Class XI Chapter 6 Thermodynamics Part 2

By: Arunesh Gupta PGT (Chemistry)

Spontaneity of a process & the second law of thermodynamics:
Spontaneous process is the process which takes place of its own or through proper initiation. It is an irreversible process & may
only be reversed by some external agency.
The spontaneous process has the tendency to take place naturally and no external work is needed to carry out the same.
Non-spontaneous process –
The non-spontaneous process is driven by external agency to do a work and cannot be performed naturally.
Example of spontaneous process & criteria:
(i) Exothermic process, ∆H < 0 or - ve & process is spontaneous. Example: H2(g) + ½ O2(g) → H2O(l) ∆cHθ = - 285.8 kJ/mol
2Na(s) + 2 H2O(l) → 2 NaOH(aq) + H2(g) + heat ∆H = - ve
(ii) Endothermic process, ∆H > 0 & process is spontaneous. Example: H2O(l) → H2O (vap). Heat is supplied by surrounding & this
evaporation process naturally become spontaneous. NaCl(s) + aq → Na+(aq) + Cl-(aq) ∆H = +ve
(iii) ∆H = 0 but the process is spontaneous.
Example: (a) Diffusion of different gases in a given volume → (∆H = 0).
(b) When a water-soluble colour is added in water, it dissolves in it with no enthalpy change & the process is
spontaneous.
So, ∆H is not the only criteria for spontaneity of a process.
It is observed the for cases (ii) & (iii) the product side (RHS) has less order & more disorder or randomness.
So, we can predict if randomness or disorderliness of a system increases, the system becomes spontaneously.
Now, we can say the if disorderliness of a system increases, the system becomes spontaneously.
The heat (q) has randomising influence on the admission.
Temperature is the measure of average chaotic motion of particles in the system.
A system at higher temperature has greater randomness in it than one at lower temperature.
Heat added to a system at lower temperature causes greater randomness than when the same quantity of heat is added to it at
higher temperature.
Driving force for a spontaneous process:
The overall driving force for a process is the resultant of (i) tendency for minimum energy (energy factor) (ii) tendency to acquire
maximum randomness (randomness factor).
Lowering of energy & increase in randomness favours spontaneous process.
The new thermodynamic quantity namely ENTROPY is used to explain spontaneity of a process.
ENTROPY (S): It is defined as the measure of degree of randomness or disorderliness of system. It is a state function.
Entropy change ∆S = Sf – Si. (Si means initial entropy & Sf means final entropy of the system.
(i) If Sf > Si ∆S > 0 or positive,→ the disorderliness of system increases & system becomes spontaneously.
(ii) If Sf < Si ∆S < 0 or negative,→ the disorderliness of system decreases & system becomes non-spontaneously.
(iii) If Sf = Si ∆S = 0 → the disorderliness of system does not change & system remains in equilibrium. When system is in
equilibrium, the entropy is maximum.
So, we conclude, the entropy of a spontaneous process increases, till it reaches maximum & at equilibrium the change in
entropy is zero.
To predict the sign of entropy change (∆S), entropy increases / decreases:
(1) Entropy increases with melting and vaporization. Solid → liquid → vapour ∆S > 0 or +ve.
(2) Entropy increases when solids or liquids mixed in water. → ∆S > 0 or +ve.
(3) Entropy decreases when gas is dissolved in water. → ∆S < 0 or – ve
(4) Entropy is lower in hard and brittle material than in malleable solids like metals. → ∆S < 0 or – ve
(5) Entropy increases with chemical complexity. → ∆S > 0 or +ve.
(6) With more no. of gaseous products, formed, entropy increases. → ∆S > 0 or +ve.
(7) For precipitation reaction entropy decreases. → ∆S < 0 or – ve
Examples:
(i) A liquid crystalises into a solid → On freezing, particles are more ordered & disorderliness of system decreases, ∆S < 0 or – ve
& entropy decreases.
(ii) Temperature of a crystalline solid increases from 0 K to 125 K → At 0 K, the entropy of a solid crystal tends to zero & is least.
So, entropy is least. When temperature is increased, the particles start to vibrate. So, system becomes more & more disordered
& entropy increases. ∆S > 0 or +ve.

