CH 18

Chapter 18
Thermodynamics
Chemistry, 7th Edition

International Student Version
Brady/Jespersen/Hyslop
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved.
Thermodynamics
 Study of energy changes and flow of energy
 Answers several fundamental questions:
 Is it possible for a given reaction to occur?
 Will the reaction occur spontaneously (without outside
interference) at a given T ?
 Will reaction release or absorb heat?
 Tells us nothing about time frame of reaction
 Kinetics
 Two major considerations
 Enthalpy changes, H (heats of reaction)
 Heat exchange between system and surroundings
 Nature's trend to randomness or disorder
 Entropy
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 2
Review of First Law of Thermodynamics
 Internal energy, E
 System's total energy
 Sum of KE and PE of all particles in system
 or for chemical reaction
 E + energy into system

 E – energy out of system
Two Methods of Energy Exchange
Between System and Surroundings
 Heat q Work w
 E = q + w
 Conventions of heat and work
q + Heat absorbed by system Esystem increases

q – Heat released by system Esystem decreases
w + Work done on system Esystem increases
w – Work done by system Esystem decreases
First Law of Thermodynamics
 Energy can neither be created nor destroyed
 It can only be converted from one form to another
 Kinetic  Potential
 Chemical  Electrical
 Electrical  Mechanical
 E is a state function
 E is a change in a state function
 Path independent
 E = q + w
Work in Chemical Systems
1. Electrical
2. Pressure-volume or PV
 w = –PV
 Where P = external pressure
 If PV only work in chemical system, then
Heat at Constant Volume
 Reaction done at constant V
 V = 0
 PV = 0, so
 E = qV
 Entire energy change due to heat absorbed or
lost
 Rarely done, not too useful
Heat at Constant Pressure
 More common
 Reactions open to atmosphere
 Constant P
 Enthalpy
 H = E + PV
 Enthalpy change
 H = E + PV
 Substituting in first law for E gives
 H = (q – PV) + PV = qP
 H = qP
 Heat of reaction at constant pressure
Converting Between E and H
For Chemical Reactions
 H   E
 Differ by H – E = PV
 Only differ significantly when gases formed
or consumed
 Assume gases are ideal
 Since P and T are constant
Converting Between E and H For
Chemical Reactions
 When reaction occurs
 V caused by n of gas
 Not all reactants and products are gases
 So redefine as ngas
 Where ngas = (ngas)products – (ngas)reactants
 Substituting into H = E + PV gives
 or
Ex. 1 What is the difference between H and
E for the following reaction at 25 °C?
2 N2O5(g)  4 NO2(g) + O2(g)
What is the % difference between H and E ?
Step 1: Calculate H using data (Table 6.2)
Recall
H ° = (4 mol)(33.8 kJ/mol) +
(1 mol)(0.0 kJ/mol) – (2 mol)(11.0 kJ/mol)
H ° = 113 kJ
Ex. 1. H and E (cont.)
Step 2: Calculate ngas
ngas = (ngas)products – (ngas)reactants
ngas = (4 + 1 – 2) mol = 3 mol
Step 3: Calculate E using

R = 8.31451 J/K mol T = 298 K
E = 113 kJ –
(3 mol)(8.314 J/K mol)(298 K)(1 kJ/1000 J)
E = 113 kJ – 7.43 kJ = 106 kJ
Ex. 1. H and E (cont.)
Step 4: Calculate percent difference
Bigger than most, but still small
Note: Assumes that volumes of solids and

liquids are negligible
Vsolid  Vliquid << Vgas
Is Assumption that
Vsolid  Vliquid << Vgas Justified?
 Consider
CaCO3(s) + 2H+(aq)  Ca2+(aq) + H2O + CO2(g)
37.0 mL 2×18.0 mL 18 mL 18 mL 24.4 L
 Volumes assuming each coefficient equal

