CHEM 101 – Chemistry for

Scientists and Engineers

“Chemistry: Science of Change”
by Oxtoby, Freeman, Block

Chapter 11:
Spontaneous Change and Equilibrium

Sesil Agopcan Çınar, Çimen Özgüç Önal

 Outline
• Heat, Work, Calorimetry (Chp 10)
• Enthalpy (Chp 10)
• Standard Enthalpies of Reaction (Chp 10)
• The First Law of Thermodynamics (Chp 10)
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• Spontaneous Change
• Entropy
• The Second Law of Thermodynamics
• The Gibbs (Free) Energy
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 Spontaneous Change

Non-natural process

Natural process

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Direction of Spontaneous Change
• Enthalpy (energy)
• Entropy
• Gibbs energy

• Equilibrium at the lowest energy.

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 Outline
• Heat, Work, Calorimetry (Chp 10)
• Enthalpy (Chp 10)
• Standard Enthalpies of Reaction (Chp 10)
• The First Law of Thermodynamics (Chp 10)
----------------------------------------------------------------
• Spontaneous Change
• Entropy
• The Second Law of Thermodynamics
• The Gibbs (Free) Energy
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 Entropy and Spontaneity
• Entropy – disorder
(randomness)

• There is tendency towards

maximum entropy
(minimum order) in nature.

Disorder Entropy
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 Examples
• Melting of ice cube

• Evaporation of liquid

• Free expansion of a gas

• Spontaneous change  Entropy increases (S > 0)

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 Calculation of Entropies
• The entropy change associated with a reversible
phase transition (at equilibrium):
∆𝐻𝑓𝑢𝑠 ∆𝐻𝑣𝑎𝑝
∆𝑆𝑓𝑢𝑠 = ∆𝑆𝑣𝑎𝑝 =
𝑇𝑚 𝑇𝑏
• Entropy change of a chemical reaction:
∆𝑆𝑟 = 𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

° °
∆𝑆𝑟° = 𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Use APPENDIX D 8
 Example 11-3
(a) Use standard molar entropy data from Appendix
D to calculate ∆𝑆𝑟° at 25°C for:
2NO (g) + O2 (g)  2NO2 (g)
(b) Calculate the standard change in entropy under
the same conditions when 40.00 g of NO(g) reacts
with excess O2(g) to give NO2(g).

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Solution (Ex. 11-3)
2NO (g) + O2 (g)  2NO2 (g)

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 Outline
• Heat, Work, Calorimetry (Chp 10)
• Enthalpy (Chp 10)
• Standard Enthalpies of Reaction (Chp 10)
• The First Law of Thermodynamics (Chp 10)
----------------------------------------------------------------
• Spontaneous Change
• Entropy
• The Second Law of Thermodynamics
• The Gibbs (Free) Energy
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 2nd Law of Thermodynamics
In any spontaneous process, the entropy of the
universe (system + surroundings) must increase.
Suniv = Ssys + Ssurr
Universe

Suniv > 0 (spontaneous)

Suniv = 0 (equilibrium – if reversible )
Suniv < 0 (non-spontaneous, impossible)

Impracticable to calculate Ssurr and Ssys as they

are both changing. 12
 const. T & P

Gibbs (Free) Energy

q = Hsurr -q = Hsys

 H sys 
S univ  Ssys  Ssurr   Ssys    0
∆𝐻𝑠𝑢𝑟𝑟 ∆𝐻
 T 
𝑠𝑦𝑠
∆𝑆𝑠𝑢𝑟𝑟 = =−
𝑇 𝑇
TSsys – Hsys > 0 (Multiply both sides by T)
Hsys – TSsys < 0 (Multiply both sides by -1)

Gsys < 0
(Spontaneous, constant T & P)

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 Gibbs (Free) Energy
For a change at constant T and P:
Gsys = Hsys – TSsys

Gsys < 0 (Spontaneous)

Gsys = 0 (Equilibrium)
Gsys > 0 (Non-spontaneous, impossible)

