May 11 Unit 3: Thermochemistry Chemistry 3202 1 May 11 Unit Outline Temperature and Kinetic Energy Heat/Enthalpy Calculation Temperature changes (q = mc∆T) Phase changes (q = n∆H) Heating and Cooling Curves Calorimetry (q = C∆T & above formulas) 2 May 11 Unit Outline Chemical Reactions PE Diagrams Thermochemical Equations Hess’s Law Bond Energy STSE: What Fuels You? 3 May 11 Temperature and Kinetic Energy Thermochemistry is the study of energy changes in chemical and physical changes eg. dissolving burning phase changes 4 May 11 Temperature , T, measures the average kinetic energy of particles in a substance - a change in temperature means particles are moving at different speeds - measured in either Celsius degrees or degrees Kelvin Kelvin = Celsius + 273.15 5 May 11 The Celsius scale is based on the freezing and boiling point of water The Kelvin scale is based on absolute zero - the temperature at which particles in a substance have zero kinetic energy. 6 May 11 p. 628 7 May 11 K °C 50.15 48 450.15 -200 8 May 11 300 K # of particles 500 K Kinetic Energy 9 May 11 Heat/Enthalpy Calculations system - the part of the universe being studied and observed surroundings - everything else in the universe open system - a system that can exchange matter and energy with the surroundings eg. an open beaker of water a candle burning closed system - allows energy transfer but is closed to the flow of matter. 10 May 11 isolated system – a system completely closed to the flow of matter and energy heat - refers to the transfer of kinetic energy from a system of higher temperature to a system of lower temperature. - the symbol for heat is q WorkSheet: Thermochemistry #1 11 May 12 Part A: Thought Lab (p. 631) 12 May 12 Part B: Thought Lab (p. 631) 13 May 12 Heat/Enthalpy Calculations specific heat capacity – the energy , in Joules (J), needed to change the temperature of one gram (g) of a substance by one degree Celsius (°C). The symbol for specific heat capacity is a lowercase c 14 May 12 A substance with a large value of c can absorb or release more energy than a substance with a small value of c. ie. For two substances, the substance with the larger c will undergo a smaller temperature change with the same loss or gain of heat. 15 May 12 FORMULA q = mc∆T q = heat (J) m = mass (g) c = specific heat capacity ∆T = temperature change = T2 – T1 = Tf – Ti 16 May 12 eg. How much heat is needed to raise the temperature of 500.0 g of water from 20.0 °C to 45.0 °C? q = m c ∆T for c, m, ∆T, T2 & T1 p. 634 #’s 1 – 4 p. 636 #’s 5 – 8 WorkSheet: Thermochemistry #2 Solve 17 May 13 heat capacity - the quantity of energy , in Joules (J), needed to change the temperature of a substance by one degree Celsius (°C) The symbol for heat capacity is uppercase C The unit is J/ °C or kJ/ °C 18 May 13 FORMULA C = mc q = C ∆T Your Turn C = heat capacity c = specific heat capacity m = mass ∆T = T2 – T1 p.637 #’s 11-14 WorkSheet: Thermochemistry #3 19 May 18 Enthalpy Changes enthalpy change - the difference between the potential energy of the reactants and the products during a physical or chemical change AKA: Heat of Reaction or ∆H 20 May 18 Endothermic