5.111SC | Fall 2014 | Undergraduate

Principles of Chemical Science

Unit V: Chemical Kinetics

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In Unit V, we consider the speed, or rate, of chemical reactions. Thermodynamics tells us if a particular reaction will be spontaneous, but not how fast it will occur. Thus, both thermodynamics and kinetics are necessary for understanding chemical reactions. By the end of this unit, viewers should be able to analyze kinetics data to determine the order of the reaction with respect to any reagent, write simple reaction mechanisms, and determine if a mechanism is consistent with experimental data. They should be familiar with the steady-state approximation, rate-determining steps, and activation energy barriers. Viewers should be able to describe the properties of a catalyst and be familiar with terms associated with enzyme catalysis.

Image excerpted from Lecture 30 Notes Lecture 30: Kinetics: Rate Laws

Image excerpted from Lecture 31 Notes Lecture 31: Nuclear Chemistry and Chemical Kinetics

Image excerpted from Lecture 32 Notes Lecture 32: Kinetics: Reaction Mechanisms

Image excerpted from Lecture 33 Notes Lecture 33: Kinetics and Temperature

Image excerpted from Lecture 34 Notes Lecture 34: Kinetics: Catalysts

Image excerpted from Lecture 35 Notes Lecture 35: Applying Chemical Principles

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Topics

Image excerpted from Lecture 30 Notes 

  1. Introduction to Kinetics
    1. Rates of Chemical Reactions
    2. Rate Expressions and Rate Laws

Lecture Video

Whether a reaction will go forward spontaneously depends on the thermodynamics. How fast a reaction goes depends on the kinetics. Decomposition of a molecule might be thermodynamically favorable (the molecule is unstable) but kinetically slow (the molecule is inert). In thinking about chemical reactions, rate matters. This lecture provides an introduction to kinetics and shows one of the coolest reactions known: the oscillating clock reaction. Watch as colors change quickly as different steps in the reaction become spontaneous.

Lecture Notes

Notes for Lecture 30 (PDF)

Clicker Questions

Lecture 30 Clicker Questions (PDF)

Textbook Reading

TOPICS 5th EDITION 4th EDITION
Reaction Rates Sections 14.1–14.5 Sections 13.1–13.5

Problems and Solutions

Problems for Lecture 30 (PDF)

Solutions for Lecture 30 (PDF)

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Topics

Image excerpted from Lecture 31 Notes 

  1. Nuclear Chemistry: Radioactive Decay
  2. Chemical Kinetics
    1. Second Order Integrated Rate Laws
    2. Relationship Between k and K
    3. Elementary Steps and Molecularity

Lecture Video

Professor Drennan recites Mala Radhakrishnan’s poem “Days of Our Half-Lives” as she provides an introduction to nuclear chemistry. With nuclear chemistry as a great example of a first order process, the lecture also goes on to talk about second order reactions. Chemical equilibrium is also revisited as the class considers the relationship between equilibrium constants and rate constants.

Lecture Notes

Notes for Lecture 31 (PDF)

Clicker Questions

Lecture 31 Clicker Questions (PDF)

Textbook Reading

TOPICS 5th EDITION 4th EDITION
Second-Order Integrated Rate Laws Section 14.6 Section 13.6
Measuring the Radiation of Nuclear Decay Section 17.7 Section 17.7

Problems and Solutions

Problems for Lecture 31 (PDF)

Solutions for Lecture 31 (PDF)

Acknowledgement

Mala Radhakrishnan’s poem “Days of Our Half-Lives” in Atomic Romances, Molecular Dances is used with permission.

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Topics

Image excerpted from Lecture 32 Notes 

  1. Investigating Reaction Mechanisms

Lecture Video

Chemists experimentally determine rate laws and then use that experimental information to propose reaction mechanisms. In an overall reaction, some steps will be fast and others slow. One step can be so slow that it governs the overall rate of the reaction; it is the rate-determining step. Learn how to predict reaction mechanisms using the steady-state approximation as well as information about fast and slow steps.

Lecture Notes

Notes for Lecture 32 (PDF)

Clicker Questions

Lecture 32 Clicker Questions (PDF)

Textbook Reading

TOPICS 5th EDITION 4th EDITION
Reaction Mechanisms Sections 14.7–14.8 Sections 13.7–13.8
Rates and Equilibrium Section 14.10 Section 13.10

Problems and Solutions

Problems for Lecture 32 (PDF)

Solutions for Lecture 32 (PDF)

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Topics

Image excerpted from Lecture 33 Notes 

  1. Effect of Temperature on Reaction Rates
  2. The Reaction Coordinate and the Activation Complex

Lecture Video

Using liquid nitrogen, we observe that lowering the temperature slows reaction rates. The concept of activation energy is introduced; there is always some energy needed when two molecules come together that allows them to react. Only molecules that have this critical energy, and can overcome this activation energy barrier, will react and go on to product. Lower temperature means that fewer molecules with have this critical amount of energy.

Lecture Notes

Notes for Lecture 33 (PDF)

Clicker Questions

Lecture 33 Clicker Questions (PDF)

Textbook Reading

TOPICS 5th EDITION 4th EDITION
Models of Reactions Sections 14.11–14.13 Sections 13.11–13.13

Problems and Solutions

Problems for Lecture 33 (PDF)

Solutions for Lecture 33 (PDF)

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Topics

Image excerpted from Lecture 34 Notes 

  1. Introduction to Catalysis
  2. Types of Catalysts
  3. Catalysts of Life and Enzyme Catalysis

Lecture Video

A catalyst is a substrate that speeds up a reaction without being consumed. Catalysts lower the activation energy barrier for a reaction without changing the equilibrium constant. In this lecture, catalysts of different types are introduced, including Nature’s catalysts, enzymes. We also hear from Chemist Jingnan Lu about why knowledge of kinetics is important for the development of biofuels.

Lecture Notes

Notes for Lecture 34 (PDF)

Clicker Questions

Lecture 34 Clicker Questions (PDF)

Textbook Reading

TOPICS 5th EDITION 4th EDITION
Catalysis Section 14.14 Section 13.14
Living Catalysts: Enzymes Section 14.16 Section 13.16

Engineering Enzyme Pathways for Biofuel Development

Jingnan Lu’s research focuses on converting carbon dioxide, an environmental pollutant, into biofuel. Jingnan explains how she engineers a carbon-storing microorganism into a biofuel production pathway. She discusses kinetic parameters she is able to change, such as using a more efficient enzyme (a catalyst) and increasing substrate concentration to speed up the production of biofuels.

Jingnan Lu’s Personal Story

Jingnan Lu describes how she overcame the challenge of learning English as a teenager when she moved to the United States from China and realized from a research experience that she can use science to help people.

Problems and Solutions

Problems for Lecture 34 (PDF)

Solutions for Lecture 34 (PDF)

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Topics

Image excerpted from Lecture 35 Notes 

  1. Review of Course Material

Lecture Video

In the final clicker competition of the semester, students are challenged to explain a biological process using the basic chemical principles that they have learned over the course of the semester. The process is the biological fixation of the greenhouse gas carbon dioxide by a micro-organism. Match your wits and knowledge and see how you score compared to the winning group of MIT students.

Lecture Notes

Notes for Lecture 35 (PDF)

Clicker Questions

Lecture 35 Clicker Questions (PDF)

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