number of moles
 So V = Vprod – Vreac = 24.363 L  24.4 L
 Yes, assumption is justified
Note: If no gases are present reduces to
Learning Check
 Consider the following reaction for picric acid:
8O2(g) + 2C6H2(NO2)3OH(l ) → 3 N2(g) + 12CO2(g) + 6H2O(l )
 Calculate Η °, Ε °
8O2(g) + 2C6H2(NO2)3OH(l ) → 3 N2(g) + 12CO2(g) + 6H2O(l )
Η °f
(kJ/mol) 0.00 3862.94 0.00 –393.5 –241.83
H ° = 12 mol(–393.5 kJ/mol) + 6 mol(–241.83 kJ/mol) +
6 mol(0.00 kJ/mol) – 8 mol(0.00 kJ/mol) – 2 mol(3862.94 kJ/mol)
ΔH ° = –13,898.9 kJ
Ε ° = H ° – ngasRT =
H ° – (15 – 8) mol × 298 K × 8.314 × 10–3 kJ/(mol K)
Ε ° = –13,898.9 kJ – 29.0 kJ = –13,930 kJ
Your Turn!
Given the following:
3H2(g) + N2(g) → 2NH3(g) Η °= –46.19 kJ mol–1
Determine E for the reaction.
A. –51.14 kJ mol–1
B. –41.23 kJ mol–1
C. –46.19 kJ mol–1
D. –46.60 kJ mol–1
 Η = E + nRT E = Η – nRT
 E = –46.19 kJ mol –
(–2 mol)(8.314 J K–1mol–1)(298 K)(1 kJ/1000 J)
 E = –51.14 kJ mol–1
Your Turn!
Given the following:
C2H2(g) + 2 H2(g) C2H6(g) Η °= –311.5 kJ mol–1
Determine E for the reaction.
A. –309.0 kJ mol–1
B. –314.0 kJ mol–1
C. –316.46 kJ mol–1
D. –306.5 kJ mol-1
Η = E + nRT E = Η – nRT
E = -311.5 kJ mol-1 – (–2 mol)(8.314 J K–1mol–1)(298 K)(1 kJ/1000 J)
E = -306.5 kJ mol-1
Enthalpy Changes and Spontaneity
 What are relationships among factors that
influence spontaneity?
 Spontaneous Change
 Occurs by itself
 Without outside assistance until finished
 e.g.
 Water flowing over waterfall
 Melting of ice cubes in glass on warm day
Nonspontaneous Change
 Occurs only with outside assistance
 Never occurs by itself:
 Room gets straightened up
 Pile of bricks turns into a brick wall
 Decomposition of H2O by electrolysis
 Continues only as long as outside assistance
occurs:
 Person does work to clean up room
 Bricklayer layers mortar and bricks
 Electric current passed through H2O
Nonspontaneous Change
 Occur only when
accompanied by some
spontaneous change
 You consume food,
spontaneous biochemical
reactions occur to supply
muscle power
 to tidy up room or
 to build wall
 Spontaneous mechanical
or chemical change to
generate electricity
Direction of Spontaneous Change
 Many reactions which occur spontaneously are
exothermic:
 Iron rusting
 Fuel burning
 H and E are negative
 Heat given off
 Energy leaving system
 Thus, H is one factor that influences
spontaneity
Direction of Spontaneous Change
 Some endothermic reactions occur
spontaneously:
 Ice melting
 Evaporation of water
 Expansion of CO2 gas into vacuum
 H and E are positive
 Heat absorbed
 Energy entering system
 Clearly other factors influence spontaneity
Your Turn!
We can expect the combustion of propane
to be:
A. spontaneous
B. non-spontaneous
C. neither
Entropy (Symbol S )
 Thermodynamic quantity
 Describes number of equivalent ways that
energy can be distributed
 Quantity that describes randomness of system
 Greater statistical probability of particular
state means greater the entropy!
 Larger S, means more possible ways to distribute
energy and that it is a more probable result
Fig. 19.6 - Entropy Distribution
 Low Entropy – (a)  High Entropy – (b)
 A absorbs E in units of 10  More ways to distribute E
 Few ways to distribute E  B absorbs E in units of 5
 ● represent E’s of  ●represent E’s of molecules
molecules of A of B
Entropy
 If Energy = money
 Entropy (S ) describes number of different ways of
counting it
Examples of Spontaneity
 Spontaneous reactions
 Things get rusty spontaneously
 Don't get shiny again
 Sugar dissolves in coffee
 Stir more—it doesn't undissolve
 Ice  liquid water at RT
 Opposite does NOT occur
 Fire burns wood, smoke goes up chimney
 Can't regenerate wood
 Common factor in all of these:
 Increase in randomness and disorder of system
 Something that brings about randomness more
likely to occur than something that brings order
Entropy, S
 State function
 Independent of path
 S = Change in entropy
 For chemical reactions or physical processes
Effect of Volume on Entropy
 For gases, entropy increases as volume increases

