Chem 131C: Thermodynamics and Chemical Dynamics

Video Lectures

Displaying all 27 video lectures.
Lecture 1
Syllabus, Homework, & Lectures
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Syllabus, Homework, & Lectures
Recorded on April 11, 2012.

Slide Information
00:20 - Introduction
00:32 - Curvature of the Conical Intersection Seam: An Approximate Second-Order Analysis
01:15 - Announcements
02:24 - Syllabus
13:50 - Lectures
15:58 - Results
17:41 - More Information about Lecture Format ("I use powerpoint...")
18:47 - Example of Lecture Format
19:23 - Each Week-Three Inputs (Lecture Format)
21:36 - What Are We Going to Learn This Quarter?
25:50 - What's in this Lecture?
25:58 - Quantum Mechanics is Discovered (Timeline)
26:20 - Pioneers in Quantum Mechanics (Timeline)
31:26 - James Clerk Maxwell
31:44 - Maxwell Invented Free Color Photography
31:57 - First color photograph Example
32:25 - Ludwig Boltzmann
33:11 - Boltzmann's Grave in Vienna
33:23 - Willard Gibbs:
35:05 - Grove Street Cemetery:
35:35 - Statistical Mechanics: Why do We Need it?
36:40 - Using Thermodynamics
37:15 - Statistical Mechanics Establishes this Connection
37:54 - The Free Energy of Ammonia
38:32 - "Elements of Statistical Thermodynamics" Book (by Leonard K. Nash)
39:32 - Books to Buy:
40:16 - ...Consider a Molecule Having Evenly Spaced Energy Levels
40:42 - We can approximate its state distribution as shown here:
40:54 - The quantum numbers of these evenly spaced (by hv...)
40:58 - ...now imagine that you have a 3-dimensional array molecules...
42:06 - Now let's add three quanta of energy to these three molecules.
43:30 - Microstate
43:38 - Ten microstates in total:
43:42 - The 10 microstates exist in just three configurations.
44:46 - Examples of Notations (Example II)
45:08 - Examples of Configurations (I, II, III)
45:20 - Counting the Microstates Associated with Each Configuration
49:14 - Formula for Determining Total Number of Microstates
Lecture 2
The Boltzmann Distribution Law
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The Boltzmann Distribution Law
Recorded on April 4, 2012.

Slide Information:
01:48 - About Quiz I
04:17 - The Boltzmann Distribution Law
04:21 - What's in This Lecture?
04:44 - Consider a Harmonic Oscillator-Like State Distribution
05:04 - Now imagine that you have a 3-dimensional array of these "molecules"
06:28 - now let's add three quanta of energy to these three molecules.
06:52 - One option is to put all three quanta into one molecule.
07:40 - We shall refer to ech of these possibilities as a microstate;
07:44 - Notation for Specifying a particular configuration (families of microstates)
08:50 - Configuration Example
09:04 - Configuration Example (I, II, III)
09:59 - Configuration II Example
11:11 - Configuration I Example
14:13 - Configuration III Example
14:41 - Formula - The Number of Microstates, W, for a Particular Configuration
15:09 - Example: Consider a system of eight molecules containing four energy quota...
17:16 - How about 5 quanta in ten "molecules" (example)?
19:07 - How about 5 quanta in ten "molecules" (example II)?
20:27 - Curious: configuration VI is favored by more than 2:1 compared the others...
21:31 - Now what happens as we increase the number of molecules?
22:14 - Flipping a Coin Example
22:55 - Flipping a Coin Outcomes and Possibilities
23:24 - N coin flips, the preference of the system for the most probably configuration increases with N...
27:32 - Question: What does the big "N" stand for on Cornhuskers Stadium?
27:57 - Knowledge of this highly preferred configuration equates to knowledge of the system as a whole!
28:17 - Configuration VI is favored by more than 2:1 compared with any other...
28:21 - ...two ways to find this highly preferred configuration...
28:41 - Knowledge of this highly preferred configuration equates to knowledge of the system as a whole!
29:48 - Consider an isolated (N & Q constant) macroscopic (N large etc.) assembly of N...
31:41 - Graphic Representation
33:28 - Number of Microstates Before and After
35:46 - ...substituting from the expressions for energy defined earlier we have...
37:25 - ...this means that the left and right sides of this equality are constants, call this constant B (beta)
39:31 - The Boltzmann Distribution Law (Formula)
41:45 - Example (Solving for N)
43:07 - Molecular Partition Function, q: Two Versions (Figure)
44:17 - Example: What are the relative populations of the states of a two level system...
47:33 - Example: A certain atom has a threefold degenerate ground level...
52:33 - How much Thermal Energy is in the System? (Figure)

