecules in a given volume the greater the pressure. Low pressure High pressure C(g) 2D(g) The pressure on the right hand side is greater than the pressure on the left hand side because there are more molecules. NOTE: 1. Pressure only affects the equilibrium of a system that involves gases. 2. A pressure change will alter equilibrium only if there are different numbers of moles of gases on each side. A(g) + B(g) C(g) + D(g) Changing pressure will not affect this equilibrium since there are the same number of moles of gas on each side of the equation. 2A(g) + B(g) C(g) + D(g) Changing pressure will affect this equilibrium since there are different numbers of moles of gases on each side of the equation. Increasing the pressure will favour the side with the lowest number of moles in the gas state. Decreasing the pressure will favour the side with the highest number of moles in the gas state. 16 Experiment 3.3—Dehydration of hydrated cobalt chloride Crystals of cobalt chloride which contain water molecules of crystallisation (hydrated cobalt chloride, CoCl2.6H2O) are pink. Anhydrous cobalt chloride, CoCl2, on the other hand is blue. The conversion of hydrated cobalt chloride to anhydrous cobalt chloride is an example of a reversible reaction, i.e. the reaction can go forwards or backwards. Experiment Add a spatula of hydrated cobalt chloride to a test tube. Heat the crystals until the water molecules are driven off. Observe the colour change. Allow the anhydrous cobalt chloride to cool before adding a few drops of water. Observe the colour change. Write up Complete a write up for this experiment to make suitable notes on your observations. 17 The equilibrium between nitrogen dioxide and dinitrogen tetroxide In chemistry, Le Chatelier's principle, also called Chatelier's principle or "The Equilibrium Law", can be used to predict the effect of a change in conditions on a chemical equilibrium. The principle states that: If a chemical system at equilibrium experiences a change in concentration, temperature, volume, or pressure, then the equilibrium shifts to counteract the imposed change and a new equilibrium is established. Experiment Pressure demo: Collect a gas syringe filled with an equilibrium mixture of brown nitrogen dioxide and colourless dinitrogen tetroxide. Press in the plunger of the syringe as far as possible. The colour of the gas mixture will become darker as the concentration of the gas mixture increases. Within a few seconds it will become paler, as the position of the equilibrium responds to the increased pressure, and brown nitrogen dioxide is converted into colourless dinitrogen tetroxide. Release the plunger and the changes will reverse themselves. Pull the plunger out to reduce the pressure and note the colour changes. Temperature demo: Fill a second syringe with 50 cm3 of air and seal with a screw clip. Clamp both syringes vertically in a 2L beaker of water so that they are immersed up to the 100cm3 mark. Note the temperature and the readings of both syringes (which should be the same). Heat the water gently with a Bunsen burner and record the temperature and the volume of gases every 10 °C or so. Before taking each reading, remove the Bunsen burner and stir the water for a couple of minutes to ensure that the temperatures of the gases are the same as that of the water. Twist the plungers of the syringes before taking each reading to ensure that they are not sticking. Continue taking readings until the temperature is about 70 or 80 °C. Plot graphs of volume against temperature for both gases on the same axes. The nitrogen dioxide/dinitrogen tetroxide mixture will expand more than air as the equilibrium responds to the increase in temperature by producing more nitrogen dioxide. If there is time, take further readings as the water cools to check for leaks. Notes A full description for this experiment can be found on the Royal Society of Chemistry web page under classic chemistry demonstrations. http://media.rsc.org/Classic%20Chem%20Demos/CCD-81.pdf 18 Effect of a Catalyst Consider the reversible reaction at equilibrium: If a catalyst is added the rates of both the forward and backward reaction will be increased. without catalyst with catalyst Potential energy Ed Ea Eb A + B Ec C+ D Reaction pathway There is the same decrease in the activation energies of the forward and backward reactions and hence there is the same increase in their rates. Therefore, a catalyst does not alter the position of equilibrium. It does however, speed up the rate at which equilibrium is attained. Equilibrium in Industry The manufacture of ammonia is a very important reaction. Ammonia is made from nitrogen and hydrogen by the Haber Process. The reaction is reversible and if the conditions were kept constant equilibrium would be attained. At equilibrium only 15% yield of ammonia is achieved however, the reaction conditions can be altered to increase the rate of the forward reaction to increase the yield of ammonia. Use of a catalyst An iron catalyst is used in the Haber Process. The catalyst does not alter the position of equilibrium. However, it does allow the process to be carried out more efficiently at a lower temperature. The use of a catalyst does not change the equilibrium it only enables the position of equilibrium to be reached more quickly. 