a) Gas separated from vacuum by partition
b) Partition removed, more ways to distribute energy
c) Gas expands to achieve more probable particle
distribution
 More random, higher probability, more positive S
Effect of Temperature on Entropy
 As T increases, entropy increases
(a) T = 0 K, particles in equilibrium lattice positions and S
relatively low
(b) T > 0 K, molecules vibrate, S increases
(c) T increases further, more violent vibrations occur and S
higher than in (b)
Effect of Physical State on Entropy
 Crystalline solid very low entropy
 Liquid higher entropy, molecules can move freely
 More ways to distribute KE among them
 Gas highest entropy, particles randomly distributed
throughout container
 Many, many ways to distribute KE
Entropy Affected by Number of Particles
 Adding particles to system
 Increase number of ways energy can be distributed
in system
 So all other things being equal
 Reaction that produces more particles will have
positive S
Your Turn!
Which represents an increase in entropy?
A. Water vapor condensing to liquid
B. Carbon dioxide subliming
C. Liquefying helium gas
D. Proteins forming from amino acids
Your Turn!
Which of the following processes have a
decrease in entropy?
A) water freezes
B) isopropanol condenses
C) methanol gas cooling down
D) carbon dioxide going from gas to solid
E) All of the above processes have a decrease
in entropy.
Entropy Changes in Chemical
Reactions
Reactions without gases
 Calculate number of mole molecules
n = nproducts – nreactants
 If n is positive, entropy increases
 More molecules, means more disorder
 Usually the side with more molecules, has less complex
molecules
Reactions involving gases
 Calculate change in number of moles of gas,
ngas
If ngas is positive , S is positive
ngas is more important than nmolecules
Entropy Changes in Chemical Reactions
Ex. N2(g) + 3H2(g)  2NH3(g)
nreactant = 4 nproduct = 2
n = 2 – 4 = –2
Predict Srxn < 0
Higher positional Lower positional

probability probability
Ex. 2 Predict Sign of S for
Following Reactions
CaCO3(s) + 2H+(aq)  Ca2+(aq) + H2O(l) + CO2(g)
 ngas = 1 mol – 0 mol = 1 mol
 since ngas is positive, S is positive
2 N2O5(g)  4 NO2(g) + O2(g)
 ngas = 4 mol + 1 mol – 2 mol = 3 mol
 since ngas is positive, S is positive
OH–(aq) + H+(aq)  H2O(l)
 ngas = 0 mol
 n = 1 mol – 2 mol = –1 mol
Brady/Jespersen/Hyslop,
since n isChemistry7E,
negative,
Copyright © S John
2015 is Wiley
negative
& Sons, Inc. All Rights Reserved. 37
Predict Sign of S in the Following:
Dry ice → carbon dioxide gas
CO2(s) → CO2(g) positive
Moisture condenses on a cool window

H2O(g) → H2O(l ) negative
positive
AB → A + B
A drop of food coloring added to a glass

positive
of
water disperses
negative
2Al(s) + 3Br (l ) → 2AlBr (s)
Your Turn!
Which of the following has the most entropy at
standard conditions?
A. H2O(l )
B. NaCl(aq)
C. AlCl3(s)
D. Can’t tell from the information
Your Turn!
Which reaction would have a negative entropy?
A.Ag+(aq) + Cl–(aq) → AgCl(s)
B.N2O4(g) → 2NO2(g)
C. C8H18(l ) + 25/2 O2(g) → 8CO2(g) + 9H2O(g)
D. CaCO3(s) → CaO(s) + CO2(g)
Your Turn!
Which of the following processes have a S > 0?
A.CH3OH (l) → CH3OH (s)
B.CO (g) + 3 H2 (g) → H2O (g) + CH4 (g)
C. 2NH3 (g) → N2 (g) + 3 H2 (g)
D. 2HBr (g) → Br2 (l) + H2 (g)
E. All of the above
Both Entropy and Enthalpy Affect
Reaction Spontaneity
 Sometimes they work together
 Building collapses
 PE decreases H is negative
 Stones disordered S is positive
 Sometimes work against each other
 Ice melting (ice/water mix)
 Endothermic
 H is positive nonspontaneous
 Increase in disorder of molecules
 S is positive spontaneous
Which Prevails?
 Hard to tell—depends on temperature!
 At 25 °C, ice melts
 At –25 °C, water freezes
 So three factors affect spontaneity:
 H
 S
T
 Next few slides will develop the
relationship between H, S, and T
that defines a spontaneous process
Second Law of Thermodynamics
 When a spontaneous event occurs, total
entropy of universe increases
 (Stotal > 0)
 In a spontaneous process, Ssystem can
decrease as long as total entropy of universe
increases
 Stotal = Ssystem + Ssurroundings
 It can be shown that
Spontaneous Reactions (cont.)
Law of Conservation of Energy
 Says q lost by system must be gained by
surroundings
 qsurroundings = –qsystem
 If system at constant P, then
 qsystem = H
 So
 qsurroundings = –Hsystem
 and
Thus Entropy for Entire Universe is
Multiplying both sides by T we get

