MT321: AUXILIARY FUNCTIONS 1

AUXILIARY FUNCTIONS

From dU = TdS - PdV - 3.12

This is for a closed system of a fixed composition which is in equilibrium but is

undergoing a process involving volume change, i.e. PV work. S and V are an
inconvenient choice of independent variables because they can not be measured easily
for experimental control. It is necessary to have the given equation comprised of
more easily measurable variables. T and P are such quantities. And also this
equation covers only volume PV work and does not cover cases such as chemical
work etc. Thus it becomes necessary to further develop this equation in order to do
this. The equation,

dU = TdS - P dV

represents the foundation of thermodynamics, but in order to use it fully, auxiliary

functions of state have to be invented which are more convenient. These functions
are:
A, the Helmholtz free energy
G, the Gibb’s free energy

μi Chemical potential of species i ;

and their inter-relations. The list of variables becomes,

P, V, T, S, μ, H, A, G

The definitions are:

A = U - TS - 5.1

G = U + PV - TS = H - TS - 5.2

Because A and G are combinations of state properties only, they themselves are state
properties.

Helmholtz Free Energy (work function A) (P56 –67 Parker)

When a system is changing from state 1 to 2,

From A = U – TS
A2 - A1 = U2 - U1 - (T2S2 - T1S1 ).
 MT321: AUXILIARY FUNCTIONS 2

For the closed system

U2 - U1 = q - w

A2 - A1 = q - w - (T2 S2 - T1S1)
For the Isothermal process,

A2 – A1 = q – w – T (S2 - S1)

From the second law, q ≤ T(S2 - S1)

So that this simplifies to

(A2 – A1) + TΔSirr = - w - 5.3

For a reversible, isothermal process , i.e. no entropy production, work done,

Wmax = Decrease in work function A

For isothermal, constant volume process, i.e. No PV work

(A2 – A1) + TΔSirr = 0 - 5.4

For such a process to be spontaneous, dA has to be negative i.e. entropy can be

produced only if A decreases.

Because at equilibrium dSirr = 0 ,

Then for such a process, equilibrium is defined by

dA = 0

Statement

For a closed system at T and V constant, A can only decrease or remain constant.
Equilibrium is at minimum A.
 MT321: AUXILIARY FUNCTIONS 3

Gibbs Free Energy G

From the definition.

G = U + PV – TS = H - TS.

When a system changes from state 1 to 2 ,

(G2 – G1) = (H2 – H1) – (T2 S2 – T1S1)

= (U2 - U1) + (P2V2 – P1V1) – (T2S2 – T1S1)

for the closed system,

U2 – U1 = q - w

Therefore

(G2 – G1) = q - w + (P2V2 – P1V1) – (T2S2 – T1S1)

if T1 = T2 = T, the temperature of the reservoir supplying or withdrawing heat

and P1 = P2 = P, constant pressure at which the surrounding have undergone a
volume change, then

(G2 – G1) = q – w + P(V2 – V1 ) – T(S2 – S1)

If w is total work including other forms of work besides PV work, then

w = w′ + P(V2 – V1 ), w′ is work other than volume work,

(G2 – G1) = q – w′ – T(S2 – S1)

again q ≤ T(S2 – S1)

and w′ ≤ - (G2 – G1)

and the equality becomes

- w′ = (G2 – G1) + TΔSirr

For Isothermal, Isobaric i.e. T constant, P constant, during which no work except
expansion work is performed, i.e. w′ = 0 , then

(G2 – G1) + TΔSirr = 0

Such a process can only occur spontaneously with entropy production if the free
energy decreases

Because at equilibrium, dSirr = 0 ,

 MT321: AUXILIARY FUNCTIONS 4

then when there is an increment of the Isothermal, Isobaric process, equilibrium is

defined by

dG = 0

Statement

For a system undergoing a process at constant T and P, Gibbs free energy can only
decrease or remain constant therefore:

At equilibrium, G is minimum for fixed T, P

Summary of equations

H = U + PV  dH = TdS + VdP

A = U - TS  dA = -SdT - PdV

G = H - TS  dG = - SdT + VdP

Composition Changes and the chemical potential

So far, only systems with fixed amount of moles have been considered. However in a
lot of systems the moles vary and composition is not fixed. In such a system
minimization of G at T and P constant occurs only if the system has a unique
composition.

