1 Title: Lesson 2 Measuring Enthalpy Changes Learning Objectives:Understand the technique of calorimetry, including the assumptions underpinning itCalculate enthalpy changes from experimental dataComplete a calorimetry experiment
2 RefreshWhich is true for a chemical reaction in which the products have a higher enthalpy than the reactants?Reaction ∆HA. endothermic positiveB. endothermic negativeC. exothermic positiveD. exothermic negative
3 7.3 MEASURING ENTHALPY CHANGES True or False?1) Exothermic reactions have a negative ΔH2) Endothermic reactions have a negative ΔH3) Breaking bonds is an exothermic reaction4) In endothermic reactions, the products have less energy than the reactants5) Standard temperature is 275K6) Standard pressure is 100kPa7) Standard enthalpy of combustion only involves fuels8) Photosynthesis is an exothermic reaction9) Endothermic reactions absorb energy10) In E = mcΔT, c is the number of moles of compound usedTFFFFTTFTF
4 7.3 MEASURING ENTHALPY CHANGES HEAT & TEMPERATURE - What is the difference?TemperatureAverage kinetic energy of the particlesIndependent of the number of particlesHeatTotal energy of all particlesEnergy of every particle is includedDependent on the number of particlesHeat always flows from high low tempQ: What has more heat, luke warm swimming pool or a red hot nail? Why?
5 Heat changes can be calculated from temperature changes If the same amount of heat is added to two different objects, the ΔT will not be the same, as the average kinetic energy of the particles will not increase by the same amount.Smaller number of particles will experience a larger temperature increase.The increase in temperature when an object is heated will depend on:Mass of objectHeat addedNature of substance
6 Specific heat capacity, C The specific heat capacity of a substance is the amount of energy required to raise the temperature of one gram (g) by one Kelvin (K).Specific heat capacity is different for different substances:SubstanceSpecific Heat CapacityJ g-1K-1Water4.18Ethanol2.44Air1.00Iron0.450Copper0.385
7 7.3 MEASURING ENTHALPY CHANGES DIFFERENT TYPES OF ΔHStandard enthalpy change of reaction (ΔHr)Enthalpy change when a reaction occurs in the molar quantities shown in the balanced chemical equation under standard conditionsStandard enthalpy change of formation (ΔHf)Enthalpy change when 1 mole of a compound is formed from its elements in their standard states under standard conditionse.g. 2C (s) + 3H2 (g) + ½O2 (g) C2H5OH (l)Standard enthalpy change of combustion (ΔHc)Enthalpy change when 1 mole of a substance is completely burned in oxygen under standard conditions in standard states
8 7.3 MEASURING ENTHALPY CHANGES USING THE EQUATION q = mcΔTNo instrument measures heat directlyTo measure enthalpy change we transfer the heat to a known mass of another substance or material, usually waterq (or ∆H) = mcΔTAssumptions:m is just the total mass of water usedThis is valid as the mass of water used is much greater than the mass of any of the other substancesC is just the specific heat capacity of water, ignoring the reactantsThis is valid as the specific heat capacity of water is much higher than most other substances, so they absorb very little of the heat∆H can easily be converted to a molar value by dividing it by the number of moles of reactant (Jmol-1)ΔT = change in temp of the solution (K)q = enthalpy or heat change (J)m = mass (in g) of solution in calorimeter (either directly or indirectly heated) this is also same as volume in cm3c = specific heat capacity of solution (4.18 Jg-1K-1)
9 Relationship between different objects Use heat capacity (c)Defined as the heat needed to increase the temperature of an object by 1K.A swimming pool has a larger heat capacity than a kettle.Note the different between specific heat capacity and heat capacity!
14 Enthalpy changes and the direction of change An exothermic reaction can be compared to a person falling off a ladder. Both changes lead to a decrease in stored energy.Products are more stable than the reactants.However, stability is relative. E.g. Hydrogen peroxide is stable compared to its elements but unstable compared to its decomposition products water and oxygen…
15 Falling up the ladder…We do not expect a person to fall up a ladder but endothermic reactions do occur…Endothermic reactions are less common and occur when there is an increase in disorder of the system, e.g. owing to a formation of a gas…
16 7.3 MEASURING ENTHALPY CHANGES HOW CAN WE CALCULATE ENTHALPY CHANGES?Simple calorimetersBomb calorimeterThere are two ways of measuring enthalpy changes:Measuring enthalpy changes of combustionMeasuring enthalpy changes of reaction
17 7.3 MEASURING ENTHALPY CHANGES KEY IDEAS Specific heat capacity (c) – the amount of energy needed to raise the temperature of 1g of substance by 1K. For water and solutions it is 4.2 Jg-1K-1KEY IDEASTwo step calculations.Work out the energy transferredWork out the energy supplied per mole.
