USE OF FREE ENERGY IN CHEMICAL EQUILIBRIA

1 MARK
HARD
1. In a certain process 678 J of heat is absorbed by a system while 290 J of work is done on the system. What is the
change in internal energy for the process?
968 J
MODERATE
1. State one application of first law of thermodynamics.
Hess’s law is an application of first law of thermodynamics.
2. For the reaction 2Al2O3 = 4Al (s) + 3O2(g) , ΔH = 334kJ, what is the enthalpy of formation of Al 2O3 ?
-1670 kJ
3. What is the free energy change for a reversible proce
Free energy change for a reversible process is equal to zero.

Easy
1. Give one example of State Function
Enthalpy.
2. Write one process where entropy decreases.
The conversion of CO2 into dry ice, here entropy decreases.
3. At inversion temperature what is the Value of Joule – Thomson coefficient?
At inversion temperature Joule Thomson Coefficient value is Zero.
4. Give one example of intensive property.
Density.
5 marks
Easy:
1.(a) Explain the term chemical potential. 1
(b) Derive the relation of EMF of cell with ΔG and ΔH. 4
For a pure substance chemical potential is equal to molar Gibbs free energy. In a system of variable composition chemical
potential of a substance is equal to the rate of change of the Gibbs free energy G of the system with respect to the moles
of i added at constant T, P and other mole numbers. Thus for a two component mixture chemical potential of the
component 1 is μ1 and is given by,
𝜕𝐺
𝜇=( )
𝜕𝑛1 𝑇 ,
𝑃,
𝑛2

(b) Relation between ΔG and EMF of a cell (E).

The relation between ΔG and E is ΔGT,P = -nFE. Electrical work is produced at the cost of decreade in Gibbs free energy.
Relation between ΔH and E
We know at constant T, P, ΔG = ΔH – TΔS
From Gibbs – Helmholtz equation for a reaction

𝜕(∆𝐺 ) 𝜕(−𝑛𝐹𝐸 ) 𝜕𝐸
∆𝑆 = [ ] = −[ ] = 𝑛𝐹 ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑃
𝜕𝑇 𝑃

We have, ΔH = ΔG + TΔS
𝜕𝐸 𝜕𝐸
Therefore, ∆𝐻 = −𝑛𝐹𝐸 + 𝑇𝑛𝐹 ( ) = −𝑛𝐹 [ 𝐸 − 𝑇 ( ) ]
𝜕𝑇 𝑃 𝜕𝑇 𝑃

2. How many types of hardness is possible? Why hard water is not suitable for boiler use? 3 + 2
Hardness of water is of two types.
(i) Temporary Hardness : It is caused due to presence of bicarbonates of calcium and magnesium. It can be removed
easily by boiling.
(ii) Permanent Hardness: It is caused due to presence of chlorides and sulphates of calcium and magnesium salts. It
cannot be removed by boiling.
Huge quantity of water is used in boilers for generation of steam. If hard water is used in the boiler, a number of
difficulties arise which are as follows:
Scale and sludge formation
Boiler Corrosion
Priming and foaming
Caustic embrittlement.
Moderate:
1. Show that, entropy of mixing of ideal gases ΔS mix > 0. 5
Mixing of two or more gases are spontaneous process, hence it should be accompanied by increase in entropy.
Let n1 moles of ideal gas A1 and n2 moles of gas A2 having volume V1 and V2 at constant pressure P and temperature T be
separated by a partition. After removing the partition, these two gas mixed spontaneously when the total pressure P and
the final temperature T remain constant and both gas occupying the entire volume, V = V1 + V2 of the cylinder.
Hence the entropy change ΔS1 = n1R ln (V1 + V2) / V1
Similarly for gas A2 ΔS2 = n2R ln (V1 + V2) / V2
Since gases are ideal, each gas acts independently of the other. Hence entropy change of mixing ΔSmix is equal to the sum
of the entropy change due to their individual isothermal volume expansion.
(𝑉1+𝑉2) (𝑉1+𝑉2) 𝑉1 𝑉 2
ΔSmix = ΔS1 + ΔS2 = 𝑛1 𝑅 ln 𝑉1
+ 𝑛2 𝑅 ln 𝑉2
= −𝑛1 𝑅𝑙𝑛 𝑉 +𝑉 − 𝑛2 𝑅𝑙𝑛 𝑉 +𝑉
1 2 1 2

