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Topic 5.3 and 5.4 Hess’s Law and Bond Enthalpies. Hess’s Law Topic 5.3. CH 4 (g) + 2O 2 (g) CO 2 (g) + 2H 2 O (l ) H = -890 KJ. shows three different pathways: A B A C B A D E B enthalpy change from reactants to products for all of these is the same.
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Hess’s LawTopic 5.3 • CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H = -890 KJ
shows three different pathways: A B A C B A D E B • enthalpy change from reactants to products for all of these is the same
if a series of reactions are added together, the enthalpy change for the net reaction (Hfinal) will be the sum of the enthalpy change for the individual reactions (Hind + Hind + Hind ….) • the change in enthalpy is the same whether the reaction takes place in one step, or in a series of steps • H is independent of the reaction pathway • depends only on the difference between the enthalpy of the products and the reactants • H = Hproducts−Hreactants • provides a way to calculate enthalpy changes even when the reaction cannot be performed directly 6
energy in products energy in reactants
Problem-Solving Strategy • work backwards from the final reaction, using the reactants and products to decide how to manipulate the other given reactions at your disposal • if a reaction is reversed the sign on ΔH is reversed • N2 (g) + 2O2 (g) → 2NO2 (g) ΔH = 68kJ • 2NO2 (g) → N2 (g) + 2O2 (g) ΔH = - 68kJ • multiply reactions to give the correct numbers of reactants and products in order to get the final reaction. • the value of Δ H is also multiplied by the same integer • identical substances found on both sides of the summed equation cancel each other out
Example 1 • Given: N2 (g) + O2 (g) 2 NO (g) DH1 = +181 kJ 2 NO(g) + O2 (g) 2 NO2 (g) DH2 = -113 kJ • Find the enthalpy change for: N2 (g) + 2 O2 (g) 2 NO2 (g) • DH = DH1 + DH2 = +181 kJ +(-113) = + 68 kJ 9
Example 2 ΔH = (- 184 kJ) + (+ 1452 kJ) + 1268 kJ
Example 3 • Given: C (s) + O2 (g) CO2 (g) DH1 = - 393 kJ mol-1 H2 (g) + ½O2 (g) H2O (g) DH2 = - 286 kJ mol-1 CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) DH2 = - 890 kJ mol-1 • Find the enthalpy change for: C (s) + 2H2 (g) CH4(g) This equation needs to be “flipped”. The CH4 is on the wrong side of the equation 11
Example 3 • Given: C (s) + O2 (g) CO2 (g) DH1 = - 393 kJ mol-1 H2 (g) + ½O2 (g) H2O (g) DH2 = - 286 kJ mol-1 CO2 (g) + 2H2O (g) CH4 (g) + 2O2 (g) DH2 = + 890 kJ mol-1 • Find the enthalpy change for: C (s) + 2H2 (g) CH4(g) • (- 393 kJ mol-1) + (- 572 kJ mol-1 ) + (+ 890 kJ mol-1 ) = - 75 kJ mol-1 2 2 - 572 1
Example 4 Calculate DH° for the reaction 2 Al (s) + 3 Cl2 (g) 2 AlCl3 (s) Use the following data: 2 Al (s) + 6 HCl (aq) 2 AlCl3 (aq) + 3 H2 (g) DH° = -1049. kJ mol-1 HCl (g) HCl (aq) DH° = -74.8 kJ mol-1 H2 (g) + Cl2(g) 2 HCl(g) DH° = -1845. kJ AlCl3 (s) AlCl3 (aq) DH° = -323. kJ mol-1 = - 6,981.8 kJ 6 3 3 - 5,535 kJ mol-1
Bond Enthalpies. Topic 5.4 • can be used to calculate the enthalpy change for a chemical reaction if we know the energy necessary to break or form bonds in the gaseous state • breaking bonds • energy is required so enthalpy is positive (endothermic) • the molecule was stable so energy was necessary to break apart the molecule • forming bonds • energy is released so enthalpy is negative (exothermic) • the new molecule is more stable than the individual atoms so energy is released
a molecule with strong chemical bonds generally has less tendency to undergo chemical change than does one with weak bonds • SiO bonds are among the strongest ones that silicon forms • it is not surprising that SiO2 and other substances containing SiO bonds (silicates) are so common • it is estimated that over 90 percent of Earth's crust is composed of SiO2 and silicates
we use average bond enthalpies • again, in the gaseous state • different amount of energy can be required to break the same bond • example- methane, CH4 • if you took methane to pieces, one hydrogen at a time, it needs a different amount of energy to break each of the four C-H bonds • every time you break a hydrogen off the carbon, the environment of those left behind changes, and the strength of the remaining bonds is affected • therefore, the 412 kJ mol-1 needed to break C-H is just an average value, may vary, and is not very accurate
The average bond enthalpies for several types of chemical bonds are shown in the table below: 17
Page 326 in text • Also see Chemistry Data Booklet p. 11
Bond Enthalpy Calculations Example 1: Calculate the enthalpy change for thereaction. Is it endo or exothermic? N2 + 3 H2 2 NH3 • Bonds broken (requires energy) • 1 N N = 945 kJ • 3 H-H 3(435) = 1305 kJ • Total = 2250 kJ • Bonds formed (releases energy) • 2x3 = 6 N-H 6 (390) = - 2340 kJ • Net enthalpy change • = (+ 2250) + (- 2340) = - 90 kJ (exothermic) H-H
Example 2 energy 2H2 + O2 2H2O course of reaction
Working out ∆H Show all the bonds in the reactants H―H + O=O energy H―H 2H2O course of reaction
O O H H H H Working out ∆H Show all the bonds in the products H―H + O=O energy H―H course of reaction
O O H H H H Working out ∆H Show the bond energies for all the bonds 436 + O=O energy 436 course of reaction
O O H H H H Working out ∆H Show the bond energies for all the bonds 436 + 498 energy 436 course of reaction
O H H Working out ∆H Show the bond energies for all the bonds 436 + 498 energy 436 464 + 464 course of reaction
Working out ∆H Show the bond energies for all the bonds 436 + 498 energy 436 464 + 464 464 + 464 course of reaction
Working out ∆H Add the reactants’ bond energies together energy 1370 464 + 464 464 + 464 course of reaction
Working out ∆H Add the products’ bond energies together energy 1370 1856 course of reaction
Working out ∆H ∆H = energy in ― energy out 1370 1856 + - energy 1370 1856 course of reaction
Working out ∆H ∆H = energy in ― energy out 1370 1856 - 486 + - 1370 energy 1856 course of reaction
Working out ∆H ∆H = energy in ― energy out ∆H = -486 exothermic energy 1370 1856 course of reaction
The average bond enthalpies for several types of chemical bonds are shown in the table below: 32
Page 326 in text • Also see Chemistry Data Booklet p. 11
Example 3 • Calculate the enthalpy change for the following reaction: • CH4 + Cl2 CH3Cl + HCl • 4(414) + 243-3(414) & (-397) + (-431) • 1,899- 2,070 • - 171 kJ mol-1 (exothermic) Cl-Cl H-Cl