13 THERMOCHEMISTRY CONCEPT MAP

ENERGY LEVEL DIAGRAM

Energy product H : positive Reactant

Energy Reactant H : negative product

Endothermic reaction Heat energy absorbs

Exothermic reaction Heat energy releases

Energy change

THERMOCHEMISTRY types of heat of reaction

Heat of precipitation Meaning, Example of chemical reaction and equation

Heat of neutralization Meaning, Example of chemical reaction and equation

Heat of displacement Meaning, Example of chemical reaction and equation

Heat of precipitation Meaning, Example of chemical reaction and equation

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ENERGY CHANGES IN CHEMICAL REACTION

( Refer to the form five text book page : 143 - 144 ) 1 What is exothermic reaction ? An exothermic reaction is a chemical reaction that gives out heat to the surroundings. Heat energy given out from the reaction is to the surroundings The temperature of the surroundings . 2 What is endothermic reaction ? An endothermic reaction is a chemical reaction that absorbs heat from the surroundings . The reactants . heat energy from the surroundings. The temperature of the surroundings . 3 Identify the following reactions as exothermic or endothermic reaction (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) Reaction Combustion of ethanol Burning of magnesium Neutralisation between acid and alkali Adding water to concentrated sulphuric acid Photosynthesis Reaction between acid and magnesium Reaction between acid and calcium carbonate Dissolving ammonium salt in water Thermal decomposition of copper(ll) carbonate Thermal decomposition of zinc nitrate Exothermic Endothermic

4 The amount of heat energy released or absorbed during a cemical reaction is called the heat of reaction. It is given a symbol . and the unit is .. 5 The heat of reaction , H = H products - H reactants Exothermic reaction : The reactants lose heat energy to form the products . Thus the products formed have less energy than the reactants, Therefore, H is . Endothermic reaction : The reactants absorbs heat energy to form the products . Thus the products formed have energy than the reactant,Therefore, H is positive sign. 6 Energy level diagram ( Refer to the text book page 145 - 146 ) (i) Energy level diagram for exothermic reaction : The products have less energy than the reactants,

Energy reactants H = negative products

Construct energy level diagram based on the chemical equation, Mg + H2SO4 ZnSO4 + H2 (reactants) ( products ) H = -467 kJ

(ii)

Energy level diagram for endothermic reaction : The products have more energy than the reactants, Energy products

reactants

H = negative

Construct energy level diagram based on the chemical equation CaCO3 CuO + CO2 H = + 178 kJ

(iii) Information that can be obtained from the energy level diagram Energy

Zn + CuSO4 H = - 190 kJ Cu + ZnSO4

Figure shows the energy level diagram for the reaction between zinc and copper(ll) sulphate, a) The reaction between and . is an .. reaction. b) During the reaction, the temperature of the mixture . c) The total energy of one mole of. and one mole of .. is . than the total energy of one mole of copper and one mole of zinc sulphate by . kJ d) When one mole of .. reacts with one mole of .. to form .. .. mole of copper and .. mole of zinc sulphate, .. kJ of heat is

Energy 2HI

H2 + I2

H = +53 kJ

Figure shows the energy level diagram for the reaction between hydrogen gas and iodine a) The reaction between and . is an .. reaction. b) During the reaction, the temperature of the mixture . c) The total energy of one mole of. and one mole of .. is . than the total energy of two moles of hydrogen iodide by kJ d) When one mole of .. reacts with one mole of .. to form .mole of hydrogen iodide..kJ of heat is 7 Explain the application of exothermic and endothermic reaction in our every day life, ( Refer to the text book page 147 - 148 ) (i) Instant cold packs : Instant cold packs are used to treat , have separate compartments of and in a plastic bag. When the barrier between the two is broken by squeezing the outer bag, the .. dissolve in .endothermically to provide instant coldness. (ii) First-aid chemical hot pack :

13.2

HEAT OF REACTION ( refer to the text book page : 149 - 169 )

HEAT OF REACTION The change in the amount of heat in a chemical reaction Symbol : . The

HEAT OF PRECIPITATION Meaning : .. .. HEAT OF NEUTRALIZATION Meaning : .. .. .. Complete the table Chemical equation Pb(NO3)2 + 2KI PbI2 + 2KNO3 Type of reaction

HEAT OF DISPLACEMENT Meaning : .. .. HEAT OF COMBUSTION Meaning : .. .. ..