TStotal = TSsystem – Hsystem
or
TStotal = – (Hsystem – TSsystem)
 For reaction to be spontaneous
 TStotal > 0 (entropy must increase)
So,
(Hsystem – TSsystem) < 0
must be negative for reaction to be spontaneous
Gibbs Free Energy
 Would like one quantity that includes all three
factors that affect spontaneity of a reaction
 Define new state function, G
 Gibbs Free Energy
 Maximum energy in reaction that is "free" or
available to do useful work
G  H – TS
 At constant P and T, changes in free energy
 G =  H – T S
Gibbs Free Energy
 G =  H – T S
G <0 Spontaneous process
G =0 At equilibrium
G >0 Nonspontaneous
 G  state function
 Made up of T, H and S = state functions
 Has units of energy
 Extensive property
 G = Gfinal – Ginitial
Criteria for Spontaneity?
 At constant P and T, process spontaneous
only if it is accompanied by decrease in free
energy of system
H  S Spontaneous?
– + G = (–) – [T (+)] = – Always, regardless of T
+ – G = (+) – [T (–)] = + Never, regardless of T
+ + G = (+) – [T (+)] = ? Depends; spontaneous
at high T, –G
– – G = (–) – [T (–)] = ? Depends; spontaneous
at low T, –G
Summary
 When H and S have
same sign, T determines
whether spontaneous or
nonspontaneous
 Temperature-
controlled reactions
are spontaneous at one
temperature and not at
another
Your Turn!
At what temperature (K) will a reaction become
nonspontaneous when H = –50.20 kJ mol–1
and S = +20.50 J K–1 mol–1?
A. 298 K
B. 1200 K
C. 2448 K
D. The reaction cannot become non-
spontaneous at any temperature
We are looking for when ΔG is 0
So T = (-ΔH/ΔS)
T = -(-50.20 kJ mol-1)/(0.02050 kJ K-1 mol-1)
T=2448 K
Your Turn!
For the reaction 2NO(g) + O2(g)  2NO2(g),
H° = -113.1 kJ/mol and S° = -145.3 J/K mol.
Which of these statements is true?

A. The reaction is spontaneous at all temperatures.
B. The reaction is only spontaneous at low
temperatures.
C. The reaction is only spontaneous at high
temperatures.
D. The reaction is at equilibrium at 25°C under
standard conditions.
Third Law of Thermodynamics
 At absolute zero (0 K)
 Entropy of perfectly ordered, pure crystalline
substance is zero
 S = 0 at T = 0 K
 Since S = 0 at T = 0 K
 Define absolute entropy of substance at higher
temperatures
 Standard entropy, S °
 Entropy of 1 mole of substance at 298 K (25 °C)
and 1 atm pressure
 S ° = S for warming substance from 0 K to 298
K (25 °C)
Consequences of Third Law
1. All substances have positive entropies as they are
more disordered than at 0 K
 Heating increases randomness
 S ° is biggest for gases—most disordered
2. For elements in their standard states
 S °  0 (but Hf° = 0)
 Units of S °  J/(mol K)
Standard Entropy Change
 To calculate S ° for reaction, do Hess's Law type
calculation
 Use S ° rather than entropies of formation
Learning Check
Calculate S ° for the following:
 CO2(s) → CO2(g)
S °: 187.6 213.7 J/mol K
S ° = (213.7 – 187.6) J/mol K
S ° = 26.1 J/mol K
 CaCO3(s) → CO2(g) + CaO(s)
S °: 92.9 213.7 40 J/mol K
S ° = (213.7 +40 – 92.9) J/mol K
S ° = 161 J/mol K
Ex. 3. Calculate S° for reduction of aluminum
oxide by hydrogen gas
Al2O3(s) + 3H2(g)  2Al(s) + 3H2O(g)
Substance S ° (J/ K mol)
Al(s) 28.3
Al2O3(s) 51.00
H2(g) 130.6
H2O(g) 188.7
Ex. 3 Calculate ΔS° (cont.)
S ° = 56.5 J/K + 566.1 J/K – (51.00 J/K + 391.8 J/K )
S ° = 179.9 J/K
Your Turn!
What is the entropy change for the following
reaction?
Ag+(aq) + Cl–(aq) → AgCl(s)
So 72.68 56.5 96.2 J K–1 mol–1
A. +32.88 J K–1 mol–1
B. –32.88 J K–1 mol–1
C. –32.88 J mol–1
D. +112.38 J K–1 mol–1
S ° = [96.2 – (72.68 + 56.5)] J K–1 mol–1
S ° = –32.9 J K–1 mol–1
Standard Free Energy Changes
 Standard Free Energy Change, G °
 G measured at 25 °C (298 K) and 1 atm
 Two ways to calculate, depending on what
data is available
 Method 1:
 G ° =  H ° – T S °
 Method 2:
Ex. 4. Calculate G ° Method 1
Calculate G ° for reduction of aluminum
oxide by hydrogen gas
Al2O3(s) + 3H2(g)  2Al(s) + 3H2O(g)