19 (a) Concentration As a result of economic considerations, the Haber Process does not actually ever attain equilibrium. In a condenser, the ammonia gas is cooled and the liquid ammonia piped off. Constantly removing the ammonia gas decreases the rate of the backward reaction. In addition, the unreacted nitrogen and hydrogen are recycled. The increase in the concentrations of the reactant gases increases the rate of the forward reaction. The effect of both of these factors is a more economical production of ammonia. (b) Pressure Since the number of product molecules is less than the number of reactant molecules, increasing the pressure increases the rate of the forward reaction. The pressure chosen is about 200 atmospheres. Beyond this pressure, the relative increase in the rate cannot justify the increased costs. SEE EXPERIMENT 3.4 (c) Temperature Since the reaction is exothermic, increasing the temperature decreases the percentage conversion of reactants to ammonia. However, if the temperature is too low the reaction is too slow. As a result, the Haber Process is carried out at a moderately high temperature of about 400oC. Experiment 3.4—Effect of pressure on equilibrium (DEMO) Take a note of the results/observations and explain what you see. Chemical Energy Enthalpy of Combustion When 1 mole of a substance burns it releases a certain amount of energy which we call the enthalpy of combustion. Definition of Enthalpy of Combustion: The enthalpy of combustion is the energy released to the surroundings when one mole of a substance burns completely in oxygen. When writing balanced equations for enthalpies of combustion it is important to ensure only 1 mole of the substance being burned is included in the equation: C + O2 --> CO2 H2 + ½ O2 --> H20 S + O2 --> SO2 CO + ½ O2 --> CO2 C3H8 + 5O2 --> 3CO2 + 4H2O 20 Enthalpy Calculations There are two types of combustion calculations. In the first type the temperature difference is not mentioned and this calculation simply requires a proportion calculation to be carried out. WORKED EXAMPLE 1 When 1g of ethanol, gram formula mass 46g, is burned 30kJ of energy is released. Calculate the Enthalpy of Combustion for ethanol. 1g 30kJ 46g 30 x 46 1 = 1380kJ This means that when 1 mole of ethanol burns it will produce 1380kJ. Since combustion is always an -1 exothermic reaction the enthalpy of combustion is - 1380 kJmol WORKED EXAMPLE 2 0.16g of methanol, CH3OH is burned in a spirit burner. The heat from this combustion causes the temperature of 100g of water to be raised from 20 oC to 27oC. Calculate the enthalpy of combustion of methanol. Step 1 Step 2 Eh = c m ΔT = 4.18 x 0.1 x 7 = 2.926 kJ 0.16g 2.926kJ 32g 2.926 x 32 0.16 Remember mass is always expressed in kg & 1cm3 of water equals 1g = 585.2kJ So Enthalpy of Combustion, ΔH = - 585.2 kJmol-1 21 Experimental 3.5—Enthalpy of combustion The enthalpy of combustion of a substance is the energy released when one mole of the substance is completely burned in oxygen. The aim of this experiment is to determine the enthalpy of combustion of ethanol i.e. the enthalpy change for the reaction: CH3CH2OH (l) + 3O2(g) 2CO2(g) + 3H2O(l) A measured mass of ethanol is burned in a spirit burner and the heat released is transferred to a copper can containing a known volume of water. From the resulting temperature rise, the enthalpy of combustion of ethanol can be calculated. In this experiment we assume that all the heat released in the combustion reaction is absorbed only by the water in the copper can. Experiment Weigh the spirit burner (already containing ~50cm3 ethanol) with its cap on and record its mass. (The cap should be kept on to cut down the loss of ethanol through evaporation) Using the measuring cylinder, measure out 100 cm3 of water into the copper can. Set up the apparatus as directed by your teacher. Measure and record the temperature of the water. Remove the cap from the spirit burner and immediately light the burner. Slowly and continuously stir the water with the thermometer. When the temperature has risen by about 10 °C, recap the spirit burner and measure and record the maximum temperature of the water. Reweigh the spirit burner and record its mass. Write up Complete a full write up for this experiment. Within the experiment calculate the enthalpy of combustion for ethanol. 22 Hess’s Law The Law of Conservation of Energy states that energy can neither be created nor destroyed, but that it can be changed from one form to another. This particular application of the conservation of energy law to chemical reactions is known as Hess’s Law. Hess’s Law: the enthalpy change in converting reactants into products is the same regardless of the route by which the reaction takes place. 1 A B ∆H1 ∆H2 2 C ∆H4 3 D ∆H5 ∆H3 ∆H6 E The total enthalpy change for route 1 = ∆H1 The total enthalpy change for route 2 = ∆H2 + ∆H3 The total enthalpy change for route 3 = ∆H4 + ∆H5 + ∆H6 According to Hess’s Law the total enthalpy change for 1, 2 & 3 will be identical. ∆H1 = ∆H2 + ∆H3 = ∆H4 + ∆H5 + ∆H6 The reaction can take place by two methods: ∆H1 Route 1 NaOH(s) ∆H2 NaCl(aq) + HCl(aq) + Route 2 NaOH(aq) According to Hess’s Law: ∆H1 = ∆H2 + ∆H3 23 + HCl(aq) ∆H3 Applications of Hess’s Law Hess’s Law can be used to calculate enthalpy changes, which are difficult or impossible to determine, by experiment. Enthalpy of Formation Definition: The enthalpy of formation is the quantity of heat energy taken in or given out when 1 mole of a substance is formed from its elements in their normal state. Calculations The information you need to tackle a calculation will either be given in the question or can be found in the data booklet. Worked Example 1 Calculate the enthalpy of formation of ethane given that the enthalpies of combustion of carbon, hydrogen and ethane are -394kJmoll-1, -286kJmoll-1 and -1561kJmol-1 respectively. The first thing that you must do is write a balanced equation for the equation that you are required to calculate the enthalpy change for. This is called the Target Equation. Target Equation : 2C(s) + 3H2(g) C2H6(g) ∆H = ? Next you need to construct balanced equations for each of the substances in your target equation, using the information given in the question. (1) (2) (3) C(s) + H2(g) + C2H6(g) + O2(g) ½O2(g) 3½O2(g) CO2(g) H2O(l) 2CO2(g) + 3H2O(l) ∆H = -394 ∆H = -286 ∆H = -1561 These equations can now be rearranged to give the target equation. Note that whatever change you make to the equation you must also make to the enthalpy value! 2 x (1) 2C(s) + 3 x (2) 3H2(g) + reverse (3) 2CO2(g) + 2O2(g) 1½O2(g) 3H2O(l) 2CO2(g) 3H2O(l) C2H6(g) + 3½O2(g) ∆H = -788 ∆H = -858 ∆H = +1561 Once everything that appears on both the reactant side and the product side have been cancelled you should be left with your target equation! 