Thermochemistry. The study of energy changes that occur during chemical : at constant volume ΔU = q V. no at constant pressure ΔH = q P

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1 Thermchemistry The study energy changes that ccur during chemical : at cnstant vlume ΔU = q V n at cnstant pressure = q P nly wrk Fr practical reasns mst measurements are made at cnstant, s thermchemistry mstly deals with. reactin Δ H = H H prducts reactants I > 0 the reactin is. I < 0 the reactin is. Fr cmparisn purpses we need t reer t the same and. T deine a standard reactin enthalpy each cmpnent the reactin must be in its the mst stable rm at bar pressure and (usually) 5 C. bar = 0 5 Pa atm =.035 bar Mdiied by Jed Macsk 9/0/006

2 Reactin Enthalpy Hess s Law The standard enthalpy change in any reactin can be expressed as the the standard enthalpy changes, at the same temperature, a reactins int which the verall reactin can be rmally divided. Cmbine chemical equatins as i equatins, e.g. A + B C C + D E + F F B + G 3 A + D E + G Δ H =Δ H+Δ H +3 Standard Reactin Enthalpy reactin enthalpy at and at T r sme ther T Mdiied by Jed Macsk 9/0/006

3 Reactin Enthalpy Standard (mlar) enthalpy Δ Heat rmatin a substance rm its elements, all substances being in their standard state. By deinitin, r all Δ H = 0 H Enthalpy r ttal xidatin a substance c Δ c H e.g. C 6 H O 6 + 6O 6CO + 6 H O Δ c H = -808 kj ml - Enthalpy when an unsaturated rganic cmpund becmes ully saturated e.g. C 6 H 6 + 3H C 6 H = -46 kj ml - Enthalpy Bnd dissciatin enthalpy r the dissciatin a mlecule int its cnstituent gaseus atms e.g. C H 6 (g) C(g) + 6H(g) = 883 kj ml - Bnd single bnd enthalpy An average value taken rm a series cmpunds and ten cmbined r a estimate e.g. (C H 6 ) = (C-C) + 6 (C-H) Mdiied by Jed Macsk 9/0/006

4 Temperature Dependence The temperature dependence reactin enthalpies can be expressed in terms the T dependence the enthalpies the reactin : where HT = HT + dt Δ =Δ + HT HT CdT Δ C = C C p p p prducts reactants T T T T p This general phenmenn is knwn as Kirch s Law. e.g. A + B C + D A + B C + D Δ H ( p p ) Δ H ( T ) = C (A) + C (B) T T +Δ H ( ) ( T ) ( T ) ( Cp(C) Cp(D) )( ) + + p p =Δ H ( T) + C C prducts reactants assuming that the C p values are independent. Mdiied by Jed Macsk 9/0/006

5 Reactins at Cnstant Vlume Δ H =Δ U + PV PV r r prducts reactants Fr and liquids Fr ideal gases 0, s gas Δ PV ΔU Δ PV =Δn RT, s Δ U +Δn RT gas e.g. C H (g) + O (g) 3CO (g) + 3H O(l) (- ) Δ H =Δ U + RT r r _ The relatinship between and ΔU is particularly imprtant when relating thermchemical enthalpies () t mlecular prperties (U mlecular ), e.g. r a single bnd energy ΔU = RT as seen in the case O (g) O(g). In practice, is usually s much smaller than that it is ten ignred. Mdiied by Jed Macsk 9/0/006

6 Enthalpies Ins in Slutin Enthalpy r slutin a substance in a stated amunt slvent Enthalpy r dilutin a slutin t a lwer cncentratin Enthalpy slutin t dilutin ininite amunt slvent sln r an The enthalpy rmatin r a species in can be und by cmbining sln with the the species: - H (g) + Cl (g) HCl(g) Δ H = 9.3 kj ml HCl(g) HCl(aq) Δ H = kj ml - sln H (g) + Cl (g) HCl(aq) Δ H (in) =Δ H + sln = kj ml - r individual ins in slutin can nly be und i ne is arbitrarily ixed. By cnventin this is. + + H(g) H(aq) + e Δ H ( Ha ) = 0 + ( Cl ) ( HCl ) ( H ) ( HCl ) q Δ H = Δ H = aq aq aq aq The state r a substance in slutin (nt just ins) is a cncentratin mle slute in kg slutin ( mlal). Mdiied by Jed Macsk 9/0/006

7 Enthalpy Frmatin an Inic Slid Cnsider individual steps in the rmatin NaCl subl Na ( N a ) Δ H = + Cl-Cl Δ H = Cl leading us t the enthalpy rmatin slid NaCl: NaCl(aq) Δ Hsl ( Na + ) +sl ( Cl ) Na(s) + ½Cl (g) NaCl(aq) ( NaClaq) Δ H ( NaClaq ) = Δ Hsubl ( Na ) + I(Na) + ( Cl-Cl) EA(Cl) +Δ Hsl( Na + ) +sl( Cl ) RT Step 5 culd be creatin slid NaCl instead slutin 5'. Na(s) + ½Cl (g) NaCl(s) ( NaCl ) ( Na ) (Na) ( Cl-Cl) E (Cl) + ( NaCl) Δ H = Δ H + I + s subl A lattice lattice NaCl Mdiied by Jed Macsk 9/0/006

8 A Cycle r NaCl Enthalpy changes can als be expressed in a diagram, e.g. Na + (g) + e + Cl(g) I subl Na ( Na) + RT Cl-Cl Na(g) + Cl(g) Na(s) + Cl(g) Na(s) + ½Cl (g) ( NaClaq) ( NaCl ) s NaCl(aq) NaCl(s) E Na+(g) + Cl (g) A ( Cl ) sl + RT lattice Since H is a state variable, the sum enthalpy changes arund the cycle must be. Cnsequently, i all but ne the enthalpy changes is knwn, it can be readily calculated. This is equivalent t using Law t sum reactin steps. Mdiied by Jed Macsk 9/0/006

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