Step 1: Calculate H° for reaction using heats of
formation below
Substance (kJ/mol)
Al(s) 0.0
Al2O3(s) –1669.8
H2(g) 0.0
H2O(g) –241.8
H ° = 0.0 kJ – 725.4 kJ – 0.00 kJ – (– 1669.8 kJ)

H ° = 944.4 kJ
Step 2: Calculate S °  see Example 3

S ° = 179.9 J/K
Step 3: Calculate
G ° = H ° – (298.15 K)S °
G ° = 944.4 kJ – (298 K)(179.9 J/K)(1 kJ/1000 J)
G ° = 944.4 kJ – 53.6 kJ = 890.8 kJ
 G ° is positive
 Indicates that the reaction is not
spontaneous
 Use Standard Free Energies of Formation
 Energy to form 1 mole of substance from its

elements in their standard states at 1 atm
and 25 °C
Calculate G ° for reduction of aluminum oxide
by hydrogen gas.
Al2O3(s) + 3H2(g)  2Al(s) + 3H2O(g)
Substance (kJ/mol)
Al(s) 0.0
Al2O3(s) –1576.4
H2(g) 0.0
H2O(g) –228.6
G° = 0.0 kJ – 685.8 kJ – 0.00 kJ

– (– 1576.4 kJ)
G° = 890.6 kJ
Both methods same within experimental error
Spontaneous Reactions Produce
Useful Work
 Fuels burned in engines to power cars or heavy
machinery
 Chemical reactions in batteries
 Start cars
 Run cellular phones, laptop computers, mp3 players
 Energy not harnessed if reaction run in an open dish
 All energy lost as heat to surroundings
 Engineers seek to capture energy to do work
 Maximize efficiency with which chemical energy is converted
to work
 Minimize amount of energy transformed to unproductive
heat
Thermodynamically Reversible
 Process that can be reversed and is always very
close to equilibrium
 Change in quantities is infinitesimally small
 Example - expansion of gas
 Done reversibly, it does most work on surroundings
G ° = Maximum Possible Work
 G ° is maximum amount of energy produced
during a reaction that can theoretically be
harnessed as work
 Amount of work if reaction done under reversible
conditions
 Energy that need not be lost to surroundings as
heat
 Energy that is “free” or available to do work
Ex. 5 Calculate G °
Calculate G ° for reaction below at 1 atm and
25 °C, given H ° = –246.1 kJ/mol, S ° =
377.1 J/(mol K).
H2C2O4(s) + ½O2(g) → 2CO2(g) + H2O(l )
G °25 = H – TS
G ° =(–246.1 – 112.4) kJ/mol

G ° = –358.5 kJ/mol
Your Turn!
Calculate G ° for the following reaction,
H2O2(l ) → H2O(l ) + O2(g)
given
H °= –196.8 kJ mol–1 and S °= +125.72 J K–1 mol–1.
A. –234.3 kJ mol–1
B. +234.3 kJ mol–1
C. 199.9 kJ mol–1
D. 3.7 × 105 kJ mol–1
G ° = –196.8 kJ mol–1 – 298 K (0.12572 kJ K–1 mol-1)
G ° = –234.3 kJ mol
Your Turn!
Calculate G ° for the following reaction,
CaO (s ) + CO2 (g) → CaCO3 (s)
given
H °= 177.8kJ mol–1 and S °= +160.5 J K–1 mol–1.
A. 130.0 kJ mol–1
B. -130.0 kJ mol–1
C. 225.62 kJ mol–1
D. -47651 kJ mol–1
G ° = 177.8 kJ mol–1 – 298 K (0.1605 kJ K–1 mol-1)
G ° = 130.0 kJ mol
G° and Position of Equilibrium
 When G ° > 0 (positive)
 Position of equilibrium lies close to reactants
 Little reaction occurs by the time equilibrium is
reached
 Reaction appears nonspontaneous
 When G ° < 0 (negative)
 Position of equilibrium lies close to products
 Mainly products exist by the time equilibrium is
reached
 Reaction appears spontaneous
G ° and Position of Equilibrium
 When G ° = 0
 Position of equilibrium lies ~ halfway between
products and reactants
 Significant amount of both reactants and products
present at time equilibrium is reached
 Reaction appears spontaneous, whether start with
reactants or products
 Can Use G ° to Determine Reaction Outcome
 G ° large and positive
 No observable reaction occurs
 G ° large and negative
 Reaction goes to completion
At Equilibrium
 G ° = –RT lnK and
K = e–G °/RT
 Provides connection between G ° and K
 Can estimate K at various temperatures if G ° is known
 Can get G ° if K is known
Relationship between K and G °
Keq G ° Reaction
Favored
>1 – Spontaneous
Energy released
Unfavorable
<1 + non-spontaneous
Energy needed
=1 0 At Equilibrium
Learning Check
Ex. 6 Given that H ° = –97.6 kJ/mol,
S ° = –122 J/(mol K), at 1 atm and 298 K, will
the following reaction occur spontaneously?
MgO(s) + 2HCl(g) → H2O(l ) + MgCl2(s)
G ° = H ° – TS °
= –97.6 kJ/mol – 298 K(–0.122 kJ/mol K)
G ° = –97.6 kJ/mol + 36.4 kJ/mol
= –61.2 kJ/mol
Effect of Change in Pressure or
Concentration on ∆G
 G at nonstandard conditions is related to
G ° at standard conditions by an expression
that includes reaction quotient Q
 This important expression allows for any

