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Outline
III. Entropy and the Second Law of Thermodynamics
•Describe the scientific and economic obstacles to more widespread recycling of plastics;
•Explain the concept of entropy in their own words;
•Deduce the sign of ΔS for many chemical reactions by examining the physical state of the
reactants and products;
•State the second law of thermodynamics in words and equations and use it to predict
spontaneity;
•State the third law of thermodynamics;
•Use tabulated data to calculate the entropy change in a chemical reaction;
•Derive the relationship between the free energy change of a system and the entropy change of
the universe; and
•Use tabulated data to calculate the free energy change in a chemical reaction.
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Recycling of Plastics
• Standard plastic soft drink bottles are made from poly(ethylene
terephthalate) or PET/PETE.
• PET is manufactured in a two step process starting with ethylene glycol and
dimethyl terephthalate.
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Recycling of Plastics
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Recycling of Plastics
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Spontaneity: Natures Arrow
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Spontaneous Processes
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Spontaneous Processes
EXAMPLE #1
SPONTANEOUS: CH4 + O2 → CO2 + 2H2O ΔH = -89 kJ
NON-SPONTANEOUS: CO2 + 2H2O → CH4 + O2 ΔH = +89 kJ
EXAMPLE #2
SPONTANEOUS: 4Fe + 3O2 → 2Fe2O3 ΔH = -1625 kJ
NON-SPONTANEOUS: 2Fe2O3 → 4Fe + 3O2 ΔH = +1625 kJ
EXAMPLE #3
SPONTANEOUS: C6H12O6 + 6O2 → 6CO2 + 6H2O ΔH = -2803 kJ
NON-SPONTANEOUS: Sunlight + 6CO2 + 6H2O → C6H12O6 + 6O2 ΔH = +2803 kJ
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Enthalpy and Spontaneity
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Spontaneity
• Depends on a combination of:
• ΔH (Enthalpy)
• ΔS (Entropy)
• Exothermic – LIKELY to be spontaneous.
• Endothermic – LIKELY to be non-spontaneous.
• ΔS increases – LIKELY to be spontaneous.
• ΔS decreases – LIKELY to be non-spontaneous.
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Entropy
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Carnot Cycle
D
C
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Probability and Spontaneous Change
• The fundamentals of
probability explained using
the rolling of dice.
• The probability of rolling a 4
for one die is 1 in 6.
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Probability and Spontaneous Change
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Probability and Spontaneous Change
wall remove the wall
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Definition of Entropy
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Definition of Entropy
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Definition of Entropy
where:
• S is entropy
• kb is the Boltzmann constant (1.38064852 × 10-23 m2 kg s-2 K-1)
• Ω is the number of microstates.
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Defining of Entropy
• The Maxwell-Boltzmann
distribution indicates the overall
collection of molecular speeds but
not the speed of individual
particles.
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Judging Entropy Changes in Processes
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Judging Entropy Changes in Processes
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Judging Entropy Changes in Processes
• A chemical reaction that generates two moles of gas when only one
mole of gas was initially present will increase the entropy of a
sample.
• The number of possible microstates increases as the number of particles
increases.
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The Second Law of Thermodynamics
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The Second Law of Thermodynamics
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Implications and Applications
• Above some temperature T, the ΔSu is less than zero, and the
formation of PMMA becomes nonspontaneous.
• The reverse reaction, the thermolysis of PMMA back into monomer, will
be spontaneous.
• The thermolysis of PMMA is one method to recycle PMMA.
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The Third Law of Thermodynamics
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The Third Law of Thermodynamics
ΔSo
S°products
S°reactants
Use data from Table 10.1 to calculate ΔSo for this reaction.
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Example Problem 1:
Products:
S° (C4H10) = 310.03 kJ/mol-K
Reactants:
S° (C2H4) = 219.5 kJ/mol-K
S° (H2) = 130.6 kJ/mol-K
REQUIRED: ΔSo
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Example Problem 1:
S° = [(1mol) (So C4H10)] – [(2mol) (So C2H4) + [(1mol) (So H2)]
S° = [(1mol) (310.03 J/mol-K)] – [(2mol) (219.5 J/mol-K) + [(1mol) (130.6 J/mol-K)]
S° =(310.03 J/K) – (439 J/K + 130.6 J/K)
S° =(310.03 J/K) – (569.6 J/K)
S° = – 259.57 J/K)
S° = – 259.6 J/K)
ΔG = ΔH – TΔS
ΔSsurr = —ΔH / T
ΔSu = ΔS + ΔSsurr
ΔG = - T ΔSsurr – T (ΔSu – ΔSsurr)
ΔG = – TΔSu
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Free Energy and Spontaneous Change
ΔG = ΔH – TΔS
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Free Energy and Spontaneous Change
ΔG = ΔH – TΔS
• For a negative ΔH and a positive ΔS, the ΔG will always be negative
and the reaction spontaneous.
ΔG = (-ΔH) – (TΔS)
ΔG = -(ΔH + TΔS)
• For a positive ΔH and a negative ΔS, the ΔG will always be positive
and the reaction nonspontaneous.
ΔG = (ΔH) – [(T)(-ΔS)]
ΔG = ΔH + TΔS
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Free Energy and Spontaneous Change
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Free Energy and Spontaneous Change
ΔG > 0 Non-spontaneous
Spontaneous
ΔG < 0
Variation in ΔG with temperature for the 4 possible combinations of arithmetic sign for ΔH and ΔS
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Free Energy and Spontaneous Change
ΔS ΔH > 0 ΔH < 0
(endothermic) (exothermic)
ΔS > 0 ΔG < 0 @ high temp. ΔG < 0 @ any temp.
(increase in Entropy) ΔG > 0 @ low temp. Process is spontaneous
Process is spontaneous @ @ any temperature.
high temperature.
ΔS < 0 ΔG > 0 @ any temp. ΔG < 0 @ low temp.
(decrease in Entropy) Process is non-spontaneous ΔG > 0 @ high temp.
@ any temperature. Process is spontaneous
@ low temperature.
Summary of the 4 scenarios for Enthalpy and Entropy changes.
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Free Energy and Spontaneous Change
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Free Energy and Spontaneous Change
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Example Problem 2:
PROBLEM: Use the signs of ΔH and ΔS to explain why ice spontaneously melts
at room temperature but not outside on a freezing winter day.
SOLUTION:
Set ΔG=0. (Adding a subscript ‘m’ to the temperature will help remind us
that this equation is only valid at the melting temperature.)
ANSWER: Tm = 410 K
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Free Energy and Work
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Free Energy and Work
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Free Energy and Chemical Reactions
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Free Energy and Chemical Reactions
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Example Problem 4:
SOLUTION:
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Implications of ΔGo for a Reaction
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Implications of ΔGo for a Reaction
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The Economics of Recycling
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The Economics of Recycling
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The Economics of Recycling
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The Economics of Recycling
OTHER REFERENCES
W.L. Masterton & C. N. Hurley. Chemistry :Principles and Reactions.
R. Chang. Chemistry.
https://www.youtube.com/watch?v=s62MuviUWYw.
https://byjus.com/physics/carnot-engine/.
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