WORK FUNCTIONS

1. Helmholtz and Gibbs Free Energy

Need for introducing new work functions: Criterion of spontaneity in terms of entropy is that

If (ΔS system + ΔS surr.) is +ve, Process is Feasible

If (ΔS system + ΔS surr.) = 0, Process is at equilibrium.

Since it is extremely difficult to find ΔS surr., therefore new state functions A and G are introduced which can
be determined easily and spontaneity of a process can be explained in terms of these functions.

1.1 Helmholtz Work Function A and its Physical Significance

A = U – TS

For a change at constant temperature

ΔA = ΔU – T ΔS ---(1)

From First Law of Thermodynamics, for a reversible process

ΔU = Qrev. + (-wrev.) (work is done by the system)

OR Qrev. = ΔU + wrev. ---(2)

𝑄𝑟𝑒𝑣.
From Second Law of Thermodynamics, ∆𝑆 = 𝑇
or TΔS = Qrev. ---(3)

Combining eq. (2) and eq. (3), TΔS = ΔU + wrev. ---(4)

Substituting eq. (4) in eq. (1),

ΔA = ΔU – (ΔU + wrev.)

ΔA = - wrev.

OR - ΔA = wrev.

Thus DECREASE IN Helmholtz free energy ‘A’ i.e., - ΔA is a MEASURE of MAXIMUM POSSIBLE WORK DONE
BY THE SYSTEM during that given change and is known as WORK FUNCTION.

1.2 GIBBS FREE ENERGY, G and its Physical Significance

G = H – TS

So that for a system undergoing change from initial state 1 to final state 2 at constant temperature

ΔG = ΔH – TΔS

OR ΔG = ΔU + PΔV – TΔS (ΔH = ΔU + PΔV )

From eq. (1), ΔA = ΔU – T ΔS

Thus ΔG = ΔA + PΔV

ΔG = -wrev. + PΔV (wrev. = wmax.)

 ΔG = - wnet OR ΔG = -wnon-mech..

OR - ΔG = wnet
DECREASE IN GIBBS FREE ENERGY G, i.e., - ΔG is a MEASURE OF NET WORK OR NON-MECHANICAL WORK
DONE BY THE SYSTEM.

1.3 RELATION BETWEEN ΔG AND ΔA

ΔA = ΔU -TΔS

And ΔG = ΔH – TΔS

ΔG = ΔU + PΔV -TΔS

OR - ΔG = Δ A + P ΔV

2. CRITERION FOR SPONTANEITY

According to Second Law of Thermodynamics, for a Reversible process involving expansion
𝑑𝑞𝑟𝑒𝑣. 𝑑𝑈+𝑃𝑑𝑉
𝑑𝑆 = =
𝑇 𝑇

TdS = dU + PdV ----(1)

Where dS is the infinitesimally small change in entropy.

𝑑𝑞𝑟𝑒𝑣.
As qirrev. < qrev., so for an Irreversible process, 𝑑𝑆 > 𝑜𝑟 𝑇𝑑𝑆 > 𝑑𝑞𝑟𝑒𝑣.
𝑇

OR 𝑇𝑑𝑆 > 𝑑𝑈 + 𝑃𝑑𝑉 ----(2)

We know that G = H – TS
= U + PV -TS
On complete differentiation dG = dU + PdV + VdP – TdS – SdT ----(3)

Placing both eq.(1) and eq. (2) conditions in eq.(3)

𝒅𝑮 ≤ 𝑽𝒅𝑷 − 𝑺𝒅𝑻
For a Process at constant T & P

(𝒅𝑮)𝑻,𝑷 ≤ 𝟎
Thus at constant T & P

(i) If ΔG = - ve, reaction is Spontaneous

(ii) If ΔG = + ve, reaction is Non-spontaneous
(iii) If ΔG = 0, reaction is at Equilibrium

Hence for a reaction to be spontaneous, ΔG is always NEGATIVE, even if it is exothermic or endothermic

and involves increase or decrease in entropy, Since FEASILIBILITY or SPONTANEITY of a process is
determined by the expression ΔG = ΔH – TΔS as a whole.

1. Exothermic reactions: ΔH = - ve
(i) When ΔS = +ve, ΔG will be -ve and hence Spontaneous at all temperatures.
(ii) When ΔS = - ve, then as ΔG = ΔH – TΔS

a. At LOW TEMP. TΔS < ΔH  ΔG = - ve and hence reaction is Spontaneous at Low T.

 b. At HIGH TEMP. TΔS > ΔH  ΔG = +ve and hence reaction is Non-Spontaneous at HIGH T.

2. Endothermic reactions: ΔH = + ve

(i) When ΔS = +ve, So as per equation, ΔG = ΔH – TΔS

a. At LOW TEMP. TΔS < ΔH  ΔG = + ve and hence reaction is NON-Spontaneous at Low T.

b. At HIGH TEMP. TΔS > ΔH  ΔG = -ve and hence reaction is Spontaneous at HIGH T.

(iii) When ΔS = - ve, ΔG will be + ve and hence NON-Spontaneous at all temperatures.

2.1 NUMERICALS
For a reaction, ΔH is 25 kJ and ΔS is 42 JK-1 mol-1. Determine the following:

(i) Nature of reaction at 350 K

(ii) Temperature above which reaction will be spontaneous.

Solution:

At 350 K: (i) ΔG = ΔH - TΔS

ΔG = 25000 J – (350K)(42 JK-1 mol-1)

ΔG = 10,300 and is +ve, Hence reaction is NON-SPONTANEOUS at 350 K.