Required attribution: Penner, Reginald Thermodynamics and Chemical Dynamics 131C (UCI OpenCourseWare: University of California, Irvine), http://ocw.uci.edu/courses/chem_131c_thermodynamics_and_chem... [Access date]. License: Creative Commons Attribution-ShareAlike 3.0 United States License. (http://creativecommons.org/licenses/by-sa/3.0/us/deed.en_US).
Lecture 3
Energy and q (The Partition Function).
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Energy and q (The Partition Function).
Recorded on April 6, 2012.

Slide Information
00:19 - Example-A certain atom has a threefold degenerate ground level...
01:02 - Function for Calculating Degeneracy of Energy Levels
01:24 - Sum of Three Energy Levels
03:35 - We need to calculate the thermal energy kT, in units...
04:22 - Energy Level Diagram
07:20 - Example: The four lowest electronic energy levels of atomic C have energies and degeneracies as follows...
07:51 - Equation: Partition Function
08:32 - In this case, q will have four terms - one for each state
08:49 - How to Calculate the Four Terms
09:59 - Example: 9.27 of 14 total states in C...
10:24 - does this makes sense (calculating thermal energy again)
10:56 - Diagram-Electronic States of Carbon
12:53 - now find the fractional population of each level for C...
14:51 - Diagram: ...now, it will be obvious to you that W must depend on energy...
15:45 - Partition Function (W must depend on energy, but how?)
20:03 - Example: the NO molecule has a doubly degenerate excited electronic level...
21:03 - Diagram--Wave Numbers
22:05 - Example - The NO molecule has a doubly degenerate excited electronic level... (continued)
22:40 - Plot (Diagram)
23:38 - Calculating Term Populations
Lecture 4
Entropy
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Entropy
Recorded on April 9, 2012.

Slide Information
00:05 - Intro Slide: Entropy
00:15 - Announcements
01:00 - Quiz I histogram
01:03 - What's in this Lecture?
01:17 - Six things we have learned about Statistical Mechanics
04:17 - Boltzman Distribution Law Diagram and Definition
04:21 - Things we Have Learned About Statistical Mechanics so Far
04:32 - The Boltzmann Distribution Law Formula (Diagram)
06:34 - Formula/Equation Diagram (the average internal energy of each of N molecules)
08:11 - Equation Diagram ("so q contains information about the averge internal energy of our system.")
09:13 - Diagram: (The NO molecule)
10:01 - Graph (b) the electronic contribution to the molar internal energy at 300K.
11:20 - Graph (b) - Evaluating formula
13:58 - (Does formula and solution make sense?)
15:37 - Chart (On p. 429 of your book, three types of ensembles are discussed as follows:)
16:24 - Chart: Microcanonical Ensembles
16:34 - About Microcanonical Ensembles
17:14 - Graph: Example: NO - it's obvious we're talking about one molecule here...
17:54 - Diagram: The Boltzmann Distribution Law in terms of the molecular partition function, q
18:14 - so q asks the question:
18:47 - Canonical Ensembles
19:38 - Well, consider just two molecules, call them a and b...
21:28 - this is the appropriate expression when the N units are distinguishable.
22:48 - Equations for two States (for two distinguishable units, we CAN tell the difference...)
24:35 - Chart: What if we had three molecules, a, b,c...
25:53 - Chart: Ensemble name| What's Constant | Its Partition Function
27:01 - Experiment: Place 100 nickels into a shoes box, all heads up
29:00 - Experiment: 1. Place 100 nickels into a shoes box, ALL heads up...
30:34 - Experiment Conclusion: "For any isolated assembly, we can always predict...
31:00 - For any isolated assembly...
31:55 - Formula: S = k In W
Lecture 5
The Equipartition Theorem
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The Equipartition Theorem
Recorded on April 11, 2012.