Arunesh Gupta PGT (chemistry) KV Barrackpore (AFS) Page - 1 /7

(iii) When the no. of moles of gaseous products is more, the randomness increases hence entropy increases. ∆S > 0 or + ve.
Example: PCl5(g) → PCl3(g) + Cl2(g)
(iv) When in a reaction, precipitate is formed, no. of free ions decreases, randomness decreases, entropy decreases. ∆S < 0 or - ve
Example: NaCl(aq) + AgNO3(aq) → AgCl(s) + NaNO3(aq)
(v) Stretching of a rubber. The randomness of polymeric chain of rubber molecules decrease due to more ordered structure on
stretching, entropy decreases & so, ∆S < 0 or - ve.
(vi) When an egg is boiled, entropy of the egg increases due to denaturation of egg proteins from secondary, tertiary & quaternary
structures into uncoiled primary structure, so randomness increases, entropy increases & ∆S > 0 or positive.
+𝐪𝐫𝐞𝐯,𝐬𝐮𝐫𝐫
** The exothermic reactions are spontaneous because ∆Ssurr = which make ∆Stotal positive.
𝐓
TRY: Problem: 6.9 page no. 177 NCERT book XI-vol 1.

The entropy change (∆S) during a process is defines as the amount of heat evolved or absorbed isothermally & reversible divided
by the absolute temperature at which the heat is evolved or absorbed.
𝐪𝐫𝐞𝐯, 𝐢𝐬𝐨
∆S = Unit of entropy: S.I. unit = J / K / mol & CGS unit = cal / K / mol
𝐓
The first law of thermodynamics states the conversion of energy in a process but does not explain the feasibility of the same. This
point gave rise to the need for the second law of thermodynamics.

The second law of thermodynamics states that (i) “the state of entropy of the entire universe as an isolated system will always
increase over time”. or
(ii) All spontaneous processes (or naturally occurring process) are thermodynamically irreversible. or
(iii) The entropy of the universe always increases in the course of every spontaneous (natural) change.
For spontaneous (natural) process, ΔSTotal = ΔSSyst + ΔSSurr > 0 or positive.

For reversible processes where the entropy of the universe remains constant, ΔSTotal = ΔSSyst + ΔSSurr = 0.
ΔSSyst = ‒ ΔSSurr
We find that both for reversible & irreversible expansion for an ideal gas, under isothermal conditions, ∆U = 0
But ∆Stotal = ∆Ssys + ∆Ssurr is not zero for irreversible process.
Thus, ∆U does not discriminate between reversible & irreversible process whereas ∆S does.

Entropy changes in thermodynamic processes:

(i) Entropy change during isothermal reversible expansion of an ideal gas

𝐪
We know, ∆S = 𝐫𝐞𝐯, 𝐢𝐬𝐨 ……………………………………………. (i)
𝐓
First law of thermodynamics: ∆U = q + w. & for isothermal expansion of an ideal gas, ∆U = 0,
V P
Hence, qrev = - wrev = n R T ln 2 = n R T ln 1
V1 P2
𝑉2 P1
Substituting the value of qrev in (i) ∆S = n R ln = n R ln
𝑉1 P2

(ii) Entropy change during adiabatic reversible expansion of an ideal gas

For an adiabatic process, q = 0 at all stage. Hence, ∆S = 0. Thus, a reversible, adiabatic processes are isoentropic.
However, free (irreversible) adiabatic expansion is not isoentropic. ∆S > 0.

(iii) Entropy changes during phase transitions.

𝐞𝐧𝐭𝐡𝐚𝐥𝐩𝐲 𝐨𝐟 𝐟𝐮𝐬𝐢𝐨𝐧 ∆𝐟𝐮𝐬 𝐇
(a) Entropy of fusion (∆fusS) = =
𝐟𝐮𝐬𝐢𝐨𝐧 𝐭𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞 𝐓𝐟
𝐞𝐧𝐭𝐡𝐚𝐥𝐩𝐲 𝐨𝐟 𝐯𝐚𝐩𝐨𝐮𝐫𝐢𝐬𝐚𝐭𝐢𝐨𝐧 ∆𝐯𝐚𝐩 𝐇
(b) Entropy of vapourisation (∆vapS) = =
𝐁𝐨𝐢𝐥𝐢𝐧𝐠 𝐩𝐨𝐢𝐧𝐭 𝐓𝐛
∆sub H
(c) Entropy of sublimation (∆subS) = So, ∆subS = ∆fusS + ∆vapS
Tb

Example: The standard enthalpy change for the transition of liquid water to steam is 40.8 kJ /mol at 373 K. Calculate the entropy
of vaporisation of water.
Solution: ∆𝑣𝑎𝑝 H = 40.8 kJ/mol = 40.8 x 103 J/mol, T = 373 K
∆vap H 40.8 𝑥 103
The entropy change when liquid water changes to steam is: ∆vapS = = = 109.4 J/K/mol
Tb 373
TRY: (i) Calculate the enthalpy of vaporisation per mol for ethanol. Given: ∆S = 109.8 kJ/mol, boiling point of ethanol = 78.5°C
[Ans. 38.59 kJ/mol.]