Heat of reaction Heat of precipitation Heat of neutralization

Precipitation reaction Displacement reaction

C2H5OH + 3O2 2CO2 + 3H2O Precipitation reaction

The heat change in a reaction can be calculated using the formula , H = mc m = mass of solution, g c = specific heat capacity of the solution, J g-1 oC-1 = temperature change Assumption : i) The solution is dilute, it has the same density as water , 1 g cm-3 ( 1 cm3 = 1g ) ii) The solution has the same specific heat capacity as water, 4.2 J g-1 oC-1

Example : heat of reaction Guidelines for the calculation of the Steps to follow: Calculate the amount of heat change when H the temperature of 200 cm3 of water Step 1 - Calculate the heat change using the formula, = mc 0 is raised fromequation 280C to 40 C, equation for the reaction that occurs Step 2 - Write chemical or ionic H = mc = 200 g the following Step 3 - Calculate the number of moles of-1reactant that reacts m using either o 0 = 200 g x 4.2 J g C x 12 C c = 4.2 J g-1 oC-1 formulae : 0 = 10080 J Number of moles = mass or = 40 - 28 = 12 C = 10.08 kJ molar mass Number of moles = MV 1000 M : Molarity of the solution V : volume of the solution in cm3

Step 4 - Link the number of moles of reactants ( step 3 ) with the heat change ( step 1 ) Calculate the heat of reaction, H, by using the following formula :

Heat of reaction , H =

heat change ( answer from step 1 ) Number of moles ( answer from step 3 )

NUMERICAL PROBLEMS RELATED TO HEAT OF REACTION 1. HEAT OF PRECIPITATION Aim : To determine the heat of precipitation of silver chloride

25 cm3 0.5 mol dm-3 sodium chloride solution

25 cm3 0.5 mol dm-3 silver nitrate solution Procedure : 1. Measure 25 cm3 0.5 mol dm-3 silver nitrate solution and pour it into the polystrene cup, 2. Put the thermometer into the silver nitrate solution. Record the initial temperature, 3. Measure 25 cm3 0.5 mol dm-3 sodium chloride solution and record the initial temperature, 4. Pour the sodium chloride solution quickly into the silver nitrate solution in the polystyrene cup. 5. Stir the solution mixture with the thermometer and record the highest temperature achieved. Result : Initial temperature of silver nitrate solution Initial temperature of silver nitrate solution Highest temperature of the mixture = 290C = 290C = 320C Average initial temperature = 290C

Calculation Step 1 : Calculate the heat change using the formula H = mc

Changes of temperature, = 320C - 290C = 30C Heat change , H = mc H = .. J m = ( 25 + 25 ) g = 50 g c = 4.2 J g-1 oC-1 = 30 C

Step 2: Write chemical equation or ionic equation for the reaction that occurs

Chemical equation : AgNO3 (aq) + NaCl(aq) AgCl (s) + NaNO3 (aq)

precipitate

Ionic equation : . Deduce the mole ratio from the ionic equation mol silver ion, Ag+ react with mol of chloride ion, Clto produce . mol of silver chloride , AgCl

Step 3 : Calculate the number of moles of reactant that reacts

Number of moles of silver ion = the number of moles of silver nitrate = .. mol Number of moles of chloride ion = the number of moles of sodium chloride = .. mol Number of moles of silver chloride formed = .. mol

