Lecture 13

Lecture 13 - Chem 338 The Gibbs Free Energy 1. Conditions...

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Chem 338 C h em 3 3 8 L e c t u r e 1 3 The Gibbs Free Energy 1. Conditions for Spontaneous Change: q rev > q irr but: w rev < w irr 2. The Gibbs function: G H - TS 3. Spontaneous Change: Δ G < 0 Equilibrium: Δ G = 0 4. The Gibbs Equations: dE ( A,B ) = α dA + β dB 5. Maxwell’s Relations: 6. C P - C V = TV α 2 / κ AB BA ∂∂ ⎛⎞⎛⎞ = ⎜⎟⎜⎟ ⎝⎠⎝⎠
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Chem 338 1. Conditions for Spontaneous Change:
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Chem 338 2. The Gibbs function: G H - TS
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Chem 338 3. Spontaneous Change: Δ G < 0 Equilibrium: Δ G = 0
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Chem 338 Δ G ( T ) = Δ H –T Δ S
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Chem 338
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Chem 338 4. The Gibbs Equations: dE ( A,B ) = α dA + β dB dU dq dw TdS PdV ≡+ =− () dA dU d TS T d SP d VT d SS d T PdV SdT ≡− −− dH dU d PV TdS PdV PdV VdP TdS VdP + + =+ dG dA d PV PdV SdT PdV VdP SdT VdP + + + dG dH d TS TdS VdP TdS SdT VdP SdT =+−−
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Chem 338 5. Maxwell’s Relations: dE ( A,B ) = α dA + β d B E ( A,B ) continuous: No phase change! AB BA ∂∂ ⎛⎞⎛⎞ = ⎜⎟⎜⎟ ⎝⎠⎝⎠ 22 (, ) B A A B EE d B A EAB dA dB E A B E E A B E ⎛⎞ =+ ⎜⎟ ⎝⎠ = = = == ⎠⎝
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Chem 338 5. Maxwell’s Relations: dE ( A,B ) = α dA + β d B AB BA ∂∂ ⎛⎞⎛⎞ = ⎜⎟⎜⎟ ⎝⎠⎝⎠ SV dU TdS PdV TP VS =− ⎛⎞ ⎜⎟ ⎝⎠ VT dA PdV SdT PS TV ⎛⎞⎛ = ⎜⎟⎜ ⎝⎠⎝ SP dH TdS VdP = + = PT dG VdP SdT =
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Chem 338
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Lecture 13 - Chem 338 The Gibbs Free Energy 1. Conditions...

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