2C(s) + 3H2(g) C2H6(g) 24 ∆H = -85kJmoll-1 Worked example 2 Use the enthalpies of combustion in your data booklet to find the enthalpy change for the reaction between ethyne and hydrogen to produce ethane. Target Equation : C2H2 (1) C2H2 + 2½O2 (2) H2 + ½O2 (3) C2H6 + 3½O (1) 2 x (2) reverse (3) + 2H2 2CO2 + H 20 2CO + C2H2 + 2½O2 2H2 + O2 2CO2(g) + 3H2O(l) C2H2 + 2H2 H 20 3H2O C2H6 ∆H = ? ∆H = -1301 ∆H = -286 ∆H = -1561 2CO2 + H20 ∆H = -1301 2H20 ∆H = -572 C2H6(g) + 3½O2(g) ∆H = +1561 ∆H= -312kJmoll-1 C2H6 Bond Enthalpies Bond enthalpies can be divided into two categories (see the Data Booklet). The bond dissociation enthalpy is the energy required to break one mole of bonds and form two separate atoms, all species being in the gaseous state. These values are accurately known but it is only possible to calculate them for diatomic molecules, e.g. H2(g) → 2H(g) N2(g) → 2N(g) HCl(g) → H(g) + Cl(g) +436 kJ mol–1 +945 kJ mol–1 +432 kJ mol–1 For molecules with more than two atoms, such as methane, it is only possible to calculate the mean bond enthalpy since the situation is much more complex with the C–H bonds breaking off one after the other to form a different fragment of the original molecule. The removal of the first hydrogen atom from CH4 does not require the same energy as the removal of the second hydrogen from the CH3 fragment and so on. The value obtained is the average or mean bond enthalpy for C–H, i.e. CH4(g) → C(g) + 4H(g) ∆H = 4 x C–H = 1648 kJ mol Therefore the mean bond enthalpy of C–H = 1648 / 4 = 412kJ mol–1 Mean bond enthalpies are quoted in data books for bonds of that type in any molecule but can also be calculated from other enthalpy changes, as shown in the following examples. 25 Experiment 3.6—Hess’s law Solid potassium hydroxide can be converted into potassium chloride solution by two different routes: Route 1 is the direct route whereby potassium chloride solution is made by adding solid potassium hydroxide directly to hydrochloric acid. Let's suppose it has an enthalpy change of ΔH1. KOH(s) + HCl(aq) KCl(aq) + H2O(l) ΔH1 Route 2 is the indirect route and involves two steps. In the first of these solid potassium hydroxide is dissolved in water: KOH(s) + aq KOH(aq) ΔH2a The resulting potassium hydroxide solution is then added to hydrochloric acid to form potassium chloride solution: KOH(s) + HCl(aq) KCl(aq) + H2O(l) ΔH2b According to Hess's Law the overall enthalpy change involved in converting solid potassium hydroxide into potassium chloride solution will be the same no matter whether the direct or indirect route is taken. The aim of this experiment is to confirm Hess's Law. 26 Experiment ROUTE 1 (direct route) Using the measuring cylinder, measure out 25cm3 of 1 mol l-1 hydrochloric acid into a plastic beaker or polystyrene cup. Measure and record the temperature of the acid. Weigh out accurately about 1.2g of potassium hydroxide into a plastic beaker or polystyrene cup and record the mass. Make sure the mass of potassium hydroxide does not exceed 1.4g. Add the acid to the potassium hydroxide. Slowly and continuously stir the reaction mixture with the thermometer until all the solid reacts. Measure and record the highest temperature reached by the reaction mixture. ROUTE 2 (indirect route) Step A The solution you prepare in this step is needed in step B - DON'T THROW ITAWAY! Using the measuring cylinder, measure out 25 cm3 of water into a plastic beaker or polystyrene cup. Measure and record the temperature of the water. Weigh out accurately about 1.2g of potassium hydroxide into a plastic beaker or polystyrene cup and record the mass. Make sure the mass of potassium hydroxide does not exceed 1.4g. Add the water to the potassium hydroxide. Slowly and continuously stir the reaction mixture with the thermometer until all the solid dissolves. Measure and record the highest temperature reached by the solution. Keep the solution you have just prepared but allow it to cool down for some time before proceeding to step B. Step B Using the measuring cylinder, measure out 25 cm3 of 1 mol l-1 hydrochloric acid into a plastic beaker or polystyrene cup. Measure and record the temperature of the acid. Measure and record the temperature of the potassium hydroxide solution you prepared in step A. Add the acid to the potassium hydroxide solution and stir the reaction mixture slowly and continuously with the thermometer. Measure and record the highest temperature reached by the reaction mixture. 27 Example Question Calculate the mean bond enthalpy of the C–H bond from the enthalpy of formation of methane and any other required data from the Data Booklet. Step 1: Write down the required equation: CH4 → C(g) + ∆H = 4 x C–H 4H(g) Step 2: Express all the information given in equation form: ∆H = –75 kJ mol–1 ∆H = + 716 kJ mol–1 ∆H = +436 kJ mol–1 (1) C(s) + 2H2(g) → CH4(g) (2) C(s) → C(g) (3) H2(g) → 2H(g) Step 3: Use the three equations to obtain the required balanced equation: (1) Reverse CH4(g) → C(s) + 2H2(g) (2) Nothing C(s) → C(g) (3) x2 2H2(g) →4H(g) ∆H = +75 kJ mol–1 ∆H = +716 kJ mol–1 ∆H = +872 kJ mol–1 Step 4: Add the three equations to give the required equation and D H: CH4(g) → C(g) + 4H(g) ∆H = 1663 kJ mol–1 1663 kJ = C–H = 1663 / 4 4 x C–H Mean bond enthalpy of C–H = 415.75kJ mol–1 REDOX Reactions A REDOX reaction involves two half reactions - oxidation and reduction. These half reactions can be written as ion-electron equations. Ion-electron equations are found on page 12 of the Data Booklet. Oxidation involves the LOSS of electrons (OIL): Fe2+ Fe + 2e Mg2+ Mg + 2e The ion-electron equation for oxidation must be written in reverse. Reduction involves the GAIN of electrons (RIG): Cu2+ + 2e Cu Ag+ + e Ag Remember, oxidation and reduction are two halves of the same chemical reaction. The combined reaction is called a Redox reaction. To form the overall redox reaction, the ion-electron equations for the oxidation and reduction must be combined, ensuring that the electrons cancel. 