Slide Information:
00:21 - Announcements
02:34 - Diagram: in real molecules, the situation is considerably more complex than the Harmonic Oscillator
03:20 - We have a very high density of translational states that are not, in reality...
03:36 - Diagram: these translational states are nested within rotational states
03:58 - Diagrams (many rotational states)
04:23 - ...we can treat each of these energetic manifolds...
05:45 - What's in this Lecture
05:51 - Your book mainly focuses attention on...
07:27 - Graph 5-13: Here is what happens to Cv as a function of T for a diatomic molecule:
10:04 - Graph 5-13 These are the rotation temperature...
11:08 - Graph 5-13 Here is what happens to Cv as a function of T...
11:37 - The Equipartition Theorum
12:10 - The Equipartition Theorum (with diagram)
13:17 - consider the classical Hamiltonian for a I D harmonic oscillator:
14:16 - now you'll recall that the heat capacity...
15:03 - Example: Formula
15:50 - Graph
16:13 - ...this is also the heat capacity for all monoatomic gases...
18:29 - For a linear molecule...
19:41 - Graph (Translation + Rotation)
20:26 - For a nonlinear molecule...
20:54 - What about for higher temperatures?
22:08 - so following through with the predictions of the equipartition theorem...
23:05 - so for a diatomic molecule...
24:24 - Example: Use the equipartition theorem to estimate...
31:18 - Example: Use the equipartition theorum to estimate... (Part B)
34:36 - Example: (Chart) "Use the equipartition theorum to estimate... (Part C)
38:55 - Calculate Each Term
39:18 - We'll Start with Translation...
39:40 - The translational energy of a classical gas molecule is:
40:15 - ...And a quantum mechanical gas has energies given by the particle-in-a-box model.
40:23 - we'll concentrate attention now on ideal monoatomic gases...
41:27 - consider first a monoatomic gas in one dimension.
43:59 - ...now these energies are very closely spaced. Consider, for example, an argon atom in a box...
45:25 - Log Scale
45:52 - ...if these states are quasi-continuous, we can rewrite this summation...
46:54 - so after integration we have...
47:05 - Example "Calculate..."
48:26 - What would...three dimensional cube?
49:36 - ...in terms of...now we calculate its transitional energy.
50:03 - ...and this yields a very simple expression
Lecture 6
The Rotational Partition Function
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The Rotational Partition Function
Recorded on April 13, 2012.

Slide Information
00:05 - Introduction
00:19 - Announcements
01:10 - What's in this Lecture?
01:25 - Neglecting electronic energy levels...
01:41 - Vibration, Rotation, Translation Diagrams
02:19 - but we're lucky. We can treat each of these energetic manifolds separately...
02:51 - ...consider first a monoatomic gas in one dimension...
03:43 - ...so its molecular partition function, q, is:
04:29 - Diagram: Calculation of Ground State and Excited State
05:02 - Diagram: ...looking at the energy spacing of the first 100 states...
05:40 - ...If these states are quasi-continuous, we can rewrite this summation...
06:08 - Diagram: ...so after integration we have:
06:13 - Example: Calculate...
07:22 - Diagram: ...is related to the molecular properties through the mass...
08:28 - In terms of...
09:24 - Diagram: the enthalpy, H...
09:52 - Chart: so we can calculate everything for ideal, monoatomic gases...
11:10 - ...this begins to fulfill the promise of Statistical Mechanics:
11:41 - ...works for all ideal molecules.
11:51 - we have a manifold of rotational states that looks like this...
12:20 - ...and the energies of these states are given by the expression...
14:13 - ...B here has units of joules:
14:53 - ...I'm easily confused, so I try to stick to Joules:
15:26 - so let's work out the expression for...
16:01 - our usual expression for q applies for each of these three orthogonal axes:
16:27 - ...so if we write out this series, here's what it is:
18:36 - when B is expressed in Joules, these are the equations for the rotational partition function that apply:
19:43 - what's a symmetry number?
21:14 - huh? what axis?
21:59 - Ammonia
22:36 - Number of Symmetries:
26:55 - Example: Exercise 17.4a What is the symmetry of:
31:11 - Example: What is the symmetry number of:
Lecture 7
Vibrational Partition Functions
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Vibrational Partition Functions
Recorded on April 16, 2013.