If X1 and X2 are the mole fraction of gas A1 and A2 respectively in the mixture, then,
X1 = n1/ (n1 + n2) = n1 / n = V1 / (V1 + V2)
X2 = n2/ (n1 + n2) = n2 / n = V2 / (V1 + V2)
Entropy of mixing:
ΔSmix = - n1R ln X1 – n2R ln X2 = -nR(n1/n ln X1 + n2/n lnX2) = -nR(X1 ln X1 + X2 ln X2)
The equation may be generalise to the mixing of N ideal gases,

ΔSmix = −𝑛𝑅 ∑𝑁
𝑖=1 𝑋𝑖 𝑙𝑛𝑋𝑖

Molar entropy of mixing

(ΔSmix)mix = −𝑅 ∑𝑁
𝑖=1 𝑋𝑖 𝑙𝑛𝑋𝑖
Since mole fraction Xi of gas always less than 1, hence lnXi always less than zero. So ΔSmix is always > 0.
Hard
1. ‘All adiabatic reversible expansions lead to a fall of temperature.’ – Comment or Justify. 5

From 1st law of thermodynamics ΔU = Q + W where W is negative for expansion process. In adiabatic process Q
= 0. So, for adiabatic process ΔU = W. In reversible expansion appreciable work is produced and ΔU is negative
for a adiabatic reversible expansion since W is negative in expansion process. For ideal gas internal energy (U)
depends only on temperature and ΔU = CvΔT. Since in adiabatic reversible expansion ΔU is negative it is seen
that for this process ΔT is negative (because C V is always positive) ΔT = T final – Tinitial. For adiabatic reversible
expansion of ideal gas T f < Ti.. For adiabatic reversible expansion there occurs a fall of temperature. (For real
gases volume increase has negligible effect on ΔU and there is cooling effect in adiabatic reversible expansion in
all cases).

15 Marks

Easy

1. (a) What is the condition of spontaneity in terms of entropy? The condition of spontaneity : ΔGx, y < 0; ΔAp,r <
0, where G is the Gibbs Free Energy and A is the Helmholtz free energy. Identify x, y, p and r. 2 + 4
(b) State whether the following properties are extensive or intensive properties:
Pressure, Concentration, Entropy, Viscosity, Temperature. 5
(c) For a reaction both ΔH and ΔS are positive. Under what conditions will the reaction be spontaneous?
What is state function? Give example. 2 + 2

(a) Condition of spontaneity in terms of entropy for isolated system ΔS > 0.

Condition of spontaneity in terms of entropy for non-isolated system ΔStotal > 0
ΔStotal = ΔSuniverse = ΔSsystem + ΔSsurrounding > 0
Condition of spontaneity in constant T, P process is ΔGT, P < 0.
Condition of spontaneity in constant T, V process is ΔAT, V < 0.
(b) Pressure : intensive property
Concentration : intensive property
Entropy: extensive property
Viscosity : intensive property
Temperature: intensive property.
(c) If TΔS > ΔH the reaction will be spontaneous. If ΔS and ΔH both are positive, then T must be high for
the spontaneity of the reaction.
A state function is a property that depends only on the state of the system and not on how the system has
been achieved. Example: Enthalpy, Entropy etc.
Moderate
1. (a) Write the Nernst equation for the cell reaction in the Daniel cell. How will the E cell effected when the concentration
of Zn2+ is increased?
(b) What do you mean by hardness of water? Explain how hard water fails to form lather with soap? What is alkalinity of
water? 5
(c) Define corrosion. What are different types of corrosion? 5
(a) Daniel Cell is represented as Zn (s) Zn2+ (aq) Cu2+ (aq) Cu (s)
The cell reaction for 2F electricity drawn is Zn (s) + Cu2+ (aq) = Zn2+ (aq) + Cu (s)
Nernst equation for the cell reaction is
𝑅𝑇
𝐸 = 𝐸 0 − 2𝐹 ln(𝑎𝑍𝑛 +2 × 𝑎𝐶𝑢 )/ (𝑎𝑍𝑛+2 × 𝑎𝐶𝑢 )

