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EXAMPLE: How much heat is required to heat 10.0 g of ice at -15.0 o C to steam at 127.0 o C ? q overall = q ice + q fusion + q water + q boil + q steam. q = (10.0g 2.09J/g o C 15.0 o C) + (10.0g 333J/g) + (10.0g 4.18J/g o C 100.0 o C) + (10.0g 2260J/g)
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EXAMPLE: How much heat is required to heat 10.0 g of ice at -15.0oC to steam at 127.0oC?qoverall = qice + qfusion + qwater + qboil + qsteam q = (10.0g 2.09J/goC 15.0oC) + (10.0g 333J/g) + (10.0g 4.18J/goC 100.0oC) + (10.0g 2260J/g) + (10.0g 2.03J/goC 27.0oC) q = (314 + 3.33×103 + 4.18×103 + 2.26×104 + 548)J = 30.9 kJ
Heat Flow in Reactions exothermic –reaction that gives off energy q < 0 isolated system E=0 heat released by reaction raises the temperature of the solvent constant T, heat is released to the surroundings endothermic – reaction that absorbs energy q > 0
Expansion Type Work w = -PDV system does work DV = Vfinal - Vinitial P V P Vinitial qp = +2kJ
130 10 0 0 Do 250 J of work to compress a gas, 180 J of heat are released by the gasWhat is E for the gas? • 430 J • 70 J • -70 J • -180 J • -250 J
Enthalpy H DE = q + w at constant V, wexpansion = 0 DE = qv at constant P, wexpansion = -PDV DE = qp - PDV DefineH=E + (PV) = E + PV at constant P Hence DH = qp
Enthalpy Enthalpy heat at constant pressure or the heat of reaction qp = DH = Hproducts - Hreactants Exothermic Reaction DH = (Hproducts - Hreactants) < 0 2 H2(g) + O2(g) 2 H2O(l)DH < 0 Endothermic Reaction DH = (Hproducts - Hreactants) > 0 2 H2O(l) 2 H2(g) + O2(g)DH > 0
State Functions • H and E along with P, T, V (or P, T, V) and many others are state functions. They are the same no matter what path we take for the change. • q and w are not state functions, they depend on which path we take between two points. q initial E=Efinal-Einitialq and w can be anything w q E w final
130 10 0 0 Which day would you like OWL quizzes due (4 AM) • Monday • Tuesday • Wednesday • Thursday • Friday
Laws of Thermochemistry 1. The magnitude of DH is directly proportional to the amount of reaction. H is for 1 mole of reaction as written 2 H2(g) + O2(g) 2 H2O(l)DH = -571.6 kJ H2(g) + ½ O2(g) H2O(l)DH = -285.8 kJ Can have ½ mole O2 just not ½ molecule
Laws of Thermochemistry 2. DH for a reaction is equal in magnitude but opposite in sign to DH for the reverse reaction. H2(g) + ½ O2(g) H2O(l)DH = -285.8 kJ H2O(l) H2(g) + ½ O2(g)DH = +285.8 kJ
Laws of Thermochemistry 3. The value of H for the reaction is the same whether it occurs directly or in a series of steps. DHoverall = DH1 + DH2 + DH3 + · · · also called Hess’ Law
Enthalpy Diagram H2(g) + ½ O2(g) H2O(l) DH = -285.8 kJ H2O(l) H2O(g) DH = +44.0 kJ H2(g) + ½ O2(g) H2O(g) DH = -241.8 kJ
130 10 0 0 Given 3 CO + 3/2 O2 3 CO2 H = -849 kJWhat is H for CO2 CO + ½ O2 ? • -283 kJ • +283 kJ • +849 kJ • -2547 kJ • +2547 kJ
Energy and Stoichiometry • Since H is per mole of reaction we can relate heat to amount of reaction • Given C2H6 + 7/2 O2 2 CO2 + 3 H2O H=-1559.7 kJ • If 632.5 kJ are released to surroundings what mass of H2O is formed? • 632.5 kJ released means H = -632.5 kJ for this much H2O