Slide Information
00:05 - Introduction: Vibrational Partition Functions
00:17 - Quiz 2 Histogram
00:41 - The Symmetry Number
04:14 - We also get this answer using my approach.
07:09 - Aluminum Chloride Atoms Example
09:45 - We also get this answer using my approach (Diagram example)
13:03 - What is the symmetry number of: benzene?
15:43 - Estimate the rotational partition function for HCl...
16:09 - Linear molecules lacking a center of symmetry:
16:41 - Estimate the rotational...(formula)
19:12 - Calculate the rotational partition function for methane.
22:02 - Vibrational States
23:23 - ...including the zero point energy, we have...
24:52 - this geometric series has the form:
25:40 - how big is...
28:04 - Example: The triatomic molecule, chlorine dioxide (OCIO) has three vibrational modes...
31:42 - Graph: What Does the T-dependence...look like?
32:45 - Of course, molecular dissociation would occur before...
32:58 - thinking about the partition functions at room temperature, we conclude...
33:24 - What about vibrational energy?
35:13 - E=RT, Equipartition Theorum
36:13 - Here's a midterm exam question from a couple of years ago:
37:55 - Midterm exam solution
39:10 - Equations Page of Exam
41:03 - Calculations and Solution
41:40 - If you are asked: calculate the fractions of molecules for which...
42:25 - Calculations: ("now one mole of...)
44:47 - Example
45:07 - B. Now one mole of...
45:18 - Example (as in 44:47)
Lecture 8
The First Law
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The First Law
Recorded on April 18, 2012.

00:01 - Announcements
00:58 - Example: the triatomic molecule, chlorine dioxide...
04:27 - Plot of equation (Diagram)
09:40 - Thermodynamics
11:39 - Energy
14:24 - In Thermodynamics, we divide the universe into the system...
15:30 - Diagram: Now there are three flavors of systems:
17:32 - Glossary of Thermodynamic Jargon (Types of Equilibrium)
18:15 - We'll be talking about closed systems until further notice.
20:23 - now, we know what heat is, but what is work?
21:28 - let's think about mechanical work...
23:54 - the external force is:
25:57 - now what happens to the volume?
28:27 - Example: Calculate the work required to compress...
30:15 - Our equation for work...
31:45 - Answer: Graphically, this experiment is as shown below...
34:23 - So instead of compressing the piston using the entire mass necessary...
35:01 - Diagram: Step 1
35:18 - Step 2
36:22 - Conclusion:
36:24 - Diagram: so, more steps means less work.
36:52 - In the thermodynamics, a reversible process is any process the direction of which can be reversed by...
38:54 - Diagram: so instead of dividing the mass into two parts...
40:07 - ...add one granule at a time to the piston
40:50 - So as an example...
43:38 - Chart: Summary:
44:37 - Let me just point out that both of these equations conform...
45:47 - other flavors of work...
46:27 - that's w, what about q?
Lecture 9
Law (review) & Adiabatic Processes Part II
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Law (review) & Adiabatic Processes Part II
UCI Chem 131C Thermodynamics and Chemical Dynamics (Spring 2012)
Lec 09. Thermodynamics and Chemical Dynamics -- The First Law (review) & Adiabatic Processes Part II --
View the complete course: http://ocw.uci.edu/courses/chem_131c_thermodynamics_and_chem...
Instructor: Reginald Penner, Ph.D.