28 Oxidation: Mg(s) Reduction: Ag+ Mg2+ + e Mg2+ Oxidation: Al(s) Al3+ Reduction: 2H+ Mg(s) + + 2e 2Ag+ 2e Ag(s) 2Ag+ Mg(s) + + (x2) + 2Ag(s) + 3e (x2) H2(g) Mg2+ (x3) + 2Ag(s) Oxidising and Reducing Agents In a redox reaction the species that is oxidised is described as a reducing agent - a species that allows reduction to occur. Similarly, a species which is reduced is described as an oxidising agent - a species that allows oxidation to occur. eg. Mg(s) + 2Ag+ Mg2+ + 2Ag(s) The elements with low electronegativities (metals) tend to form ions by losing electrons (oxidation) and so can act as reducing agents. The strongest reducing agents are found in group 1. The elements with high electronegativities (non-metals) tend to form ions by gaining electrons (reduction) and so can act as oxidising agents. The strongest oxidising agents are found in group 7. Using the Data Booklet When writing redox equations you must first identify the oxidation and reduction half reactions and then combine them to give the redox reaction. Use the Electrochemical Series on page 12 of the data booklet. Example: Iron (II) sulfate solution is reacted with potassium permanganate solution until the first appearance of a permanent pink colour. Step 1: What four ions are present in the two solutions? Step 2: Write the ion-electron equation for the oxidation reaction. Step 3: Write the ion-electron equation for the reduction reaction. Step 4: Add the two half equations together to give the redox equation (remember to balance the electrons first) 29 Experiment 3.7—OXIDISING AND REDUCING AGENTS Halogen displacement Experiments with halogen displacement can be used to compare the strength of elements as oxidising agents. In this experiment you will be using chlorine, bromine and iodine water firstly to test their effect on pH paper, and secondly to test their reaction with potassium halides. Experiment Put a piece of Universal Indicator paper onto a white tile. Use a glass stirring rod to transfer a few drops of the chlorine water onto the indicator paper. Repeat this with a fresh piece of paper and the bromine water then the iodine water. In a test-tube, add some chlorine water to a solution of potassium bromide. Add some chlorine water to a solution of potassium iodide. Add some bromine water to a solution of potassium chloride Add some bromine water to a solution of potassium iodide Add some iodine water to a solution of potassium chloride Add some iodine water to a solution of potassium bromide Complete the table noting your observations Results table Effect on indicator paper Reaction with potassium chloride solution Chlorine water Bromine water Iodine water 30 Reaction with potassium bromide solution Reaction with potassium iodide solution Experiment 3.8—OXIDISING AND REDUCING AGENTS Blue bottle experiment The blue bottle reaction is a chemical reaction in which in a closed bottle an aqueous solution containing dextrose (D-glucose), sodium hydroxide and a methylene blue and some air turns from colorless to blue upon shaking and which then decolorizes again after a while. After shaking again the blue color returns and this cycle can be repeated several times. The reaction will work with other reducing sugars besides glucose and also with other reducing dyes. This experiment allows you to see that dextrose acts as a reducing agent and oxygen acts as an oxidising agent. Blue Bottle NOT Blue Bottle Experiment (Note the optimum temperature for this reaction is 25-300C) Using a measuring cylinder, measure 30cm3, 0.5mol l-1 sodium hydroxide into a 100cm3 conical flask, volumetric flask or bottle Add 1g of D-glucose and swirl until the solids are dissolved. Add 1cm3 of the methylene blue solution. The blue colour will turn colourless after about one minute. Stopper the flask or bottle. Shake the flask vigorously so that air dissolves in the solution. The colour will change to blue. This will fade back to colourless over about 30 seconds. The more shaking, the longer the blue colour will take to fade. The process can be repeated for over 20 cycles. After some hours, the solution will turn yellow and the colour changes will fail to occur. Write up Complete a full write up for this experiment. Make a note of any observations that you see. 31 More Complicated Half-Equations There are some ion-electron equations that are not given in the data book. You must learn the rules to work them out for yourself. Worked example Write an ion-electron equation for the following reaction: Cr2O72Step 1: If necessary, balance the central atom / ion. Cr2O72- Step 2: + 7H2O 2Cr3+ + 7H2O Calculate the total electrical charge on each side of the equation. Cr2O72- + 14H+ (12+) Step 5: 2Cr3+ Balance the hydrogen in the water by adding hydrogen ions. Cr2O72- + 14H+ Step 4: 2Cr3+ Add water (H2O) if it is needed to balance the oxygen atoms. Cr2O72- Step 3: Cr3+ 2Cr3+ + 7H2O (6+) Add electrons to balance the electrical charges. Cr2O72- + 14H+ + 6e(12+) + (6-) 2Cr3+ + 7H2O (6+) Chemical Analysis Chromatography Chromatography is a method of separating and analysing a mixture of soluble chemical substances. There are different types of Chromatography techniques. The most common is paper chromatography. Uses of Chromatography Chromatography can be used to follow the course of a chemical reaction or to establish the products of a chemical reaction. It can also be used to identify additives in foods, analyse fibres found at a crime scene and fingerprinting. 32 Paper Chromatography During paper chromatography a small sample of the mixture being tested is spotted onto the base line (a straight line usually drawn in pencil above the level of the solvent) on the filter paper. The filter paper is then placed in a solvent. By capillary action the solvent moves up the paper. This is when different components of the mixture are separated. Components can move quickly or slowly up the paper depending on the solvent used. There are two stages in paper chromatography; the Mobile Phase and the Stationary Phase. The solvent is the mobile phase in paper chromatography and the wet paper is the stationary phase. Why does separation occur? Separation of the mixture occurs due to the polarity and size of the molecules within the mixture. Depending on what solvent is used depends on how the molecules behave. For example, if a mixture contains very polar molecules and non-polar molecules and a polar solvent, such as ethanol, is used the polar molecules move much quicker up the filter paper. This is because the less polar molecules will be more attracted to the mobile phase. In terms of large and small molecules smaller molecules move much quicker and further up the filter paper compared to larger molecules. The Retention Factor (Rf) Values The Rf factor can be used to compare the different components found in a sample. The Rf values of a mixture being tested can be compared with known samples. Note: if two substances on chromatography paper have the same Rf value it is likely that they are the same compound. If they do not have the same Rf value then they are definitely different compounds. The Rf value of the red, green and blue particles can be measured and calculated to prove that certain molecules are present in the mixture. 