Chapter 18

Thermodynamics

Brady and Senese 5th

Edition

1
Index
18.1 Internal energy can be transferred as heat or work, but it cannot be
created or destroyed
18.2 A spontaneous change is a change that continues without outside
intervention
18.3 Spontaneous processes tend to proceed from states of lower
probability to states of higher probability
18.4 All spontaneous processes increase the total entropy of the universe
18.5 The third law of thermodynamics makes experimental measurement
of absolute entropies possible
18.6 The standard free energy change, G°, is G at standard conditions
18.7 G is the maximum amount of work that can be done by a process
18.8 G is zero when a system is at equilibrium
18.9 Equilibrium constants can be estimated from standard free energy
changes
18.10 Bond energies can be estimated from reaction enthalpy changes
2
State Function
• Any characteristic of a system that is independent of
pathway, designated with capital letters e.g. H, T, V, P
• A system is frequently characterized by changes in the
state function, ΔX
• Note that state functions depend on the quantities
involved
• ΔXrxn = Σ(nΔXfinal) - Σ(nΔXinitial) where n = the number
of moles of that substance in the reaction

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 3
destroyed
Learning Check
Calculate ΔH° for the following reactions.
H2O(l) + CO2(g) → H2CO3(aq) kJ/mol
−285.9 −393.5 -698.7 ΔHf°298K

-19.3 kJ
NH3(g) + HCl(g) → NH4Cl(s)
−46.19 −92.30 −315.4 ΔHf°298K

-176.9 kJ

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 4
destroyed
Your Turn!
Given the following information, what is the enthalpy of
reaction at 500 K?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. 97.3 kJ
B. -97.3 kJ
C. -189.9 kJ Ηf ° Gf °, 298K Sf°
(kJ/mol) (kJ/mol) (J/mol K)
D. -141.6 kJ
MgCl2(s) -641.8 -592.5 89.5
MgO(s) -601.7 -569.4 26.9
H2O(l) -285.9 -237.2 69.96
H2O(g) -241.8 -228.6 188.7
HCl(g) -92.30 -95.27 186.7

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 5
destroyed
First Law of Thermodynamics

For an isolated system the internal energy is

constant:
ΔE = Ef - Ei = 0
• We can’t measure the internal energy of
anything, so we measure the changes in energy
• E = work + heat or E = w + q

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 6
destroyed
Work (w) = Force × Distance = -Patm × ΔV
• In reactions, work is most often due to the expansion or
contraction of a system due to changing moles of gas.
• The deployment of an airbag is one example of this
process
1 C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g)
6 moles of gas → 7 moles of gas
• Since PV = nRT, PΔV = ΔnRT.
• Thus, we can predict the work: w = - ΔnRT

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 7
destroyed
Enthalpy (H) and Internal Energy (E)
• Enthalpy is the heat transferred at constant pressure,
thus, ΔH = qp
• ΔE = q + w
 If there is no change in the moles of gas,
then ΔE = qp
 If the reaction occurs in a fixed volume container,
ΔE = qv
 If the moles of gas change,
ΔE = qv= qp – ΔnRT = ΔH – ΔnRT
• Generally ΔH is very close in value to ΔE, unless
work term is huge like in an explosion
18.1 Internal energy can be transferred as heat or work, but it cannot be created or 8
destroyed
Learning Check
• Consider the nitrogen triiodide decomposition,
2NI3(s) → N2(g) + 3I2(g), is ΔΗ° ≈ ΔΕ°? Why?

• For the following reaction for picric acid, calculate ΔΗ°,

ΔΕ° at 25 °C
8O2(g) + 2C6H2(NO2)3OH(l) → 3N2(g) + 12CO2(g) + 6H2O(g)

ΔΗ°f
(kJ/mol) 0 3862.9 0 -393.5 -241.8

ΔH° = -13,898.7 kJ -ΔnRT = -32.2 kJ

ΔE = -13,930.9 kJ
18.1 Internal energy can be transferred as heat or work, but it cannot be created or 9
destroyed
Your Turn!
Given the following information, what is the internal energy
of reaction at 500 K?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. -97.3 kJ
B. -90.8 kJ
Ηf ° Gf °, 298K Sf°
C. +90.8 kJ (kJ/mol) (kJ/mol) (J/mol K)
D. -93.4 kJ MgCl2(s) -641.8 -592.5 89.5
MgO(s) -601.7 -569.4 26.9
H2O(l) -285.9 -237.2 69.96
H2O(g) -241.8 -228.6 188.7
HCl(g) -92.30 -95.27 186.7

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 10
destroyed
Standard State
• Most stable form of the pure substance at
 1 atm pressure
 Stated temperature. If temp is not specified, assume 25 °C
 Solutions are 1 M in concentration.
• Measurements made under standard state conditions
have the ° mark: ΔH°