License: Creative Commons BY-NC-SA
Terms of Use: http://ocw.uci.edu/info.
More courses at http://ocw.uci.edu

Description: In Chemistry 131C, students will study how to calculate macroscopic chemical properties of systems. This course will build on the microscopic understanding (Chemical Physics) to reinforce and expand your understanding of the basic thermo-chemistry concepts from General Chemistry (Physical Chemistry.) We then go on to study how chemical reaction rates are measured and calculated from molecular properties. Topics covered include: Energy, entropy, and the thermodynamic potentials; Chemical equilibrium; and Chemical kinetics.

Thermodynamics and Chemical Dynamics (Chem 131C) is part of OpenChem: http://ocw.uci.edu/openchem/
This video is part of a 27-lecture undergraduate-level course titled "Thermodynamics and Chemical Dynamics" taught at UC Irvine by Professor Reginald M. Penner.

Recorded on April 23, 2012.

00:07 - In Today's Lecture
00:20 - heat, q, and work, w
00:51 - The Sign Convention
01:16 - Formula and Diagram ("surroundings")
03:19 - Diagram: (heat, q...)
04:11 - Other Flavors of Work:
04:30 - That's w, what about q?
05:27 - Since chemical reactions are typically carried out at a constant...
06:01 - Formula: it's convenient to give the quantities in parentheses a name...
06:33 - "Two forms of.." Calcite and Aragonite photo
06:55 - Problem: The change in U when 1.0 mole of calcite is...
09:43 - The heat capacity is the slope of the U (or H)
11:14 - Problem: a common method for measuring heat capacities...
13:31 - "Heat capacity over constant pressure..." (formulas and solutions)
14:16 - Problem: Find ΔH for the heating of 2.0000 moles...
16:47 - Adiabatic Processes
20:58 - Graph ("Isotherm...")
23:18 - Problem: 2.0 moles of neon that expands adiabatically...

Required attribution: Penner, Reginald Thermodynamics and Chemical Dynamics 131C (UCI OpenCourseWare: University of California, Irvine), http://ocw.uci.edu/courses/chem_131c_thermodynamics_and_chem... [Access date]. License: Creative Commons Attribution-ShareAlike 3.0 United States License. (http://creativecommons.org/licenses/by-sa/3.0/us/deed.en_US).
Lecture 10
Jim Joule
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Jim Joule
Recorded on April 23, 2012.

Index of Topics:
04:13 - In an adiabatic process, q=0 for the process...
07:51 - note: The change in P with an expansion is larger...
08:04 - Isotherm Graph
10:21 - ...now it's not obvious from these equations...
13:27 - About Jim Joule
14:20 - Joule's dad was a brewer
18:24 - Now, you should know that Joule was quite an experimentalist.
20:09 - Diagram: He actually did this experiment quantitatively
21:04 - The quantity of work that must be expended at sea-level...
22:35 - 77255 and California DMV
22:58 - Diagram: ...so in 1853, he did the following experiment
23:44 - So why did Joule expect a temperature change?
23:49 - ...this is the Leonard-Jones 6-12 potential.
27:29 - For an ideal gas, the intermolecular potential...
27:38 - Diagram: At high pressures, you're here.
28:17 - Diagram: At "normal" pressures, you're here.
28:43 - Well, recall that for a real gas, the compressibility factor...
29:09 - The compressibility factor, Z, for a real gas...
30:29 - The compressibility factor, Z, for a real gas reflects these two manifolds...
31:00 - (Diagram) Now, let's do a thought experiment...
32:33 - question: where does the energy come from?
34:03 - 1853: Jim Joule tried to measure...
35:05 - 1854: Joule teams up with a new friend, William Thompson (AKA Lord Kelvin)
36:40 - The Joule-Thompson Effect...
39:43 - so, the Joule-Thompson process occurs at constant enthalpy.
41:12 - but Joule and Thompson were delighted to find that for real gases...
41:52 - Problem: The Joule-Thompson coefficient of air at 300K and 25 atm...
45:13 - "Plot from your Chapter 14...temperature as a function of pressure."
45:54 - note that real gases have two inversion temperatures at each pressure value:
47:13 - The Linde Refrigerator: A mechanical heat pump...
Lecture 11
Midterm I Review
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Midterm I Review
Recorded on April 25, 2012.