33 Experiment 3.10—CHEMICAL ANALYSIS Wool chromatography Chromatography is the collective term for a set of laboratory techniques for the separation of mixtures. The mixture is dissolved in a fluid called the mobile phase, which carries it through a structure holding another material called the stationary phase. The various constituents of the mixture travel at different speeds, causing them to separate. This experiment uses white wool as the stationary phase and ethanol as the mobile phase. You will be using this technique to separate the colour constituents of a felt tip pen. Experiment Cut a length of white wool approximately 1m long Fill a 100cm3 beaker with approximately 20cm3 of methylated spirits Make a 1cm long mark on one end of the wool approximately 20cm from the end with your chosen pen. Allow the ink to dry. Attach a crocodile clip to each end of the wool and set the beaker of methylated spirits on the edge of a table Carefully lower the end of wool with the ink into the beaker making sure the ink is not submerged, drape the wool over the spout of the beaker and allow it to hang towards the floor with an empty beaker on the floor under the wool. Watch as the alcohol is wicked up the wool and towards the floor under the influence of gravity. The alcohol dissolves and separates the different colour components of the ink at different rates resulting in a series of coloured band moving towards the floor. 34 Redox Titrations As with volumetric titrations there has to be a way of determining the end-point of the reaction. For many reactions an indicator must be used however, for some redox reactions the end-point can be recognised from a colour change in one of the reactants, for example, when potassium permanganate solution (purple) reacts with iron(II) sulfate solution, the permanganate ions are reduced to colourless manganese ions. When a colour change involving one of the reactants is used to determine the end-point the reaction is said to be self-indicating. Worked example: 20cm3 of iron(II)sulphate were titrated with 0.01mol -1 potassium permanganate solution until a permanent pink colour was observed. If the volume of potassium permanganate used was 25.6cm 3, what is the concentration of the iron(II) sulfate solution? Step 1: write the ion-electron equations and combine to give the redox equation. MnO4- Fe2+ + 8H+ + 5e- Fe3+ + e(x5) 2+ Mn + 4H20 5Fe2+ + MnO4- + 8H+ Step 2: 5Fe3+ + Mn2+ + 4H2O calculate the number of moles of the ‘known’ substance Moles MnO4- = c x v 0.01 x 0.0256 0.000256 moles using the mole ratio: Step 3: calculate the concentration of the iron(II) sulfate solution C = = moles / v 0.00128 0.02 0.064moll-1 35 Experiment 3.11—CHEMICAL ANALYSIS Redox titration of Vitamin C Vitamin C (ascorbic acid) is an important component of our diet. In its absence the protein, collagen, cannot form fibres properly and this results in skin lesions and blood vessel fragility. Although vitamin C occurs naturally in many fruits and vegetables many people take vitamin C tablets to supplement their intake. Vitamin C can undergo a redox reaction with iodine in which the vitamin C is oxidised and the iodine molecules are reduced. The aim of this experiment is to determine the mass of vitamin C in a tablet by carrying out a redox titration using a solution of iodine of accurately known concentration and starch solution as an indicator. 36 Experiment Add a vitamin C tablet to the beaker. Add some deionised water (approximately 50cm3) to the beaker and stir the mixture until the tablet has dissolved. Carefully add the resulting solution to the 250cm3 volumetric flask. Rinse out the beaker several times with water and add the washings to the flask. Add water to the standard flask to bring the volume of the solution up to the graduation mark on the neck. Stopper the flask and invert it several times to make sure the solution is thoroughly mixed. After rinsing the pipette with a little of the vitamin C solution, pipette 25cm 3 of it into the conical flask. Add a few drops of starch solution to the vitamin C solution in the conical flask. After rinsing the burette with a little iodine solution, fill the burette with the iodine solution. Note the initial burette reading. Since the solution has a dark colour, it is difficult to see the bottom of the meniscus. Take the burette reading from the top of the meniscus. Add the iodine solution slowly from the burette whilst gently swirling the solution in the conical flask. Initially you will see a blue/black colour as the iodine reacts with the starch but this will rapidly disappear as the iodine reacts with the vitamin C. Near the end-point of the titration the colour disappears more slowly. At this point add the iodine solution drop by drop until the solution just turns a blue/black colour and remains so. This is the end-point of the titration i.e. all the vitamin C has reacted. Note the final burette reading. Wash out the conical flask. Repeat the titrations until concordant results are obtained. Write up Complete a full write up for this experiment. Show all calculations and determine the mass of Vitamin C in the tablet. 