18.1 Internal energy can be transferred as heat or work, but it cannot be created or 11
destroyed
Spontaneous Reactions
• Occur efficiently (product-favored as written)
• Occurs without continual intervention
• Often, but not always accompanied by exothermic
processes

18.2 A spontaneous change is a change that continues without outside intervention 12

Entropy (S)
• A measure of randomness
• The more possible arrangement of particles, the higher the
entropy
• Processes favor high probability (p)
frequency of outcome
p
number of possible outcomes

18.3 Spontaneous processes tend to proceed from states of lower probability to states of 13
higher probability
Factors Affecting Entropy (ΔS)

• Mixing
• Volume
change of gas
• Temperature -
not a
significant
change if state
is the same

18.3 Spontaneous processes tend to proceed from states of lower probability to states of 14
higher probability
Factors Affecting Entropy (ΔS) (Cont.)
• State
• Number of particles
• Number of bonds
• The entropy of a pure crystalline solid at 0 K is
defined as 0.

18.3 Spontaneous processes tend to proceed from states of lower probability to states of 15
higher probability
Predict the Sign of ΔS in the Following:
• Dry ice → carbon dioxide gas
• Moisture condenses on a cool window
• AB →A + B
• A drop of food coloring added to a glass of water
disperses
• 2Al(s) + 3Br2(l) → 2AlBr3(s)

18.3 Spontaneous processes tend to proceed from states of lower probability to states of 16
higher probability
Your Turn!
Which of the following has the most entropy in
standard conditions?
A. H2O(l)
B. NaCl(aq)
C. AlCl3(s)
D. Can’t tell from the information

18.3 Spontaneous processes tend to proceed from states of lower probability to states of 17
higher probability
The Second Law of Thermodynamics
• ΔStotal = ΔSsystem + ΔSsurroundings
 Since ΔSsurroundings = qsurroundings/T
 And since qsurroundings = -qsystem
 Then ΔSsurroundings = -qsystem/T = -ΔHsystem/T
• ΔStotal = ΔSsystem- ΔHsystem/T
 ΔStotal = (TΔSsystem- ΔHsystem)/T
 TΔStotal = TΔSsystem- ΔHsystem = -(ΔHsystem – TΔSsystem)
 Since ΔStotal is (+) for all spontaneous reactions,
 -(ΔHsystem – TΔSsystem) > 0
• ΔHsystem – TΔSsystem < 0 for all spontaneous reactions.
18.4 All spontaneous processes increase the total entropy of the universe 18
Gibb’s Free Energy (G)
• Represents the maximum work output
• G = H - TS, thus
• ΔG = ΔH - TΔS
 Note that ΔG is highly dependent on temperature.
 Reactions whose ΔG < 0 are "spontaneous" or
"efficient“
 ΔG = 0 at equilibrium.
 ΔG > 0 inefficient (non-spontaneous)

18.4 All spontaneous processes increase the total entropy of the universe 19
The Driving Forces of a Reaction
• Reactions typically occur spontaneously when
the ΔH is (-) or if ΔS is (+)
 If ΔH > TΔS term, reaction is “enthalpy
driven”
 If TΔS term > ΔH term, reaction is “entropy
driven”
• Free energy was derived to give the overall
picture of both of the driving forces

18.4 All spontaneous processes increase the total entropy of the universe 20
Temperature-Controlled Reactions
• Temperature-controlled
reactions are spontaneous at
one temperature and not at
another
• Such reactions have the same
sign for ΔH and ΔS
• Change spontaneity when T =
ΔH/ΔS

18.4 All spontaneous processes increase the total entropy of the universe 21
The Third Law of Thermodynamics
• The entropy of a pure crystalline solid at 0 K is
defined as 0
• All others states and materials have S > 0
• ΔS = ΔSproducts - ΔSreactants
• Note that the units are J/mol·K

18.5 The third law of thermodynamics makes experimental measurement of absolute 22

entropies possible
Learning Check
Calculate ΔS° for the following:
• CO2(s) → CO2(g)
187.6 213.7 S° (J/mol·K)
26.1 J mol-1 K-1

• CaCO3(s) → CO2(g) + CaO(s)

92.9 213.7 40 S° (J/mol·K)
161 J mol-1 K-1

18.5 The third law of thermodynamics makes experimental measurement of absolute 23

entropies possible
Your Turn
Given the following information, what is the change in
entropy for the reaction at 500 K?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. 64.7 J mol -1K-1 Ηf ° Gf °, 298K Sf°
(kJ/mol) (kJ/mol) (J/mol K)
B. -64.7 J mol-1 K-1
MgCl2(s) -641.8 -592.5 89.5
C. -122.1 J mol K -1 -1
MgO(s) -601.7 -569.4 26.9
D. 122.1 Jmol K-1 -1
H2O(l) -285.9 -237.2 69.96
H2O(g) -241.8 -228.6 188.7
HCl(g) -92.30 -95.27 186.7

