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Unformatted text preview: 1 Introduction to Bioenergetics and Metabolic Control Thermodynamics Free energy Equilibrium Coupled reactions Steady state High energy bonds Redox potential Thermodynamics Review First Law : For any physical or chemical change, the total amount of energy in the universe remains constant. Energy may change form or be transported, but it cannot be created or destroyed. Second Law : In all natural processes, the entropy of the universe (total S) increases. System / Surroundings / Universe  Energy, Heat, Work  influence on system 1 J = (Kgm 2 / sec 2 ) ; 1 cal = 4.184 J Enthalpy (H) and Entropy (S) H = E + PV or H = E + P V (easy to measure on bench top) S = k lnW or S = k ln( W f /W i ); S = Δq/T R= N k = 1.99 cal/mol ° K =8.31 J/mol ° K At 298 K, RT = 0.59 Kcal/mol ° K = 2.48 KJ/mol ° K (this energy ‘available’ under normal conditions) 2 Entropy of dilution S = k ln W where W = “ways” of arranging solute. There are N I ways to place first solute, N I 1 for second etc. BUT since N I >>>NA, these are all same, W I N I x N I x N I … = N I NA and W F = N F NA . The entropy upon dilution is S F S I S = k ln N F NA – k ln N I NA = k ln [N F NA / N I NA ] = N A k ln N F /N I For N A = 1 mole, S = R ln N F /N I and given that V F ~ N F etc. S = R ln V F /V I A similar, but more complicated derivation shows for a given solute: S = R ln C F /C I 3 Heat and entropy • The statistical models are almost useless in Biochem. It can be shown, though, that entropy can be measured via heat change. • A small addition of heat to a hot system adds little entropy (already stirred up), but adding the same heat to a cold system makes a larger entropic change. • S ~ q/T the lower the absolute T, the greater entropy change • The system we are focused on may increase or decrease entropy during a living reaction, but the entropy of the universe always increases. • If the temperature is NOT constant, we must sum heat change over each T as: S > ∫ dq/T An example of spontaneous reaction showing increasing entropy 4 Free energy combines enthalpy and entropy • G = HTS this property is nonlinear with concentration (recall the logarithmic nature of the entropy term) • For any molecule type, G varies with concentration. • G=G + RT lnC • =G + RT 2.303 logC • =G + 5.7 KJ/mol logC G refers to STANDARD state free energy, ie. reactants at 1 M, 25 ° C, 1 Atm Usually biochemical energies are G 0’ , that is standard free energies at pH 7....
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 Spring '09
 RAYMONDS
 Thermodynamics, Redox, High Energy, log Keq, Kcal/mol log Keq

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