Arunesh Gupta PGT (chemistry) KV Barrackpore (AFS) Page - 2 /7

(ii) Calculate the entropy change when 10 moles of an ideal gas expand reversibly and isothermally from an initial volume of 10 L
to 100 L at 300 K. [Ans: 191.47 J/K]

Standard entropy of formation (∆fSθ) of a compound is the entropy change that takes place when one mole of the compound in
the standard state is formed from the elements in the standard state.
The standard entropy of formation & the standard absolute entropy of elementary substances is not zero (unlike ∆ fHθ & ∆fGθ)

Entropy changes for an ideal gas:

Entropy change ∆S of n moles of an ideal gas with change in P, V & T may be derived as:
2 𝑑𝑇 2 𝑑𝑉
∆S = nCv ∫1 + nR∫1
𝑇 𝑉
T2 V2 T2 P1
∆S = n Cv ln + n R ln & ∆S = n Cp ln + n R ln
T1 V1 T1 P2
V2 P1
For isothermal process, T1 = T2 So, ∆S (isothermal) = n R ln = n R ln
V1 P2
T2
For isochoric process (volume constant) V1 = V2 So, ∆S (isochoric) = n Cv ln
T1
T2
For isobaric process (pressure constant) P1 = P2 So, ∆S (isobaric) = n Cp ln
T1
Gibbs energy (G) and spontaneity:

For most of the chemical reactions there are changes in both enthalpy & entropy. So, neither decrease in enthalpy nor increase
in entropy alone can determine the direction of spontaneous change for these systems.

So, we define a new thermodynamic function the Gibbs energy or Gibbs function (G).
Gibbs energy of a system is defined the maximum amount of energy available to a system during a process that can be
converted into useful work.
It is a thermodynamic quantity (or function) which is a measure of capacity of a system to do a useful work. It is given by
G = H -TS where H is the enthalpy & S is the entropy of a system. It is a state function.
Gibbs energy change ∆Gsyst = ∆Hsyst - ∆(TS)syst = ∆Hsyst - T∆Ssyst - Ssyst∆T. So, at constant temperature, ∆T = 0
∆Gsyst = ∆Hsyst - T∆Ssyst
Or we can write for simplicity, ∆G = ∆H - T∆S This is called Gibbs Helmholtz equation.
Unit of ∆G is kJ / mol or J / mol.
(1) Problem: Calculate the Gibbs free energy for the reaction of conversion of ATP into ADP at 293 Kelvin the change in enthalpy
is 19.07 Kcal and the change in entropy is 90 cal/K.
Ans: ΔG = ΔH – TΔS; here ΔH = 19.07 kcal and ΔS = 90 cal/K,
ΔG = 19.07 Kcal – 293(90 cal/K) = 19.07 Kcal – 26.37 k cal = –7300 cal = -7.3 k cal.
The Gibbs free energy change is –7.3 Kcal.
Standard Gibbs energy of formation (∆fGθ) of a substance is defined as the Gibbs energy change when one mole of the substance
is formed from its elements in their standard states.
Thus standard Gibbs energy change of a reaction is ∆rGθ = ∑(∆fGθ) all products - ∑ (∆fGθ) all reactants.
∆rGθ = (Sum of standard Gibbs energy of all products) – (Sum of standard Gibbs energy of all reactants).
TRY: (1) Consider the reaction: 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(l) ∆rGθ = - 1010.5 kJ. Calculate ∆rGθ of [NO(g] if ∆rGθ
values of NH3(g), & H2O(l) are – 16.6 & - 237.2 kJ/mol respectively. [Ans: 86.8 kJ/mol]
(2) Consider the reaction: 2 NO(g) + O 2(g) → 2 NO2(g). Calculate thr standard Gibbs energy change of reaction at 298 K & predict
whether the reaction is spontaneous or not. ∆rGθ for NO(g) & NO2(g) are 86.89 & 51.84 kJ/mol respectively.
[Ans.- 69.7 kJ, spontaneous reaction)
Gibbs energy change (∆G) for predicting feasibility of a reaction.
The total entropy change ∆Stotal determines the spontaneity of a process. ∆Stotal = ∆Ssyst + ∆Ssurr
If the system is in thermal equilibrium with the surrounding, then the temperature of the system and surroundings are same.
So, the increase in enthalpy of system = decrease in enthalpy of surroundings and at constant pressure ∆H syst = qsyst
So, we can say (qP)surr = - (qP)syst = - ∆Hsyst Heat lost by system = heat gained by surroundings & vice versa.
(qP )surr ∆Hsyst
The entropy change of the surroundings is ∆Ssurr = =-
T T
∆Hsyst
Hence, ∆Stotal = ∆Ssyst + ∆Ssurr = ∆Ssyst + (- ) Multiplying both the sides by T, we have
T
T∆Stotal = T∆Ssyst - ∆Hsyst
or, - T∆Stotal = ∆Hsyst - T∆Ssyst We know that ∆Gsyst = ∆Hsyst - T∆Ssyst
So, - T∆Stotal = ∆Gsyst
Hence ∆Gsyst = - T ∆Stotal So, for spontaneous process, ∆Stotal > 0 & hence ∆Gsyst < 0 or negative.

