Chapter10 Entropy 2nd Law STUD

Chemistry: for
Engineering Students
Chapter 10: Entropy and the Second Law of Thermodynamics

10.1 INSIGHT INTO Recycling of Plastics
10.2 Spontaneity
10.3 Entropy
10.4 The Second Law of Thermodynamics
10.5 The Third Law of Thermodynamics
10.6 Gibbs Free Energy
10.7 Free Energy and Chemical Reactions
Apr-16 Chapter-10 1
Chemistry: for
Engineering Students Recycling of Plastics
Polyethylene
Do we really recycle Plastics?
Terephthalate
(PET plastic)
PET chains degrade spontaneously during the recycling process

Chop into
Compress uniform-sized flakes
Sort
Melt and Extrude PET Pellets (but not good

for bottles!)
Apr-16 Chapter-10 2
Chemistry: for
Engineering Students Entropy
Entropy and spontaneous change: A lattice model of a mixture process
A definition of Entropy S = R ln Ω
N reds M-N colorless
A mixing process increases entropy because many

more configurations become accessible at the molecular level.
S final = R ln Ω final >> Sinit = R ln1 = 0

Apr-16 Chapter-10 3
Chemistry: for
Entropy and spontaneous change: Entropy of Probability Distributions
From Chapter 4: The
probability distribution
function ρ(v) that describes
the speeds of a collection S1000K>>S500K
of molecules in a fluid is
the Maxwell-Boltzmann
distribution
2
Mv 2
 M  2 − 2 RT
ρ ( v ) = 4π 
3
 ve
 2π RT 
Another statistical S = − R ln ρ ( v ) = − R ∫ ρ ( v ) ln ρ ( v ) dv
definition of Entropy
Heating a system increases its entropy because there is a larger uncertainty

in the speed and positioning of its molecular components ( a wider ρ)
Apr-16 Chapter-10 4
Chemistry: for
Entropy explains: why is impossible to convert q completely into w ?
Work is done on a system

by stimulating
the coherent motion of WORK
the constituent particles
coherent motion
Apr-16 Chapter-10 5
Chemistry: for
Entropy explains: why is impossible to convert q completely into w ?
A system is heated by
stimulating the
random motion of its HEAT
constituent particles
Random motion
Apr-16 Chapter-10 6
Chemistry: for
Engineering Students The Second Law of Thermodynamics
Statement of the 2nd Law based on S
Every irreversible
(spontaneous) process that ∆Suniv=∆Ssurr + ∆Ssyst ≥ 0
occurs in an isolated system
increases its entropy. (∆Suniv=0 reversible process)
2nd Law The Entropy of the Universe

tends to a maximum value
The Energy of the

1st Law
Universe is constant
Apr-16 Chapter-10 7
Chemistry: for
Engineering Students The Second Law of Thermodynamics
Implications and Applications: The case of MMA polymerization
Addition polymerization: two-single bonds are formed, two double bond are
transformed into single bonds per 2 monomer (overall balance: exothermic process)
P, T const.
Reactor≡System
∆S syst = ∆ r S < 0
O O ∆r H < 0
O O
n + Heat
n
methyl-methaacrylate PMMA
∆r H
Heat reservoir ≡ Surroundings ∆Ssurr = − >0
T
∆r H > 0 T↓
∆Suniv = ∆Ssurr + ∆S syst =− + ∆r S 
T < 0 T↑
Apr-16 Chapter-10 8
Chemistry: for
Engineering Students The Third Law of Thermodynamics
Absolute Entropy
T2
C pgas
∆ cal S = ∫
T1
T
dT
The entropy Absolute S ∆ vap H

of a pure ∆ vap S =
crystalline
Tb
substance
at absolute
0 K is zero
T2
Cp
∆ cal S = ∫T dT
∆ melting H
T1 ∆ melting S =
Tm
S0solid(0 K)=0
3rd Law
Apr-16 Chapter-10 9
Chemistry: for
Absolute entropies of pure substances
Compound S0 Compound S0 Compound S0