Bomb Calorimeter measure qv qrxn + qcal = 0 qrxn = -qcal qrxn = - ccalT Erxn = qrxn/moles rxn Erxn≈ Hrxn H = E + (PV) H = E + RTngas @298K RT = 2.5 kJ/mol
“Coffee Cup” Calorimeter qp Photo by George Lisensky
Measuring H • When 25.0 mL of 1.0 M H2SO4 are added to 50.0 mL of 1.0 M KOH, both initially at 24.6C the temperature rises to 33.9C. What is H for H2SO4 + 2 KOH K2SO4 + 2 H2O ? (Assume d = 1.00 g/mL, c = 4.18 J/g.C) • qsoln = mcT • m = (25.0 + 50.0)mL×1.00g/mL = 75.0 g
Measuring H cont. • q=mcT • qsoln = 75.0 g × 4.18 J/g.C × (33.9-24.6)C • qsoln = 2916 J • qrxn + qsoln = 0 • qrxn = -2916 J • Hrxn = qrxn/moles rxn
Measuring H cont • How many moles rxn? • 1 mol rxn / 1 mol H2SO4 • 1 mol rxn / 2 mol KOH Stoichiometric mixture so 0.025 mol rxn
Measuring H cont • Hrxn = qrxn/moles rxn • Hrxn = -2916 J / 0.025 mol rxn • Hrxn = -116622 J / mol rxn • Hrxn = -117 kJ • His per mole of reaction as written
130 10 0 0 If excess Al is added to 50 mL of 0.250 M H2SO4 how many moles of the following reaction occur?2 Al + 3 H2SO4 Al2(SO4)3 + 3 H2 • 0.0125 mol • 0.0375 mol • 0.025 mol • 0.00625 mol • 0.00417 mol
Hess’s Law • Can find H for an unknown, or hard to measure, reaction by summing measured H values of known reactions.
EXAMPLE H for formation of CO cannot readily be measured since a mixture of CO and CO2 is always formed. C (s) + ½ O2 (g) CO (g) H = ? C (s) + O2 (g) CO2 (g) H1 = -393.5 kJ CO (g) + ½ O2 (g) CO2 (g) H2 = -283.0 kJ C (s) + ½ O2 (g) CO (g) H = H1 - H2 H = H1 - H2 = -393.5 – (-283.0) = -110.5 kJ
Standard Enthalpy of Formation the enthalpy associated with the formation of 1 mol of a substance from its constituent elements under standard state conditions at the specified temperature For an element this is a null reaction O2 (g) O2 (g) H = 0 Hf = 0 for all elements in their standard states
130 10 0 0 For which one of these reactions is ΔHºrxn = ΔHºf? • N2(g) + 3 H2(g) 2 NH3(g) • C(graphite) + 2 H2(g) CH4(g) • C(diamond) + O2(g) CO2(g) • CO(g) + ½O2(g) CO2(g) • H2(g) + Cl2(g) 2 HCl(g)
Calculation of DHo DHo = Smols DHfoproducts – Smols DHforeactants We can always convert products and reactants to the elements. Hess’s law says H is the same whether we go directly from reactants to products or go via elements
ExampleWhat is the value of DHrxn for the reaction:2 C6H6(l) + 15 O2(g) 12 CO2(g) + 6 H2O(g) from Appendix J Text C6H6(l)DHfo = + 49.0 kJ/mol O2(g) DHfo = 0 CO2(g) DHfo = - 393.5 H2O(g)DHfo = - 241.8 D Hrxn = [S mols D Hfo]product –[S mols D Hfo]reactants
ExampleWhat is the value of DHrx for the reaction:2 C6H6(l) + 15 O2(g) 12 CO2(g) + 6 H2O(g)from Appendix J TextC6H6(l)DHfo = + 49.0 kJ/mol; O2(g) DHfo = 0CO2(g) DHfo = - 393.5; H2O(g)DHfo = - 241.8D Hrxn = [S mols D Hfo]product - [S mols D Hfo]reactants D Hrxn = [12(- 393.5) + 6(- 241.8)]product - [2(+ 49.0 ) + 15(0)]reactants kJ/mol = - 6.2708 103 kJ
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