1

The implication of entropy for polymer synthesis or recycling?

What about the role of entropy in recycling?
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 Chapter 10 3
Entropy and the Second Law of Thermodynamics
 Spontaneity
 Entropy
 Recycling of plastics &The economics of recycling
 The second law of thermodynamics
 The third law of thermodynamics
 Gibbs free energy
 The movement of a physicochemical system towards
4
equilibrium is controlled by two factors (Energy and Entropy)

 In a system of constant energy, the position of equilibrium is that of maximum entropy

 In a system of constant entropy, the position of equilibrium is that of minimum energy
Spontaneity What gives Which chemical
nature reactions will
direction? actually occur?
5

 Polymethyl methacrylate  The melting of an ice cube

 The combustion of gasoline

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Enthalpy (H) Entropy (S) Gibbs Free Energy (G)

∆H = 𝑞𝑝 ∆S =
𝑑𝑞
𝑇 ∆G = ∆H −T∆S
❑ kJmol−1 kJmol−1 K −1
❑ ❑ kJmol−1 K −1
❑ Endothermic (+) ❑ State function ❑ State function
❑ Exothermic (−) ❑ Extensive property ❑ Extensive property
❑ State function
❑ Extensive property
 7

Figure 10.2 In the Carnot cycle, an ideal gas undergoes a series of four processes. Two of these (labeled 1 and 3 in the figure) are
isothermal, which means they occur at constant temperature. The other two steps (2 and 4) are adiabatic, meaning that q 5 0 for those
parts of the cycle. Carnot showed that the sum of the quantity q/T for the entire cycle is equal to zero. Because the cycle begins and
ends with the system in the same state, this means that there must be a state function equal to q/T. We call this state function entropy.
 Entropy : A measure of the randomness or disorder of 8
a system

Figure 10.4 The Maxwell- Boltzmann distribution tells us the overall collection of molecular speeds but does not specify the
speed of any individual particle. Energy exchange during molecular collisions can change the speed of individual molecules
without disrupting the overall distribution.
 Judging Entropy Changes in Processes
9
 Entropy of the universe is unchanged
Reversible Process
 ∆Su = ∆Ssys + ∆Ssurr = 0

Irreversible Process
 Entropy of the universe is increased  Entropy of the universe is increased
 ∆Su = ∆Ssys + ∆Ssurr > 0  ∆Su = ∆Ssys + ∆Ssurr > 0
1. Process of Dissolution 1. CaCO3 (s) → CaO s + CO2 (g)
2. Entropy increases as temperature increase 2. Entropy increases as temperature increase
3. Phase Changes 3. Phase Changes
Solid → Liquid
Liquid → Gas
Solid → Gas
Recycling of plastics The economic of recycling 10

Cost of recycling plastics?

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Table 10.4 Plastic recycling information

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 The 2nd Law of Thermodynamics
13
 It is impossible to convert heat completely to  In any spontaneous process, the total entropy change
work of the universe is positive, (∆Su > 0)
 Heat flows due to random collisions of  ∆Su = ∆Ssys + ∆Ssurr
molecules and an increase in temperature
 Polymerization (MMA to PMMA, Exo)
increases the random motions of molecules
∆Ssurr = − ∆Ssys
 Work requires moving a mass some distance. To
yield a net movement. There must be a direction ∆Ssurr = −
∆H
T
associated with a motion, and that direction
implies that there is an order to the motion  Depolymerization (PMMA to MMA, High T above 400℃)

 Converting to heat into work is a process that Thermolysis (advanced recycling or feedstock
moves from random motions toward more recycling)
ordered ones
 The 3rd Law of Thermodynamics
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 The entropy of a Enperfect crystal of any pure
tro
substance approaches
py zero as the temperature
approaches absolute zero
 1 mole of any given chemical substance under
standard conditions
∆S 0 (T = 0 K to 298 K, P = 1 atm)
 Table 10.1 Standard molar entropy values (page
- 341)
 Example Problem 10.1 (page – 342)
 Check Your Understanding (page – 343)
Figure 10.5 Entropy is a state function, so the value of S must be
 ∆𝑆 0 = σ𝑖 𝑛𝑖 𝑆 0 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − σ𝑗 𝑛𝑗 𝑆 0 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
independent of the path taken from reactants to products. When working
with tabulated standard molar entropies, we implicitly choose a path in
which reactants are converted to pure perfect crystals of elements at 0 K,
followed by the reaction of those elements to form the desired products.
Such a path is obviously not feasible. Nevertheless, it allows us to obtain
accurate values of entropy changes.
Concept of free energy changes in thermodynamic processes
15
Free energy

Helmholtz free energy Gibb’s free energy

(Constant V & T) (Constant P & T)
 Gibbs Free Energy
 Can predict whether or not a process is spontaneous under conditions of constant pressure and 16
temperature
 G = H – TS
 ∆G = ∆H − T∆S (at Temp const.) ………………………….(1)
 How is the change in free energy connected to the spontaneity of a process?

 ∆Su = ∆Ssys + ∆Ssurr

 ∆Ssurr = qsurrΤT
qsys
 ∆Ssurr = − ൗT
 At constant Pressure, qsys = ∆H
∆H
 ∆Ssurr = − T
∆H
 ∆Su = ∆Ssys − T
 − 𝑇 ∆Su = −𝑇∆Ssys + ∆H (or) − 𝑇 ∆Su = ∆H − 𝑇∆Ssys ……………………(2)
 ∆G = −T∆Su
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− −

 Example Problem 10.2 and Example Problem 10.3 (page 345)

 Check Your Understanding (page 346)
 Gibbs Free Energy (Con’t)
18
 Why is free energy?
 The change in Gibbs free energy can be equal to the maximum useful work that can be
done by the system
 ∆G = − wmax (how much energy is “free” or available to do something useful)
 Standard State (P = 1 atm and Conc = 1M)
∆𝐺° = σ𝑖 𝑛𝑖 ∆𝐺 0 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − σ𝑗 𝑛𝑗 ∆𝐺 0 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
 Note that ∆𝐺° = 0 for elements in their standard states
 Example Problem 10.4 (page 348)
 Check Your Understanding (page 348)
 Table 10.3 Free energy changes of formation

Values of the free energy change of formation, G°f , for selected compounds. A much 19
larger list appears in Appendix E.

substance ∆Gf° (kj mol−1) substance ∆Gf° (kj mol−1)

H2(g) 0 CO2(g) − 394.4

O2(g) 0 C4H10(g) − 15.71

H2O(ℓ) − 237.2 CH4(g) − 50.75

H2O(g) − 228.6 C2H4(g) 68.12

NH3(g) − 16.5 C3H6(g) 62.75

 Example Problem 10.4 (page 348)

 Check Your Understanding (page 348)
 Gibbs Free Energy (Con’t)
20
 Thermal depolymerization (or thermolysis) of PMMA as a possible alternative to mechanical recycling

 ∆H 0 = − 56 kJ and ∆S 0 = − 117 J/K (− 0.117 𝑘𝐽/𝐾)

 ∆G0 = − 21 kJ

∆G = ∆H −T∆S

 ∆G0 = + 21 kJ
∆H − 56 kJ
 T= = = 480 𝐾
∆S − 0.117 𝑘𝐽/𝐾