J mol-1 K-1 J mol-1 K-1 J mol-1 K-1
O2(g) 205.0 C(graphite) 5.69 C6H6(l) 172.8
N2(g) 191.5 C(diamond) 2.43 C2H5OH(g) 282.7
H2O(g) 188.8 CO(g) 197.9 NaCl(s) 72.33
H2O(l) 69.9 CO2(g) 213.6 CaCl2(s) 104.6
Zn(s) 41.63 CH4(g) 186.3 CaCO3(s) 92.88
Fe(s) 27.15 C2H4(g) 219.4 CH3COOH(l) 159.8
Hg(s) 77.40 C3H8(g) 269.9 C6H12O6(s) 212.1
Hg(l) 174.89 C4H10(g) 310.0
The absolute entropy, S0, is the change in entropy experienced by a pure

substance ongoing from its crystalline solid phase at 0 K to its standard state.
Apr-16 Chapter-10 10
Chemistry: for
Standard Reaction Entropy
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) Irreversible!
State function
∆ r S 0 = S products
0
− S reactants
0
= S 0 (CO2 ) + 2S 0 (H 2O ) − S 0 (CH 4 ) − 2S 0 (O2 )
= (213.6 + 2·188.8 − 186.3 − 2·205.0)

J J
= −5.1
K mol K mol
product reactants
Exact!
In general… ∆r S 0 = ∑ii−
ν
i
S 0
∑ j j
ν
j
S 0 …and slightly negative
•Calculate the variation of standard entropy for the combustion

of glucose C6H12O6(s).
Chemistry: for
Engineering Students Gibbs Free Energy
Spontaneity condition at
Gibbs Function G constant P and T :
G = H − TS T∆Suniv = −∆H syst + T∆S syst ≥ 0
A new state function The 2nd law is a powerful tool

for making predictions
Spontaneous
process at ∆G=∆H−T∆S ≤ 0 ∆Suniv≥0
constant P and T
Chemistry: for
System
magnitudes
∆G=∆H−T∆S ≤ 0
Enthalpic Entropic
factor factor
•Molecular configurations
•Chemical bonds
Spatial distribution of
•Intermolecular
molecules and kinetic
interactions
H/S balance energies
controlled by T
Chemistry: for
Gibbs free energy and spontaneous change
∆G=∆H−T∆S ≤ 0
∆H ∆S ∆G
− + − Spontaneous at whatever T
+ − + Non-spontaneous at whatever T
− − − Spontaneous at low T
Non-Spontaneous at high T
+
+ + + Non-Spontaneous at low T
Spontaneous at high T
−
Assuming that ∆H and ∆S remain
approx. constant with T
Chemistry: for
Implications and Applications: The effect of temperature
change on the spontaneity of MMA polymerization
P, T const.
J
∆ r S = −117
0
K
O O
O O ∆ r H 0 = −56 kJ < 0
n + Heat
n
methyl-methaacrylate PMMA
∆H ∆S ∆G
− − − Spontaneous at low T
+ Non-Spontaneous at high T
∆ H 0
−56 kJ
∆rG0 = ∆r H 0 − T ∆r S 0 < 0 T ∆r S > ∆r H
0 0
T < r
= = 408 K
∆r S 0
−0.117
kJ
∆rS<0 ! K
Chemistry: for
Gibbs free energy and spontaneous change

The spontaneity of phase changes is
always controlled by a delicate balance
Tm=273 K between entropic and enthalpic effects
Phase equilibrium
Ice ∆ fus G = ∆ fus H − Tm ∆ fus S = 0
Water ∆ fus H
Tm =
∆ fus S
∆fusH ∆fusS ∆fusG
+ + + Non-Spontaneous at low T
− Spontaneous at high T
Chemistry: for
• Poly(tetrafluoroethylene) melts at approximately 327°C. If the heat of fusion

