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Thermochemistry

Thermochemistry. Chapter 8. Energy is the capacity to do work Thermal energy is the energy associated with the random motion of atoms and molecules Chemical energy is the energy stored within the bonds of chemical substances

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Thermochemistry

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  1. Thermochemistry Chapter 8

  2. Energyis the capacity to do work • Thermal energy is the energy associated with the random motion of atoms and molecules • Chemical energy is the energy stored within the bonds of chemical substances • Nuclear energy is the energy stored within the collection of neutrons and protons in the atom • Electrical energy is the energy associated with the flow of electrons • Potential energy is the energy available by virtue of an object’s position or composition.

  3. Temperature = Thermal Energy 900C 400C Energy Changes in Chemical Reactions Heat is the transfer of thermal energy between two bodies that are at different temperatures. Temperature is a measure of the thermal energy. greater thermal energy

  4. SURROUNDINGS SYSTEM Thermochemistry is the study of heat change in chemical reactions. The system is the specific part of the universe that is of interest in the study. open closed isolated energy nothing Exchange: mass & energy

  5. Thermodynamics State functions are properties that are determined by the state of the system, regardless of how that condition was achieved. energy , pressure, volume, temperature Potential energy of hiker 1 and hiker 2 is the same even though they took different paths.

  6. The specific heat(s) [most books use lower case c] of a substance is the amount of heat (q) required to raise the temperature of one gram of the substance by one degree Celsius. The heat capacity(C) of a substance is the amount of heat (q) required to raise the temperature of a given quantity (m) of the substance by one degree Celsius. C = ms Heat (q) absorbed or released: q = msDt q = CDt Dt = tfinal - tinitial

  7. How much heat is given off when an 869 g iron bar cools from 940C to 50C? s of Fe = 0.444 J/g •0C Dt = tfinal – tinitial = 50C – 940C = -890C q = msDt = 869 g x 0.444 J/g •0C x –890C = -34,000 J

  8. Constant-Pressure Calorimetry qsys = qwater + qcal + qrxn qsys = 0 qrxn = - (qwater + qcal) qwater = msDt qcal = CcalDt Reaction at Constant P DH = qrxn No heat enters or leaves!

  9. DH = qrxn Constant-Volume Calorimetry qsys = qwater + qbomb + qrxn qsys = 0 qrxn = - (qwater + qbomb) qwater = msDt qbomb = CbombDt Reaction at Constant V DH~qrxn No heat enters or leaves!

  10. TWO Trends in Nature • Order  Disorder   • High energy  Low energy 

  11. 2H2(g) + O2(g) 2H2O (l) + energy H2O (g) H2O (l) + energy energy + 2HgO (s) 2Hg (l) + O2(g) energy + H2O (s) H2O (l) Exothermic process is any process that gives off heat – transfers thermal energy from the system to the surroundings. Endothermic process is any process in which heat has to be supplied to the system from the surroundings.

  12. Enthalpy (H) is used to quantify the heat flow into or out of a system in a process that occurs at constant pressure. DH = H (products) – H (reactants) DH = heat given off or absorbed during a reaction at constant pressure Hproducts < Hreactants Hproducts > Hreactants DH < 0 DH > 0

  13. H2O (s) H2O (l) DH = 6.01 kJ Thermochemical Equations Is DH negative or positive? System absorbs heat Endothermic DH > 0 6.01 kJ are absorbed for every 1 mole of ice that melts at 00C and 1 atm.

  14. DH = -890.4 kJ CH4(g) + 2O2(g) CO2(g) + 2H2O (l) Thermochemical Equations Is DH negative or positive? System gives off heat Exothermic DH < 0 890.4 kJ are released for every 1 mole of methane that is combusted at 250C and 1 atm.

  15. 2H2O (s) 2H2O (l) H2O (s) H2O (l) H2O (l) H2O (s) DH = -6.01 kJ DH = 6.01 kJ/mol ΔH = 6.01 kJ DH = 2 mol x 6.01 kJ/mol= 12.0 kJ Thermochemical Equations • The stoichiometric coefficients always refer to the number of moles of a substance • If you reverse a reaction, the sign of DH changes • If you multiply both sides of the equation by a factor n, then DH must change by the same factor n.

  16. How much heat is evolved when 266 g of white phosphorus (P4) burn in air? x H2O (l) H2O (g) H2O (s) H2O (l) 3013 kJ 1 mol P4 x DH = 6.01 kJ DH = 44.0 kJ 1 mol P4 123.9 g P4 Thermochemical Equations • The physical states of all reactants and products must be specified in thermochemical equations. P4(s) + 5O2(g) P4O10(s)DHreaction = -3013 kJ = 6470 kJ 266 g P4

  17. DH0 (O2) = 0 DH0 (O3) = 142 kJ/mol DH0 (C, graphite) = 0 DH0 (C, diamond) = 1.90 kJ/mol f f f f Standard enthalpy of formation (DH0) is the heat change that results when one mole of a compound is formed from its elements at a pressure of 1 atm. f The standard enthalpy of formation of any element in its most stable form is zero.