Reaction Products PE ∆H Reactants Reaction Progress 21 May 18 Endothermic Reaction Products PE Enthalpy ∆H ∆H Reactants Reaction Progress 22 May 18 Products Enthalpy ∆H is + Reactants Endothermic 23 May 18 reactants Enthalpy ∆H is products Exothermic 24 May 18 Enthalpy Changes in Reactions All chemical reactions require bond breaking in reactants followed by bond making to form products Bond breaking requires energy (endothermic) while bond formation releases energy (exothermic) see p. 639 25 May 18 26 May 18 Enthalpy Changes in Reactions endothermic reaction - the energy required to break bonds is greater than the energy released when bonds form. ie. energy is absorbed exothermic reaction - the energy required to break bonds is less than the energy released when bonds form. ie. energy is produced 27 May 18 Enthalpy Changes in Reactions 1. ∆H can represent the enthalpy change for a number of processes Chemical reactions ∆Hrxn – enthalpy of reaction ∆Hcomb – enthalpy of combustion (see p. 643) 28 May 18 2. Formation of compounds from elements ∆Hof – standard enthalpy of formation The standard molar enthalpy of formation is the energy released or absorbed when one mole of a compound is formed directly from the elements in their standard states. (see p. 642) eg. C(s) + ½ O2(g) → CO(g) ΔHfo = -110.5 kJ/mol 29 May 18 Use the equation below to determine the ΔHfo for CH3OH(l) 2 C(s) + 4 H2(g) + O2(g) → 2 CH3OH(l) + 477.2 kJ 1 C(s) + 2 H2(g) + ½ O2(g) → 1 CH3OH(l) + 238.6 kJ ∆H = -238.6 kJ/mol 30 May 18 Use the equation below to determine the ΔHfo for CaCO3(s) 2 CaCO3(s) + 2413.8kJ → 2 Ca(s) + 2 C(s) + 3 O2(g) 2 Ca(s) + 2 C(s) + 3 O2(g) → 2 CaCO3(s) + 2413.8kJ 1 Ca(s) + 1 C(s) + 1.5 O2(g) → 1 CaCO3(s) + 1206.9 kJ ∆H = -1206.9 kJ/mol 31 May 18 Use the equation below to determine the ΔHfo for PH3(g) 4 PH3(g) → P4(s) + 6 H2(g) + 21.6 kJ a) +21.6 kJ/mol b) -21.6 kJ/mol c) +5.4 kJ/mol d) -5.4 kJ/mol 32 May 18 Phase Changes (p.647) ∆Hvap – enthalpy of vaporization (l → g) 3. ∆Hfus – enthalpy of melting (fusion: s → l) ∆Hcond – enthalpy of condensation (g → l) ∆Hfre – enthalpy of freezing (l → s) eg. H2O(l) H2O(g) Hg(l) Hg(s) ΔHvap = +40.7 kJ/mol ΔHfre = -23.4 kJ/mol 33 May 18 4. Solution Formation (p.647, 648) ∆Hsoln – enthalpy of solution eg. ΔHsoln, of ammonium nitrate is +25.7 kJ/mol. NH4NO3(s) + 25.7 kJ → NH4NO3(aq) ΔHsoln, of calcium chloride is −82.8 kJ/mol. CaCl2(s) → CaCl2(aq) + 82.8 kJ 34 May 18 Three ways to represent an enthalpy change: 1. thermochemical equation - the energy term written into the equation. 2. enthalpy term is written as a separate expression beside the equation. 3. enthalpy diagram. 35 May 18 eg. the formation of water from the elements produces 285.8 kJ of energy. 