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 Gibbs Energy and Spontaneity
Gsys = Hsys – TSsys
Disorder
Heat Spontaneity

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 Example 11-5
Carbon disulfide (CS2) is a liquid at room T
(a) Calculate the Gvap (the Gibbs energy for the
vaporization of CS2), at 25°C and 1 atm given that
Svap equals 86.39 J K-1 mol-1 and Hvap equals
27.66 kJ mol-1.
(b) Compute the normal boiling point of CS2
assuming that Svap and Hvap at the normal
boiling point equal their values at 25°C and 1 atm

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Solution (Ex. 11-5)

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 Standard Molar Gibbs Energy
of Formation
aA + bB  cC + dD
Gr  c Gf (C)  d Gf (D)  a Gf (A)  b Gf (B)

3 NO (g)  N2O (g) + NO2 (g)

Gr, 298.15  Gf ( N 2O)  Gf ( NO 2 )  3 Gf ( NO)
 (104.18kJ mol-1 ) + (51.29 kJ mol-1 )  3(86.55kJ mol-1 )
  104.18kJ mol-1
Use APPENDIX D
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 Example 11-8
A slow reaction in the Earth’s interior combines dolomite
with quartz to produce diopside and carbon dioxide:
CaMg(CO3)2 (s) + 2 SiO2 (s)  CaMgSi2O6 (s) + 2 CO2 (g)
The standard enthalpy and standard entropy of this
reaction at 298.15 K are 155 𝑘Jmol−1 and 331 JK−1mol−1

Assume that the CO2 produced is at atmospheric pressure

(not very accurate), and estimate the temperature ranges
in which this reaction is and is not spontaneous.
Strategy: Assume ∆𝐻𝑟° and ∆𝑆𝑟° do not change
with T, find the T at which ∆𝐻𝑟° = 𝑇 ∆𝑆𝑟° 19
Solution (Ex. 11-8)

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 Gibbs Energy and
Equilibrium Constant
Gr  Gr   RT ln Q
Q = Reaction quotient

At equilibrium: ΔGr = 0 and Q = K   Gr   RT ln K

Equilibrium constants can be calculated from standard

Gibbs energies of reaction ∆𝐺𝑟° (via ∆𝐺𝑓° tables - APP.D)

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 Example 11-9
The ΔGr° at 25°C for 3 NO (g)  N2O (g) + NO2 (g)
was obtained as –104.18 kJ mol-1. Calculate the
equilibrium constant of this reaction at 25°C.

Solution:

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 Summary
• 1st Law of Thermodynamics – the energy of the
universe is always conserved.
• 2nd Law of Thermodynamics – in any spontaneous
process, the entropy of the universe must increase.
• Enthalpy (H), internal energy (E), entropy (S), Gibbs
energy (G) – state functions (path independent)
• Work (w) and heat (q) – process quantities (path
dependent)
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 Problem 11-12
Without consulting App. D, predict the sign of the
entropy change (S) for the following processes:
(a) Ar(g, 600 K)  Ar(g, 200 K) at 1 atm
(b) 2NH4ClO4(s)  N2(g) + Cl2(g) + 4H2O(g) + 2O2(g) at
400 K and 4 atm
(c) P4(g)  2P2(g) at 298.15 K and 1 atm
(d) C6H5CH3(g)  C6H5CH3(l) at 298.15 K and 1 atm

Disorder Entropy
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 Solution (Pb. 11-12)
(a) Ar(g, 600 K)  Ar(g, 200 K) at 1 atm
Cooling at const. P, no transformation:
(b) 2NH4ClO4(s)  N2(g) + Cl2(g) + 4H2O(g) + 2O2(g)
at 400 K and 4 atm
Const. T & P, mole number increasing:
(c) P4(g)  2P2(g) at 298.15 K and 1 atm
Const. T & P, mole number increasing:
(d) C6H5CH3(g)  C6H5CH3(l) at 298.15 K and 1 atm
Const. T & P, gas condenses to liquid:
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 Problem 11-24
Quartz (SiO2(s)) does NOT spontaneously decompose
to silicon and oxygen at 25°C in the reaction. Why?
SiO2(s)  Si(s) + O2(g) ∆𝑆𝑟° = +182.02 JK-1mol-1

