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8. Ionic Crystals; Born-Haber Cycle

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Session Overview

Modules Bonding and Molecules
Concepts ionic bonding: octet stability by electron sharing, energy of ion pairs vs. ion lattice, and properties of ionic crystals, enthalpy of reaction: Hess's law, Born-Haber cycle
Keywords Born exponent, cation, anion, covalent bond, ionic bond, valence shell electron pair repulsion model (VSEPR), interionic separation, crystal array, omnidirectional bond, unsaturated bond, Avogadro's number, electrostatic energy, ionic solid, Madelung constant, melting point, boiling point, electrical insulator, hardness, brittle, soluble, polar solvent, noble gas, ionic liquid, photon, transparency, binding energy, hybridized bond, elasticity, enthalpy, ionization energy, sublimation, electron affinity, lattice energy, bonding electron, nonbonding electron, molecular architecture
Chemical Substances sodium chloride (NaCl), manganese (Mn), sodium (Na), potassium (K), silver iodide (AgI), neon (Ne), magnesium oxide (MgO), aluminum (Al), aluminum oxide (Al2O3), cryolite (Na3AlF6)
Applications design of thermal abrasion resistance materials, design of inert anode materials

Prerequisites

Before starting this session, you should be familiar with:

  • Octet stability and what it means in terms of shell filling; ionic bonding and its formation as a result of Coulombic attraction between a cation and an anion (Session 7)

Looking Ahead

Prof. Sadoway discusses the shortcomings of ionic bonding and Lewis's concept of shell filling by electron sharing including the Lewis dot notation (Session 9); and returns to the valence shell electron pair repulsion (VSEPR) model in Session 11: The Shapes of Molecules.

Learning Objectives

After completing this session, you should be able to:

  • Describe quantitatively the energetic factors and characteristics involved in the formation of an ionic bond.
  • Understand the valence shell electron pair repulsion (VSEPR) model.
  • Sketch the potential energy as a function of inter-ionic separation.
  • List the properties of ionic crystals, and relate them to the lattice energy.
  • Explain what features of a crystal are reflected in its Madelung constant.
  • Understand that the energy change in chemical reactions is path independent.
  • Define electron affinity.

Reading

Archived Lecture Notes #1 (PDF), Sections 6, 7

Archived Lecture Notes #2 (PDF), Sections 1, 2

Book Chapters Topics
[A&E] 7.3, "Energetics of Ion Formation." Ionization energies; electron affinities; electronegativity
[A&E] 8.1, "An Overview of Chemical Bonding." Review of chemical bonding; comparison of covalent and ionic bonds
[A&E] 8.2, "Ionic Bonding." Electrostatic attraction and repulsion; potential energy at the bond distance
[A&E] 8.3, "Lattice Energies in Ionic Solids." Calculating lattice energies; the relationship between lattice energies and physical properties; the Born-Haber cycle; predicting the stability of ionic compounds
[A&E] 12.5, "Correlation between Bonding and the Properties of Solids." Ionic solids; molecular solids; covalent solids; metallic solids

Lecture Video

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Resources

Lecture Slides (PDF - 1.2MB)

Transcript (PDF)

Lecture Summary

In this lecture, Prof. Sadoway discusses the following topics:

  • Energetics of pair attractions
    • Energy gained upon converting a gas of ion pairs to a crystal array
    • Attraction energy
    • Madelung's constant
  • Transparent materials
  • Hess's Law – energy change in a chemical reaction is path independent
  • Hybridized bonding in molecules

This lecture also introduces the valence shell electron pair repulsion (VSEPR) model, properties of covalent (saturated, directional) and ionic bonds, rules for determining molecular shapes, and the classification of each electron as a bonding electron (B) or a nonbonding electron (NB). Equal bond energies imply equal spatial disposition, and the electronic structure dictates bond disposition, which dictates molecular architecture.

Homework

Problems (PDF)

Solutions (PDF)

Textbook Problems

[A&E] Sections Conceptual Numerical
[A&E] 8.3, "Lattice Energies in Ionic Solids." 7, 9 4, 5, 6
[A&E] 8.4, "Lewis Electron Dot Structures." 2 none
[A&E] 8.5, "Lewis Structures and Covalent Bonding." 3 7, 9, 13, 18
[A&E] 8.6, "Exceptions to the Octet Rule." 2 4
[A&E] 9.1, "Predicting the Geometry of Molecules and Polyatomic Ions." none 1, 5

For Further Study

Textbook Study Materials

See the [A&E] companion website from Pearson for PowerPoint outlines of each chapter, plus online quizzes, interactive graphs and 3D molecular animations:

Supplemental Readings

Buy at Amazon Born, Max. My Life: Recollections of a Nobel Laureate. New York, NY: Scribner, 1978. ISBN: 9780684156620.

Buy at Amazon Born, Max. Physics in My Generation. New York, NY: Springer-Verlag, 1969.

Buy at Amazon Born, Max. Atomic Physics. New York, NY: Hafner Publications, 1970. ISBN: 9780486659848.

Buy at Amazon Stoltzenberg, Dietrich. Fritz Haber: Chemist, Nobel Laureate, German, Jew. Philadelphia, PA: Chemical Heritage Press, 2004. ISBN: 9780941901246.

Buy at Amazon Charles, Daniel. Master Mind: The Rise and Fall of Fritz Haber, the Nobel Laureate who Launched the Age of Chemical Warfare. New York, NY: Ecco, 2005. ISBN: 9780060562724.

People

Fritz Haber - 1918 Nobel Prize in Chemistry

Charles Hall

Paul Heroult

Germain Hess

Erwin Madelung

Max Born - 1954 Nobel Prize in Physics

Other OCW and OER Content

Content Provider Level Notes
5.111 Principles of Chemical Science MIT OpenCourseWare Undergraduate (first-year)

Lecture 10: Covalent Bonds

Lecture 11: Lewis Structures

Lecture 12: Ionic Bonds

Chemical Bonds HyperPhysics: Chemistry High school  

 

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