Step 4 Calculate the heat of precipitation of silver chloride, H

Heat of reaction , H =

heat change ( answer from step 1 ) Number of moles of silver chloride

= J H = - kJ mol - 1

Draw an energy level diagram for the reaction that occurs in this experiment

2. HEAT OF DISPLACEMENT Aim : To determine the heat of displacement of copper metal from a copper (ll) sulphate solution by zinc metal

zinc powder

25 cm3 0.2 mol dm-3 copper(ll) sulphate solution Procedure : 1. Measure 25 cm3 0.2 mol dm-3 copper(ll) sulphate solution and pour into a polystirene cup. 2. Put the thermometer into the silver nitrate solution. Record the initial temperature, 3. Add half a spatula of zinc powder( in excess) quickly into copper(ll) sulphate solution. 5. Stir the mixture with the thermometer and record the highest temperature achieved. Result : Initial temperature of silver nitrate solution Highest temperature of the mixture Calculation Step 1 : Calculate the heat change using the formula H = mc Step 2: Write chemical equation or ionic equation for the reaction that occurs Step 3 : Calculate the number of moles of reactant that reacts Step 4 Calculate the heat of displacement of copper, H = 300C = 400C

Changes of temperature, = 400C - 300C = 100C Heat change , H = mc H = .. J Chemical equation : Zn (s) + CuSO4(aq) Cu (s) + ZnSO4 (aq)
copper displaced

m = 25 g c = 4.2 J g-1 oC-1 = 100C

Deduce the mole ratio from the equation mol copper metal, Cu is displaced from .. mol of copper(ll) sulphate solution, CuSO4 by zinc Number of moles copper(ll) sulphate = .. mol Number of moles of copper = .. mol

Heat of reaction , H =

heat change ( answer from step 1 ) Number of moles copper

= J H = - kJ mol - 1 Draw an energy level diagram for the reaction that occurs in this experiment

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3. HEAT OF NEUTRALISATION Aim : To determine the heat of neutralisation between a strong acid ( hydrochloric acid solution ) and a strong alkali ( sodium hydroxide )

50 cm3 2.0 mol dm-3 sodium hydroxide solution

50 cm3 2.0 mol dm-3 hydrochloric acid solution Procedure : 1. Measure 50 cm3 2.0 mol dm-3 sodium hydroxide solution and pour it into the polystrene cup, 2. Put the thermometer into the sodium hydroxide solution. Record the initial temperature, 3. Measure 50 cm3 2.0 mol dm-3 hydrochloric acid solution and record the initial temperature, 4. Pour the hydrochloric acid solution quickly into the sodium hydroxide solution in the polystyrene cup. 5. Stir the mixture with the thermometer and record the highest temperature achieved. Result : Initial temperature of silver nitrate solution Initial temperature of silver nitrate solution Highest temperature of the mixture Calculation Step 1 : Calculate the heat change using the formula H = mc Step 2: Write chemical equation or ionic equation for the reaction that occurs = 290C = 290C = 420C Average initial temperature = 290C

Changes of temperature, = 420C - 290C = .0C Heat change , H = mc H = .. J Chemical equation : . Ionic equation : . Deduce the mole ratio from the ionic equation : m = ( 50 + 50 ) g = 100 g c = 4.2 J g-1 oC-1 = .0C

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 mol hydrogen ion, H+ react with mol of hydroxide ion, OHto produce . mol of water , H2O Step 3 : Calculate the number of moles of reactant that reacts Number of moles of H+ = the number of moles of hydrochloric acid = .. mol Number of moles of OH- = the number of moles of sodium hydroxide = .. mol Number of moles of water formed = .. mol Step 4 Calculate the heat of neutralisation of hydrochloric acid and sodium hydroxide, H Heat of reaction , H = heat change ( answer from step 1 ) Number of moles water

= J H = - kJ mol - 1

Draw an energy level diagram for the reaction that occurs in this experiment

4. HEAT OF COMBUSTION Aim : To determine the heat of combustion of ethanol

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Experiment to show heat of combustion. Procedure : 1. Measure 200 cm3 of water and pour it into a copper can. Record the initial temperature of the water and place the copper can on a tripod stand. 2. Fill a lamp with ethanol and weight it. Record the mass of the lamp together with its content. 3. Light up the wick of the lamp immediately. Stir the water continuously until the temperature of the water increases by about 30 0C. 5. Put off the flame and record the highest temperature reached by the water. Result : Mass of lamp before burning Mass of lamp after burning Initial temperature of water Highest temperature of water Calculation Step 1 : Calculate the heat change using the formula H = mc = 46.50 g = 46.15 g = 29.00C = 59.00C

