To accompany Inquiry into Chemistry PowerPoint Presentation prepared by Robert Schultz robert.schultz@ei.educ.ab.ca Chemistry 30 – Unit 1 Thermochemical Changes Preparation Info • Systems: Open, closed, and isolated definitions • First Law of Thermodynamics – Total energy of the universe is constant (energy can’t be created or destroyed) • Second Law of Thermodynamics – In the absence of energy input, a system becomes more disordered (its entropy increases) Preparation • Meaning? • A system at lower temperature will be more ordered as the particles have less average kinetic energy • Two systems in thermal contact will transfer energy such that the more ordered (cooler) one gains energy and becomes more disordered • Consequence: heat always flows from hotter systems to cooler ones Preparation Important Definitions: • Thermal Energy: the total kinetic energy of all particles of a system • Temperature: a measure of the average kinetic energy of the particles of a system • Heat: a transfer of thermal energy between 2 systems Chapter 9, Section 9.1 Questions: • Which has more thermal energy, a hot cup of coffee or an iceberg? • Which has a larger average thermal energy, a hot cup of coffee or an iceberg? • If an iceberg and a hot cup of coffee come into contact, in which direction will heat flow? Preparation • Heat energy transferred will be related to the temperature change of the system • It takes different amounts of heat energy to change the temperature of 1 g of a substance by 1°C • This number is called the specific heat capacity, c, and is measured in units of: J g C Preparation • Water has a c value of 4.19 J g C • This means that it takes 4.19 J of heat to raise the temperature of 1 g of water by 1°C • Water has a very large c compared to most other common substances Preparation • To determine the amount of heat transferred the formula used is Q mc t • Despite what your text says on page 337, I would always take ∆t as positive • If heat is absorbed, temperature of surroundings will decrease; if heat is released temperature of surroundings will increase • Examples: Practice Problems 1 and 4, page 337 Preparation • Practice Problem 1, page 337 Q mc t 0.100 kg 2.44 kJ kg C 25C 6.1kJ • Since 1 J is such a small amount of heat energy I start my questions in kJ as shown above • If necessary I move into MJ or GJ Preparation • Practice Problem 4, page 337 Q mc t c 4.937 kJ Q 0.790 kJ kg C 0.790 J g C m t 0.25000 kg 25.0 C • Putting kilo top and bottom cancels out and c stays the same • The substance is granite • Worksheet: WS 43 (Nelson) then BLM 9.1.1 (back only) Chapter 9, Section 9.1 • Energy changes in chemical reactions crucial to life • Not just in photosynthesis, fuels, and batteries, but in the very way that your body metabolizes food and makes the energy available for life processes • Thermodynamics: the study of energy and energy changes Chapter 9, Section 9.1 • Recall the first law of thermodynamics: ∆Euniverse= 0 • If a system loses energy, the surroundings gain energy (get warmer) • If a system gains energy, the surroundings lose energy (get cooler) ∆Esystem = - ∆Esurroundings Chapter 9, Section 9.1 • Energy types: • Kinetic energy, Ek, energy of motion of particles of a system • Temperature is a measure of the average Ek of the particles of a system • Potential energy, Ep, stored energy, usually in chemical bonds Chapter 9, Section 9.1 • Transfer of Ek: heat flows from hotter objects to cooler ones (Preparation section of notes) • Breaking bonds always requires energy (endothermic); forming bonds always releases energy (exothermic) • Chemical reaction: breaking bonds + energy1 forming bonds + energy2 input output • If energy1 > energy2, reaction is endothermic • If reverse is true, it is exothermic • Worksheet BLM 9.1.3 