18.5 The third law of thermodynamics makes experimental measurement of absolute 24

entropies possible
Gibb’s Free Energy (G)
• ΔG° = ΔH° - TΔS°
 ΔG° is highly dependent on temperature
 May be calculated using ΔGf° data only at 298 K
 Note that ΔG° implies standard conditions. If the
concentrations and pressures vary, we must correct for
this to calculate ΔG

18.6 The standard free energy change, G°, is G at standard conditions 25

Learning Check
Calculate ΔG° for the following using both
approaches at 298 K:
 CaCO3(s) → CO2(g) + CaO(s)
 Which approach is needed if you want ΔG° at 500 K?
ΔHrxn = 178 kJ mol-1 ΔSrxn = 160.7 J mol-1 K-1
ΔG°298,rxn = 178 – (298 K × 0.1607 kJ mol-1 K-1) = 130 kJ
ΔG°500rxn = 97.7 kJ
CaCO3 CO2 CaO
ΔHf° −1207 −393.5 −635.5
Sf° 92.9 213.6 40
ΔGf, 298° −1128.8 −394.4 −604.2
18.6 The standard free energy change, G°, is G at standard conditions 26
ΔG° for Reversible Reactions
• A process is defined as thermodynamically
reversible if it can be reversed and
• If it is always very close to equilibrium (the
change in quantities is very small)
• For reversible reactions, ΔG° represents the
maximum work output

18.7 G is the maximum amount of work that can be done by a process 27

ΔG = 0 at Equilibrium
• Thus, 0 = ΔH - TΔS
• T = ΔH/ΔS for all equilibrium processes, including
phase changes.
• What is the expected melting point for Cu?

ΔH = 341.1 kJ mol-1 ΔS = 133.19 kJ mol-1 K-1

T = (341.1/0.13319) K = 2561 K

ΔHf° (kJ/mol) ΔGf° (kJ/mol) S (J/mol·K)

Cu(l) 341.1 301.4 166.29
Cu(s) 0 0 33.1
18.8 G is zero when a system is at equilibrium 28
Your Turn
Given the following information, what is the change
in standard free energy for the reaction at 500 K?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. -36.5 kJ
B. 24.8 kJ Ηf ° Gf °, 298K Sf°
(kJ/mol) (kJ/mol) (J/mol K)
C. -6.10(104) kJ
MgCl2(s) -641.8 -592.5 89.5
D. -122. J MgO(s) -601.7 -569.4 26.9
H2O(l) -285.9 -237.2 69.96
H2O(g) -241.8 -228.6 188.7
HCl(g) -92.30 -95.27 186.7

18.8 G is zero when a system is at equilibrium 29

Your Turn
Given that
ΔH° = -97.3 kJ , S° = -0.1221 kJ mol-1 K-1,
is the reaction favored at higher or lower temperatures?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. Higher
B. Lower
C. Not enough information given

18.8 G is zero when a system is at equilibrium 30

The Non-Standard Reaction
• If the system is not standard, thermodynamics
still apply. The relationship between ΔG and
ΔG° is:
• ΔG = ΔG° + RT ln Q
 Where R = 8.314 J mol-1 K-1
 Q is the Reaction Quotient
• Use ΔG = ΔH° - TΔS° + RT ln Q
 This makes sure that you don’t neglect temperature
variations in ΔG°

18.9 Equilibrium constants can be estimated from standard free energy changes 31
Your Turn
Given that ΔH° = -97.3 kJ , S° = -122.1 J mol-1 K-1, the
pressure of HCl is 2 atm, and that of H2O is 1.0 atm, what is
the change in free energy for the reaction at 500. K?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. +60,900 kJ
Q = 1/22 = 0.25
B. +55,200 kJ
ΔGº = -97.3 kJ - 500(-0.1221)=
C. -93.4 kJ -36.25 kJ
D. -5921 J ΔG = -36.25 kJ + (0.008314 × 500)ln 0.25
E. None of these = -42.0 kJ

18.9 Equilibrium constants can be estimated from standard free energy changes 32
How Does This Relate to Equilibrium?
• ΔG° = -RT ln K
• Thus, if you can find ΔG°, you can find K
• Don’t forget that the ΔG° that you use must be
for the temperature that you are using.
• ΔH° - TΔS° = -RT ln K
• Thus,
    
