Petrucci • Harwood • Herring • Madura

GENERAL
Ninth
Edition

CHEMISTRY
Principles and Modern Applications

Chapter 12: Liquids, Solids, and

Intermolecular Forces
Philip Dutton
University of Windsor, Canada
Prentice-Hall © 2007
Petrucci • Harwood • Herring • Madura

GENERAL
Ninth
Edition

CHEMISTRY
Principles and Modern Applications

Chapter 19: Spontaneous Change:

Entropy and Free Energy
Philip Dutton
University of Windsor, Canada
Prentice-Hall © 2007

Slide 1 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 19-1 Spontaneity: The Meaning of
Spontaneous Change

Slide 2 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Spontaneous Process

¨ A process that occurs in a system left to itself.

• Once started, no external actions is necessary to make
the process continue.
¨ A non-spontaneous process will not occur without
external action continuously applied.

4 Fe(s) + 3 O2(g) → 2 Fe2O3(s)

H2O(s) H2O(l)

Slide 3 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 19-2 The Concept of Entropy

¨ Entropy, S.
• The greater the number
of configurations of the
microscopic particles
among the energy
ΔU = ΔH = 0 levels in a particular
system, the greater the
entropy of the system.

ΔS > 0 spontaneous

Slide 4 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Entropy Change

qrev
ΔS =
T
For changes occurring
at constant temperature

Slide 5 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Absolute Entropies

¨ Third law of thermodynamics.

• The entropy of a pure perfect crystal at 0 K is zero.
¨ Standard molar entropy.
• Tabulated in Appendix D.

ΔS = [ SnpS°(products) - SnrS°(reactants)]

Slide 6 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Entropy as a Function of Temperature

Slide 7 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Vibrational Energy and Entropy

Slide 8 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 19-4 Criteria for Spontaneous Change:
The Second Law of Thermodynamics.

ΔStotal = ΔSuniverse = ΔSsystem + ΔSsurroundings

The Second Law of Thermodynamics:

ΔSuniverse = ΔSsystem + ΔSsurroundings > 0

All spontaneous processes produce an

increase in the entropy of the universe.

Slide 9 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Free Energy and Free Energy Change
¨ Hypothetical process:
• only pressure-volume work, at constant T and P.

qsurroundings = -qp = -ΔHsys

¨ Make the enthalpy change reversible.

• large surroundings, infinitesimal change in temperature.
¨ Under these conditions we can calculate entropy.

Slide 10 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Free Energy and Free Energy Change
For the universe:
TΔSuniv. = TΔSsys – ΔHsys = -(ΔHsys – TΔSsys)

-TΔSuniv. = ΔHsys – TΔSsys

For the system:

G = H - TS

ΔG = ΔH - TΔS

ΔGsys = - TΔSuniverse

Slide 11 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Criteria for Spontaneous Change
ΔGsys < 0 (negative), the process is spontaneous.
ΔGsys = 0 (zero), the process is at equilibrium.
ΔGsys > 0 (positive), the process is non-spontaneous.

J. Willard Gibbs
1839-1903

Slide 12 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Table 19.1 Criteria for Spontaneous
Change

Slide 13 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 19-5 Standard Free Energy Change, ΔG°

¨ The standard free energy of formation, ΔGf°.

• The change in free energy for a reaction in which a
substance in its standard state is formed from its
elements in reference forms in their standard states.

¨ The standard free energy of reaction, ΔG°.

ΔG° = [ Snp ΔGf°(products) - Snr ΔGf°(reactants)]

Slide 14 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 19-8 Coupled Reactions

¨ In order to drive a non-spontaneous reactions we

changed the conditions (i.e. temperature or
electrolysis).
¨ Another method is to couple two reactions.
• One with a positive ΔG and one with a negative ΔG.
• Overall spontaneous process.