concentration or pressure
 Recall:
Ex. 7 Calculating G at Nonstandard
Conditions
 Calculate G at 298 K for the Haber process
 N2(g) + 3H2(g)  2NH3(g) G ° = –33.3 kJ
 For a reaction mixture that consists of 1.0
atm N2, 3.0 atm H2 and 0.5 atm NH3
Step 1 Calculate Q
Ex. 7 Calculating G at Nonstandard
conditions
Step 2 Calculate G = G ° + RT lnQ
G = –33.3 kJ/mol +
(8.314 J/K mol)(1 kJ/1000J)(298K)(ln(9.3  10–3))
= –33.3 kJ/mol + (2.479 kJ/mol)(ln(9.3  10–3))
= –33.3 kJ + (–11.6 kJ/mol)
= – 44.9 kJ/mol
 At standard conditions all gases (N2, H2 and NH3) are
at 1 atm of pressure
 G becomes more negative when we go to 1.0 atm
N2, 3.0 atm H2 and 0.5 atm NH3
 Indicates larger driving force to form NH3
 Preactants > Pproducts
Free Energy Diagrams
 G is different than G°
Non-spont. G ° > 0
 G interpreted as the
slope of the free energy
curve and tells which
direction reaction proceeds
to equilibrium
 Minimum, at G = 0,
indicates composition of
equilibrium mixture
 Because G ° is positive
equilibrium lies closer to
reactants
Free Energy Diagrams
Spontaneous Rxn G ° < 0  Reaction proceeds
toward equilibrium
from either A or B
where slope, G , is
not zero
 The curve minimum,
where G = 0, lies
closer to the product
side for spontaneous
reactions. This is
determined by G °
How K is related to G°
 Use relation G = G ° + RT lnQ to derive
relationship between K and G °
 At Equilibrium
∆G = 0 and Q = K
 So 0 = G ° + RT lnK
G ° = –RT lnK
Taking antilog (ex) of both sides gives
K = e–G ° /RT
Ex. 8 Calculating G ° from K
 Ksp for AgCl(s) at 25 °C is 1.8  10–10
Determine G ° for the process
 Ag+(aq) + Cl–(aq)  AgCl(s)
 Reverse of Ksp equation, so
1 1 9
K   10
 5.6  10
K sp 1.8  10
G ° = –RT lnK =
–(8.3145 J/K mol)(298 K) × ln(5.6  109)(1 kJ/1000 J)
 G ° = –56 kJ/mol
 Negative G ° indicates precipitation will occur
Your Turn!
Calculate Kp for the following reaction,
H2O2(l ) → H2O(l ) + O2(g)
given G ° = –234.3 kJ mol
A. 1.103
B. 0.906
C. 8.5 x 10-42
D. 1.17 × 1041
G ° = –RT lnK
K = e–G ° /RT
System at Equilibrium
 Neither spontaneous nor nonspontaneous
 In state of dynamic equilibrium
 Gproducts= Greactants
 G = 0
 Consider freezing of water at 0˚C
 H2O(l )  H2O(s)
 System remains at equilibrium as long as no heat added
or removed
 Both phases can exist together indefinitely
 Below 0 °C, G < 0 freezing spontaneous
 Above 0 °C, G > 0 freezing nonspontaneous
No Work Done at Equilibrium
 G = 0
 No “free” energy available to do work
 Consider fully charged battery
 Initially
 All reactants, no products
 G large and negative
 Lots of energy available to do work
 As battery discharges
 Reactants converted to products
 ∆G less negative
 Less energy available to do work
 At equilibrium
 G = Gproducts – Greactants = 0
 No further work can be done
 Dead battery
Phase Change = Equilibrium
 H2O(l )  H2O(g)
 G = 0 = H – TS
 Only one temperature possible for phase
change at equilibrium
 Solid-liquid equilibrium
 Melting/freezing temperature (point)
 Liquid-vapor equilibrium
 Boiling temperature (point)
H
 Thus H = TS and S 
H T
 or T 
S
Ex. 9 Calculate Tbp
Calculate Tbp for reaction below at 1 atm and
25 °C, given H ° = 31.0 kJ/mol,
S ° = 92.9 J/ mol K
Br2(l ) → Br2(g)
For T > 334 K, G < 0 and reaction is spontaneous