Example:

CO + ½ O2 = CO2 , T, P, const.

G is minimum only when the equilibrium for the reaction is established. G is an

extensive property so that it is necessary to establish the number of moles in the
system.

G = G (T, P, ni, nj, nk, ….)

ni, nj , nk, etc = number of moles of species i, j, k etc

Differentiating this equation

 MT321: AUXILIARY FUNCTIONS 5

 G   G   G   G 
dG =   P,ni,nj,nkdT +   T,ni,nj, nkdP +   P,T,nj,nk dni +   T,P,ni,nkdnj
 T   P   ni   ni 
+ ….. etc - 5 – 14

If all the moles remain constant, then

dG = -SdT + VdP

and

 G 
  P,ni,nj,… = - S
 T 

 G 
  T,ni,nj,… = V
 P 

substituting in 5.14 gives

ik
 G 
dG = - SdT + VdP +   ni  T,P,nj...dni
i 1
5-15

 G 
The term   P,T,nj, is called the chemical potential of species i and is
 ni 
designated µi , i.e.
 G 
  P,T,nj, ≡ µi
 ni 

Formal definition. of µi

The chemical potential of species i in a homogeneous phase is the rate of increase of

G with ni when the species i is added to the system at constant T, P and number of
moles of all of the other species.

Alternately

If the system is so large that the addition of 1 mole of i does not measurably change

the composition of the system, then µi is the increase in G for the system

accompanying the addition of 1 mole of i.

 MT321: AUXILIARY FUNCTIONS 6

µi is the amount by which the capacity of the system for doing work other than the
work of expansion is increased per mole of i added at constant T, P and composition,
The last equation can be written as,

dG = -SdT + VdP + Σµidni - 5 – 17

The above equation is applied to open systems which exchange matter as well as heat
with their surroundings and to closed systems which undergo composition change.

The equations:
ik
 G 
dU = TdS - PdV +   ni 
i 1

dA = -SdT + PdV
dH = TdS - VdP

can be similarly represented as

dU = TdS - PdV + ∑µidni - 5.22

dH = TdS + VdP + Σµi dni - 5.23

dA = - SdT - PdV + Σµi dni - 5.24

dG = - SdT + VdP + Σµidni - 5.25

the equation 5. 25, is termed the fundamental equation

From the first law,

dU = δq - δw

but dU = TdS - PdV + Σµidni

The term Σµidni is the chemical work done by the system earlier denoted as w′,

while total work w is the sum of the work of volume change and the chemical work.

 G   G 
  = - S and   = V
 T   P 

From G = H - TS
G = U + PV - TS

Taking differentials
 MT321: AUXILIARY FUNCTIONS 7

dG = dU + PdV + VdP - TdS - SdT

But,
dU = δq - δw = δq - PdV
and,
δq = dU + PdV
Also,
δq = TdS = dU + PdV

dG = TdS + VdP - TdS - SdT

dG = VdP - SdT

At constant T,
dG = VdP
 G 
  = V
 P 

At constant P
dG = -SdT
 G 
  = -S
 T 

Gibbs - Helmholtz equation

G = H - TS

 G 
 P = - S given
 T 

when P is constant,

 dG 
G = H + T P
 dT 

GdT = HdT + TdG

re-arranging

TdG - GdT = - HdT

Divide through by T2

 TdG  GdT   HdT 

  = -  2 
   T 
2
T
 MT321: AUXILIARY FUNCTIONS 8

vdu  udv
On comparison with d(u/v) =
v2

d (G / T ) H
= - 2
dT T

For a change of state, P constant, Composition fixed,

d ( G / T ) H
= -
dT T2

This is the Gibbs Helmholtz equation. It is used in experimental thermodynamics.

ΔH the heat of reaction can be determined from the experimentally determined
variation of ΔG with temperature.

Or ΔG can be determined from an experimentally measured ΔH.

A and U

A = U - TS

 A 
At constant V,  V = - S
 T 

 A 
A = U +T  V
 T 

So that

d(A/T ) U
= - 2
dT T

for fixed composition processes, V constant.

