7-Thermochemistry - BioE 5. Thermochemistry Hess Law of...

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Molecular BioEngineering Laboratory BioE 5. Thermochemistry ± Hess’ Law of Heat Summation ± Heat of combustion ± Heat of reaction ± Heat of Formation ± Bond energy ± Dilution heat
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BioE Heat measurement ± Constant volume ± d U= δ Q-P ext dV = δ Q V ± Constant pressure ± d H= d U+ d (PV) = d U+P d V+V d P = d d V = δ Q P
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BioE Hess Law of Heat Summation ) 373 ( ) 273 ( ) 273 ( ) 273 ( ) 273 ( 373 273 373 273 373 273 vap liq P fus vap P vap fus vap P sub H C H C H H C H Δ + + Δ = + Δ + Δ = + Δ
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BioE 373 273 dT C liquid P ) 273 ( fus H Δ ) 273 ( sub H Δ 373 273 dT C vapor P ) 373 ( vap H Δ Water 273K Ice 273K Water 373K Vapor 373K Vapor 273K ) 273 ( vap H Δ
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BioE Heat of combustion () RT n T U T H dT C dT C Q T U T U dT C dT C dT C dT C T U T T C Q g O H g CO g O s O H C g T T O H V T T CO V V T T O V T T glc V T T O H V T T CO V r calorimete V H Δ + Δ = Δ = Δ Δ + + = + + Δ = = + ⎯→ + = Δ ) ( ) ( ) ( ) ( ) ( ) ( 6 ) ( 6 ) ( 6 ) ( 1 1 1 2 1 1 2 2 2 ? 2 6 12 6 2 1 2 2 1 2 2 1 2 2 1 2 1 2 2 1 2
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BioE H 1 , product H 2 , product U 1 , product U 2 , product H 1 , reactant U 1 , reactant H 2 , reactant U 2 , reactant Δ H(T 2 ) Δ H(T 1 ) Q V 2 1 product , T T V dT C n reactant RT 1 n product RT 2 n product RT 1 Δ U(T 1 ) Δ U(T 2 ) 2 1 reactant , T T V dT C n reactant RT 2
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BioE Bomb calorimeter ± Δ U = Q + W = Q V ± Δ H = Δ U + Δ (PV) = Δ U + Δ n g RT
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BioE Flow calorimeter ± Δ H = Q p ± Δ H = Δ U + Δ (PV) = Δ U + Δ n g RT
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BioE
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BioE
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BioE
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BioE
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BioE Heat of reaction ) ( 4 ) ( 6 ) ( 2 3 2 2 g NH g H g N H ⎯→ + Δ ) ( 2 ) ( ) ( 5 . 180 ) 298 ( 2 2 g NO g O g N kJ H + = Δ ) ( 6 ) ( 4 ) ( 5 ) ( 4 2 54 . 1169 ) 298 ( 2 3 l O H g NO g O g NH kJ H + + = Δ ) ( 2 ) ( 2 1 ) ( 2 83 . 285 ) 298 ( 2 2 l O H g O g H kJ H + = Δ kJ H g NO g O g N 361 ) 298 ( ) ( 4 ) ( 2 ) ( 2 2 2 = Δ + kJ H l O H g O g H 83 . 98 . 1714 ) 298 ( ) ( 6 ) ( 3 ) ( 6 2 2 2 = Δ + kJ H g O g NH l O H g NO 54 . 1169 ) 298 ( ) ( 5 ) ( 4 ) ( 6 ) ( 4 2 3 2 = Δ + + kJ H g NH g H g N H 44 . 184 ) 298 ( ) ( 4 ) ( 6 ) ( 2 3 2 2 = Δ + Δ
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BioE 6H 2 2N 2 6H 2 O 4NO 4NH 3 Δ H
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BioE Heat of Formation Enthalpy of formation of each element at its most stable state is set to zero.
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BioE Example kJ H g NH g H
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7-Thermochemistry - BioE 5. Thermochemistry Hess Law of...

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