is ∆fusH=5.28 kJ mol-1, what is the molar entropy change of fusion (∆fusS)?
• The normal boiling point of Br2(l) is 58.8 oC, and its molar enthalpy of
vaporization is ∆vapH=296 kJ/mol. (a) When Br2(l) boils at its normal boiling
point, does its entropy increase or decrease? (b) Calculate the value of ∆S
when 1.00 mol of Br2(l) is vaporized at 58.8 oC.
Chemistry: for
Free energy and work
Constant P and T
∆G=qP+wuseful−T∆S
∆G=∆H−T∆S
∆H=∆U+P∆V
∆Suniv=∆Ssurr + ∆S = 0
∆U=q+w=
−qP/T qP/T
=qP−P∆V+wuseful
For a reversible
The free energy of a process the Universe
process is the maximum entropy does not
amount of useful work change, that is, all
(not expansion work) that ∆Grev= wuseful entropy change in the
can be done on/by the system is due to the heat
system. exchange with the
surroundings.
Chemistry: for
Engineering Students Free Energy and Chemical Reactions
Standard Gibbs energies of formation of pure substances

Substance ∆fG0 Substance ∆fG0 Substance ∆fG0
kJ·mol−1 kJ·mol−1 kJ·mol−1
O2(g) 0.0 C(graphite) 0.0 C6H6(l) 124.5
N2(g) 0.0 C(diamond) 2.84 C2H5OH(l) -174.76
H2O(g) -105.48 CO(g) -137.2 NaCl(s) -384.0
H2O(l) -237.13 CO2(g) -394.4 CaCl2(s) -748.1
Zn(s) 0.0 CH4(g) -50.8 CaCO3(s) -1128.76
Fe(s) 0.0 C2H6(g) -32.0 CH3COOH(l) -392.4
Hg(l) 0.0 C3H8(g) -23.47 C6H12O6(s) -910.28
Hg(g) 31.76 C4H10(g) -15.71
product reactants
∆rG0 = ∑ i f i−
ν
i
∆ G 0
∑ j f j
ν ∆
j
G 0
Chemistry: for
Standard Gibbs energies of formation