00:05 - Announcements
00:28 - Midterm Exam
00:52 - Partition Functions: Enjoy in any of Four Flavors...
01:51 - Example: The NO molecule has a doubly degenerate...
03:24 - Plot It:
05:01 - ...(b) the electronic contribution to the molar internal energy...
05:08 - Equations
05:22 - More Equations
05:38 - (Diagram) The electronic contribution to the molar internal energy...
06:32 - Here's a midterm exam question from a couple of years ago.
08:42 - Which equation(s) do I need?
10:31 - If you are asked: calculate the fraction of molecules...
10:48 - so what were we asked again? B. Now one mole of...
12:06 - The equipartition theorem:
13:33 - now you'll recall that the heat capacity...
14:15 - Formula: the equipartition theorem tells us...
14:17 - the equipartition theorem tells us that translation contributes...
14:41 - Graph: the contribution of molecular translation...
14:55 - Formula: ...this is also the heat capacity for all monoatomic gases
16:01 - For a linear molecule:
16:44 - Graph: translation + rotation
16:53 - For nonlinear molecule:
17:45 - ...well, let's go back to the classical Hamiltonian again.
18:12 - so following through with the predictions of the equipartition...
18:58 - Formula: in the specific case of a diatomic, we get:
19:02 - Formula Graph:
19:10 - Example: Use the equipartition theorem to estimate...
20:05 - Too subjective, let's use this rule of thumb:
Lecture 12
Entropy and The Second Law
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Entropy and The Second Law
Recorded on April 30, 2012.

Slide Information
00:09 - Introduction
01:02 - Announcements
02:11 - where are we (chapter and timeline)?
04:00 - 1st Law: Energy is conserved for an isolated system ΔU = 0.
05:32 - Coin Experiment
06:35 - experiment: conclusion (the most important one so far)
06:51 - Boltzmann postulated that this parameter
07:11 - We can readily apply this equation to this expansion of gas.
08:11 - Now, what is the probability that...
09:05 - Problem: Gas A and Gas B are located in two halves of a container
13:07 - What if instead of the change in entropy...
13:33 - Formula (S =)
14:09 - Calculate the standard molar entropy of neon gas at (a) 200K, (b) 298.15K.
15:53 - Sadi Carnot
17:54 - match the scientist with his country
18:44 - entropy
19:28 - the Carnot Cycle
21:00 - A heat engine extracts work from a temperature gradient
21:41 - The Carnot Cycle (graph)
23:31 - what do we know for sure? (graph continued from Carnot Cycle)
24:18 - how efficient is a heat engine?
25:10 - efficiency (slide at 24:18 continued)
26:24 - how efficient is a Carnot Cycle?
27:28 - let's prove this:
27:52 - now, this pair of (T,V) data points lie on an adiabat:
29:55 - Problem: A heat pump is used to maintain the temperature of a building at 18°C...
32:03 - Problem: What is the entropy change, ΔS, for each of the four steps as a reversible Carnot cycle
32:31 - Diagram: Since S is a state function, we can write:
33:50 - so we represented in a Temperature-Entropy diagram...
34:48 - Since S is a state function, we can write:
Lecture 13
The Carnot Cycle
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The Carnot Cycle
Recorded on May 2, 2012.

Slide Information
00:06 - Introduction: The Carnot Cycle (Lecture 13)
01:02 - Announcements
02:39 - Midterm I Score
07:04 - How Am I Doing (Scores)?
09:37 - Sadi Carnot
10:52 - A heat engine extracts work from a temperature gradient.
11:38 - The Carnot Cycle
12:43 - The Carnot Cycle (Graph)
12:56 - ...ANY process can be decomposed into a large number of Carnot Cycles, so...
14:59 - how efficient is a heat engine?
16:12 - Let's prove this:
16:37 - (Graph) now, this pair of (T,V) data points lie on an adiabat:
20:27 - Problem: What is the entropy change...
21:05 - Since S is a state function, we can write:
24:07 - Formulas: What do we know?
25:55 - so (once again) represented in a Temperature-Entropy...
26:43 - What if one or more steps of the process are irreversible?
30:13 - Rudolf Clausius!
30:50 - T-shirt of Clausius
31:31 - and a more general statement of this is called the Clausius Inequality
31:59 - let's say we transition from state I to state 2...
33:02 - according to the Clausius inequality:
33:42 -The Second Law of Thermodynamics.
33:48 - This equation makes predictions about 3 types of processes:
34:30 - If we consider, in particular, an isolated system...
35:18 - some simple but important examples:
36:55 - some simple but important examples: (II)
39:53- Because S, like U, is a state function, you can add...
40:34 - example - Calculate the entropy change when Ar gas...
Lecture 14
The Gibbs Energy
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The Gibbs Energy
Recorded on May 7, 2012.