  18. The standard enthalpy of reaction (DH0 ) is the enthalpy of a reaction carried out at 1 atm. rxn aA + bB cC + dD - [ + ] [ + ] = DH0 DH0 rxn rxn DH0 (products) dDH0 (D) aDH0 (A) bDH0 (B) cDH0 (C) f f f f f - DH0 (reactants) S S = f Hess’s Law: When reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps. (Enthalpy is a state function. It doesn’t matter how you get there, only where you start and end.)

  19. 2C6H6(l) + 15O2(g) 12CO2(g) + 6H2O (l) - S S = DH0 DH0 DH0 - [ ] [ + ] = rxn rxn rxn [ 12 × -393.5 + 6 × -285.8 ] – [ 2 × 49.04 ] = -6535 kJ = 12DH0 (CO2) 2DH0 (C6H6) f f = - 3267 kJ/mol C6H6 6DH0 (H2O) -6535 kJ f 2 mol DH0 (reactants) DH0 (products) f f Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. How much heat is released per mole of benzene combusted? The standard enthalpy of formation of benzene is 49.04 kJ/mol.

  20. C(graphite) + O2(g) CO2(g)DH0 = -393.5 kJ rxn S(rhombic) + O2(g) SO2(g)DH0 = -296.1 kJ rxn CS2(l) + 3O2(g) CO2(g) + 2SO2(g)DH0 = -1072 kJ rxn 2S(rhombic) + 2O2(g) 2SO2(g)DH0 = -296.1x2 kJ C(graphite) + 2S(rhombic) CS2 (l) C(graphite) + 2S(rhombic) CS2 (l) rxn rxn C(graphite) + O2(g) CO2(g)DH0 = -393.5 kJ + CO2(g) + 2SO2(g) CS2(l) + 3O2(g)DH0 = +1072 kJ rxn DH0 = -393.5 + (2x-296.1) + 1072 = 86.3 kJ rxn Calculate the standard enthalpy of formation of CS2 (l) given that: 1. Write the enthalpy of formation reaction for CS2 2. Add the given rxns so that the result is the desired rxn. 6.6

  21. C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) DH = -2801 kJ/mol Chemistry in Action: Fuel Values of Foods and Other Substances 1 cal = 4.184 J 1 Cal = 1 kcal = 1000 cal = 4184 J

  22. The enthalpy of solution (DHsoln) is the heat generated or absorbed when a certain amount of solute dissolves in a certain amount of solvent. DHsoln = Hsoln - Hcomponents Which substance(s) could be used for melting ice? Which substance(s) could be used for a cold pack?

  23. The Solution Process for NaCl DHsoln = Step 1 + Step 2 = 788 – 784 = 4 kJ/mol

  24. Energy Diagrams Exothermic Endothermic • Activation energy (Ea) for the forward reaction • Activation energy (Ea) for the reverse reaction • (c) Delta H

  25. H2O (s) H2O (g) Molar heat of sublimation (DHsub) is the energy required to sublime 1 mole of a solid. Sublimation Deposition DHsub = DHfus + DHvap ( Hess’s Law)

  26. Molar heat of fusion (DHfus) is the energy required to melt 1 mole of a solid substance.

  27. Sample Problem • How much heat is required to change 36 g of H2O from -8 deg C to 120 deg C? Step 1: Heat the ice Q=mcΔT Q = 36 g x 2.06 J/g deg C x 8 deg C = 593.28 J = 0.59 kJ Step 2: Convert the solid to liquid ΔH fusion Q = 2.0 mol x 6.01 kJ/mol = 12 kJ Step 3: Heat the liquid Q=mcΔT Q = 36g x 4.184 J/g deg C x 100 deg C = 15063 J = 15 kJ

  28. Sample Problem • How much heat is required to change 36 g of H2O from -8 deg C to 120 deg C? Step 4: Convert the liquid to gas ΔH vaporization Q = 2.0 mol x 44.01 kJ/mol = 88 kJ Step 5: Heat the gas Q=mcΔT Q = 36 g x 2.02 J/g deg C x 20 deg C = 1454.4 J = 1.5 kJ Now, add all the steps together 0.59 kJ + 12 kJ + 15 kJ + 88 kJ + 1.5 kJ = 118 kJ

  29. Bond Enthalpies (Bond Energy) Strength of a chemical bond is measured by the bond enthalpy, DHB Bond enthalpies are positive, because heat must be supplied to break a bond. Bond breaking is endothermic (DH is positive). Bond formation is exothermic (DH is negative). H2(g) --> 2 H DHo = +436 kJ DHB = 436 kJ/mol

  30. Mean bond enthalpy: average molar enthalpy change accompanying the dissociation of a given type of bond.

  31. Estimate the enthalpy change of the reaction between gaseous iodoethane and water vapor. CH3CH2I(g) + H2O(g) --> CH3CH2OH(g) + HI(g) Reactant: break a C-I bond and an O-H bond DHo = 238 kJ + 463 kJ = 701 kJ Product: to form a C-O bond and an H-I bond DHo = -360 kJ + -299 kJ = -659 kJ Overall enthalpy change = 701 kJ - 659 kJ = 42 kJ

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