1. H2(g) + ½ O2(g) → H2O(l) + 285.8 kJ thermochemical equation 2. H2(g) + ½ O2(g) → H2O(l) ∆Hf = -285.8 kJ/mol 36 enthalpy diagram H2(g) + ½ O2(g) 3. Enthalpy (H) examples: questions ∆Hf = -285.8 kJ/mol H2O(l) May 18 pp. 641-643 p. 643 #’s 15-18 WorkSheet: Thermochemistry #4 37 May 24 Calculating Enthalpy Changes FORMULA: q = n∆H q = heat (kJ) n = # of moles m n M ∆H = molar enthalpy (kJ/mol) 38 May 24 eg. How much heat is released when 50.0 g of CH4 forms from C and H ? (p. 642) n 50.0 g 16.05 g / mol 3.115 mol q = nΔH = (3.115 mol)(-74.6 kJ/mol) = -232 kJ 39 May 24 eg. How much heat is released when 50.00 g of CH4 undergoes complete combustion? (p. 643) 50.0 g n 16.05 g / mol 3.115 mol q = nΔH = (3.115 mol)(-965.1 kJ/mol) = -3006 kJ 40 May 24 eg. How much energy is needed to change 20.0 g of H2O(l) at 100 °C to steam at 100 °C ? Mwater = 18.02 g/mol ΔHvap = +40.7 kJ/mol 20.0 g n 18.02 g / mol 1.110 mol q = nΔH = (1.110 mol)(+40.7 kJ/mol) = +45.2 kJ 41 May 24 ∆Hfre and ∆Hcond have the opposite sign of the above values. 42 May 24 eg. The molar enthalpy of solution for ammonium nitrate is +25.7 kJ/mol. How much energy is absorbed when 40.0 g of ammonium nitrate dissolves? 40.0 g n 80.06g / mol 0.4996 mol q = nΔH = (0.4996 mol)(+25.7 kJ/mol) = +12.8 kJ 43 May 24 What mass of ethane, C2H6, must be burned to produce 405 kJ of heat? ΔH = -1250.9 kJ - 405 kJ n q = - 405 kJ 1250.9 kJ m=? q = nΔH q n H n = 0.3238 mol m= nxM = (0.3238 mol)(30.08 g/mol) = 9.74 g 44 Complete: p. 645; #’s 19 – 23 pp. 648 – 649; #’s 24 – 29 p. 638 #’ 4 – 8 pp. 649, 650 #’s 3 – 8 p. 657, 658 #’s 9 - 18 May 24 WorkSheet: Thermochemistry #5 45 19. (a) -8.468 kJ (b) -7.165 kJ 20. -1.37 x103 kJ 21. (a) -2.896 x 103 kJ (b) -6.81 x104 kJ 21. (c) -1.186 x 106 kJ 22. -0.230 kJ 23. 3.14 x103 g 24. 2.74 kJ 25.(a) 33.4 kJ (b) 33.4 kJ 26.(a) absorbed (b) 0.096 kJ 27.(a) NaCl(s) + 3.9 kJ/mol → NaCl(aq) (b) 1.69 kJ (c) cool; heat absorbed from water 28. 819.2 g 29. 3.10 x 104 kJ 46 May 25 Heating and Cooling Curves Demo: Cooling of p-dichlorobenzene Time (s) Temperature (°C) Time (s) Temperature (°C) 47 May 25 Cooling curve for p-dichlorobenzene Temp. 80 (°C ) 50 KE liquid PE freezing KE solid 20 Time 48 May 25 Heating curve for p-dichlorobenzene 80 Temp. (°C ) 50 KE PE 20 KE Time 49 May 25 What did we learn from this demo?? During a phase change temperature remains constant and PE changes Changes in temperature during heating or cooling means the KE of particles is changing 50 May 25 p. 651 51 May 25 p. 652 q = mc∆T q = n∆H 52 May 25 p. 656 q = n∆H q = mc∆T 53 May 25 54 May 25 Heating Curve for H20(s) to H2O(g) 1. 2. A 40.0 g sample of ice at -40 °C is heated until it changes to steam and is heated to 140 °C. Sketch the heating curve for this change. Calculate the total energy required for this transition. 55 May 25 q = mc∆T 140 100 q = n∆H q = mc∆T Temp. (°C ) q = n∆H 0 q = mc∆T -40 Time 56 May 25 Data: cice = 2.01 J/g.°C cwater = 4.184 J/g.°C csteam = 2.01 J/g.°C ΔHfus = +6.02 kJ/mol ΔHvap = +40.7 kJ/mol 57 warming ice: (from -40 ºC to 0 ºC) q = mc∆T = (40.0)(2.01)(0 - -40) = 3216 J May 26 warming water: (from 0 ºC to 100 ºC) q = mc∆T = (40.0)(4.184)(100 – 0) = 16736 J 58 May 26 warming steam: (from 100 ºC to 140 ºC) q = mc∆T = (40.0)(2.01)(140 -100) = 3216 J moles of water: n = 40.0 g 18.02 g/mol = 2.22 mol 59 melting ice: (fusion) q = n∆H = (2.22 mol)(6.02 kJ/mol) = 13.364 kJ May 26 boiling water: (vaporization) q = n∆H = (2.22 mol)(40.7 kJ/mol) = 90.354 kJ 60 May 27 Total Energy 90.354 kJ 13.364 kJ 3216 J 3216 J 16736 J 127 kJ 61 May 27 Practice p. 655: #’s 30 – 34 WorkSheet: pp. 656: #’s 1 - 9 Thermochemistry #6 p. 657 #’s 2, 9 p. 658 #’s 10, 16 – 20 30.