of ionic species in aqueous solutions
Substance ∆fG0 Substance ∆fG0 Substance ∆fG0
kJ·mol−1 kJ·mol−1 kJ·mol−1
H+(aq) 0 Fe2+(aq) -84.94 OH– (aq) -157.30
Li+(aq) -293.8 Fe3+(aq) -10.5 NO3– (aq) -110.5
Na+(aq) -261.87 F– (aq) -276.5 SO42– (aq) -741.99
K+(aq) -282.28 Cl– (aq) -240.0 PO43– (aq) -1013
Mg2+(aq) -456.01 Br– (aq) -102.82
NH4+(aq) I– (aq) -51.67
Chemistry: for
• Consider the following reaction between oxides of nitrogen.
N 2 O( g ) + NO2( g ) 
→ 3NO( g )
(a) Use tabulated data to predict how ∆G0 for the reaction varies with increasing
temperature. (b) Calculate ∆G0 at 800 K, assuming that ∆H0 and ∆S0 do not change
with temperature. Under standard conditions is the reaction spontaneous at 800 K? (c)
Calculate at 1000 K. Is the reaction spontaneous under standard conditions at this
temperature? (d) Determine the minimum temperature at which this reaction is
spontaneous at standard conditions.
• Phosphorus exists in multiple solid phases, including two known as red phosphorus
and white phosphorus. Consider the phase transition between white and red
phosphorus: P4(s, white) →P4(s, red). Use tabulated data to determine which form of
phosphorus is more stable at 25°C. Is this form of the solid more stable at all
temperatures? If not, what temperatures are needed to make the other form more
stable?
Chemistry: for
Engineering Students Problems and Exercises
10.4 Why is recycled PET rarely used to make new soft drink bottles?
10.9 If the combustion of butane is spontaneous, how can you carry a butane
lighter safely in your pocket?
10.13 Are any of the following exothermic processes not spontaneous
under any circumstances?
(a) Snow forms from liquid water.
(b) Liquid water condenses from water vapor.
(c) Fossil fuels burn to form carbon dioxide and water.
(d) Monomers react to form a polymer.
10.15 When a fossil fuel burns, is that fossil fuel the system? Explain your answer.
10.18 The vessel on the left contains a mixture of oxygen and nitrogen at
atmospheric pressure. The vessel on the right is evacuated.
(a) Describe what will happen when the stopcock is opened.
(b) If you could see the individual molecules, what would
you observe after a period of time has passed?
(c) Explain your answers to (a) and (b) in terms of probabilities.
(d) What is the probability that at any one moment all the oxygen molecules will be
in one vessel and all the nitrogen molecules will be in the other? Explain.
Chemistry: for
10.27 Without doing a calculation, predict whether the entropy change will be positive
or negative when each of the following reactions occurs in the direction it is written.
(a) CH3OH(l) + 3/2 O2(g) → CO2(g) + 2 H2O(g)
(b) Br2(l) + H2(g) → 2 HBr(g)
(c) Na(s) + 1/2 F2(g) → NaF(s)
(d) CO2(g) + 2 H2(g) → CH3OH(l)
(e) 2 NH3(g) → N2(g) + 3 H2(g)
10.47 Use tabulated thermodynamic data to calculate the standard entropy change of
each of the reactions listed below. Account for the sign of the entropy change.
(a) Fe(s) + 2 HCl(g) → FeCl2(s) + H2(g)
(b) 3 NO2(g) + H2O(l) → 2 HNO3(l) + NO(g)
(c) 2 K(s) + Cl2(g) → 2 KCl(s)
10.51 Through photosynthesis, plants build molecules of sugar containing several
carbon atoms from carbon dioxide. In the process, entropy is decreased. The reaction
of CO2 with formic acid to form oxalic acid provides a simple example of a reaction in
which the number of carbon atoms in a compound increases:
CO2(g) + HCOOH(l) → H2C2O4(s)
(a) Calculate the standard entropy change for this reaction and discuss the sign of
∆S°. (b) How do plants carry out reactions that increase the number of carbon atoms
In a sugar, given the changes in entropy for reactions like this?
Chemistry: for
10.36 Why do we need to consider the surroundings of a system when applying the
second law of thermodynamics?
10.42 Which reaction occurs with the greater increase in entropy? Explain your
reasoning. (a) 2 H2O(l) → 2 H2(g) + O2(g) ; (b) C(s) + O2(g) → CO2(g).
10.44 Methanol is burned as fuel in some race cars. This makes it clear that the
reaction is spontaneous once methanol is ignited. Yet the entropy change for the
reaction 2 CH3OH(l) + 3 O2(g) → 2 CO2(g) + 4 H2O(l) is negative. Why doesn’t this
violate the second law of thermodynamics?
10.49 Calculate ∆S° for the dissolution of magnesium chloride: MgCl2(s) → Mg2+(aq) + 2
Cl-(aq). Use your understanding of the solvation of ions at the molecular level to
explain the sign of ∆S°.
10.54 Look up the value of the standard entropy for the following substances: SiO2(s),
NH3(g), C2H6(g). Rank the compounds in order of increasing entropy and then explain
why this ranking makes sense.
10.60 Discuss the effect of temperature change on the spontaneity
of the following reactions at 1 atm.
(a) Al2O3(s) + 2 Fe(s) → 2 Al(s) + Fe2O3(s) ∆H° =1851.5 kJ; ∆S° =138.5 J/K
(b) N2H4(l) → N2(g) + 2 H2(g) ∆H°=250.6 kJ; ∆S°=0.3315 kJ/K
(c) SO3(g) → SO2(g) + ½ O2(g) ∆H°= 98.9 kJ; ∆S° =10.0939 kJ/K
Chemistry: for
10.64 For the reaction NO(g) + NO2(g) → N2O3(g), use tabulated thermodynamic data
to calculate ∆H° and ∆S°. Then use those values to answer the following questions:
(a) Is this reaction spontaneous at 25°C? Explain your answer.
(b) If the reaction is not spontaneous at 25°C, will it become spontaneous at higher
temperatures or lower temperatures?
(c) To show that your prediction is accurate, choose a temperature that corresponds
to your prediction in part (b) and calculate ∆G. (Assume that both enthalpy
and entropy are independent of temperature.)
10.66 Natural gas (methane) is being used in experimental vehicles as a clean-
burning fuel.
(a) Write the equation for the combustion of CH4(g), assuming that all reactants and
products are in the gas phase.
(b) Use tabulated data to calculate ∆S° for this reaction.
(c) Calculate ∆G° and show that the reaction is spontaneous at 25°C.
10.79 When polymers are recycled, the ends of the long-chain polymer molecules
tend to break off, and this process eventually results in a degradation of physical
properties, rendering the recycled polymer unusable. Explain why the breaking off of
the ends of the polymer molecules is favorable from the standpoint of the entropy of
the system.
Chemistry: for
10.82 Calculate the entropy change, ∆S°, for the vaporization of ethanol, C2H5OH, at the
boiling point of 78.3°C. The heat of vaporization of the alcohol is 39.3 kJ/mol.
10.65 The combustion of acetylene is used in welder’s torches

