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Topic 15 Energetics (HL)

Topic 15 Energetics (HL). 15.1 Standard enthalpy changes of reaction 15.2 Born-Haber cycle 15.3 Entropy 15.4 Spontaneity. 15.1 Standard Enthalpy Change of reaction . Standard state: 101kPa, 298K. Standard enthalpy of formation D H f q.

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Topic 15 Energetics (HL)

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  1. Topic 15 Energetics (HL) • 15.1 Standard enthalpy changes of reaction • 15.2 Born-Haber cycle • 15.3 Entropy • 15.4 Spontaneity

  2. 15.1 Standard Enthalpy Change of reaction Standard state: 101kPa, 298K

  3. Standard enthalpy of formation DHfq DHfq: The energy absorbed or evolved when 1 mol of the substance is formed from its elements in their standard states. The enthalpy of formation of any element is zero. ½ H2(g) + O2(g) H2O(l)DHfq= -285 kJ/mol DH = SDHf(products) - SDHf(reactants)

  4. Decomposition of ammonium nitrate NH4NO3(s) N2O(g) + 2 H2O(l) • NH4NO3(s) DHfq= -366 kJ/mol • N2O(g) DHfq= +82 kJ/mol • H2O(l)DHfq= -285 kJ/mol DH = [DHf(N2O(g)) + DHf(H2O(l))] – [DHf(NH4NO3(g)] = =[82 + 2(-285)] - [-366] = -122 kJ/mol

  5. Standard enthalpy of combustion,DHcq • When a substance is fully combusted in oxygen CH4+ 2O2 CO2 + 2H2O DHcq= ?

  6. 15.2 Born-Haber cycle • To determine the lattice enthalpy and the degree of ionic character of a salt • To find an unknown value (Hess’ law)

  7. Lattice enthalpy, DHlattice • Relates to the endothermic process MX(s) M+(g) + X-(g) in which the gaseous ions of a crystal are separated to an infinitive distance from each other. • NaCl(s) Na+(g) + Cl-(g) DHlattice= 769 kJ/molEndothermic reactions

  8. Factors affecting the lattice enthalpy • The greater the charge of the ions, the stronger the electrostaticattraction http://www.chemhume.co.uk/A2CHEM/Unit%202b/9%20Lattice%20enthalpy/Ch9Latticec.htm

  9. Factors affecting the lattice enthalpy (2) The smaller the ionicradius, the shorter the distance, the strongerthe electrostaticattraction

  10. Electron affinity (electron gain enthalpy) • The enthalpy change when an atom gain one electron in gas phase e.g. Cl(g) + e-(g) Cl-(g) DHe.a. = -349 kJ/mol. • Electron affinity can be both exothermic and endothermic depending on element.

  11. Born-Haber cycle for the formation of NaCl (s) • Enthalpy of atomisation of Na Na (s) →Na (g) DHat= +108 kJ/mol • Enthalpy of atomisation of Cl ½ Cl2(s) →Cl(g) DHat= +121 kJ/mol (½ energy of Cl-Cl bond)

  12. Born-Haber cycle for the formation of NaCl (s)(2) • Electron affinity of Cl Cl(g) + e-→ Cl-(g)DHea= -349 kJ/mol • Ionisation energy of Na Na (g)→ Na+ (g) + e-DHie= + 496kJ/mol

  13. Born-Haber cycle for the formation of NaCl (s)(3) • Lattice enthalpy of NaCl Cl-(g)+ Na+ (g) →NaCl (s) DHlatt= -769 kJ/mol

  14. Theoretical value of Enthalpy of formation of NaCl = -411kJ/mol Using Hess Law: Enthalpy of formation of NaCl DHf(NaCl)= DHat(Na) + DHie(Na) + DHat(Cl) + DHea(Cl) + DHlatt(NaCl) 108+494+121+(-364) + (-771)= -393 kJ/mol

  15. Use of Born-Haber cycles • In the Chemistry Data Booklet the lattice enthalpies is given booth as: • Experimental values (obtained by Born-Haber cycle) • Theoretical values (calculated from electrostatic principles) • If the value differ in a significant way => indicate more covalent character of the salt

  16. 15.3 Entropy- disorder • Entropy, S Unit: J/K*mol • DS = change in disorder • DS = Sproducts- Sreactants • It’s possible to measure absolute values of S

  17. Increasing entropy- DS positive • Solid Liquid  Gas increase in S Ice  Water  Steam 48.0 69.9 188.7 JK-1mol-1 • Mixing different types of particles- dissolving NaCl in water • Increasing no of particles- N2O4 (g) →2 NO2 (g)

  18. Decreasing entropy- DS negative • System becomesmoreordered • Formation of solid ammonium chloride from hydrogen chloride and ammonia gas NH3(g) + HCl(g) NH4Cl(s)DS = - 285 J/K*mol

  19. In any conversion there is both a change in DH and DS. DS is probably positive if number of mol of gas increases and number of mol of solid/liquid decrease. NH4Cl(s) NH3(g) + HCl(g) DS = + 285J/K*mol Pb2+(aq) + 2 I- PbI2(s)DS = - 70 J/K*mol

  20. 15.4 Spontaneity of a reaction- DG • Nature likes low internal energy (DH to decrease) and high disorder (DS to increase) • Spontaneity: is a reaction going to occur • A reaction will occur if the final state is more probable than the initial state. => Decrease in DH => Increase in DS

  21. DGq= DHq -TDSq • Standard free energy, DGq (or Gibbs free energy) • Temperature is importantfor spontaneity • A reaction will be spontaneous if DG has a negative value (DGq < 0) • A positive DGq is a non-spontaneous reaction. • If DGq = 0 then its a equilibrium

  22. DGq= DHq -TDSq

  23. Just the fact that a reaction is spontaneous doesn’t mean that it will occur at once- it might need activation energy (topic 6)

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