(b) 3.73 x103 kJ 31.(b) 279 kJ 32.(b) -1.84 x10-3 kJ 33.(b) -19.7 kJ -48.77 kJ 34. -606 kJ 62 May 30 Law of Conservation of Energy (p. 627) The total energy of the universe is constant ∆Euniverse = 0 First Law of Thermodynamics Universe = system + surroundings ∆Euniverse = ∆Esystem + ∆Esurroundings ∆Euniverse = ∆Esystem + ∆Esurroundings = 0 OR OR ∆Esystem = -∆Esurroundings qsystem = -qsurroundings 63 May 30 Calorimetry (p. 661) calorimetry - the measurement of heat changes during chemical or physical processes calorimeter - a device used to measure changes in energy 2 types of calorimeters 1. constant pressure or simple calorimeter (coffee-cup calorimeter) 2. constant volume or bomb calorimeter. 64 May 30 Simple Calorimeter p.661 65 May 30 a simple calorimeter consists of an insulated container, a thermometer, and a known amount of water simple calorimeters are used to measure heat changes associated with heating, cooling, phase changes, solution formation, and chemical reactions that occur in aqueous solution 66 May 30 to calculate heat lost or gained by a chemical or physical change we apply the first law of thermodynamics: qsystem = -qcalorimeter Assumptions: - the system is isolated - c (specific heat capacity) for water is not affected by solutes - heat exchange with calorimeter can be ignored 67 May 30 eg. A simple calorimeter contains 150.0 g of water. A 5.20 g piece of aluminum alloy at 525 °C is dropped into the calorimeter causing the temperature of the calorimeter water to increase from 19.30°C to 22.68°C. Calculate the specific heat capacity of the alloy. 68 May 31 aluminum alloy m = 5.20 g T1 = 525 ºC T2 = 22.68 ºC FIND c for Al water m = 150.0 g T1 = 19.30 ºC T2 = 22.68 ºC c = 4.184 J/g.ºC qsys = - qcal mcΔT = - mc ΔT (5.20)(c)(22.68 - 525 ) = -(150.0)(4.184)(22.68 – 19.30) -2612 c = -2121 c = 0.812 J/g.°C 69 May 31 eg. The temperature in a simple calorimeter with a heat capacity of 1.05 kJ/°C changes from 25.0 °C to 23.94 °C when a very cold 12.8 g piece of copper was added to it. Calculate the initial temperature of the copper. (c for Cu = 0.385 J/g.°C) 70 copper m = 12.8 g T2 = 23.94 ºC c = 0.385 J/g.°C May 31 calorimeter C = 1.05 kJ/°C T1 = 25.00 ºC T2 = 23.94 ºC FIND T1 for Cu qsys = - qcal mcT = - CT (12.8)(0.385)(23.94 – T1) = -(1050)(23.94 – 25.0) 4.928 (23.94 – T1) = 1113 23.94 – T1= 1113/4.928 23.94 – T1= 225.9 T1= -202 ºC 71 May 31 Homework p. 664, 665 #’s 1b), 2b), 3 & 4 p. 667, #’s 5 - 7 72 p. 665 # 4.b) (60.4)(0.444)(T2 – 98.0) = -(125.2)(4.184)(T2 – 22.3) 26.818(T2 – 98.0) = -523.84(T2 – 22.3) 26.818T2 - 2628.2 = -523.84T2 + 11681 550.66T2 = 14309.2 T2 = 26.0 °C 73 6. System (Mg) m = 0.50 g = 0.02057 mol Find ΔH Calorimeter v = 100 ml so m = 100 g c = 4.184 T2 = 40.7 qMg = -qcal T1 = 20.4 nΔH = -mcΔT 7. System ΔH = -53.4 kJ/mol n = CV = (0.0550L)(1.30 mol/L) = 0.0715 mol Calorimeter v = 110 ml so m = 110 g c = 4.184 T1 = 21.4 Find T2 74 June 1 Bomb Calorimeter 75 Bomb Calorimeter used to accurately measure enthalpy changes in combustion reactions the inner metal chamber or bomb contains the sample and pure oxygen an electric coil ignites the sample temperature changes in the water surrounding the inner “bomb” are used to calculate ΔH 76 to accurately measure ΔH you need to know the heat capacity (kJ/°C) of the calorimeter. must account for all parts of the calorimeter that absorb heat Ctotal = Cwater + Cthermom.