37 Word Meaning Atom Economy The proportion of reactant atoms which are incorporated into the desired product of a chemical reaction. % atom economy = Mass of desired product(s) x 100 Total mass of reactants Batch processes Bond Dissociation Enthalpy These involve mixing one batch of reactants in a vessel, allowing the reaction to complete, then removal of the products, before reloading with a fresh batch of reactants. Energy required to break one mole of bonds to form two separate atoms, all species being in the gaseous state. Capital costs Capital costs are incurred in the initial building of the plant and associated infrastructure. Cash flow Cash flow is the movement of money into and out of a business, and is a measure of profitability. Continuous processes These take place in a plant where reactants are fed in continuously at one end, and products are removed continuously from the other. Chromatography A method of separating and analysing a mixture of soluble chemical substances. Dynamic equilibrium A dynamic equilibrium is achieved when the rates of two opposing processes become equal, so that no net change results Electrodes The electrodes (one negative and one positive) dip into the electrolyte and form the connection to the electric wires. Any chemical reactions occur at their surfaces. Electrolysis Electrolytes are liquids containing ions which are free to move, and are therefore capable of conducting electricity. Electrolyte Electrolytes are liquids containing ions which are free to move, and are therefore capable of conducting electricity. Electrolytic cell An electrolytic cell is the equipment used to carry out electrolysis – oxidation occurs at the positive electrode and reduction at the negative electrode. 38 Equilibrium Chemical equilibrium is the state reached by a reaction mixture when the rates of forward and reverse reactions have become equal Excess Reactant added which is not all used up in the reaction. Feedstock Feedstocks are the reactants from which other chemicals can be extracted or synthesised. Fixed costs Fixed costs are incurred irrespective of whether a plant is operating at maximum or only at partial capacity. Hess’s law The enthalpy change for a chemical reaction is independent of the route taken, providing the starting point and finishing point is the same for both routes. Molar Volume The volume, in litres, occupied by one mole of gas under standard conditions of temperature and pressure. Ion-electron equations An ion-electron equation is a half-equation, either an oxidation or a reduction, which in combination of the opposite type, can be part of a complete redox equation. Oxidation An oxidation is a loss of electrons by a reactant in any reaction. Oxidising agent An oxidising agent is a substance which accepts electrons. Pilot plant A pilot plant is a small scale chemical plant, built with similar materials to a fullscale one, to investigate the chemical and engineering aspects of a process before a full-scale plant is built. Raw materials Raw materials are the initial starting materials from which the a process’s feedstock is derived. Reducing agent A reducing agent is a substance which donates electrons. Reduction A reduction is a gain of electrons by a reactant in any reaction. Stoichiometry Stoichiometry means literally ’measuring elements’ and is concerned with the quantities of substances reacting and the quantities of substances produced as derived from the balanced equation, i.e. it is concerned with mole relationships. Variable costs Variable costs are dependent on a plant’s output. Yield Quantity of product obtained in a reaction, usually given as % yield = actual/theoretical x100. 39 The Chemical Industry Exercise 1 1. The chemical industry will design a process to Maximise what? Minimise what? 2. Describe the stages in the manufacture of a new product. 3. What does the term Feedstock mean? 4. What are the main raw materials used in the chemical industry? 5. Give examples of capital, fixed and variable costs. 6. Describe a continuous process, giving advantages and disadvantages. 7. Describe a batch process, giving advantages and disadvantages. 8. Along with economic viability suggest other factors that will impact on the location and route used to manufacture a new product. 9. Aluminium is extracted from its purified oxide by molten electrolysis. Suggest two advantages and disadvantages of siting the aluminium smelters in the Scottish Highlands. The Chemical Industry 1. Which element is NOT a raw material in the chemical Industry? A B C D 2. Nitrogen Oxygen Sodium Sulfur The costs involved in the industrial production of a chemical are made up of fixed costs and variable costs. Which of the following is most likely to be classified as a variable cost? A B C D 3. Exercise 2 Past Paper Questions The cost of land rental The cost of plant construction The cost of labour The cost of raw materials Which of the following is produced by a batch process? A B C D Sulfuric acid from sulfur and oxygen Aspirin from salicylic acid Iron from iron ore Ammonia from nitrogen and hydrogen 40 The flow chart summarises some industrial processes involving ethene. The feedstocks for ethene in these processes are A B C D 5. A B C D ethane and glycol ethane and ethanol glycol and poly(ethene) glycol, poly(ethene) and ethanol. Which of the following compounds is a raw material in the chemical industry? Ammonia Calcium carbonate Hexane Nitric acid 6. Cerium metal is extracted from the mineral monazite. The flow diagram for the extraction of cerium from the mineral is shown on the previous page. Name the type of chemical reaction taking place in Step A. In Step B, cerium hydroxide is heated to form cerium oxide, Ce2O3, and compound Z. Name compound Z. In Step C, cerium metal is obtained by electrolysis What feature of the electrolysis can be used to reduce the cost of cerium production? 41 7. About 2.5 million tonnes of sulfuric acid are produced each year in the UK. Sulfuric acid was made industrially by the Chamber Process. The following chemical reactions are involved. Sulfur is burned to produce sulfur dioxide. Sulfur dioxide reacts with water to produce sulfurous acid. Nitric oxide is produced by the catalytic oxidation of ammonia; water is also a product of this reaction. Nitric oxide reacts with oxygen to form nitrogen dioxide Nitrogen dioxide reacts with sulfurous acid to form sulfuric acid and regenerate nitric oxide. Copy and complete the flow diagram below of the Chamber process with the names of the chemicals involved (2 Marks) To show the name of a chemical To Show a reaction Sulfuric acid 42 The Mole Revision Moles and mass Exercise 3 1.) a) c) Write the formula and then work out the gram formula mass (mass of 1 mole) of: hydrogen sulfide (b) magnesium bromide hydrogen sulfate (d) hydrogen nitrate 2.) What is the mass of the following? a) c) 10 moles of calcium carbonate (b) 0.5 moles of lithium fluoride (d) 3.) How many moles of compound are present in: a) c) 14 g of nitrogen gas 85 g of lithium chloride 3 moles of sodium chloride 0.2 moles of methane (CH4) (b) 400 g of copper(I) oxide (d) 117 g of sodium sulfide Moles and concentration 1) Calculate the number of moles of: a) sodium chloride in 1000 cm3 of 1 mol l-1 solution. b) sodium chloride in 500 cm3 of 0.5 mol l-1 solution. c) potassium nitrate in 250 cm3 of 0.5 mol l-1 solution. 