because it produces a very hot flame.
C2H2(g) + 5/2 O2(g) → 2 CO2(g) + H2O(g) ∆H°=−1255.5 kJ
(a) Use data in Appendix E to calculate ∆S° for this reaction.
(b) Calculate ∆G° and show that the reaction is spontaneous at 25°C.
(c) Is there any temperature range in which this reaction is not spontaneous?
(d) Do you think you could use Equation ∆G=∆Η −T ∆S to calculate such a temperature
range reliably? Explain your answer.
10.92 Suppose that you need to know the heat of formation of 2-pentene, C5H10, but the
tables you have do not provide the value. You have a sample of the chemical. What
could you do to determine the heat of formation?
10.97 Thermodynamics provides a way to interpret everyday occurrences. If you live in

northern climates, one common experience is that during early winter, snow falls but
then melts when it hits the ground. Both the formation and the melting happen
spontaneously. How can thermodynamics explain both of these seemingly opposed
events?
Chemistry: for
19.3 (TCS) a) What are the signs of ∆S and ∆H for the
process depicted here? (b) How might temperature
affect the sign of ∆G ? (c) If energy can flow in and out
of the system to maintain a constant temperature during
the process, what can you say about the entropy
change of the surroundings as a result of this process?
19.5 (TCS) The accompanying diagram shows how entropy

varies with temperature for a substance that is a gas at the
highest temperature shown. (a) What processes correspond
to the entropy increases along the vertical lines labeled 1 and
2? (b) Why is the entropy change for 2 larger than that for 1?
19.8 (TCS) The accompanying diagram shows how ∆G for a

hypothetical reaction changes as temperature changes.(a) At
what temperature is the system at equilibrium? (b) In what
temperature range is the reaction spontaneous? (c)Is ∆H
positive or negative? (d)Is ∆S positive or negative?

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Chemistry: for

Chapter 10: Entropy and the Second Law of Thermodynamics

PET chains degrade spontaneously during the recycling process

Melt and Extrude PET Pellets (but not good

A mixing process increases entropy because many

S final = R ln Ω final >> Sinit = R ln1 = 0

Heating a system increases its entropy because there is a larger uncertainty

Entropy explains: why is impossible to convert q completely into w ?

Work is done on a system

Statement of the 2nd Law based on S

2nd Law The Entropy of the Universe

The Energy of the

The entropy Absolute S ∆ vap H

Absolute entropies of pure substances

Compound S0 Compound S0 Compound S0

The absolute entropy, S0, is the change in entropy experienced by a pure

CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) Irreversible!

= (213.6 + 2·188.8 − 186.3 − 2·205.0)

•Calculate the variation of standard entropy for the combustion

G = H − TS T∆Suniv = −∆H syst + T∆S syst ≥ 0

A new state function The 2nd law is a powerful tool

Gibbs free energy and spontaneous change

Gibbs free energy and spontaneous change

• Poly(tetrafluoroethylene) melts at approximately 327°C. If the heat of fusion

Standard Gibbs energies of formation of pure substances

Hg(g) 31.76 C4H10(g) -15.71

Standard Gibbs energies of formation

10.65 The combustion of acetylene is used in welder’s torches

10.97 Thermodynamics provides a way to interpret everyday occurrences. If you live in

19.5 (TCS) The accompanying diagram shows how entropy

19.8 (TCS) The accompanying diagram shows how ∆G for a

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