+ Cstirrer + Ccontainer NOTE: C is provided for all bomb calorimetry calculations 77 eg. A technician burned 11.0 g of octane in a steel bomb calorimeter. The heat capacity of the calorimeter was calibrated at 28.0 kJ/°C. During the experiment, the temperature of the calorimeter rose from 20.0 °C to 39.6 °C. What is the enthalpy of combustion for octane? 78 May 31 system (octane) m = 11.0 g Find ΔHcomb n = 11.0 g 114.26 g/mol = 0.09627 mol calorimeter C = 28.0 kJ/ºC T2 = 39.6 ºC T1 = 20.0 ºC qsys = - qcal n ΔH = -CΔT (0.09627) ΔH = - (28.0)(39.6 – 20.0) ΔH = -5700 kJ/mol 79 May 31 eg. 1.26 g of benzoic acid, C6H5COOH(s), is burned in a bomb calorimeter. The temperature of the calorimeter and contents increases from 23.62 °C to 27.14 °C. Calculate the heat capacity of the calorimeter. (∆Hcomb = -3225 kJ/mol) benzoic acid m = 1.26 g ΔHcomb = -3225 kJ/mol calorimeter T1 = 23.62 ºC T2 = 27.14 ºC Find C 80 May 31 n = 1.26 g 122.13 g/mol = 0.01032 mol qsys = - qcal n ΔH = -CΔT (0.01032) ΔH = - (C)(27.14 – 23.62) C = 9.45 kJ/ ºC Homework p. 675 #’s 8 – 10 WorkSheet: Thermochemistry #7 81 June 2 Hess’s Law of Heat Summation the enthalpy change (∆H) of a physical or chemical process depends only on the beginning conditions (reactants) and the end conditions (products) ∆H is independent of the pathway and/or the number of steps in the process ∆H is the sum of the enthalpy changes of all the steps in the process 82 June 2 eg. production of carbon dioxide Pathway #1: 2-step mechanism C(s) + ½ O2(g) → CO(g) ∆H = -110.5 kJ CO(g) + ½ O2(g) → CO2(g) ∆H = -283.0 kJ C(s) + O2(g) → CO2(g) ∆H = -393.5 kJ 83 June 2 eg. production of carbon dioxide Pathway #2: formation from the elements C(s) + O2(g) → CO2(g) ∆H = -393.5 kJ 84 Using Hess’s Law June 2 We can manipulate equations with known ΔH to determine an unknown enthalpy change. NOTE: Reversing an equation changes the sign of ΔH. If we multiply the coefficients we must also multiply the ΔH value. 85 June 2 multiply ? reverse ? eg. Determine the ΔH value for: H2O(g) + C(s) → CO(g) + H2(g) using the equations below. C(s) + ½ O2(g) → CO(g) ΔH = -110.5 kJ H2(g) + ½ O2(g) → H2O(g) ΔH = -241.8 kJ 86 June 2 eg. Determine the ΔH value for: 4 C(s) + 5 H2(g) → C4H10(g) using the equations below. Switch ΔH (kJ) C4H10(g) + 6½ O2(g) → 4 CO2(g) + 5 H2O(g) -110.5 H2(g) + ½ O2(g) → H2O(g) -241.8 C(s) + O2(g) → CO2(g) Multiply by 4 Multiply by 5 -393.5 87 June 2 4 CO2(g) + 5 H2O(g) → C4H10(g) + 6½ O2(g) +110.5 5(H2(g) + ½ O2(g) → H2O(g) 4(C(s) + O2(g) → CO2(g) -241.8) 4 CO2(g) + 5 H2O(g) → C4H10(g) + 6½ O2(g) 5 H2(g) + 2½ O2(g) → 5 H2O(g) 4C(s) + 4 O2(g) → 4 CO2(g) +110.5 -1209.0 -1574.0 -393.5) Ans: -2672.5 kJ 88 June 2 Practice pg. 681 #’s 11-14 WorkSheet: Thermochemistry #8 89 Review June 3 ∆Hof (p. 642, 684, & 848) The standard molar enthalpy of formation is the energy