Slide Information
02:15 - Introduction (The Gibbs Energy)
03:30 - ...just one of these guys won Nobel Prize - which one?
07:14 - J. Willard Gibbs (1839 - 1903)
10:44 - ...has its own Facebook page
10:57 - buried in the Grove Street cemetery...
11:10 - Map "...Yale campus"
11:37 - Map II
12:10 - we now know some basic thermodynamics concepts and their statistical...
12:52 - Diagram: The system and the surroundings: Three flavors...
13:39 - Diagram: For an isolated system, the entropy of the system increases during a spontaneous process:
14:13 - Diagram: If the system isn't isolated, then the entropy of both the system...
15:03 - For an isolated system, the entropy of the system increases...
16:26 - (cont) q is a conserved quantity...
17:59 - now multiply by...
26:04 - but in chemistry, T is frequently constant...
28:02 - for any process occurring at const. volume...
Lecture 15
Getting to Know The Gibbs Energy
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Getting to Know The Gibbs Energy
Recorded on May 7, 2012.

Slide Information
00:06 - Introduction: Getting to know the Gibbs Energy
00:51 - Announcements:
01:54 - UC Irvine wins NCAA men's volleyball title...
02:19 - Today's tasks
02:42 - Diagram: The system and the surroundings: Three flavors...
04:22 - Formula (spontaneous process: nonisolated system)
04:43 - q is a conserved quantity...
06:09 - Chart: in Friday's lecture...
07:20 - in chemistry, T is frequently constant...
07:55 - let's consider...
09:57 - to achieve the const. volume condition...
11:16 - for any process occurring at const. volume and temperature...
11:50 - In chemistry, it is even more useful to be able to make predictions...
14:17 - for any process occurring at const. pressure...
14:37 - today (and, ahem, last Friday)
14:54 - Chart
15:56 - Graph ("reaction coordinate...")
19:10 - Among these four thermodynamic "potentials"...
20:37 - How does G depend on temperature?
21:00 - conclusions:
21:20 - plot (Gibbs energy and temperature)
22:04 - now, if we substitute from this equation for S...
22:31 - substitute and solve for the derivative
23:30 - now, to go further, note the chain rule that tells us that:
24:40 - (cont) this bad boy is called the Gibbs-Helmholtz Eq.
25:56 - Ok, now how does G depend on pressure...
27:35 - conclusion: Gibbs energies of solids and liquids...
28:18 - Gibbs energies of gases depend strongly on P.
29:20 - Diagram, Formula
30:19 - We define a standard molar Gibbs...
31:08 - Graph, Formula
32:54 - exercise 15, 29b: The change in the Gibbs energy of 25 g...
39:20 - exercise 15.24b: Calculate the standard Gibbs free energy change...
Lecture 16
The Chemical Potential
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The Chemical Potential
Recorded on May 9, 2012.

