Chem 340 - Lecture Notes 7 – Fall 2013 – Gibbs & Helmholtz Free Energy

With entropy we found a state function that indicates direction of a spontaneous process,
however it requires consideration of the entropy change of both system and surroundings,
as chemists we prefer to focus on the system, usually not isolated, i.e. in contact with
surroundings, and often we work in conditions of constant pressure and sometimes also at
constant temperature. Alternatively one can imagine cases where constant volume is a
characteristic. Use of these ideas helps design two new new state functions that can
indicate direction of a process and one of which most useful for chemistry. The Clausius
inequality will be critical in making the indication work.

dS ≥ ᵭq/T  T dS ≥ ᵭq recall: only equal for reversible process, dqrev

recall 1st law: dU = ᵭq + ᵭw rearrange, substitute dq: TdS ≥ dU - ᵭw or TdS + ᵭw - dU ≥ 0

now there are two kinds of work, external or expansion, and non-expansion work, split up:
TdS - PextdV + ᵭwnonexp - dU ≥ 0
Spontaneity now a function of state functions: U, V, S, T, and path dependent ones  w

Consider isothermal process: (const T)

Define new state function, Helmholtz free energy: A = U - TS

or equivalently:

A is a state function that calculates maximum work from system on surround, i.e. A = wrev

Now if add constraint: constant V and only expansion work possible then dA ≤ 0

Chemists prefer const P conditions, at const T,P: d(PV) = PdV, d(TS) = TdS, back to inequ.
dU - TdS + PdV ≤ 0  d(U +PV –TS) = d(H - TS) ≤ ᵭwnonexp
let new state function be Gibbs Free energy: G = H – TS,
dG ≤ ᵭwnonexp or if ᵭwnonexp = 0, then dG ≤ 0 indicates spont, const T,P only PV work

so now have two criterion for spontaneity, each works best under different conditions,
dA for constant V, dG for constant P. Go back to Clausius

dS - ᵭq/T ≥ 0 recall dSsur = - ᵭq/T so dS - dSsur ≥ 0 or the spontaneity condition

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but for G and A - criteria for spontaneity - not depend on surroundings, also from Clausius.
G = H - TS and G < 0  spontaneous isothermal, constant P process

See both enthalpy and entropy contribute to spontaneity,

Entropy greater impact at higher temperatures
Chemical reaction spontaneous if H < 0 (exothermic) and S > 0
Chemical reaction never spontaneous if H > 0 (endothermic) and S < 0
Balance of H and S control reaction, if H < 0 & S < 0 or H > 0 & S > 0

Similar for constant V change

 A = U - TS and A < 0  spontaneous isothermal, constant V process

Examples: -from Engel,on web site, but - sign/magnitude problems in text!!

Calculating A, U, S and w for reversibly contracting collagen from l = 0.20.1 m with
absorption of qrev = 0.15 J at const T = 310 K, let tension  = - l,  = 10 Nm-1
For this, Uw = -q, A = wrev = -0.15 J  same mechanical stretch w = -∫dl = ∫ldl
S = qrev/T = 0.15 J / 310 K = 4.83x10-4 JK-1 10Nm-1.½.(-0.03 m2) = -0.15 J

If dU = TdS – PdV - dl determine (G/l)P,T and maximum work obtainable by contract
dG = dH – d(TS) = d(U +PV) – d(TS)
= TdS – PdV - dl + PdV + VdP – TdS – SdT
= - dl + VdP – SdT sign issue! l for contraction
Constant P,T: dT = dP = 0  (G/l)P,T = - l, dG =ldl
Integrate and get G =∫ldl = -0.15 J = wrev and see same as A = wrev

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Example of RNA stretching. If hook opposite ends of strand to two polystyrene beads,
can pull apart and measure force required a function of distance. Need very small scale
and to grab spheres (~1m)  laser tweezer can hold an object and measure force exerted
See (middle, black stretch, red refold) at 10 pNs-1, the path not reversible, but at 1 pNs-1
(right) black and red overlap, approximately reverses. See at ~13 pN an abrupt increase in
length, this is unfolding, and length difference (~20 nm) is length of the RNA.
From this work, determined: G = 174 kJ/mol, compare to melting (phase trans) at ~80 C