Arunesh Gupta PGT (chemistry) KV Barrackpore (AFS) Page - 3 /7

So, we can say,
(i) For spontaneous process, ∆Stotal > 0 or positive & hence, ∆Gsyst < 0 or negative.
(ii) For non-spontaneous process, ∆Gsyst > 0 or positive
∆H
(iii) For a process in equilibrium, ∆Gsyst = 0 So, we can say T =
∆S

** [ Gibbs energy change & non mechanical work done (useful work done).

Gibbs energy change of a process is equal to the maximum possible work that can be derives as
First law of thermodynamics, ∆U = q – w where q is the heat absorbed & w is the work done by the system.
w = wexpansion + wnon expansion wexpansion = P∆V
∆U = q – wexpansion - wnon expansion or, ∆U = q - P∆V – wnon expansion
q = ∆U + P∆V + wnon expansion We have ∆H = ∆U + P∆V
q = ∆H + wnon expansion
qrev,
For a process carried out reversibly & isothermally (T constant), ∆S = or qrev = T∆S
T
So, T∆S = ∆H + wnon expansion
∆H - T∆S = - wnon expansion or ∆G = - wnon expansion = wuseful
Thus, the decrease in free energy of a system during a process is a measure of maximum useful work done by the system during
the change. So. Gibbs energy (G) of a system is a measure of its capacity to do useful work.
Also, we have ∆G = -nFEcell & at standard states, ∆G° = -nFE°cell ]

Effect of temperature on spontaneity of reactions: We have, ∆Gsyst = ∆Hsyst - T∆Ssyst

∆H ∆S T∆S ∆G Nature of process
1) – ve, exothermic +ve (favourable) -ve at all temperature -ve Spontaneous process at all temperature
(favourable)
2) + ve, endothermic -ve (unfavourable) +ve at all temperature +ve Non-spontaneous process at all temperature
(unfavourable)
3) +ve endothermic +ve (favourable) At low temperature +ve Non-spontaneous process at low temperature
(unfavourable) ∆H > T∆S
At high temperature - ve Spontaneous process at high temperature
∆H < T∆S
4) -ve, exothermic -ve (unfavourable) At low temperature - ve Spontaneous process at low temperature
Favourable ∆H > T∆S (magnitude)
At high temperature + ve Non spontaneous at high temperature
∆H < T∆S (magnitude)
TRY: 1) Explain: (a) All exothermic processes are spontaneous.
(b) All endothermic processes are non-spontaneous.
2) Under what conditions an endothermic process can becomes non spontaneous?
3) For exothermic process, at low temperature the disorderliness of a system decreases. Can it be spontaneous or non-
spontaneous?
Gibbs energy change & equilibrium: We know that ∆Gsyst = ∆Hsyst - T∆Ssyst
‘Reversible’ under strict thermodynamic sense is a special way of carrying out a process such that system is at all times in perfect
equilibrium with its surroundings. For a reversible chemical reaction in equilibrium, A + B ⇌ C + D, ∆rG = 0.
Gibbs energy for a reaction in which all reactants & products are in standard states, ∆rGθ is related to the equilibrium constanr K
as follows: ∆rG = ∆rGθ + RT ln K
At equilibrium, ∆rG = 0. So, 0 = ∆rGθ + RT ln K
∆rGθ = - RT ln K or, ∆rGθ = - 2.303 RT log K
So, we can say, ∆rGθ = ∆rHθ - T ∆rSθ = - RT ln K = - 2.303 RT log K
−∆𝐫 𝐆𝛉 −∆𝐫 𝐆𝛉
We can write K = 𝐞 𝐑𝐓 = 𝟏𝟎𝟐.𝟑𝟎𝟑 𝐑𝐓
So, we can conclude, (i) K < 1, when ∆rGθ > 0
(ii) K > 1 when ∆rGθ < 0
Also, ∆rHθ - T ∆rSθ = - RT ln K
𝐓∆𝐫 𝐇𝛉 − ∆𝐫 𝐇𝛉
or ln K =
𝐑𝐓