(S ° dominates)
For T < 334 K, G > 0 and reaction is
nonspontaneous (H ° dominates)
For T = 334 K, G = 0 and T = normal boiling point
Learning Check
What is the expected melting point for Cu?
Hf° (kJ/mol) Gf° (kJ/mol) S (J/mol K)
Cu(l ) 341.1 301.4 166.29
Cu(s) 0 0 33.1
Cu(s)  Cu(l )
H = 1mol(341.1 kJ/mol – 1mol(0 kJ/mol)
H = +341.1kJ
S = 1mol(166.29 J/mol K – 1mol(33.1 J/mol K)
S = 133.19 J/K
Effect of Temperature on G °
 Reactions often run at temperatures other
that 298 K
 Position of equilibrium can change as G °
depends on temperature
G ° = H ° – TS °
 For temperatures near 298 K, expect only
very small changes in H ° and S °
 For reaction at temperature, we can write:
Ex. 10 Determining Effect of
Temperature on Spontaneity
 Calculate G ° at 25 °C and 500 °C for the Haber
process
N2(g) + 3H2(g)  2NH3(g)
 Assume that H ° and S ° do not change with
temperature
 Solving strategy
Step 1. Using data in Tables 6.2 and 18.2 calculate H °
and S ° for the reaction at 25 °C
 H ° = – 92.38 kJ
 S ° = – 198.4 J/K
Step 2. Calculate G ° for the reaction at 25 °C
using H ° and S °
N2(g) + 3H2(g)  2NH3(g)
 H ° = –92.38 kJ
 S ° = –198.4 J/K
 G ° = H ° – TS°
 G ° = –92.38 kJ – (298 K)(–198.4 J/K)
 G ° = –92.38 kJ + 59.1 kJ = –33.3 kJ
 So the reaction is spontaneous at 25 °C
Step 3. Calculate G ° for the reaction at
500 °C using H ° and S °.
 T = 500 °C + 273 = 773 K
 H ° = – 92.38 kJ
 S ° = – 198.4 J/K
 G ° = H ° – TS °
 G ° = –92.38 kJ – (773 K)(–198.4 J/K)
 G ° = –92.38 kJ + 153 kJ = 61 kJ
 So the reaction is NOT spontaneous at 500 °C
Ex. 10 Does this answer make sense?
 G ° = H ° – TS °
 H ° = –92.38 kJ
 S ° = –198.4 J/K
 Since both H ° and S ° are negative
 At low temperature
 G ° will be negative and spontaneous
 At high temperature
 TS ° will become a bigger positive number and
 G ° will become more positive and thus
eventually, at high enough temperature, will
become nonspontaneous
Ex. 11 Calculating K from G°
Calculate K at 25 °C for the Haber process
N2(g) + 3H2(g)  2NH3(g)
 G ° = –33.3 kJ/mol = –33,300 J/mol
Step 1 Solve for exponent
Step 2 Take e x to obtain K

 G  / RT 13.4 5
K e e  7  10
Large K indicates NH3 favored at room temp.
Your Turn!
Calculate the equilibrium constant for the
decomposition of water at 298 K given
G ° = 474.4 kJ mol.
A. 1.47 × 10-83
B. 1.21 x 100
C. 7 × 10-84
D. 1.17 × 1041
Ex. 12 Calculating K from G°, First
Calculate G°
Calculate the equilibrium constant at 25 °C for
the decarboxylation of liquid pyruvic acid to
form gaseous acetaldehyde and CO2.
O O
C OH C + CO2
H3C C H3C H
Ex. 12 First Calculate ∆G° from ∆Gf°
Compound ∆Gf°, kJ/mol

CH3COH –133.30
CH3COCOOH –463.38
CO2 –394.36
Ex. 12 Next Calculate Equilibrium
Constant
K = 1.85  1011
Temperature Dependence of K
 G ° = –RT lnK = H ° – TS °
 Rearranging gives
 Equation for line

 Slope = –H °/RT
 Intercept = S °/R
 Also way to determine
K if you know H ° and S °
Ex. 12 Calculate K given H ° and S °
Calculate K at 500 °C for Haber process
N2(g) + 3H2(g)  2NH3(g)
 Given H ° = –92.38 kJ and
S ° = –198.4 J/K
Assume that H ° and S ° do not change with T
ln K = + 14.37 – 23.86 = –9.49

