Chapter 5

Gibbs and Helmholtz Energies and

Their Applications

Defining Spontaneity
We can use the 2nd Law to determine if a process
is spontaneous DSuni = DSsys + DSsurr > 0
This is not ideal, since we need DSsurr and cant
determine spontaneity based solely on the system
G = H TS
A = U TS

Gibbs Energy

G = H TS

dG = dH TdS SdT

At constant T dG = dH TdS

From 2nd law

dSuniv 0 dSuniverse = dSsys + dSsurr 0
dSsys qsys/T 0
qsys = dH at constant P
dSuniverse = dSsys dHsys/T 0
TdSuniverse = TdSsys dHsys 0
-TdSuniverse = dHsys TdSsys 0

-TdSuniverse = dG 0
dG 0 at constant T, P
< 0 for spontaneous, = 0 at equilibrium
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Helmholtz Energy

A = U TS

dA = dU TdS SdT

At constant T dA = dU TdS

From 2nd law

dSuniv 0 dSuniverse = dSsys + dSsurr 0
dSsys qsys/T 0
qsys = dU at constant V

dSuniverse = dSsys dUsys/T 0

TdSuniverse = TdSsys dUsys 0
-TdSuniverse = dUsys TdSsys 0

-TdSuniverse = dA 0
dA 0 at constant T, V
< 0 for spontaneous, = 0 at equilibrium
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Criteria for Spontaneity

For an isolated system,

DSuniv 0
At constant T and V
DA = DU + T D S 0
At constant T and P
DG = DH + TD S < 0
We derived DA and DG straight from the
2nd Law Only entropy was used
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DG?
(a) Ice melts at 0 C and 1 atm?
(b)

Water boils at 100 C and 1 atm

(c)

Ice melts at 5 C and 1 atm

The A for the mixing of two ideal gases

at constant T and V
A = U T S
U = 0
Smix = nAR lnxA nBR lnxB
= (nAR lnxA + nBR lnxB)
A = nARTlnxA + nB lnxB

G for the mixing of two ideal gases

at constant P and T??

Meaning of Helmholtz Energy

DA is useful to calculate the maximum
amount of work accompanying a process

wmax = wrev = dA, wmax = DA

How do we prove this?
dA = dU TdS
For a reversible change, dqrev = TdS
dA = dU dqrev = dqrev + dwrev dqrev
dA = dwrev
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Meaning of Gibbs Energy

Maximum non-expansion work,
Wrev = WPV + WnonPV
D WnonPV = DG
How can we prove this?
dG = d(H TS) = dH TdS SdT
= d(U + PV) TdS SdT
= dU + PdV + VdP TdS SdT
= (qrev + wpv + wnon-pv)+PdV + VdP TdS SdT
= TdS PdV + wnon-pv+ PdV + VdP TdS SdT
= wnon-pv +Vdp - SdT
At constant T and P dG = wnon-pv G = wnon-pv
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DH

TDS = DG < 0

A + B C

positive at all T
Rxn reverses
negative at all T
Rxn progresses
Low T, DH dominates
High T, DS dominates

High T, DS dominates
Low T, DH dominates
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2H2O2 (l) 2H2O(l) + O2 (g)

D rH

Exothermic DrH < 0

TDrS

D rG

DG
0

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H2 (g) 2H(g)
D rH

Endothermic DrH > 0

TDrS

D rG

DG
0

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 A certain reaction is spontaneous at 72 C

and 1 atm. If the enthalpy change for the
reaction is 19 kJ, what is the minimum
value of DS (in joules per Kelvin) for the
reaction?
H = 19 kJ

T = 345 K

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 Determine H for the reaction shown which

is spontaneous at 25 C
2NO2(g)

N2O4(g)

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Standard Molar Gibbs Energy of Formation

Standard Gibbs energy, DrG

aA + bB cC + dD
rG = rH T rS
DrGcan be expressed in terms of DfG
DfG = 0 for element in its stable state
rG = nfGm(products) nfGm(reactants)

aA + bB cC + dD
Grxn = c Gm,f(C) + d Gm,f(D) a Gm,f(A)
b Gm,f(B)

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Standard Molar Gibbs Energy of Formation

rG = nfGm(products) nfGm(reactants)
DfG = 0 for element in its stable state

DfG (graphite) = 0
DfG (Br2(l)) = 0
DfG (Cl2(g)) = 0 at 298 K

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