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(i) For endothermic reactions, ∆rHθ is positive & large, so, K will be much smaller than 1. This means the reaction is unlikely to form
products.
(ii) For exothermic reactions, ∆rHθ is large & negative, So, K will be larger than 1. This means, exothermic reactions should have
large K value & the reactions go to near completion.
∆rGθ is also dependant upon ∆rSθ.
It is possible to have an estimate of ∆rGθ from the measurement of ∆rHθ & ∆rSθ & then calculate equilibrium constant K, at any
temperature for economic yield of the products.

Problem: (1) For the reaction at 298K, 2A(g) + B(g) → 2D(g), ∆Uθ = - 10.5 kJ & ∆Sθ = - 44.1 J/K. Calculate ∆Gθ for the reaction &
predict whether the reaction is spontaneous or not.
Solution: We know, ∆Hθ = ∆Uθ + ∆ngRT
Given: ∆Uθ = - 10.5 kJ & ∆Sθ = - 44.1 J/K = - 44.1 x 10-3 kJ/K, T = 25°C = 298 K
For the given reaction, 2 A(g) + B(g) → 2D(g) where Δng = 2 – (1+2) = –1 mole
Substituting the value of ΔUθ in the expression of ΔH:
ΔHθ = ΔUθ + ΔngRT
= (–10.5 kJ) – (–1) (8.314 × 10–3 kJ K–1 mol–1) (298 K) = –10.5 kJ – 2.48 kJ or, ΔHθ = –12.98 kJ
Substituting the values of ΔHθ and ΔSθ in the expression of ΔGθ:
ΔGθ = ΔHθ – TΔSθ
= –12.98 kJ – (298 K) (–44.1 J K–1) = –12.98 kJ + 13.14 kJ or, ΔGθ = + 0.16 kJ
Since ΔGθ for the reaction is positive, the reaction will not occur spontaneously.

(2) Calculate the Standard Free Energy Change at 25℃ given the Equilibrium constant of 1.3 × 104.
Answer. ΔGӨ = –2.303 RT log K
ΔGӨ = – 2.303 RT log K = –8.314 × 298 × log 1.3 × 104 = –23469 J = –23.4 KJ

(3) Using Gibbs energy change, ΔGӨ = +63.3 kJ for the reaction Ag2CO3 ⇄ 2Ag+ + CO32–.
Calculate the Ksp for Ag2CO3 in water at 25°C.
Answer. The relationship between solubility product and Gibbs free energy is: ΔGӨ = –2.303 RT log Ksp
On substituting the values: 63.3 × 103 = –2.303 × 8.31 × 298 log Ksp or, –11.09 = log Ksp or, Ksp = 8 × 10–12.
Hence, the Ksp for Ag2CO3 in water at 25°C is 8 × 10–12.

(4) Is the reaction rate affected by Gibbs free energy?

