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3.5 Helmholtz & Gibbs Energy: Du DQ
3.5 Helmholtz & Gibbs Energy: Du DQ
3.5 Helmholtz & Gibbs Energy: Du DQ
Spontaneity 1
TdS ≥ dU TdS ≥ dH
dU − TdS ≤ 0 dH − TdS ≤ 0
A = U − TS G = U − TS
Helmholtz energy Gibbs energy
Maximum Work 2
dWmax = dA
Wmax = ∆A with ∆A = ∆U − T∆S
Example 3.4
Remarks on Gibbs Energy
H = U + pV
dH = dq + dw + d ( pV )
G = H − TS
dG = dH − TdS − SdT = dq + dw + d ( pV ) − TdS − SdT
when the change is isothermal (dT = 0)
dG = dq + dw + d ( pV ) − TdS
when the change is reversible (dw = dwrev and dq = dqrev = TdS )
dG = TdS + dwrev + d ( pV ) − TdS = dwrev + d ( pV )
= (− pdV + dwadd ,rev ) + pdV + Vdp
if the change occurs at const. pressure (dp = 0)
dG = dwadd ,rev Maximum non-expansion (additional) work
for a measurable change, wadd ,rev = ∆G