18 Calorimetry – Enthalpy of combustion Calorimetry is used to measure the amount of heat released/absorbed in a reaction.The reaction is used to heat some water, and the temperature change measuredIf we know the mass of water used, the specific heat capacity of the water and the temperature change, we can calculate the heat change.If we are being accurate, we should also take into account the heat capacity of the calorimeter itself as this also heats up.
19 Enthalpy of combustion experiment Boardworks AS ChemistryEnergeticsEnthalpy of combustion experiment
20 Boardworks AS Chemistry Energetics The bomb calorimeter
21 CALCULATING ENTHALPY CHANGE OF COMBUSTION STEP 1:Calculate the heat lost or gained using q = mcΔT Convert Joules to kilojoulesSTEP 2:Calculate number of moles of one of fuel that caused the enthalpy change, from the mass that reacted use n = mass ÷ Molar massSTEP 3:Calculate ΔHc (in kJmol-1) using actual heat change (q in kJ) and number of moles of fuel that burned (n)Use equation: ΔHc = q ÷ n
22 CALCULATING ENTHALPY CHANGE OF COMBUSTION E.g. 1.16g of a fuel is burned in oxygen raising the temp of 100g of water from 295.3K to 357.8K. Mr of the fuel is 58. Calculate ΔHcStep 1:q = mcΔT = 100 x 4.18 x (357.8 – 295.3) = J = kJStep 2:n = mass ÷ Mr = ÷ 58 = moles of fuelStep 3:ΔHc = q ÷ n = ÷ = kJmol-1
23 The IB data booklet value is -1367 kJ/mol… Can you think of 3 reasons why the experimental value is less than the literature value?
24 The difference between the values can be accounted for by any of the following factors: Not all the heat produced by the combustion reaction is transferred to the water. Some is needed to heat the calorimeter and some has passed to the surroundings.The combustion is unlikely to be complete due to the limited oxygen available.The experiment was not performed under standard conditions.
30 ENTHALPY CHANGES OF REACTION Enthalpy changes are determined by simple calorimetry experiments.Known volumes, masses (m) and concentrations are used. The initial (pre-reaction) temperature is taken (t1OC). The reaction is allowed to proceed and then the final temperature is recorded (t2OC).Overall temperature change ΔT is t2OC- t1OC
31 Enthalpy of neutralization experiment Boardworks AS ChemistryEnergeticsEnthalpy of neutralization experiment
32 CALCULATING ENTHALPY CHANGE OF REACTION 7.3 MEASURING ENTHALPY CHANGESCALCULATING ENTHALPY CHANGE OF REACTIONSTEP 1:Calculate the heat lost or gained using q = mcΔT Convert Joules to kilojoulesSTEP 2:Calculate number of moles (n) of one of the reactants that caused the enthalpy change, from the mass that reacted use n = mass ÷ molar mass OR n = (concn x volume) ÷ 1000STEP 3:Calculate ΔHr (in kJmol-1) using actual heat change (q in kJ) and number of moles (n)Use equation: ΔHr = (q ÷ n) x number of moles reacting in balanced equation
33 CALCULATING ENTHALPY CHANGE OF REACTION 7.3 MEASURING ENTHALPY CHANGESCALCULATING ENTHALPY CHANGE OF REACTIONE.g. 30g of ammonium chloride (NH4Cl) is dissolved in water. Temperature decreases from 298K 296K. Total mass of the solution was 980g. Calculate the standard enthalpy change of reactionBalanced equation: NH4Cl (s) NH4+ (aq) + Cl- (aq)Molar mass, M, of NH4Cl = 14 + (4 x 1) = 53.5 gmol-1
34 CALCULATING ENTHALPY CHANGE OF REACTION 7.3 MEASURING ENTHALPY CHANGESCALCULATING ENTHALPY CHANGE OF REACTIONStep 1:q = mcΔT = 980 x 4.18 x ( ) = J = kJStep 2:n = mass ÷ molar mass = 30g ÷ 53.5gmol-1 = moles of NH4ClStep 3:The balanced reaction involves 1 mole of NH4Cl, so:ΔHr = (q ÷ n) x 1 = ÷ = kJmol-1Remember: IF temp increases need to add a minus to q value!