Answer. There are two variables in the Gibbs Free Energy equation–ΔH, which is a system’s enthalpy, and ΔS, which is its
entropy. Gibbs Free Energy indicates whether a chemical change is thermodynamically possible. The Gibbs Free energy ΔG must
be – ve for a reaction to be spontaneous. ΔH < 0 and ΔS > 0 to attain this.
As a result, the temperature and entropy that affect Gibbs Free Energy also affect the reaction rate indirectly.
Hence, we can say that the reaction rate is affected by Gibbs energy.
TRY: Calculate ΔG° for the reaction 2CO + O2 → 2CO2 at 298.15 K. Given ΔH = – 128.3 kJ, ΔS = – 159.5 J K–1
Third law of thermodynamics:
The entropy of the system will approach a constant value as its temperature approaches absolute zero is the empirical
statement of the third law of thermodynamics.
It states that “at absolute zero (0 K), the entropy of a perfectly crystalline substance is taken as zero”.
If a solid substance has defect or imperfections, its entropy at zero kelvin may not be zero.
The third law of thermodynamics helps to calculate the absolute entropies of pure substances at different temperatures.
The entropy (S) of the substance at different temperature, T may be calculated by the measurement of heat capacity changes.
If S0 be the entropy of the substance at 0 K & ST be its entropy at T K, then,
T Cp
ΔS = ST – S0 = ∫0 dT
T
T Cp
According to third law, S0 = 0, ST = ∫0 dT = Cp ln T = 2.303 Cp log T
T
Cp
The value of integral can be calculated from the graph of vs T. The area under the curve between 0 K to T K gives the value of
T
integral & thus the value of ST at T kelvin.
When the entropy of one mole of the substance is expressed of standard state, it is called standard molar enthalpy of the
substance (Sm0)
So, for a reaction, ∆rS0 = ∑S0(products) - ∑ S0(reactants)
aA + bB → cC + dD → ∆rSm0 = [c Sm0(C) + d Sm0(D)] – [a Sm0(A) + b Sm0(B)]
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Limitations of the 3rd Law of Thermodynamics: Some molecules like Carbon dioxide, carbon monoxide, nitric oxide, nitrous
oxide, Solid chlorine, and Ice do not follow the third Law.

Zeroth Law of Thermodynamics:

When a body, ‘A’, is in thermal equilibrium with another body, ‘B’, and also separately in thermal equilibrium with a body ‘, C’,
then body, ‘B’ and ‘C’, will also be in thermal equilibrium with each other. This statement defines the zeroth law of
thermodynamics. The law is based on temperature measurement.

In simple terms, “Systems that are in thermal equilibrium exist at the same temperature”.
So, the zeroth law of thermodynamics states that if the systems are in thermal equilibrium, no heat flow will take place.
Some conceptual questions:

1) What is the value of ∆G at melting point of ice?

Ans. At melting point: Ice ⇌ water liquid which remains in equilibrium, so, ∆G = 0.

2) For a reaction, both ∆H & ∆S are positive, under what conditions will the reaction occur spontaneously?
Ans. The reaction will occur spontaneously only if ∆G < 0 or negative. It is possible when ∆H < T∆S, This is possible at high
temperature using the relation: ∆G = ∆H - T∆S.

3) The standard molar entropy of H2O(l) is 70 kJ/mol. Will the standard molar entropy of H2O(s) be more or less than 70
kJ/mol?
Ans. It is less than 70 kJ/mol because ice is more ordered than H2O(l).

4) Why is entropy of substance taken as zero at absolute zero of temperature?

Ans. At absolute zero, there is completely orderly molecular arrangement in the crystalline substance with no defect. Therefore,
there is no randomness at 0 K and entropy is taken as zero (according to third law of thermodynamics).
5) For an isolated system, ∆U = 0, what will be ∆S?
Ans. Consider an isolated system such as two gases contained separately in two bulbs connected by a stopcock. The ststem is
isolated from the surroundings so that ∆U = 0. On opening the stopcock, the two gases mix up (i.e. the system becomes more
disordered. This means that ∆S > 0.

6) For the reaction: 2 Cl(g) → Cl2(g). What are the signs of ∆H & ∆S ?
Ans. The reaction involves the formation of bonds & hence energy is released i.e. ∆H = - ve or < 0.
Since two particles give I particle, randomness decrease, so that ∆S = - ve < 0.

7) Which quantity out of ∆rG or ∆rG0 will be zero at equilibrium?

Ans. ∆rG will be zero.
∆rG0 will be zero for equilibrium constant K = 1 because ∆G0 = - RT ln K.
∆rG0 will be non-zero for other values of K.
8) Although heat is a path function but heat absorbed by the system under certain specific conditions is independent of path.
What are the conditions?
Ans. The two conditions are
(i) Heat absorbed at constant pressure. according to 1st law of thermodynamics, q = ∆U + P∆V
At constant pressure, q = qP so, qp = ∆U + P∆V
But, ∆H = ∆U + P∆V, therefore, qP = ∆H = change in enthalpy. Since, ∆H is a state function, q p is also a state function.
(ii) Heat absorbed at constant volume, ∆V = 0
q = ∆U + P∆V, So, q = qV = ∆U
Since, ∆U is a state function, qV is also a state function.

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