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SECOND LAW OF THERMODYNAMICS

The second law of Thermodynamics helps us to determine the direction in which energy can be transformed. It also helps us to predict whether a given process or chemical reaction can occur spontaneously or not.

According to Kelvin: It is impossible to use a cyclic process to extract heat from a reservoir and to convert it into work without transferring at the same time a certain amount of heat from a hotter to colder part of the body.

Entropy Change: Entropy change is the state function and it is the ratio of heat change in a reversible process by the temperature.

S = qrev / T

Thermodynamically irreversible process is always accompanied by an increase in the entropy of the system and its surroundings taken together while in a thermodynamically reversible process, the entropy of the system and its surroundings taken together remains unaltered.

Solved example. Calculate entropy change for vaporization of 1 mole of liquid water to steam at -1 100C if HV = 40.8 kJmol .

Solution:

For entropy change of vaporization

Sv = Hv / T

Sv = 40.8 10 / 373 = 109.38 Jk

mol

Solved example. A system changes its state irreversibly at 300 K in which it absorbs 300 cals of heat. When the same change is carried out reversibly the amount of heat absorbed is 900 cals. The change in entropy of the system is equal to

(A) 1 cal K

(B) 3 cals K

(C) 2 cal K

(D) 1.5 cals K

Solution:

(B)

Physical Significance of Entropy: Entropy is the measure of disorderness because spontaneous processes are accompanied by increase in entropy as well as increase in the disorder of the system. Thus, increase in entropy implies increase in disorder.

solution.

Which of the following statement is true?

(i) A closed system shows exchange of mass and not energy with surroundings.

(ii) Entropy change for fusion reaction is positive.

(iii) Heat is a measure of quantity of energy whereas temperature is a measure of intensity of energy.

Solution:

(i) False

(ii) True

(iii) True

Some Other State Function: For a spontaneous process entropy change is positive and if it is zero, the system remains in a state of equilibrium. Two other functions are also there to decide the feasibility of the reactions like work function A and free energy change G.

A = E TS.(i)

G = H TS.(ii)

And A = E - TS(iii)

G = H - TS...(iv)

(for a finite change at constant temperature)

Since, S = qrev./T Hence from eq. (i)

A = E qrev..(v)

and according to first law of Thermodynamics

E - qrev =wrev. .(vi)

If during the change, work is done by the system, it would carry a negative sign,

-wrev = E qrev.(vii)

Comparing the equation (v) and (vii)

-A = wrev

Since the process is carried out reversibly where w represents the maximum work. It is thus clear that decrease in function A gives maximum work done that can be done by the system during the given change. The work function A is also called as Helmholtz function.

From equation (iv)

G = H - TS

and H = E + PV

G = E + PV - TS

Comparing it with eq. (iii)

G = A + PV

Since, A is equal to w, hence.

G = - w + PV.

- G = w- PV

Hence decrease in free energy gives maximum work obtainable from a system other than that due to change of volume at constant temperature and pressure. This is called as Net Work.

Net Work = w-PV = -G

The Net Work may be electrical work or chemical work. Criterion of spontaneity: For a spontaneous process G should be -ve

GIBBS FREE ENERGY

This is another thermodynamic quantity that helps in predicting the spontaneity of a process, is called Gibbs energy (G).

It is defined mathematically by the equation.

G = H - TS

Where H = heat content, S = entropy of the system, T = absolute temperature

Solved example. Which of the following will fit into the blank?

When two phases of the same single substance remain in equilibrium with one another at a constant P and T, their molar _________ must be equal.

(A) Internal energy

(B) Enthalpy

(C) Entropy

(D) Free energy

Solution:

(D)

Free energy change

For isothermal process.

G = G2 G1 = H TS

G = change in Gibbs free energy of the system.

It is that thermodynamic quantity of a system the decrease in whose value during a process is equal to the maximum possible useful work that can be obtained from the system.

Solved example. Calculate free energy change when one mole of NaCl is dissolved in water at 1 25C. Lattice energy = 700 kJ/mol.S at 25C = 26.5 Jmol , Hydration energy of NaCl = -696 kJ/mol.

(A) -3.9 kJ

(B) -8kJ

(C) -12kJ

(D) -16kJ

Solution:

(A)

RELATIONSHIP BETWEEN FREE ENERGY AND EQUILIBRIUM CONSTANT


The free energy change of the reaction in any state, G (when equilibrium has not been attained) is 0 related to the standard free energy change of the reaction, G (which is equal to the difference in free energies of formation of the products and reactants both in their standard states) according to the equation. G = G + RT InQ Where Q is the reaction quotient When equilibrium is attained, there is no further free energy change i.e. G = 0 and Q becomes equal to equilibrium constant. Hence the above equation becomes. G = RT In K(eq)
o o

or G = 2.303 RT log K(eq)

In case of galvanic cells. Gibbs energy change G is related to the electrical work done by the cell.

G = -nFE(cell) where n = no. of moles of electrons involved

F = the Faraday constant

E = emf of the cell

If reactants and products are in their standard states G = nFE

o cell

Solved example. Calculate G for conversion of oxygen to ozone 3/2 O2 (g) > O3 (g) at 298 -29 K, if Kp for this conversion is 2.47 10 .

Solution:

G = 2.303 RT log Kp

Where R = 8.314 J/K mol, Kp = 2.47 10 , T = 298K

-29

G = 16300 J/mol = 163 KJ/mol

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