Solution:
The fundamental criterion for spontaneity is the
sign of Suniverse for the process. The large positive
∆𝑆𝑟° (Ssystem) applies to the reactants and products
only. The Ssurr in the proposed process is
apparently negative and even larger in magnitude
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 Problem 11-30
Solid tin (Sn) exists in two forms: white and gray.
For the phase change: Sn (white)  Sn (gray)
∆𝐻𝑟° = −2.1 𝑘𝐽𝑚𝑜𝑙 −1 and ∆𝑆𝑟° = −7.4 𝐽𝐾 −1 𝑚𝑜𝑙 −1
(a) Calculate the ∆𝐺𝑟° of the conversion of white tin to
gray tin at -30°C.
(b) Calculate the ∆𝐺𝑟° accompanying the conversion of
2.50 mol of white tin to gray tin at -30°C.
(c) Does white tin convert spontaneously to gray tin at -
30°C and 1 atm?
(d) Estimate the temperature at which white tin and gray
tin are in equilibrium at a pressure of 1 atm.
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Solution (Pb. 11-30)

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 Problem 11-50
Use the thermodynamic data from Appendix D to
calculate equilibrium constants at 25°C for the
following reactions and write an equilibrium
expression in each case:
(a) H2(g) + N2(g) + 2O2(g) 2HNO2(g)
(b) Ca(OH)2(s) CaO(s) + H2O(g)
(c) Zn2+(aq) + 4NH3(aq) Zn(NH3)42+(aq)

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 Solution (Pb. 11-50)
 Gr   RT ln K

(a) H2(g) + N2(g) + 2O2(g) 2HNO2(g)

(b) Ca(OH)2(s) CaO(s) + H2O(g)

(c) Zn2+(aq) + 4NH3(aq) Zn(NH3)42+(aq)

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 Problem 10-32
Using
P4(g) + 5O2(g)  P4O10(s) ∆H1 = -3035.7 kJ mol-1
4P(l) + 5O2(g)  P4O10(s) ∆H2 = -2977.0 kJ mol-1
Find ∆Hr for 4P(l)  P4(g)

Solution:

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 Problem 10-66
A battery harnesses a chemical reaction to extract energy in the form of
useful electrical work.
(a) A certain battery runs a toy truck and becomes partially discharged.
In the process it performs a total of 117 J of work on the
surroundings. It also gives off 3 J of heat, which the surroundings
absorb. No other work or heat is exchanged with the surroundings.
Compute q, w, and ∆E of the battery, making sure each quantity has
the proper sign.
(b) The same battery is now recharged exactly to its original condition.
This requires 210 J of electrical work from an outside generator.
Determine q for the battery in this process. Explain the sign of q.

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Solution (Pb. 10-66)

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Solution (Pb. 10-66)

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 Problem 1
Entropy is the thermodynamic property which constitutes
a quantitative measure of the:

a. heat content of a system.

b. degree of disorder of a system.
c. internal energy of system.
d. all of these
e. none of these

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 Problem 2
For which of the following is ΔHf° = 0 at 25°C?

a. C (s,graphite)
b. NaCl (s)
c. HF (g)
d. all of these
e. none of these

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 Problem 3
The second law of thermodynamics states that:

a. energy is conserved in a spontaneous process.

b. the entropy of the universe increases during a
spontaneous process.
c. the heat content of the universe increases during a
spontaneous process.
d. All of these are valid components of the second law.
e. None of these is correct.
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 Problem 4
Under what conditions will the reaction,
2N2(g) + O2(g) → 2 N2O(g), be spontaneous?

At 25°C ΔGf° and ΔHf° for dinitrogen oxide are 104.2 kJ mol–1
and 82.0 kJ mol–1, respectively.
a. under all conditions
b. under no conditions
c. at high temperature
d. at low temperature
e. This cannot be answered without additional information.
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Solution (Pb. 4)

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