Chapter 9, Section 9.1 • New term: enthalpy (not entropy) • Enthalpy (change), ∆H: the difference in potential energy between reactants and products, measured at constant pressure – measured in kJ (or MJ, etc) • Molar Enthalpy (change), ∆rH: the enthalpy change for 1 mole of a specified substance – measured in kJ/mol (or MJ/mol etc) • In common usage the word change gets left out Chapter 9, Section 9.1 • Negative ∆H’s are exothermic (think lose heat) and temperature of surroundings increases • Positive ∆H’s are endothermic (think gain heat) and temperature of the surroundings decreases • Note: this increase → negative, and decrease → positive is a stumbling block for many students Chapter 9, Section 9.1 • Chemical reactions can be written using ∆H notation: C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(l) ∆H=-2802.5 kJ value for the reaction as written 4 NO(g) + 6 H2O(g) 4 NH3(g) + 5 O2(g) ∆H=+906 kJ • They can also be written with the heat as a term in the equation: C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(l) + 2802.5 kJ 4 NO(g) + 6 H2O(g) + 906 kJ Do ∆H Worksheet! 4 NH3(g) + 5 O2(g) Chapter 9, Section 9.1 • Potential energy diagrams for the same 2 reactions are shown below: H (kJ) C6H12O6(s) + 6 O2(g) reactants ∆H = -2802.5 kJ H (kJ) 6 CO2(g) + 6 H2O(l) products 4 NO(g) + 6 H2O(g) products ∆H = +906 kJ 4 NH3(g) + 5 O2(g) reactants Chapter 9, Section 9.2 • Recalling that breaking bonds always endothermic and forming new bonds is always exothermic, more complete Ep diagrams might be shown as follows: Endothermic Exothermic intermediate products ΔH reactants Ep (kJ) Ep (kJ) intermediate reactants products ΔH Chapter 9, Section 9.1 • Alternate forms of potential energy diagram (from Chemistry 30 Diploma Exam Bulletin) Chapter 9, Section 9.1 • Example: Practice Problem 3, page 346 a) C(s) + 2 H2(g) CH4(g) + 74.6 kJ b) C(s) + 2 H2(g) CH4(g) ∆H = -74.6 kJ H (kJ) c) C(s) + 2 H2(g) reactants ∆H = -74.6 kJ CH4(g) products Do Ep diagrams for formation of Cr2O3(s), simple decomp* of AgI(s), and formation of SO2(g) Chapter 9, Section 9.2 Formation of Cr2O3(s) Ep (kJ) 2 Cr(s) + 3/2 O2(g) ΔH=ˉ1139.7 kJ Cr2O3(s) reaction coordinate formation of SO2(g) simple decomposition of AgI(s) ΔH=+61.8 kJ AgI(s) reaction coordinate Ep (kJ) Ep (kJ) Ag(s) + ½ I2(s) 1/8 S8(s) + O2(g) ΔH=ˉ296.8 kJ SO2(g) reaction coordinate Chapter 9, Section 9.1 • Molar enthalpy of combustion: the enthalpy change for the complete combustion of 1 mol of a substance • Complete combustions of fossil fuels always yields CO2(g) and H2O • Open systems – constant pressure – gases escape – H2O(g) • Isolated systems – H2O(l) • Human body – cellular respiration - H2O(l) Chapter 9, Section 9.1 • Table of Molar Enthalpies of Combustions of alkanes, page 347 • Practice Problem 5b, page 347 (open system) C4H10(g) + 13/2 O2(g) OR: 2 C4H10(g) + 13 O2(g) 4 CO2(g) + 5 H2O(g) ∆H = -2657.3 kJ note change in units! 8 CO2(g) + 10 H2O(g) ∆H = -5314.6 kJ • In thermodynamics it is acceptable to write equations with fractional coefficients – don’t do this elsewhere • Try question 5a, page 347 Chapter 9, Section 9.1 • Question 5a page 347 C5H12(l) + 8 O2(g) 5 CO2(g) + 6 H2O(g) ∆H = -3244.8 kJ • Note that the value of ∆H varies directly as the number of moles of reacting substances H n r H • This formula gets used to calculate enthalpy changes for ∆Ep like phase changes, chemical reactions, and nuclear reactions Chapter 9, Section 9.1 • Example Practice Problem 3a, page 349 r HC5H12 3244.8 kJ mol Note: from table, page 347 - comment H n r H Find H for 56.78 g of pentane 56.78 g H n r H 3244.8 kJ mol 2553 kJ 72.17 g / mol mol of pentane Chapter 9, Section 9.1 • Example Practice Problem 6, page 349 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g) ΔH = -906 kJ • molar enthalpy