4.1. Irreversibility and evolution of natural phenomena:
The first principle of thermodynamics is a principle of energy conservation, stating that energy cannot be created or destroyed, but only transformed into different forms. The first principle allows us to assert that the following transformations are possible between two states, A and B. A B ΔH = HB-HA B A ΔH = HA-HB However, experimentation shows that when a transformation is spontaneous (the final state is more stable than the initial state), the reverse transformation does not occur spontaneously. The first principle does not provide information about the direction of the transformation's evolution; it only allows for the determination of ΔU and ΔH. Therefore, spontaneous (or natural) transformations are not reversible under the conditions in which they occur. Example : When a hot body comes into contact with a cold body, heat transfers from the hot body to the cold body until thermal equilibrium is reached. The reverse transformation never occurs spontaneously. However, the first principle of thermodynamics does not prohibit this transformation; it only requires the conservation of energy. In chemistry, it is important to determine the direction of the reaction's evolution. The second principle of thermodynamics is a principle of evolution based on the concept of entropy.
4.2. Concept of entropy:
4.2.1. Thermodynamic definition: Let's consider a closed system that undergoes a transformation from an initial state (A) to a final state (B) while exchanging heat with the external environment at temperature T. We define a new state function called "Entropy," denoted as S, and its variation ΔS = S B - SA is given by the following expressions: a. For a reversible transformation: ΔSsyst = SB - SA = ∫ b. For an irreversible transformation: ΔSsyst > ∫ This inequality is called the Clausius inequality. ΔSsyst = Sc + ∫ ΔSsyst = Sc + Se
Sc : Entropy generated during the evolution
Se : Entropy accompanying thermal exchanges with the external environment
Note : Sc = 0 for a reversible transformation. Sc >0 for an irreversible transformation For an isolated system (Q = 0), Se = 0 and thus, it follows ΔSsyst = Sc, the entropy variation is maximum. Mme S.CHERIFI L1 ST 1 Chapter 4 The second principle of thermodynamics
S is an extensive quantity, expressed in J.K-1.J.K-1.
4.2.2. Physical meaning of entropy:
The concept of entropy is related to the possibilities of movements existing at the microscopic scale (vibration, rotation and translation movements). Entropy constitutes a sort of measure of the disorder reigning at the molecular scale. Entropy = disorder
If ΔS>0 increase in disorder at the microscopic scale.
4.2.3. Statement of the second principle:
The second principle of thermodynamics, in its most general formulation, states that during a transformation of a system, the total entropy cannot decrease. ΔStot = ΔSsys + ΔSext ≥ 0 "During a spontaneous transformation, the entropy of the universe (system + surroundings) can only increase. Its variation is zero for a reversible transformation and positive for an irreversible transformation." Reversible transformation: ΔU = Qrev + Wrev = 0 (isothermal) Qrev = - Wrev = nRTln
ΔSsys = = nRln Since the transformation is reversible, the work done by the system will be equal to the work received by the surroundings. Therefore, the heat received by the system is equal to the heat released by the surroundings. Qext = -Qsys = - Qrev = - nRln
ΔSext = - nRln ΔSunivers = ΔSsys + ΔSME = 0 The increase in entropy of the system is equal to the decrease in entropy of the surroundings, thus the entropy of the universe remains constant. There is conservation of entropy in the universe during a reversible transformation. Irreversible transformation: ΔSsys = =- = nRln > 0 ΔU = Qirr + Wirr = 0 Qirr = - Wirr = Pext (V2-V1) ΔSext = - = =- <0
Mme S.CHERIFI L1 ST 2 Chapter 4 The second principle of thermodynamics
For an adiabatic transformation. = 0, as a result,
ΔS = 0
4.2.6. Expression of entropy for ideal gases:
a. Expression of entropy as a function of T and V: dS = = TdS dU = Q + W ncvdT = TdS – PdV PV = nRT ncvdT = TdS - nRT
dS= ncv + nR
Mme S.CHERIFI L1 ST 3 Chapter 4 The second principle of thermodynamics
b. Expression of entropy as a function of T and P:
H = U + PV, dH = dU + PdV + VdP ncpdT = TdS – PdV + PdV + VdP ncpdT = TdS + VdP V=
ncpdT = TdS + nRT
dS= ncP - nR
c. Expression of entropy as a function of P and V:
dS= ncv + nR et dS= ncP - nR
ncv + nR = ncP - nR
n(cp – cv) = nR( + )
D’après la relation de Mayer cp – cv = R Donc = + dS= ncP - nR = ncP ( + ) - nR
dS = ncv + ncp
4.2.7. Variation of entropy for phase changes:
Definition: In the case where the system undergoes a change in physical state, such as fusion, vaporization, or sublimation, ΔS is given by:
ΔS = n (ou m) = n (ou m)
Fusion : ΔSfus = n (ou m)
Vaporization: ΔSvap = n (ou m)
2. Calculation of entropy change during heating of a pure substance:
Consider a pure substance in the solid state characterized by an initial temperature T1. It is heated at constant pressure until it reaches the gaseous state characterized by a final temperature T2. The change in entropy is expressed as follows:
Mme S.CHERIFI L1 ST 4 Chapter 4 The second principle of thermodynamics
Exercise: Calculate: a) The amount of heat involved. b) The change in internal energy. c) The change in enthalpy. d) The change in entropy. When: 1. Heating 2 kg of air from 30 to 100°C at constant pressure. 2. Heating 2 kg of air enclosed in a rigid balloon from 30 to 100°C. In the case where 2 kg of air is heated from 30 to 100°C at constant pressure: Qp = mcp(T2 –T1) = 33,18 kcal ΔU = mcv (T2 – T1) avec cv = = 0,168 kcal/K.mol Therefore, ΔU = 23,52 Kcal The work can be deduced from this: ΔU = Qp + W W = ΔU - Qp = -9,66 kcal = -40,38 Kj ΔH = Qp = mcp(T2 –T1) = 33,18 kcal ΔS = mcpln = 0,0985 kcal
In the case where 2 kg of air enclosed in a rigid balloon is heated from 30 to 100°C. At constant volume: Qv = mcv(T2 –T1) = 23,52 kcal. W=0 ΔU = Qv = 23,52 kcal. ΔH = mcp(T2 –T1) = 33,18 kcal. ΔS = mcvln = 0,0698 kcal
4.3. Statement of the Third Law:
The Third Law of thermodynamics states that: "At absolute zero (0 K), the entropy of a pure crystal (a solid with ordered structure) is zero, S0K = 0." This principle, also known as the "Nernst's postulate," asserts that at 0 K, there is perfect order, meaning there is no thermal agitation at this temperature, and the crystal is in a perfect state.