ln K   S
RT R

18.9 Equilibrium constants can be estimated from standard free energy changes 33
 Learning Check
Determine the value of K at 298 K and 500 K
CaCO3(s) → CO2(g) + CaO(s)
ΔHrxn = 178 kJ ΔSrxn = 160.7 J/·K
ΔG0298,rxn = [-394.4 + (-604.2)] - [-1128.8] = 130.2 kJ
ΔG°298,rxn = 130.2 kJ
ΔG0500,rxn= 178 – (500 K × 0.1607 kJ mol-1 K-1) = 97.8 kJ
ΔG°500,rxn = 97.8 kJ
ΔG° = -RT ln K CaCO3 CO2 CaO
K = e(-ΔG°/RT) ΔHf° −1207 −393.5 −635.5
K298 = e(-130.2/(0.008314 × 298)) S ° 92.9 213.6 40
f
= 1.5 × 10-23
ΔGf,298° −1128.8 −394.4 −604.2
K500 = 6.06 × 10-11
18.9 Equilibrium constants can be estimated from standard free energy changes 34
 Learning Check
Determine the Value of K at 298 K and 500 K
2C6H6(l) + 15O2(g) → 12CO2(g) + 6H2O(g)

ΔG° = ΔH°- TΔS° = -RT ln K; K = e(ΔG°/RT)

K298 = e(+7146.6/(0.008314 × 298))
= e2884 huge!
K500 = e1862
C6H6 O2 CO2 H2O
ΔHrxn = -6285.8 kJ
ΔHf° +49.0 0 −393.5 −241.8
ΔSrxn = 3128.8 J/·K
Sf° 173.3 205.0 213.6 188.7
ΔG°298 = -6368 kJ
ΔGf298° +124.3 0 −394.4 −228.6
ΔG°500 = -7850.2 kJ
18.9 Equilibrium constants can be estimated from standard free energy changes 35
Your Turn!
Given that ΔH° = -97.3 kJ , S° = -122.1 J mol-1 K-1, the
pressure of HCl is 2 atm, and that of H2O is 1.0 atm, What
is the value of K at 500. K?
MgO(s) + 2HCl(g) → H2O(g) + MgCl2(s)
A. 0.99
B. 1.01 ΔG˚ = -97.3 - (500 × -0.1221)
C. 8.20
D. 0.27 -36.25 kJ
E. None of these -(-36.54/(0.008314 × 500))
e
6.11 × 103

18.9 Equilibrium constants can be estimated from standard free energy changes 36
Chemical Potential Energy is Stored in the Bonds
ΔHrxn° = Σ{D(Bonds broken)} - Σ{D(Bonds formed)}

Bond Bond Energy (kJ mol−1) Bond Bond Energy (kJ mol−1)
C–C 348 C–Br 276
C═C 612 C–I 238
C≡C 960 H–H 436
C–H 412 H–F 565
C–N 305 H–Cl 431
C═N 613 H–Br 366
C≡N 890 H–I 299
C–O 360 H–N 388
C═O 743 H–O 463
C–F 484 H–S 338
C–Cl 338 H–Si 376

18.10 Bond energies can be estimated from reaction enthalpy changes 37

 Calculating ΔHrxn Using Bond Dissociation
Energies
ΔH° = Σ{D(Bonds broken)} - Σ{D(Bonds formed)}

CH4(g) + 3Cl2(g) → CHCl3(g) + 3HCl(g)

Examine structures of each and decide what bonds must be broken

and what bonds must be formed.
• Broken: 4C–H, 3Cl–Cl. Formed: 1C–H, 3C–Cl, 3H–Cl
• Exothermic reactions form stronger bonds in the product than in
the reactant
18.10 Bond energies can be estimated from reaction enthalpy changes 38
Learning Check
Given the reaction S8(s) + 12O2(g) → 8SO3(g), Calculate ΔΗ°
from ΔΗ°f . Given that S–S bonds have D = 225 kJ/mol
bond, and that O=O has D = 498 kJ/mol, what is the bond
dissociation energy for the sulfur to oxygen bonds?
Bonds Broken - Bonds Made = ΔHrxn
[8 mol (225 kJ mol-1) + 12 mol (498 kJ mol-1)] - [24 mol (S=O)] = ΔHrxn
ΔHf,products - ΔHf,reactants = ΔHrxn= [8(-395.2)] - [1(0) + 12(0)] = -3161.6 kJ
7776 kJ - 24 mol (S=O) = -3161.6 kJ
24 mol (S=O) = 10,937.6 kJ
S=O = 455.7 kJ/mol S S O
S S + 12 O O 8
oxygen S O

S S O
S S sulfur trioxide
sulfur

18.10 Bond energies can be estimated from reaction enthalpy changes 39

Your Turn
Given that D for H–H is 104.2 kJ/mol bond and that for N≡N
is 226 kJ/mol bond, what is the experimental bond dissociation
energy for the N-H in NH3?
1/2N2(g) + 3/2H2(g) → NH3(g) ∆Hf° = -45.9 kJ mol-1
A. 105 kJ mol-1
B. -105 kJ mol-1
C. 125.4 kJ mol-1
D. None of these

18.10 Bond energies can be estimated from reaction enthalpy changes 40