For a change of state

d ( A / T ) U
= -
dT T2

Working With Gibbs Free Energy

The standard free energy change of a reaction at 298K, 25oC is given as

 MT321: AUXILIARY FUNCTIONS 9

ΔGo298 = Σ ΔGo298 PRO DUCTS - ΣΔGo298 REACTANTS

For a reaction

aA + bB → c C + dD

ΔGo298 = cGo298c + dGo298D - aGo298A - bGo298B

As applies for enthalpies the absolute values of G for substances are not known and
only changes can be dealt with. Therefore free energies like enthalpies must have
some reference point with respect to which the actual values for various substances
can be calculated. This reference is stated as “The free energies of the stable form of
the elements at 25oC and 1 atm pressure are arbitrarily assigned a zero value”

The free energies of formation of compounds are calculated on the basis of the above
assumption and the value is described as the standard free energy of reaction or
formation. The standard free energy of formation of a compound is “the free energy
change accompanying the reaction by which it is formed from its elements when all
reactants and products are in their standard states” and it will be expressed in terms of
J/mol. It is reported as ΔGo298. e.g. the standard free energy of formation of NiO at
25oC is 212 488.6 J/mol i.e 212.489 KJ/mol NiO. It follows that the standard free
energy change for the reaction.

Ni(s) + ½ O2(g) = Ni O

Is 212 489 J. The free energy changes of reactions can be added or subtracted e.g.

Given that

NiO(s) = Ni(s) + ½ O2(g) ; ΔGo298 = 212,489 J

And H2O(v) = H2(g) + ½ O2(g) ; ΔGo298 = 230, 103 J

The above reactions can be subtracted to obtain,

NiO(s) + H2(g) = Ni(s) + H2O(v)

ΔGo298 = 212, 489 – 230,103

= - 176 14 J

Example:
 MT321: AUXILIARY FUNCTIONS 10

calculate the standard free energy change of the reaction

MoO3(s) + 3H2 = Mo(s) + 3 H2 O(v)

At 727oC and 1 atm pressure given that;

ΔGo1000K MoO3(s) = - 502, 080 J/mol

Also comment on the possibility of reducing MoO3 with H2 at 727oC and 1 atm pr
from the data:

Mo(s) + 3/2 O2(g) = MoO3(s) ; ΔGo1000K = - 502,080 J

H2(g) + ½ O2(g) = H2O(v) ; ΔGo1000K = - 190,372

For the reaction

MoO3(s) + 3 H2(g) = Mo(s) + 3H2O(v)

ΔGo1000K = Σ ΔGoPRODUCTS - Σ ΔGoREACTANTS

= 3 (- 190,372) - (-502,080)

= - 571 116 + 502,080

= - 69036 J

Because the standard free energy change of this reaction is negative at 727oC and 1
atm pressure, it is possible to reduce MoO3 by H2.

Determination of ΔG at any temperature

ΔGo at any temperature T can be calculated from the expression:

T
 o T
CpdT 
ΔGoT = ΔHo298 + 298 CpdT  T 

S 298  
298
T 


Transformations in phase such as melting etc have to be taken appropriately into

consideration.

Example:

Calculate the standard free energy change of the reaction

Ni(s) + ½ O2(g) = NiO(s)

 MT321: AUXILIARY FUNCTIONS 11

At 327oC, given;

ΔHo298 NiO = - 240,580 J

So298

Ni(s) = 29.79
O2(g) = 205.09
NiO(s) = 38.07

CP

Ni (s) = 25.23 + 43.68 x 10-6T - 10.46 x 10-3T

O2(g) = 29.96 + 4.18 x 10-3T – 1.67 x 105T

NiO (s) = 54.01

Solution

Ni (s) + ½ O2(g) = NiO(s)

ΔHo298 = - 240,580

600
ΔHo600 = ΔHo298 +  CpdT
298

ΔCp = 13.807 + 8.368 x 10-3 T - 43.68 x 10-6 T + 0.8368 x 105T-2

600
600 600


298
CpdT = 
298
(13.807 + 8.368 x 10-3T - 43.68 x 10-6T + 0.8368 x 105T-2 )dT

ΔHo600 = - 237894 J

Similarly
CpdT
600
ΔSo600 = ΔSo298 + 
298
T

= - 87.89

ΔGoT=600 = - 237894 - (-87.69)600

= - 185,276 J
 MT321: AUXILIARY FUNCTIONS 12

REPRESENTANTION AND TABULATION OF ΔGOT