released or absorbed when one mole of a substance is formed directly from the elements in their standard states. ∆Hof = 0 kJ/mol for elements in the standard state The more negative the ∆Hof , the more stable the compound 90 Using Hess’s Law and ΔHf June 3 Use the formation equations below to determine the ΔH value for: C4H10(g) + 6½ O2(g) → 4 CO2(g) + 5 H2O(g) 4 C(s) + 5 H2(g) → C4H10(g) H2(g) + ½ O2(g) → H2O(g) C(s) + O2(g) → CO2(g) ΔHf (kJ/mol) -2672.5 -241.8 -393.5 91 June 3 Using Hess’s Law and ΔHf ΔHrxn = ∑ΔHf (products) - ∑ΔHf (reactants) eg. Use ΔHf , to calculate the enthalpy of reaction for the combustion of glucose. C6H12O6(s) + 6 O2(g) → 6 CO2(g) + 6 H2O(g) 92 June 3 ΔHrxn = ∑ΔHf (products) - ∑ΔHf (reactants) CO2(g) H2O(g) C6H12O6(s) ΔHf -393.5 kJ/mol -241.8 kJ/mol -1274.5 kJ/mol C6H12O6(s) + 6 O2(g) → 6 CO2(g) + 6 H2O(g) ΔHrxn = [6(-393.5) + 6(-241.8)] – [1(-1274.5)+ 6(0)] = [-2361 + -1450.8] - [-1274.5 + 0] = - 2537.3 kJ 93 June 3 Use the molar enthalpy of formation to calculate ΔH for this reaction: Fe2O3(s) + 3 CO(g) → 3 CO2(g) + 2 Fe(s) −824.2 kJ/mol −110.5 kJ/mol −393.5 kJ/mol ΔHrxn = [3(-393.5) + 2(0) ] – [3(-110.5)+ 1(-824.2)] = [-1180.5 + 0] - [-331.5 + -824.20] = - 24.8 kJ 94 June 7 Eg. The combustion of phenol is represented by the equation below: −393.5 kJ/mol C6H5OH(s) + 7 O2(g) → 6 CO2(g) + 3 H2O(g) −241.8 kJ/mol If ΔHcomb = -3059 kJ/mol, calculate the heat of formation for phenol. ΔHcomb = -27.4 kJ/mol 95 Bond Energy Calculations (p. 688) The energy required to break a bond is known as the bond energy. Each type of bond has a specific bond energy (BE). (table p. 847) Bond Energies may be used to estimate the enthalpy of a reaction. 96 Bond Energy Calculations (p. 688) ΔHrxn = ∑BE(reactants) - ∑BE (products) eg. Estimate the enthalpy of reaction for the combustion of ethane using BE. 2 C2H6(g) + 7 O2(g) → 4 CO2(g) + 6 H2O(g) Hint: Drawing the structural formulas for all reactants and products will be useful here. 97 C-C = 347 C-H = 338 O=O = 498 2 C C C=O = 745 H-O = 460 + 7O=O → 4 O=C=O + 6 H-O-H [2(347) + 2(6)(338) + 7(498)] - [4(2)(745) + 6(2)(460)] 8236 - 11480 = -3244 kJ p. 690 #’s 23,24,& 26 p. 691 #’s 3, 4, 5, & 7 98 Energy Comparisons Phase changes involve the least amount of energy with vaporization usually requiring more energy than melting. Chemical changes involve more energy than phase changes but much less than nuclear changes. Nuclear reactions produce the largest ΔH eg. nuclear power, reactions in the sun 99 STSE What fuels you? (Handout) 100 aluminum alloy m = 5.20 g T1 = 525 ºC T2 = ºC FIND c for Al water m = 150.0 g T1 = 19.30 ºC T2 = 22.68 ºC c = 4.184 J/g.ºC qsys = - qcal mcT = - mc T (5.20)(c)(22.68 - 525 ) = -(150.0)(4.184)(22.68 – 19.30) -2612 c = -2121 c = 0.812 J/g.°C 101 copper m = 12.8 g T2 = ºC c = 0.385 J/g.°C calorimeter C = 1.05 kJ/°C T1 = 25.00 ºC T2 = 23.94 ºC FIND T1 for Cu qsys = - qcal mcT = - CT (12.8)(0.385)(23.94 – T1) = -(1050)(23.94 – 25.0) 4.928 (23.94 – T1) = 1113 23.94 – T1= 1113/4.928 23.94 – T1= 225.9 T1= -202 ºC 102 q heat J or kJ c Specific heat capacity Heat capacity J/g.ºC C ΔH Molar heat or molar enthalpy kJ/ ºC or J/ ºC kJ/mol 103