𝑅𝑇
= 𝐸0 − ln 𝐶𝑍𝑛+2 /𝐶𝐶𝑢+2
2𝐹
Assuming activity if ion equal to concentration of the ion and activity of solid = 1.
The Nernst equation shows that if concentration of Zn2+ is increased cell potential E decreases. [ ΔGT, P = -nFE. For
spontaneous reaction E is positive and ΔG is negative. Decrease of E with increase of concentration of Zn2+ makes ΔG
less negative. The tendency of forward reaction is diminished and this is an accord with Le – Chatelir principle that if a
product species is added the reaction is shifted to the left side.]
(b) Hardness is the characteristic of water which prevents formation of lather with soap. This is due to the presence of
certain salts of calcium, magnesium and other heavy metals dissolved in it. The salts are calcium chloride, calcium
carbonate, calcium bicarbonate, magnesium chloride, magnesium carbonate, magnesium bicarbonate etc.
Hard water, when treated with soap (sodium or potassium salt of higher fatty acid like oleic, palmitic or stearic) does not
produce lather, but forms scum or precipitate. The reactions of soap (sodium stearate) with calcium and magnesium salts
are depicted below.
2 C17H35COONa + CaSO4 (C17H35COO)2 Ca + 2Na2SO4
2 C17H35COONa + MgCl2 (C17H35COO)2 Mg + 2NaCl
When all the Ca & Mg removed then hard water getting soft and it produces lather.
The alkalinity of natural water is ordinarily due to presence of carbonates, bicarbonates of calcium and magnesium. The
alkalinity of water can be considered mainly due to Hydroxide, Carbonates and Bicarbonates.
The alkalinity of water can be estimated separately by titration against standard acid solution.
Corrosion may be defined as the process of slow deterioration of surface of metal due to direct attack by atmospheric
gases, moisture present in the atmosphere or by any other chemical or electrochemical environment.
Different type of corrosion:
Dry Corrosion
Liquid – metal corrosion
Wet Corrosion (Electrochemical corrosion)
(i) Wet corrosion of metal with evolution of H2gas
(ii) Wet corrosion of metal by absorption of O2.
Hard
1. An ideal gas is allowed to expand reversibly and isothermally (25°C) from a pressure of 1 atm to a pressure of
0.1 atm. What is the change in molar Gibbs Energy? What would be the change in molar Gibbs energy if the
process occurred irreversibly? 6
If infinitesimal change of pressure (dP) occurs at constant pressure P then the change of Gibbs free energy dG is given by,
dG = V dP
For one mole substance, dG = V dP
For one mole ideal gas V = RT/P dP, hence we have dG = RT/P dP
For isothermal reversible change of pressure from 1 atm to 0.1atm the change of Gibbs energy is given by
2 0.1 𝑎𝑡𝑚
𝑑𝑃 0.1𝑎𝑡𝑚
∫ 𝑑𝐺 = ∆𝐺 = 𝑅𝑇 ∫ = 𝑅𝑇 ln
1 1 𝑎𝑡𝑚 𝑃 1𝑎𝑡𝑚

= (8.314 J K-1mol-1) (298K) ln (0.1) = - 5708 J mol-1.

Why bond energy is taken average value? 3
The bond energy depends upon the environment i.e. , the nature of other atoms or groups attached with the concerned
atom. For example, the bond energy of C – Cl bond in H3CCl is different from that of in CCl4. Even in CCl4, the bond
energy of the 4C – Cl bonds is not the same. On breaking each C – Cl bond, the environment changes and therefore bond
energy also changes. Thus we take the average bond energy.
Why some reactions are exothermic, while some others are endothermic? 3
During chemical reactions the total energy content of the reactants and products is different. When enthalpy (heat content)
of the reactant is higher than that of the products, the difference ( H P – HR ) is released as heat energy and the reaction are
exothermic. When heat content of the reactants is lesser as compared to the products, heat energy is absorbed by the
reactants to change into products and the reactions are endothermic.
Under what conditions, would you expect the reaction : N2 (g) + 3H2 (g ) 2NH3 (g) + Heat to occur spontaneously.
3
At low temperature.
Reason: ΔH = negative and ΔS = negative ( because volume of product is less than the volume of reactants). So the value
of ΔG = ΔH – TΔS can be negative only at low temperature. So, at low temperature the reaction to proceed
spontaneously.