Fundamental equations - Differential forms of U, H, A, G

Start from definitions and re-express as differentials in terms of thermodynamic variables:
H = U + PV method use dU = dq + dw but recognize state function
A = U – TS dU = dqrev + dwrev = TdS - PdV
G = H – TS assume only P,V work
Take differentials:
dH = dU + d(PV) = TdS – PdV + PdV + VdP = TdS + VdP
dA = dU – d(TS) = TdS – PdV – TdS – SdT = -SdT – PdV
dG = dH – d(TS) = TdS + VdP – TdS – SdT = -SdT + VdP
Used a lot, called the fundamental equations:
dU = TdS – PdV
dH = TdS + VdP
dA = -SdT – PdV
dG = -SdT + VdP - text calls this fundamental equation of chemical thermodynamics

these are used to develop a set of ”natural variables”; total differential two variables, U(S,V)


Coefficients of dS and dV must be same in both equations for dU

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Same for the other equations (left): right use: (/V(U/S)V)S = (/S(U/V)S)V

Left, define variances of thermodynamic right, Maxwell relationships, shows inter-

state functions in terms of variables relationships of variables (T,P,V,S)
for example H inc. with S,P (T,V = +) note first two have derivative at const S
but G dec. w/ T and inc. w/ P (S,V = +) since dS=dqrev/T, const S  dq=0 adiabatic

these relations look obscure but allow express state fct. in measurable things : T,P,V,

Example from text: in Notes 4 introduced internal pressure (U/V)T = T = T(P/T)V – P

From complete differential: dU = (U/S)VdS + (U/V)SdV divide through by dV, at const T
(U/V)T = (U/S)V(S/V)T + (U/V)S
Now use (U/S)V = T and (U/V)V = - P  T = (U/V)T = T(S/V)T – P
and then use Maxwell relation: (S/V)T = (P/T)V 
T = T(P/T)V – P (result)

Dependence of Free energies on P, V, T

Just described how free energy depends on “natural variables:

So since S and P always positive, see A always decreases with increasing T or V

Similarly for G; S and V always positive

So G always decreases with T and increases with P

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If at const T, and want change in free energy from standard state, can integrate over P
Liquid and solid, V~ const, so simplify:

But in gases volume strongly depends on P, so substitute in for V in integral:

See Gm  - ∞ as P 0, since for gas that means V∞ and S = nR ln(Vf/Vi)  large +,
See text, fig 3.19, 3.20 p. 125, show high T,P dependence of G for gas, more S,V

Standard molar Gibbs Free Energy

Normally only use G, so absolute values not needed, but for standard state can get a Gom
If we take Hom = 0 in its standard state, for a pure element, then
Gom = Hom - TSom = - TSom (since for elements in std. state: HomHof = 0)
Pure compounds are formed from elemental react – formation: Gof = Gom prod +iGom, react i
Rearrange: Gom = Gof + iTSom, react i - reactants in formation i - only elements
so only TSom, react i term and i all negative, since reactant
note for molar enthalpy, equation simpler, misses elements, no Som contribut.: Hom = Hof

Example. Calculate Gom (a) for Ar(g) and (b) for H2O(l) at T=298 K, P=1 bar
(a) Gom = Hom - TSom = - TSom = -298Kx155 JK-1mol-1 = - 4.62 kJ/mol (Som from table)
(b) Gom = Gof + iTSom =Gof (H2O) - TSom(H2) -1/2 TSom(O2) (- for reactants)
= -237kJ/mol – 298K(131 + 205/2) J/Kmol = -307 kJ/mol

Can just extend this to a Hess’s law formulation as well, Gof = ProdGof - ReacGof
using standard free energy of formation: Gof = Hof - TSof [- for reactant]
So problems solved by just looking up G f values or alternatively H f and Sof in tables
o o

For ionic solutions, need to have both cations and anions, so define H+aq for reference as 0:
Gof (H+aq) = 0

Text example: HCl formation in solution:

½ H2 + ½ Cl2  H+aq +Cl-aq Gof = -131 kJ/mol
But Gof =Gof (H+aq) +Gof (Cl-aq) = Gof (Cl-aq) or Gof (Cl-aq ) = -131 kJ/mol
Now consider: Ag(s) + ½ Cl2  Ag+aq +Cl-aq Gof = -54 kJ/mol
This implies Gof (Ag+aq) = 77 kJ/mol (i.e. -54 –(-131) = 77)