Changes of temperature, = 59.00C - 29.00C = 300C Mass of water, m = 200 g Heat change , H = mc c = 4.2 J g-1 oC-1 = 300C H = .. J

Step 2: Write a balance chemical equation for the combustion of ethanol Step 3 : Calculate the number of moles of ethanol that is used in the experiment,

C2H5OH

O2

Mass of ethanol burnt/used = 46.50 - 46.15 = 0.35 g Number of moles of ethanol burnt = 0.35 = 0.35 molar mass ..

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[ Relative atomic mass : H, 1 : C,12; O,16 ] Step 4 Calculate the heat of combustion of ethanol, H Heat of reaction , H =

.. mol

heat change ( answer from step 1 ) Number of moles of ethanol

= J H = - kJ mol - 1

Draw an energy level diagram for the combustion of ethanol in this experiment

EXTRA ACTIVITY ( Refer to the Chemistry Form Five text book page 149 - 168 ) 1 The thermochemical equation for the precipitation of calcium carbonate is given below, Ca2+ (aq) + CO32- (aq) CaCO3 (s) H = +12.6 kJ mol - 1 In an experiment, calcium carbonate, CaCO3 is precipitated when 100 cm3 of 0.5 mol dm-3

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calcium nitrate, Ca(NO3)2 solution is added to 100 cm3 of 0.5 mol dm-3 sodium carbonate, Na2CO3 solution. What is the temperature change in the reacting mixture ? [ Specific heat capacity of solution : 4.2 J g-1 oC-1 . Density of solution : 1 g cm-3 ] Solution Step 1 : Calculate the number of moles of precipitate formed : Number of moles of calcium ion, Ca2+ = Number of moles of calcium nitrate, Ca(NO3)2 solution = . mol Number of moles of carbonate ion, CO32- = Number of moles of sodium carbonate, Na2CO3 solution = .mol Based on the ionic equation : Ca2+ (aq) + CO32- (aq) CaCO3 (s) 1 mol 1 mol 1 mol 1 mol of calcium ion, Ca2+ reacts with 1 mol of carbonate ion, CO32- to form . mol of calcium carbonate, CaCO3 From the calculation : . mol of calcium ion, Ca2+ reacts with . mol of carbonate ion, CO32- to form . mol of calcium carbonate, CaCO3 Step 2 : Calculate the heat change by using the heat of precipitation, Given that H = +12.6 kJ mol - 1 , this means that when 1 mol of calcium carbonate, CaCO3 is precipitated, the heat absorbed is Therefore when ..mol (from step 1 ) of calcium carbonate, CaCO3 pricipitated, the heat absorbed = kJ = ..J --------- (i) Step 3: Calculate the temperature change by using the heat change Mass of solution , m ..g Heat change (absorbed ) ,H = J ( from (i) ) H = mc = . x . x = J = 0C 2 In an experiment, excess magnesium powder is added to 50 cm3 of 0.5 mol dm-3 iron(ll) sulphate solution at 29.0 0C. The thermochemical equation is shown below, Mg(s) + Fe2+ (aq) Mg2+ (aq) + Fe (s) H = -80.6 kJ mol - 1