(iii) ΔG = ΔH – TΔS
0 = 25000 – T (42)

OR T = 595.24 K

Thus ΔG will be – ve and reaction will be spontaneous above 595.24 K.

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For a solid, enthalpy of fusion, ΔHf = 7.42 kJmol-1 and entropy of fusion, ΔSfusion = 28.5 JK-1mol-1. At what
temperature, will the liquid freeze spontaneously?

Solution:

ΔHfusion = 7.42 kJ mol-1

 ΔHfreezing = - 7.42 kJmol-1

= - 7.42 x 103 Jmol-1

Similarly ΔSfreezing = - ΔSfusion

= - 28.5 JK-1mol-1

Temperature at which ΔG will be ZERO

ΔG = ΔH - TΔS

0 = (- 7.42 x 103) – T(-28.5)

T = 260.35 K
 Thus ΔG = 0 at T = 260.35 K

So the liquid will freeze spontaneously BELOW temperature 260.35 K.

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3. Variation of Free Energy Change (ΔG) with Temperature and Pressure

G = H – TS

G = U + PV – TS

On Complete Differentiation dG = dU + PdV + VdP – TdS – SdT ----(1)

From First Law of Thermodynamics, dU = dq + dw

For a reversible process involving expansion, dU = dq + (-PdV)

OR dq = dU + PdV ----(2)

From Second Law of Thermodynamics,

𝑑𝑞
𝑑𝑆 = or TdS = dq ----(3)
𝑇

Combining eq. (2) and (3) and putting it in eq. (1),

dG = VdP - SdT ----(4)

At constant T, dT = 0,

So Eq. (4) reduces to (dG)T = VdP

𝑑𝐺
OR ( ) =𝑉 ---- (5) [variation of dG with P]
𝑑𝑃 𝑇

For n moles of an ideal gas,

𝑛𝑅𝑇 𝑛𝑅𝑇
dG = . 𝑑𝑃 as PV = nRT, so V =
𝑃 𝑃

For finite changes, integrating this equation between limits G1→G2 as pressure is changed from P1 → P2.
𝐺
2 2 𝑃 𝑛𝑅𝑇
∫𝐺1 𝑑𝐺 = ∫𝑃1 𝑃
. 𝑑𝑃

Or ΔG = G2 – G1 = nRT 𝑛𝑅𝑇 ln 𝑃2
𝑃
1

At constant P, dP = 0,

So eq. (4) reduces to (dG)P = -SdT

𝑑𝐺
OR ( ) = −𝑆 ----(6) [variation of dG with T]
𝑑𝑇 𝑃
3. GIBBS-HELMHOLTZ EQUATION

G = H – TS

G = U + PV – TS

On Complete Differentiation dG = dU + PdV + VdP – TdS – SdT ----(1)

From First Law of Thermodynamics, dU = dq + dw

For a reversible process involving expansion, dU = dq + (-PdV)

OR dq = dU + PdV ----(2)

From Second Law of Thermodynamics,

𝑑𝑞
𝑑𝑆 = or TdS = dq ----(3)
𝑇

Combining eq. (2) and (3) and putting it in eq. (1),

dG = VdP - SdT ----(4)

At constant P, dP = 0,

So eq. (4) becomes (dG)P = -SdT ----(5)

Let in the initial state

G1 is the Free energy of system at temperature T1.

So that G1 + dG1 is the free energy of the system at temperature T1 + dT, where dT is infinitesimal
small increase in temperature.

Similarly in the Final State

G2 is the Free energy of system at temperature T2.

So that G2 + dG2 is the free energy of the system at temperature T2 + dT.

 dG1 = -S1dT and dG2 = -S2dT

Hence d(ΔG) = - (ΔS)dT

As P is kept constant, hence d(ΔG)P = - (ΔS)dT

𝑑(∆𝐺) 𝑑(∆𝐺)
OR [ ] = −∆𝑆 where [ ] is known as Temperature coefficient.
𝑑𝑇 𝑃 𝑑𝑇 𝑃

As ΔG = ΔH – TΔS

Hence 𝒅(∆𝑮) ---Gibbs-Helmholtz equation

∆𝑮 = ∆𝑯 + 𝑻 [ ]
𝒅𝑻 𝑷
3.1 NUMERICALS
Free energy change for a given process is -79.86 kJ at 27 0C and -76.28 kJ at 37 0C. What will be the
enthalpy of this process at 32 0C.

Solution:

ΔG1 at 300 K = -79.86 kJ

ΔG2 at 310 K = -76.28 kJ

𝒅(∆𝑮)
According to Gibbs- Helmholtz equation ∆𝑮 = ∆𝑯 + 𝑻 [ 𝒅𝑻 𝑷
] ----(1)

𝒅(∆𝑮) −𝟕𝟔.𝟐𝟖 𝒌𝑱−(−𝟕𝟗.𝟖𝟔 𝒌𝑱)

Thus temperature coefficient, 𝑻 [ 𝒅𝑻 𝑷
] = 𝟑𝟏𝟎 𝑲−𝟑𝟎𝟎 𝑲
= 𝟎. 𝟑𝟓𝟖 𝒌𝑱𝑲−𝟏

And ΔG at 305 K is just the average of ΔG values at 300 K and 310 K.

79.86 𝑘𝐽+76.28 𝑘𝐽
 ΔG at 305 K = − ( 2
) = −78.07 𝑘𝐽

Substituting ΔG305 K and temp. coefficient values in eq. (1)

-78.07 kJ = ΔH + (305 K)(0.358 kJ K-1)

OR ΔH = - 187.26 kJ

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