Remember that the process of forming an aqueous ion involves going from the element to
the ion and then dissolving ion, so need to construct a cycle to model it (text p.120)

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Gibbs-Helmholtz equations
For temperature dependence, one normally looks at the variation of G/T because
equilibrium constants depend on G/T. This results in the Gibbs-Helmholtz equations:

This is also written, using; d(1/T)/dT = -1/T2 as:

(look ahead, Keq will depend on G/T and if get variation of it with 1/T gives solution for H)

For a reaction at constant P need to substitute G and H in equation above,

and next “multiply” both sides by d(1/T), then if integrate both sides get:

Where in the last step we assume H is constant over the T range

This equation lets you determine G at some temperature, if know Go and Ho at 298K

Example: Calculate Gf for glycine, H2N(CH2)COOH, at 350K if Gof = -378 kJ/mol and
Hof = -537 kJ/mol at T=298 K. Assume Hof constant over T range.
Gf (T2) = T2[Gf (T1)/T1 + Hf (T1)x(1/T2 – 1/T1)]
= 350K [-378/398 – 537(1/350 -1/298)]kJ/mol K = -350 kJ/mol (accident that [ ]≈1)

Gm varies with T and P as

Slopes of surface give –S and V

Gas has large S, steep dG/dT

Solid least slope

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Example. Hydrolysis is the reaction to break up protein peptide bonds to form amino acids.
As a test of protein stability, determine the standard free energy for hydrolysis of Gly-Gly, at
T=298 K, p = 1 bar.
Reaction: +H3NCH2CONHCH2COO- + H2O  2 +H3NCH2COO-
Look up std free energy values, note only solid values available, but Gsolliq small for Gly
Go = 2Go(Gly) – Go(GlyGly) - Go(H2O)
Go = [2(-378) – (-491) – (-237)]kJ/mol = - 28 kJ/mol
So this process appears to be spontaneous – luckily it is slow unless one has proteolytic
enzymes around, such as in digestion or in cell regulation pathways or cell death

But our body functions at ~37 C, is it still spontaneous?

Need Gibbs Helmholtz for this, which requires H, or use (G/T)P = -S  G = S(T)
1st determine Ho and So using Hess’s law/standard state methods (like for Go)
 Ho = [2(-537)-(-745)-(286)]kJ/mol = -43 kJ/mol
So = [2(104)-190-70]J/molK = -53 J/molK
Use So  Go(310) = Go(298) -So(298)x(310-298) = [-28-12x(-0.53)]kJ/mol = -27 kJ/mol
Use Ho  Go/T2 = Go/T1 +Ho(1/ T2 -1/T1) = [-28/298 + (-43)(1/310 -1/298)]kJ/molK
Go(310) /310K = -0.087 kJ/molK
Go(310) = - 27 kJ/mol
Both give same results, but need to assume Ho and So constant, which is OK for T=12o

Pressure dependence: (G/P)T = V  ∫dG = ∫VdP = G(P2) – G(P1)

For gas, if ideal: G(P2) – G(P1) = nRT∫dP/P = nRT ln(P2/P1)
For solid, liquid: G(P2) – G(P1) ≈ V(P2 – P1)
For solution reaction: G(P2) – G(P1) ≈ V(P2 – P1) where V=V(prod)-V(react)
So if volume of products greater than reactants, increased P increases G,
if a gas, then ignore sol-liq volumes : G(P2) – G(P1) ≈ nRT ln(P2/P1)

Example. Can you make diamond form graphite at T=298, P=1 bar?
C(s,graphite)  C(s,diamond) has Go = +2.9 kJ/mol
So no, it does not work, sorry!
How much pressure does it take? Use G(P2) – G(P1) ≈ V(P2 – P1) want G(P2)=0
From densities: (g) = 2.25 g/cm3 and (d) = 3.51 g/cm3
Get molar volumes: Vm (g) = 5.33 cm3/mol and Vm (d) = 3.42 cm3/mol
 G(P) = G(1) + V(P – 1) = [2.84 + (3.42-5.33)(P-1)] kJ/mol = 0
P = 1 + 2.84/1.94x10-4 = 15k bar = P (eq)
Problem, P so large that V will not be constant, so actual P is higher, but does work
Increasing T will not help because S = -3.4 J/molK so adds to G