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What is the highest temperature reached in this experiment ? Solution Step 1 : Calculate the number of moles of iron, Fe displaced The number of moles of iron(ll) ions , Fe2+ = the number of moles of iron(ll) sulphate solution =. mol Based on the ionic equation : Mg(s) + Fe2+ (aq) Mg2+ (aq) + Fe (s) 1 mol 1 mol 1 mol of iron(ll) ion, Fe2+ produces 1 mol of iron, Fe mol of iron(ll) ion, Fe2+ produces .mol of iron, Fe Step 2 : Calculate the amount of heat given out from the heat of displacement Given that H = -80.6 kJ mol - 1 This means that when 1 mol of iron, Fe is displaced, the heat given out is . kJ Therefore when mol of iron, Fe is displaced in the experiment, The heat given out , H = .kJ = .J --------- (i) Step 3 : Calculate the highest temperature reached using the heat given : Mass of the solution, m = .g The heat given out , H = . J ( from (i) )

H = mc = . x . x = J = 0C ---------- (ii) Therefore, the highest temperature reached : = 29.00C + = 0C

The thermochemical equation for the reaction between ethanoic acid and sodium hydroxide is given below,

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CH3COOH (aq) + NaOH (aq) NaCH3COO (aq) + H2O (l)

H = -55 kJ mol - 1

Calculate the heat given out when 200 cm3 of ethanoic acid 0.5 mol dm-3 is added to 200 cm3 of sodium hydroxide 0.5 mol dm-3 Solution Step 1: Calculate the number of moles of water produced Number of moles of hydrogen ion, H+ = Number of moles of ethanoic acid solution = . mol Number of moles of hydrogen ion, OH- = Number of moles of sodium hydroxide solution = . mol The ionic equation : H+(aq) + OH- (aq) H2O (l) 1 mol 1 mol 1 mol Based on ionic equation, 1 mol of hydrogen ion, H+ reacts with 1 mol of hydroxide ion, OHto produce 1 mol of water, H2O, Therefore, mol of hydrogen ion, H+ reacts with mol of hydroxide ion, OHto produce mol of water, H2O --------- (i) Step 2 : Calculate the heat given out using the heat of neutralisation, Given that H = -55 kJ mol - 1 This means that when 1 mol of water is produced , the heat given out is 55 kJ Therefore, when .. ( from (i) ) is produced, The heat given out = .kJ = J

EXTRA EXERCISE

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The table below shows the heat of combustion for alcohols . Type of alcohol Methanol Ethanol Propanol Butanol Molecular formula CH3OH C2H5OH C3H7OH C4H9OH Relative molecular mass 32 46 60 74 Heat of combustion/ kJ mol-1 - 715 - 1376 - 2017 - 2679

Based on information given in the table answer the following questions, (a) Draw a graph of the magnitude of the heat of combustion against the number of carbon atoms in an alcohol (b) State the relationship between the number of carbon atoms in an alcohol and the heat of combustion, . . (c) Predict the heat of combustion of hexanol (d) The fuel value of a fuel is the amount of heat energy given out when one gram of the fuel is completely burnt in excess of oxygen. By using the formula below, calculate the fuel value of the following alcohols Fuel value ( kJ g-1 ) = heat of combustion of alcohol ( kJ mol-1 ) molar mass (i) Methanol

(ii) Butanol

(e) Which alcohol is more effective to be used as fuel ? Give one reason for your answer .. 2 .. Table shows three thermochemical equations for experiment l, ll and lll

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Experiment l ll lll

Thermochemical equation HCl (aq) + NaOH ( aq) NaCl (aq) + H2O(l) H = -57 kJ mol -1

CH3COOH(aq) + NaOH(aq) NaCH3COO(aq) + H2O(l) H = -55 kJ mol -1 H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l) H = -114 kJ mol -1

Based on the thermochemical equations, answer the following questions (a) Explain why there is a difference in the heat of reaction for (i) Experiment l and ll (ii) Experiment l and lll [ 12 marks ] (b) If experiment lll is repeated by replacing the sodium hydroxide solution with potassium hydroxide solution, (i) predict the heat of reaction for the experiment (ii) Explain your answer in (b) (i) [ 5 marks ] (c) Based on thermochemical equation in experiment ll, calculate the heat change when 100 cm3 2 mol dm-3 ethanoic acid solution react with 100 cm3 2 mol dm-3 sodium hydroxide solution [ 3 marks ]

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