4.4. Absolute molar entropy:
The third principle makes it possible to attribute an absolute entropy to any pure body brought to temperature T. In the standard state, the absolute molar entropy is denoted S°T.
Mme S.CHERIFI L1 ST 5 Chapter 4 The second principle of thermodynamics
4.5. Calculation of the absolute molar entropy of a pure substance:
A A Initial state Final state Tinitial = 0 K Tfinal = T
Absolute molar entropy at temperature T Absolute molar entropy at T = 0 K
The absolute entropy of a pure compound A at temperature T is the change in its entropy between zero Kelvin and temperature T.
4.6. Entropy of a chemical reaction:
Consider a chemical reaction taking place at constant temperature and pressure: aA + Bb cC + dD
ΔSR = Sfinal – Sinitial = cS (C) + d S(D) – aS (A) – b S (B)
ΔSR= ∑υj ST (products) - ∑υi ST (reactants)
Under standard conditions at 298 K, the entropy change ΔS°298K is: ΔS°298 = ∑υj S°298 (products) - ∑υi S°298 (reactants)
Example 1: Let's determine the entropy change ΔS°298 during the formation of one mole of hydrochloric acid according to the following reaction carried out at 298 K, under a pressure of 1 atmosphere: ½ H2 (g) + ½ Cl2 HCl (g) ΔS°298 = S°298(HCl) – ½ S°298 (Cl2) – ½ S°298(H2) = 2,35 cal/mol.K > 0
Example 2: CaCO3 (s) CaO (s) + CO2 (g) ΔS°298 = S°298 (CaO) + S°298 (CO2) – S°298 (CaCO3) = 38,4 cal/mol.k > 0 (appearance of a new phase).
Example 3: 2 C (s) + 3 H2 C2H6 (g) ΔS°298 = S°298 (C2H6) – 2 S°298 (C) – 3 S°298 (H2) = - 41,57 cal/mol.k < 0 ΔS°298 < 0 The disorder decreases as the number of gas moles has decreased.
4.7. Variation of ΔS°R with temperature:
Consider a chemical reaction taking place at constant pressure: aA + Bb cC + dD
Mme S.CHERIFI L1 ST 6 Chapter 4 The second principle of thermodynamics
By knowing ΔS°298 of this reaction, we can determine ΔS°T using the following Kirchhoff's equation: ΔS°T = ΔS°298 + ∫ at p = constant Δcp = ∑υj cp,j (products) - ∑υi cp,i (reactants)
If the reaction occurs at constant volume, Kirchhoff's relation becomes:
ΔS°T = ΔS°298 + ∫ à V = constant Δcp = ∑υj cv,j (products) - ∑υi cv,i (reactants)
Exercise: 1. Calculate the entropy change of formation of one mole of liquid water from its elements under standard conditions of temperature and pressure. Interpret the result. 2. Calculate this change in the case of one mole of liquid water at 80°C and 1 atm. Interpret the result. Given: Compound S°298 (J/K.mol) Cp (J/K.mol) H2 130,45 28,42 O2 204,83 29,16 H2O 69,85 75,22
1. The reaction involved is H2 (g) + ½ O2 (g) H2O (l)
The entropy change of this reaction is given by Hess's Law: ΔS°298 = S°298 (H2O) – ½ S°298 (O2) – S°298 (H2) = - 163,02 J/k.mol This value reflects a significant decrease in disorder: we start with 1.5 moles of gas and end up with 1 mole of liquid. 2. At 80°C (353 K) and under 1 atm, the entropy change is given by Kirchhoff's equation: ΔS°353 = ΔS°298 + ∫ Δcp = ∑υj cp,j (products) - ∑υi cp,i (reactants) Δcp = cp (H2O) – cp(H2) – ½ cp (O2) = 32,22 J/mol ΔS°353 = -157,56 J/K.mol If we compare the entropy change at the two temperatures, we can make the following observation: The formation reaction at 25°C results in a slightly greater decrease in disorder compared to that at 80°C (the state of liquid water at 80°C is less ordered than at 25°C); molecular disorder increases with temperature.