35 Calorimetry calculation examples Boardworks AS ChemistryEnergeticsCalorimetry calculation examples
36 Another exampleWhen 200 cm3 of 1.00 mol dm-3 sodium hydroxide solution was added to 200 cm3 of a mol dm-3 solution of sulphuric acid, the temperature rose from 24.5oC to 30.0oC and a neutral solution was obtained. Determine the enthalpy change when one mole of sulphuric acid is fully neutralised by sodium hydroxide.Determine ∆H:∆H = -m.C∆.T∆H = -( ) x 4.18 x ( ) = -9,196 JDetermine n(H2SO4):n(H2SO4) = conc. x vol. = x (200/1000) = molDetermine Molar ∆H:Molar ∆H = ∆H / n(H2SO4) = / = J = -115 kJ mol-1
37 Using experimental results Boardworks AS ChemistryEnergeticsUsing experimental resultsTeacher notesThe first point after the addition of the solution is lower than may be expected because the solution takes some time to heat up. This explains why measuring the temperature before and as soon as possible after addition, and subtracting the values, is a poor method for working out temperature change. Students could be led towards this conclusion.It could be highlighted that the line of best fit before the addition should be straight, and the line for after the addition should curve with decreasing gradient. Such curves of temperature against time are sometimes known as ‘cooling curves’.
38 Sources of error and assumptions for measuring enthalpy in a polystyrene cup Heat is lost from the system as soon as the temperature rises above the temperature of the surroundings (around 20oC)Maximum recorded temperature is lower than the true value obtained in a perfectly insulated system.Excess zinc powder is added to a calorimeter of a known volume of copper sulphate solutionWe can make allowances for heat loss by extrapolating the cooling line back to when the reaction started…
39 To proceed with our calculations we have made the following assumptions… No heat loss from the systemAll heat goes from reaction to the waterThe solution is dilute: V(CuSO4) = V(H2O)Water has a density of 1.00gcm-3
47 Calorimetry calculation problems Boardworks AS ChemistryEnergeticsCalorimetry calculation problems
48 7.3 MEASURING ENTHALPY CHANGES SUMMARY QUESTIONSmol of a compound dissolves in water, causing the temperature to increase from 298K to 301K. Total mass is 220g. Calculate the enthalpy change in kJmol-1. Assume c = 4.18 Jg-1K-12. A calorimeter, containing 200g of water, was used to calculate ΔHc of pentane (C5H12) (Mr = 72). 0.5 g of pentane was burnt, increasing the water temp by 29K. a) calculate ΔHc; b) Suggest reasons why your value may be different to the value given in a data book3. ΔHc of octane is kJmol-1, its Mr is 114. Some octane was burnt in a calorimeter with 300g of water. The temperature increase was 55K. Calculate the mass of propane burnt.Extension Worksheet questions
49 7.3 MEASURING ENTHALPY CHANGES SELF ASSESSmol of a compound dissolves in water, causing the temperature to increase from 298K to 301K. Total mass is 220g. Calculate the enthalpy change in kJmol-1. Assume c = 4.18 Jg-1K-1q = mcΔT = 220 x 4.18 x (301 – 298) = J = KJΔH = q ÷ n = ÷ = kJmol-1REMEMBER: the minus symbol as temp went up!Extension Worksheet questions
50 7.3 MEASURING ENTHALPY CHANGES SELF ASSESS2. A calorimeter, containing 200g of water, was used to calculate ΔHc of pentane (C5H12) (Mr = 72). 0.5 g of pentane was burnt, increasing the water temp by 29K. a) calculate ΔHc; b) Suggest reasons why your value may be different to the value given in a data bookq = mcΔT = 200 x 4.18 x 29 = J = KJn = m ÷ Mr = 0.5g ÷ 72 = moles of fuelΔH = q ÷ n = ÷ = kJmol-1b) Some heat from combustion will be transferred to the surroundings and not the water. May not have been complete combustion. May not have been standard conditions. Inaccuracies in the measuring equipmentExtension Worksheet questions
51 7.3 MEASURING ENTHALPY CHANGES SELF ASSESS3. ΔHc of octane is kJmol-1, its Mr is 114. Some octane was burnt in a calorimeter with 300g of water. The temperature increase was 55K. Calculate the mass of propane burnt.q = mcΔT = 300 x 4.18 x 55 = J = KJΔH = q ÷ n rearranges to n = q ÷ ΔH= ÷ = moln = mass ÷ Mr rearranges to mass = n x Mr= x 114= 1.43g octaneExtension Worksheet questions
52 Calorimetry in Practice In this experiment you will determine the enthalpy change for the reaction of magnesium with sulphuric acid.To do this accurately, you will first need to determine the heat capacity of the calorimeter.Follow the instructions here
53 ∆H = -m.C.∆T Units: Joules, J Key Points∆H = -m.C.∆T Units: Joules, JAssumptions:Specific heat capacity of solutions is the same as that of waterTotal mass is the same as the volume of solution used