K = e–9.49 = 7.56 × 10–5
Bond Energy
 Amount of energy needed to break chemical
bond into electrically neutral fragments
 Useful to know
 Within reaction
 Bonds of reactants broken
 New bonds formed as products appear
 Bond breaking
 First step in most reactions
 One of the factors that determines reaction rate
 e.g. N2 very unreactive due to strong NN bond
Bond Energies
 Can be determined spectroscopically for simple
diatomic molecules
 H2, O2, Cl2
 More complex molecules, calculate using
thermochemical data and Hess’s Law
 Use H °formation enthalpy of formation
 Need to define new term
 Enthalpy of atomization or atomization energy,
Hatom
 Energy required to rupture chemical bonds of one
mole of gaseous molecules to give gaseous atoms
Determining Bond Energies
 Ex. CH4(g)  C(g) + 4H(g)
 H atom = energy needed to break all bonds in
molecule
 H atom /4 = average bond C—H dissociation
energy in methane
 D = bond dissociation energy
 Average bond energy to required to break all bonds in
molecule
 How do we calculate this?
 Use H °f for forming gaseous atoms from elements in
their standard states
 Hess’s Law
Determining Bond Energies
 Path 1: Bottom
 Formation of CH4 from its elements = H°f
 Path 2: Top 3 step path
 Step 1: break H—H bonds
 Step 2: break C—C bonds
 Step 3: form 4 C—H bonds
1. 2H2(g)  4H(g) H °1 = 4H °f (H,g)
2. C(s)  C(g) H °2 = H °f (C,g)
3. 4H(g) + C(g)  CH4(g) H °3 = –H °atom
2H2(g) + C(s)  CH4(g) H ° = H °f(CH4,g)
Calculating H atom and Bond Energy
H °f(CH4,g) = 4H °f(H,g) + H °f(C,g) – H atom
 Rearranging gives
H atom= 4H °f(H,g) + H °f(C,g) – H °f(CH4,g)
 Look these up in Table 18.3, 6.2 or appendix C
H atom= 4(217.9kJ/mol) + 716.7kJ/mol –
(–74.8kJ/mol)
H atom= 1663.1 kJ/mol of CH4
= 415.8 kJ/mol of C—H bonds

Table 18.4 Some Bond Energies
Using Bond Energies to Estimate H ˚f
 Calculate H ˚f for CH3OH(g) (bottom reaction)
 Use four step path
 Step 1: break C—C bonds
 Step 2: break H—H bonds
 Step 3: break O—O bond
 Step 4: form 4 C—H bonds
Using Bond Energies
H °f(CH3OH,g) =
H ˚f (C,g) + 4H ˚f (H,g) +  H ˚f (O,g)
– H atom (CH3OH,g)
 H °f(C,g) + 4H ˚f (H,g) + H ˚f (O,g)
= [716.7 +(4 × 217.9) + 249.2] kJ = +1837.5 kJ
 H atom (CH3OH,g) = 3DC—H + DC—O + DO—H
= (3 × 412) + 360 + 463 = 2059 kJ
 H °f(CH3OH,g) = +1837.5 kJ – 2059 kJ = –222 kJ
 Experimentally find  H ˚f (CH3OH,g) = –201
kJ/mol
 So bond energies give estimate within 10% of actual

CH 18

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CH 18

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Chapter 18

Chemistry, 7th Edition

 or for chemical reaction

 E + energy into system

q + Heat absorbed by system Esystem increases

 Since P and T are constant

Step 3: Calculate E using

Bigger than most, but still small

Note: Assumes that volumes of solids and

 Volumes assuming each coefficient equal

 For chemical reactions or physical processes

 For gases, entropy increases as volume increases

Higher positional Lower positional

Moisture condenses on a cool window

A drop of food coloring added to a glass

Multiplying both sides by T we get

Which of these statements is true?

S ° = 56.5 J/K + 566.1 J/K – (51.00 J/K + 391.8 J/K )

Al2O3(s) + 3H2(g)  2Al(s) + 3H2O(g)

H ° = 0.0 kJ – 725.4 kJ – 0.00 kJ – (– 1669.8 kJ)

Step 2: Calculate S °  see Example 3

 Energy to form 1 mole of substance from its

G° = 0.0 kJ – 685.8 kJ – 0.00 kJ

G ° =(–246.1 – 112.4) kJ/mol

 This important expression allows for any

For T > 334 K, G < 0 and reaction is spontaneous

Step 1 Solve for exponent

Step 2 Take e x to obtain K

Compound ∆Gf°, kJ/mol

 Equation for line

ln K = + 14.37 – 23.86 = –9.49

= 415.8 kJ/mol of C—H bonds

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