2) What volume of water is required to make: a) 3 moles of potassium hydroxide into a 1.5 mol l -1 solution? b) 0.5 moles of sodium chloride into a 2 mol l -1 solution? c) 0.1 moles of lithium oxide into a 0.05 mol l -1 solution? 3) What concentration of solution is obtained if we dissolve: a) 2 moles of sodium hydroxide in 500 ml of water? b) 1 mole of lithium chloride in 2 L of water? c) 1.5 moles of magnesium bromide in 100 cm3 of water? 4) What concentration of solution is obtained if we dissolve: a) b) c) 5) What volume of water is required to make: a) b) c) 6) 40 g of sodium hydroxide in 1 litre of water? 58.5 g of sodium chloride in 100 cm3 of water? 585 g of sodium chloride in 10 litres of water? 56 g of potassium hydroxide into a 1.5 mol l -1 solution? 117 g of sodium chloride into a 2 mol l-1 solution? 15 g of lithium oxide into a 0.05 mol l-1 solution? What mass of substance is required to make: a) b) c) 500 cm3 of 2 mol l-1 aluminium nitrate solution? 2 L of 0.5 mol l-1 potassium bromide solution? 100 cm3 of 3 mol l-1 calcium sulfate solution? 43 Balancing Equations and Calculations from Balanced Equations Revision 1. Balance the following equations: a) b) c) d) N2 N2 Na CH4 2. 2Mg + O2 + H2 + O2 + H 2O + O2 NH3 NO NaOH + H2 CO2 + H2O MgO Calculate the mass of oxygen required to burn 6 g of magnesium. 3. CaCO3 CaO + CO2 What mass of CaCO3 is required to form 2.8 g of calcium oxide? 4. N2 + 3H2 2NH3 What mass of ammonia (NH3) is produced from 7 g of nitrogen? Excess Calculations Exercise 4 In each of the following reactions calculate which reactant is in excess 1. a) Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g) 6.5 g of Zinc added to 25 cm3 of dilute sulfuric acid, concentration 2 mol l-1 b) Mg (s) + 2HCl(aq) MgCl2(aq) + H2(g) 2.4 g of magnesium added to 100 cm3 of dilute hydrochloric acid, concentration 1 mol l-1 c) Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g) 3.6 g of Zinc added to 50 cm3 of dilute hydrochloric acid, concentration 0.5 mol l-1 d) Mg (s) + H2SO4(aq) MgSO4(aq) + H2(g) 4.7 g of magnesium added to 25 cm3 of dilute sulfuric acid, concentration 1 mol l-1 2.) Iron(II) sulfide reacts with hydrochloric acid as follows: FeS(s) + 2HCl(aq) FeCl2(aq) + H2S(g) If 4.4 g of iron(II) sulfide was added to 160 cm 3 of 0.5 mol l-1 hydrochloric acid, show by calculation which substance is in excess. 44 3. A student added 0.20 g of silver nitrate, AgNO3, to 25 cm3 of water. This solution was then added to 20 cm3 of 0.0010 mol l-1 hydrochloric acid. The equation for the reaction is: AgNO3(aq) + HCl(aq) AgCl(s) + HNO3(aq) Show by calculation which reactant is in excess. 4. What mass of ammonia gas is produced when 1.32 g of ammonium sulfate is heated with 1 g of sodium hydroxide? (NH4)2SO4 + 2NaOH 2NH3 + Na2SO4 + 2H2O 5. What mass of sulfur dioxide is produced when 1.26 g of sodium sulphite is added to 50cm 3 of dilute hydrochloric acid , concentration 2 mol l -1 Na2SO3 6. + 2HCl 2NaCl + H 2O + SO2 Calcite is a very pure form of calcium carbonate which reacts with nitric acid as follows: CaCO3(s) + 2HNO3(aq) Ca(NO3)2(aq) + H2O(l) + CO2(g) A 2.14 g piece of calcite was added to 50.0 cm3 of 0.200 mol l-1 nitric acid in a beaker. Calculate the mass of calcite, in grams, left unreacted. 7. Copper(II) oxide reacts with sulfuric acid as follows: CuO(s) + H2SO4(aq) CuSO4(aq) + H2O(l) 1.6 g of copper(II) oxide is added to a beaker containing 50 cm 3 of 0.25 mol l-1 sulfuric acid. Calculate the mass of copper(II) oxide remaining after the reaction was complete. 8. Lead reacts with hydrochloric acid as follows: Pb(s) + 2HCl(aq) PbCl2(aq) + H2(g) If 6.22 g of lead was added to 50 cm3 of 1 mol l-1 hydrochloric acid, calculate the mass of lead left unreacted. 9. A strip of zinc metal weighing 2.00 g is placed in an aqueous solution containing 10.00 g of silver nitrate. The reaction that occurs is Zn(s) + 2AgNO3(aq) 2Ag(s) + (a) Determine which reactant is in excess. (b) Calculate how many grams of silver will be formed. 45 Zn(NO3)2(aq) 10. A piece of lithium with a mass of 1.50 g is placed in an aqueous solution containing 6.00 g of copper (II) sulfate. The reaction that occurs is: 2Li(s) + CuSO4(aq) Cu(s) + Li2SO4 (aq) (a) Determine which reactant is in excess. (b) Calculate how many grams of copper will be formed. Molar Volume 1. Exercise 5 Decide which has the greater volume, measurements made at the same temperature and pressure a) b) c) d) 17 g of ammonia or 17 g of methane 20 g of neon or 20 g of nitrogen 4 g of hydrogen or 44 g of carbon dioxide 6.4 g of sulfur dioxide or 8 g of oxygen 2. The volume of 0.22 g of propene C 3H6 is 118 cm3. Calculate the volume of 2 moles of propene at this temperature and pressure . 3. Calculate the volume of 2.4 g of ethane, C2H4. (take the molar volume to be 23.6 litres mol-1) 4. The volume of 1 g of hydrogen is 11.6 litres. Calculate the volume of 4 moles of hydrogen at this temperature and pressure. 5. 3 g of an alkane occupies a volume of 2.24 litres. What is the molecular formula of the alkane (take the molar volume to be 22.4 litres mol-1) 6. Using the densities in the data booklet calculate the volume of 10 g of (a) (b) 7. Using the densities in the data booklet calculate the mass of 10 litres of (a) (b) 8. Hydrogen Argon Helium Nitrogen From the following data calculate the approximate formula mass of the gas X. Mass of plastic bottle empty Mass of plastic bottle + Gas X Capacity of plastic bottle Molar volume of gas X = = = = 112.30 g 113.52 g 1 litre 23.6 litres 46 9. A flask, capacity 600 cm3 was used to calculate the molar volume of sulfur dioxide. The following data was obtained: Mass of evacuated flask Mass of flask + sulfur dioxide 10. = = 512.97 g 514.57 g Some of liquid Z is injected into a large syringe and it evaporates. The following results were recorded: Mass of syringe before injection Mass of syringe after injection Syringe reading before injection Syringe reading after injection = = = = 4.648 g 4.774 g 0 cm3 84 cm3 Calculate the relative formula mass of liquid Z (Molar volume = 30.6 litre mol-1) Balanced Equations Using Mass and Volumes Exercise 6 Molar volume 24 litres unless stated otherwise 1.) What volume (in l) of carbon dioxide would be produced by completely reacting 60 g of carbon with oxygen? C 2.) 