Slide 15 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 Smelting Copper Ore

Δ
Cu2O(s) → 2 Cu(s) + ½ O2(g) ΔG°673K = +125 kJ

Non-spontaneous reaction: Cu2O(s) → 2 Cu(s) + ½ O2(g) +125 kJ

Spontaneous reaction: C(s) + ½ O2(g) → CO(g) -175 kJ

Cu2O(s) + C(s) → 2 Cu(s) + CO(g) -50 kJ

Spontaneous reaction!

Slide 16 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 !"#$%&'( Coupled Reactions in
Biological Systems

Slide 17 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

 The Biological Standard State

ADP3- + HPO42- + H+ → ATP4- + H2O

ΔG° = -9.2 kJ mol-1

aATPaH2O
ΔG = ΔG° + RT ln
aADPaPiaH3O+

But [H3O+] = 10-7 M not 1.0 M.

ΔG = -9.2 kJ mol-1 + 41.6 kJ mol-1

= +32.4 kJ mol-1 = ΔG°'
ADP to ATP is not spontaneous and biological systems use glucose.
Slide 18 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007
 Focus On Coupled Reactions in
Biological Systems

Glucose → 2 lactate + 2 H+ -218 kJ

2 ADP3- + 2 HPO42- + 2 H+ → 2 ATP4- + 2 H2O +64 kJ

2 ADP3- + 2 HPO42- + glucose → 2 ATP4- + 2 H2O + 2 lactate -153 kJ

Slide 19 of 44 General Chemistry: Chapter 19 Prentice-Hall © 2007

12-1 Intermolecular Forces and Some
Properties of Liquids
♦ Cohesive Forces
• Intermolecular forces between like molecules.
♦ Adhesive Forces
• Intermolecular forces between unlike molecules.

♦ Surface Tension γ
• Energy or work required to increase the surface area
of a liquid.
♦ Viscosity η
• A liquids resistance to flow
Intermolecular Forces
Intermolecular Forces
12-2 Vaporization of Liquids:
Vapor Pressure
ΔHvap = Hvapor – Hliquid = - ΔHcondensation
 Boiling Point

Mercury Vapor Pvap Pvap Pvap

manometer pressure independent independent dependent on
of liquid of Vliq of Vgas T
Vapor Pressure and Boiling Point
 The Critical Point

Slide 10 of 54 General Chemistry: Chapter 12 Prentice-Hall © 2007

 12-3 Some Properties of Solids
Freezing Point Melting Point

ΔHfus(H2O) = +6.01 kJ/mol

Vapor Boils at Low Pressure
Sublimation

ΔHsub = ΔHfus + ΔHvap

= -ΔHdeposition
 12-4 Phase Diagrams
Iodine
 Phase Diagrams
Carbon dioxide
Supercritical Fluids
Decaffeination with Supercritical CO2
Water
Interpreting a Phase Diagram

Prentice-Hall © 2007
 12-5 Van der Waals Forces

♦ Instantaneous dipoles.
• Electrons move in an orbital to cause a polarization.
♦ Induced dipoles.
• Electrons move in response to an outside force.
♦ Dispersion or London forces.
• Instantaneous dipole – induced dipole attraction.
• Related to polarizability.
Phenomenon of Induction
Instantaneous and Induced Dipoles

< 10 kJ/mol
Dipole Dipole Interactions

5 to 20 kJ/mol
 Electrostatic Potential Maps

Slide 26 of 54 General Chemistry: Chapter 12 Prentice-Hall © 2007

12-6 Hydrogen Bonding

15 to 40 kJ/mol
Hydrogen Bonding
Hydrogen Bonding in HF(g)
 Hydrogen Bonding in Water

around a molecule in the solid in the liquid

Other examples of H-Bonds
12-7 Network Covalent Solids and
Ionic Solids
Other Carbon Allotropes
Interionic Forces
12-8 Crystal Structures
Unit Cells in the Cubic Crystal System
Holes in Crystals
Face Centered Cubic Unit Cell
Hexagonal Close Packed (hcp)
Counting Cell Occupancy
Cesium Chloride
Atomic Radii from Crystal Structures
Sodium Chloride