change for? 906 kJ • a) ammonia H r • b) oxygen 227 kJ mol 4 mol NH3 906 kJ r HO2 181 kJ mol 5 mol • c) nitrogen monoxide 906 kJ r HNO 227 kJ mol 4 mol • d) water r HH2O 906 kJ 151 kJ mol 6 mol Chapter 9, Section 9.1 • Do Worksheet BLM 9.1.6 Chapter 9, Section 9.2 • Finding the value of energy changes experimentally: calorimetry • Device: calorimeter • The following diagrams show the principle behind calorimetry – note arrow directions Chapter 9, Section 9.2 • A simple calorimeter like the one you will use 2 nested styrofoam cups containing a measured volume of water sitting in a beaker so that it doesn’t fall over 3rd styrofoam cup inverted on top with hole for thermometer (stirrer) Chapter 9, Section 9.2 • Assumptions in styrofoam cup calorimetry: • Amount of energy transferred to cups and thermometer is small and can be ignored • The system is isolated • The solution produced has the same density and specific heat capacity as water • The process occurs at constant pressure Chapter 9, Section 9.2 • The enthalpy change of a chemical reaction = energy lost or gained, and is indicated by the symbol ΔH • Energy gained or lost by the water causes a temperature change and is indicated by the symbol Q • In an ideal calorimeter ΔH = Q • But recall: H n r H • Therefore and Q mc t n r H mc t system calorimeter “water” calorimetry equation Chapter 9, Section 9.2 • I will redo the example on page 354 using this formula mc t mc t r H n cv limiting reagent, if not stated, or substance question asks about • remember m c Δt is for the “water” and n (c v) for the CuSO4(aq) 2 0.05000 kg 4.19 kJ kg C 24.60 21.40 C H 89.4 kJ r 0.300 mol L 0.05000 L Since the temperature has gone up the process is exothermic Correct answer: 89.4 kJ mol mol Chapter 9, Section 9.2 • Practice Problem 9, page 355 • Note that question asks for molar enthalpy of reaction for sodium • n will be moles of sodium (question asks) n r H m c t m c t 0.175 kg 4.19 kJ kg C 25.70 19.30 C r H 2.9 10 2 kJ mol 0.37 g n 22.99 g mol • Since temperature increases, answer is correctly expressed as 2.9 102 kJ mol or 0.29 MJ mol Do Practice Problems 7, 10, 12, page 355 Chapter 9, Section 9.2 • Investigation 9.A page 356 (goes with the questions you’ve been doing) • Molar enthalpy of combustion: Investigation 9.B, page 357 Chapter 9, Section 9.2 • Bomb Calorimetry: a bomb calorimeter is used to make accurate and precise measurements Chapter 9, Section 9.2 • Reaction takes place inside an inner container called the “bomb” that contains pure oxygen • Chemicals are electrically ignited and heat is released to or absorbed from calorimeter water • Calorimeter materials: stirrer, thermometer, containers are not ignored • With calorimeter filled to a set level with water, all of their heat capacities are combined as shown: Chapter 9, Section 9.2 n r H mH2OcH2O t mther cther t mstir cstir t mcontainsccontains t n r H mH2OcH2O mther cther mstir cstir mcontains ccontains t n r H C t bomb calorimeter equation Heat capacity of calorimeter • Note that C contains the mass and specific heat capacity of each component of the calorimeter • How do you know when to use n r H C t versus n r H mc t ? Chapter 9, Section 9.2 • Look for: - words “bomb calorimeter” - no mention of the mass or volume of water - words “heat capacity” rather than “specific heat capacity” - units J/°C rather than J/g°C • Question 2, Worksheet 46 n r H C t C t 40.00 kJ C 3.54C r H 286 kJ mol 1.00 g n 2.02 g mol • Since temperature increases, answer is -286 kJ/mol • Do rest of Worksheet 46 Chapter 9, Section 9.2 • More practice with • WS 9.1.5 Q mc t Chapter 9, Section 9.2 • Review: page 366-7 good questions: 1, 3, 4 (no actual calculation needed), 5c (data page 347), 6a (data page 347), 8, 10, 13, 15, 16, 17, 18, 19, 21 Chapter 9, Section 9.2