4.) O2 CO2 What volume (in l) of hydrogen would be produced by completely reacting 60 cm 3 of hydrochloric acid of concentration 1.2 mol l –1 with zinc? Zn 3.) + + 2HCl ZnCl2 + H2 What volume (in l) of carbon dioxide would be produced by completely reacting 10 g of calcium carbonate with hydrochloric acid? CaCO3 + 2HCl Mg(s) + 2HCl(aq) CaCl2 + H 2O + MgCl2(aq) + CO2 H2(g) What volume of hydrogen gas is produced when 5 g of magnesium is added to 100 cm 3 of dilute hydrochloric acid concentration 2 mol l -1 ( Molar volume =23.6 Litres mol-1) 5.) What mass of magnesium oxide is obtained when 24 g of magnesium is ignited in 5 litres of oxygen Mg(s) + O2(g) MgO(s) (Molar volume is 22.8 litres mol-1) 47 6. What mass of water is produced when 2 litres of hydrogen is burned in excess oxygen (use the density of hydrogen given in the data book) 7. Calculate the volume of oxygen required for the complete combustion of 1 g of ethane C2H4 (Molar volume is 32.2 litres mol-1) 8. Chlorine gas can be produced by heating calcium hypochlorite, Ca(OCl) 2, in dilute hydrochloric acid. Ca(OCl)2(s) + 2HCl(aq) Ca(OH)2(aq) + 2Cl2(g) Calculate the mass of calcium hypochlorite that would be needed to produce 0·096 litres of chlorine gas. (Take the molar volume of chlorine gas to be 24 litres mol –1.) 9.) Hydrogen fluoride gas is manufactured by reacting calcium fluoride with concentrated sulfuric acid. CaF2 + H2SO4 CaSO4 + 2HF What volume of hydrogen fluoride gas is produced when 1.0 kg of calcium fluoride reacts completely with concentrated sulfuric acid? (Take the molar volume of hydrogen fluoride gas to be 24 litres mol –1.) 10.) In the lab, nitrogen dioxide gas can be prepared by heating copper(II) nitrate. Cu(NO3)2(s) CuO(s) + 2NO2(g) + ½O2(g) Calculate the volume of nitrogen dioxide gas produced when 2.0 g of copper (II) nitrate is completely decomposed on heating. (Take the molar volume of nitrogen dioxide to be 24 litres mol –1.) 48 Reacting Volumes 1. Exercise 7 In each of the following reactions decide the ratio of the volume of product(s) to the volume of reactant(s). a) b) c) d) 2. H2(g) N2(g) 2C(s) C2H4(g) + + + + F2(g) 3H2(g) O2(g) 3O2(g) 2HF(g) 2NH3(g) 2CO(g) 2CO2(g) N2(g) + 2O2(g) 2NO2(g) + 2H2O(l) What volume of nitrogen dioxide is produced when 100 cm3 of nitrogen is sparked in excess oxygen? 3. When the following gases are burned calculate the volume of oxygen required and the volume of carbon dioxide produced a) b) c) 4. 50 cm3 of methane 200 cm3 of ethane 250 cm3 of carbon monoxide 10 cm3 of butane gas is mixed with 75 cm3 of oxygen and the mixture exploded. Calculate the volume and composition of the resulting gas mixture. C4H10(g) + 6.5 O2(g) 4CO2(g) + 5H2O(l) 5. If 100cm3 of propene is burned completely with 900 cm3 of oxygen what will be the volume and composition of the resulting gas mixture? 6 50 cm3 of ethyne, C2H2 is burned completely in 220 cm3 of oxygen a) b) What will be the volume and composition of the resulting gas mixture? What will be the volume and composition of the resulting gas mixture if the experiment was repeated at 200oC? 49 7. What volume of oxygen (in litres) would be required for the complete combustion of a gaseous mixture containing 1 litre of carbon monoxide and 3 litres of hydrogen? 8. 20 cm3 of ammonia gas reacted with an excess of heated copper(II) oxide. 3CuO + 2NH3 3Cu + 3H2O + N2 Assuming all measurements were made at 200 °C, what would be the volume of gaseous products? 9. 2C2H2(g) ethyne + 5O2(g) 4CO2(g) + 2H2O(l) What volume of gas would be produced by the complete combustion of 100 cm 3 of ethyne gas? All volumes were measured at atmospheric pressure and room temperature. 10. The equation for the complete combustion of propane is: C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) 30 cm3 of propane is mixed with 200 cm3 of oxygen and the mixture is ignited. What is the volume of the resulting gas mixture? (All volumes are measured at the same temperature and pressure.) 50 Percentage Yield and Atom Economy 1.) CH3OH Methanol + Exercise 8 C2H5COOH propanoic acid C2H5COOCH3 + methyl propanoate H 20 In preparation, 40.4 g of methyl propanoate is obtained from 18.3 g of methanol. (a) Calculate the percentage yield (b) Calculate the atom economy in regards to methyl propanoate 2.) oxidation C3H7OH Propan-1-ol C2H5CHO Propanal In a preparation, 3.2 g of propanal is obtained from 3.9g of propan-1-ol. Calculate the percentage yield. 3.) C3H6 + Br2 C3H6Br2 20.4 g of 1,2-dibromopropane is obtained from 5.2 g of propene. Calculate the percentage yield 4.) N2 + 3H2 2NH3 Under test conditions, 2 kg of hydrogen reacts with excess nitrogen to produce 1.5 kg of ammonia. Calculate the percentage yield 5.) 2SO2 + O2 2SO3 Under test conditions, 1 kg of sulfur dioxide reacts with excess oxygen to produce 0.8 kg of sulfur trioxide. Calculate the percentage yield 51 6. 2FeCl2 + Cl2 2FeCl3 5.072 g of iron (II) chloride yields 4.869 g of iron (III) chloride, calculate the percentage yield. 7. 8. Calculate the atom economy for the production sulfur trioxide assuming that all the reactants are converted into products. H2SO4 H 2O + SO3 Which reaction below has the highest atom economy for producing water? 2C2H6 + 7O2 4CO2 + 6H2O C3H6 9. 4NH3 + + 5O2 4½O2 3CO2 4NO + + 3H2O 6H2O a) 1.68 x 103 kg of NO was produced from1.36 x103 kg calculate the percentage yield. b) Calculate the atom economy in terms of the production of NO 10. Fe2O3 + 3CO 2Fe + 3CO2 6.65 x 104 kg of an iron ore which is impure iron (III) oxide is reacted with an excess of carbon monoxide, producing 2.79 x 104 kg of iron. a) Calculate the mass of pure iron (III) oxide in the ore. (Assuming that all the iron (III) oxide is reduced to iron and that the impurities do not take part in the reaction) b) Calculate the percentage by mass, of the iron (III) oxide in the ore. 52