3.091SC | Fall 2010 | Undergraduate

Introduction to Solid State Chemistry

Amorphous Materials

22. Engineering Glass Properties; Introduction to Kinetics

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Session Overview

Modules Amorphous Materials, Reactions and Kinetics
Concepts

Amorphous Materials

engineering glasses: network formers, network modifiers, and intermediates, properties of silicate glasses

Reactions and Kinetics

introduction to kinetics: activation energy, the rate equation, and the Arrhenius equation, radiocarbon dating

Keywords

Amorphous Materials

thermal shock, glass, silicate glass, network former, network modifier, solidification, molar volume, coefficient of thermal expansion, melting point, glass transition temperature, quenching, excess volume, processing temperature, fluidity, bridging oxygen, terminal oxygen, index of refraction, atomic mobility, rate of cooling, viscosity, lehr, network connectivity, annealing, strain, tempering, free volume, ion exchange, toughness, hardness

Reactions and Kinetics

law of mass action, chemical kinetics, rate of conversion, species concentration, rate of reaction, products, reactants, conservation of mass, kinetic theory, order of reaction, rate constant, rate equation, activation energy, Arrhenius equation, activated complex, Maxwell-Boltzmann, reaction coordinate diagram, radiocarbon dating, Shroud of Turin, radioactive decay, half-life, barrier energy, reaction mechanism, thermal promotion

Chemical Substances

Amorphous Materials

silicate glass (SiO2), sodium oxide (Na2O), calcium oxide (CaO), magnesium oxide (MgO), borate glass (B2O3), aluminum oxide (Al2O3), potassium oxide (K2O), potassium chloride (KCl)

Reactions and Kinetics

sodium azide (NaN3), nitrogen gas (N2), sodium (Na), potassium nitrate (KNO3), carbon monoxide (CO), chlorine gas (Cl2), phosgene gas (COCl2)

Applications

Amorphous Materials

automobile windshields, Pyrex, lead crystal, windows, glass cookware and labware, case-hardened/carburized/tool steel

Reactions and Kinetics

automobile airbags, phosgene gas, radiocarbon dating

Prerequisites

Before starting this session, you should be familiar with:

  • Properties, composition, and manufacturing of glass (Session 21)
  • The shapes of molecules and factors affecting their mobility (Session 8 through Session 12)
  • How to write chemical equations (Session 2)
  • The distribution of energies per the Maxwell-Boltzmann curve (Session 14)

Looking Ahead

The solution hardening processes (chemically toughened glass, carburized steel) described in this session involve diffusion along concentration gradients, as quantified in Session 23 and Session 24.

Learning Objectives

After completing this session, you should be able to:

  • Describe how to design glasses with the following properties: thermal shock resistance; low working temperature; high yield stress; high index of refraction; high optical clarity.
  • Explain how intermediates act as network formers in some mixes and modifiers in others.
  • Contrast thermal strengthening of glass with chemical strengthening.
  • Write the rate law for a given chemical reaction, and determine the values of the rate constant k, rate order n, and activation energy Ea from the available data.
  • Explain the effect of temperature on chemical reactions using the Maxwell-Boltzmann distribution.
  • For a multi-step reaction, determine which step is rate-limiting and write the overall rate law.
  • Describe how radioisotope dating works, and calculate the age of artifacts using their 14C content.

Reading

Archived Lecture Notes #7 (PDF)

Archived Lecture Notes #8 (PDF)

Book Chapters Topics
[Saylor] 14.5, “Half-Lives and Radioactive Decay Kinetics.” Half-lives, radioactive decay rates, radioisotope dating techniques
[Saylor] 14.6, “Reaction Rates – A Microscopic View.” Molecularity and the rate-determining step, chain reactions
[Saylor] 14.7, “The Collision Model of Chemical Kinetics.” Activation energy, graphing the energy changes during a reaction, the Arrhenius equation
[JS] 12.2, “Glasses – Noncrystalline Materials.” Network formers, modifiers, and intermediates; commercial silicate glasses; nonsilicate glasses; applications of amorphous solids
[JS] 12.3, “Glass-Ceramics.” Heat treatment and crystallization, mechanical and thermal shock resistance, nucleating agents, glass processing techniques

Lecture Video

Resources

Lecture Slides (PDF)

Lecture Summary

Glasses can be engineered for specific applications by altering their proportions of network formers, network modifiers, and intermediates (e.g. Al2O3), and through careful processing. For example, glass can be strengthened by introducing compressive stress near the surface, by thermal (e.g. tempering) or chemical treatment (e.g. solution hardening).

The next unit covers chemical kinetics, the study of reaction rates and mechanisms. For a generalized reaction system, the rate of change of ci (concentration of species i) is proportional to the instantaneous concentration of ci; the exact values of the rate constant k and the rate order n are typically determined by experiment. The rate constant can be increased by raising the temperature and/or lowering the activation energy. Radiocarbon dating, although not a chemical reaction, has a first-order rate law, resulting in a constant decay rate over time.

Homework

Problems (PDF)

Solutions (PDF)

MATDL VirtualDL Lessons 1-4

Textbook Problems

[saylor] Sections Conceptual Numerical Application
[Saylor] 14.2, “Reaction Rates and Rate Laws.” none 5, 6 none
[Saylor] 14.6, “Reaction Rates – A Microscopic View.” 4 3 none
[Saylor] 14.7, “The Collision Model of Chemical Kinetics.” 1 1, 4, 5 none
[Saylor] 14.9, “End-of-Chapter Material.” none none 5

For Further Study

Supplemental Readings

Libby, Willard F. Radiocarbon Dating. Chicago, IL: University of Chicago Press, 1969.

People

Svante Arrhenius1903 Nobel Prize in Chemistry

Willard Libby1960 Nobel Prize in Chemistry

Culture

Chambers, Joe, and Willie Chambers. “Time Has Come Today.” The Time Has Come. Performed by The Chambers Brothers. Columbia Records, 1967.

Other OCW and OER Content

Content Provider Level Notes
Fracture of Glass DoITPoMS Undergraduate  
5.60 Thermodynamics and Kinetics MIT OpenCourseWare Undergraduate (elective) Lecture 30: Introduction to Reaction Kinetics

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Course Info

As Taught In
Fall 2010
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Course Introduction
Exams with Solutions
Lecture Notes
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Problem Sets with Solutions
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