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A Chemical Thermodynamics Refresher

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Chem 1b

1) For any spontaneous process in a universe (isolated from all else), Suniv 0 ; universe processes move to highest probability. Equilibrium-state probability is so high compared to any other states probability that it is always the final state. 2) Suniv = Ssys + Ssurr ; divide universe into system (on which we want to concentrate) and surroundings. 3) No work done on surroundings, only energy exchange (heat = q) between system and universe so Suniv = qsurr/T = -qsys/T = -Hsys/T for constant pressure process. 4) Then Suniv = Ssys + Ssurr = Ssys - Hsys/T 0. Multiply through by (T) which changes to . Thus, Hsys TSsys 0 for any spontaneous process in our universe. Now we can concentrate just on system parameters. 5) Define a new function G, the free energy, as H TS. Then for any spontaneous process at constant pressure in our universe: Hsys TSsys = Gsys 0. We will drop the system labels; they will be understood: G = H TS 0 Deriving Relationship Between G and the Equilibrium Constant 1) Start with definition of G and H: G = H - TS = E + PV - TS because H = E + PV. We are now going to use a little calculus: dG = dE + PdV + VdP - TdS - SdT Now use First Law of thermodynamics, E = q + w, so dE = dq + dw. Substituting gives: dG = dq + dw + PdV + VdP - TdS - SdT Now we will simplify by considering constant T (dT = 0), reversible (dq = TdS), and only PV work (dw = -PdV) processes which cancels all terms but VdP: dG = dq + dw + PdV + VdP - TdS - SdT = VdP 2) Consider one mole of an ideal gas where V = RT/P so dG = VdP = (RT/P)dP = RT (dP/P). Then integrating, dG = RT(1/P) dP = RT (1/P)dP G2 = G1 + RT n (P2/P1) (Were done with calculus!)

Let state 1 be our standard state of 1 atm, partial pressure and make state 2 be any other state: G = Go + RT n (P/Po) where Po = 1 atm. Lets abbreviate P/Po as a, the activity. So, if we have gas A, then aA = PA/PAo . Then,

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Chem 1b

3) For the general reaction aA + bB cC + dD, G is found by using the above expression: Gr = dGD + cGC - bGB - aGA = dGoD + cGoC - bGoB - aGoA + RT[dnaD + cnaC - bnaB - an aA] Gr = G r

o

The ratio of activities is just the ratio of concentrations (or pressures) raised to their stoichiometric coefficients which is just the reaction quotient Q!!! So, Gr = Gor + RT n Q which is the expression given to you (w/o proof) in your text!!

4) At equilibrium, there is no spontaneous reaction so Gr = 0 and Q Keq which is the ratio of the product concentrations and reactant concentrations raised to their respective stoichiometric coefficients at equilibrium. So, 0 = Gor + RT n Keq or Keq = e-(Gor) / RT So we can get Keq from calculation of the free energy change of a reaction under standard state conditions which we can determine from the Gof in the table in the back of your text. Temperature Dependence of Keq Using the expressions in the first section above: Gor = Hor TSor = - RT n Keq n Keq = (Hor/RT) + Sor/R We then have the temperature dependence of Keq if Hor and Sor are independent of temperature (which is often a good approximation)! Also, if we measure Keq at several temperatures, we can determine Hor and Sor from a plot of n Keq vs. -(1/RT)! E.g., lets take the phase change of vaporization: L G; Keq = aG/aL = (PG/Po) / 1 = (PG/Po)

o o o So, n (PG/P ) = (H vap/RT) + S vap/R. Thus, the vapor pressure of a gas decreases with increasing enthalpy of vaporization (a measurement of the attraction between the liquid molecules) and increases with entropy of vaporization (a measurement of the structure in the liquid phase). Finally, the vapor pressure of the gas increases exponentially with an increase in temperature.

Nernst Equation We have for a reaction not at equilibrium: Gr = Gor + RT n Q. Using G = -nFE, we have: E = Eo - (RT/nF) n Q ; which is the Nernst Equation.

fjg2007apr

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