Slide Information
00:05 - Announcements:
01:41 - Today:
02:40 - The Chemical Potential
02:50 - ...from last Monday, and last Friday:
03:48 - useful | more useful
04:49 - Graph (What does...)
06:28 - How does G depend on temperature?
08:28 - The third law of thermodynamics...
09:50 - Graph
10:32 - We usually consider the temp. dependence of...
11:26 - This bad boy is called the Gibbs-Helmholtz Eq.
12:09 - This bad boy...(cont)
12:43 - Ok, now how does G depend on pressure...
13:54 - but, for phases, like solids and liquids, that are essentially...
14:17 - For ideal gases:
14:47 - conclusion: Gibbs energies of solids and liquids...
15:40 - The T-dependence of the Gibbs function:
17:31 - Now, as we transition (however briefly) into...
18:06 - How do individual reactant and product species...
18:17 - Matter matters: How is G affected by transfers...
18:45 - we haven't said much about open systems that exchange matter:
18:54 - consider the mixing of two isotopes of hydrogen (experiment)
21:10 - since G is an extensive variable
22:09 - we understand the T and P dependencies of G already...
23:57 - we know, after we open the valve, the isotopes will...
26:06 - combining these statements allows us to express...
28:05 - so with the valve open, mixing stops when...
29:33 - The partial molar Gibbs free energy is to..
33:34 - the partial molar Gibbs free energy (cont)
32:44 - The figure from your book really helps...
34:54 - the partial molar Gibbs free energy is too important
39:38 - exercise 16.4b: A mixture of ethanol and water is prepared...
42:34 - Now, we already understand that G is minimized upon an approach to equilibrium...
42:39 - In other words...
44:00 - This is called the Gibbs-Duhem Eq.
44:57 - Graph: This permits an understanding of thermal phase transactions:
45:36 - We already know how this works for, say, water:
49:13 - "the system "selects" the phase of lowest..."
49:24 - now, before we go further, let's clear up some mystery...
Lecture 17
Finding Equilibrium
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Finding Equilibrium
Recorded on May 9, 2012.

Slide Information
00:06 - Introduction Finding Equilibrium
00:21 - today:
00:58 - how do individual reactant and product...
01:22 - what can we deduce about the equilibrium state...
01:35 - we know, after we open the valve...
02:19 - so with the valve open, we showed that the mixing stops when:
03:35 - the chemical potential of species I.
04:47 - really? yes, think about it this way:
07:16 - you should know...
10:18 - Now, we already understand that G is minimized upon...
10:31 - now, before we go further, let's clear up a mystery...
11:25 - let's return to our two gas bulbs:
11:42 - ...let's return to...
12:02 - Diagram: ...we open the valve...
12:31 - Let's calculate G:
14:49 - hey, that's not on the line.
15:51 - now, since we know: ΔG = ΔH - TΔS...
16:38 - Graph
17:59 - resveratrol makes things live longer...what things?
18:22 - resveratrol makes things live longer...what things (photos)
18:46 - it also prevents cancer in mice...
19:20 - and resveratrol is found in red wine.
19:42 - does this have anything to do with thermodynamics?
20:19 - consider this generic isomerization reaction:
21:01 - Example
21:14 - now, our plot of G versus reaction coordinate...
21:46 - we define the slope of this plot at any value...
23:08 - so under conditions of const. P and...
24:58 - "that means there's three types of reactions..."
25:20 - It's a strange word, infrequently used even by chemists...
25:51 - Exergonic
25:57 - ok, but we still have not learned any more about WHERE equilibrium...
26:40 - we define a standard molar Gibbs free energy...
28:19 - ok, now for every value of...
29:45 - in other words...
30:00 - what does this mean?
31:23 - ...refresher on...
Lecture 18
Equilibrium In Action
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Equilibrium In Action
Recorded on May 14, 2012.

Slide Information
00:06 - Introduction - Equilibrium in Action
00:21 - Good job on Quiz 5
01:19 - Today
01:45 - the chemical potential of species...
02:34 - ...think about this way "...Gibbs energy"
03:33 - about μ, you should know...
04:44 - now, before we go further, let's clear up a mystery...
05:31 - Diagram
06:36 - Diagram: This is the positive entropy of mixing - the reason equilibrium exists.
07:39 - Consider this generic reaction ("extent of reaction...)
08:07 - For example, if ΔΕ...
08:30 - now, our plot of G versus reaction coordinate can be recast...
08:48 - we define the slope of this plot at any value of E...
09:47 - so under conditions of const. P and...
10:54: so as a function of E...
11:35 - ok, but we still have not learned any more about WHERE equilibrium is located...
12:43 - we define a standard molar Gibbs free energy...
13:41 - ok, now for every value...
15:10 - In other words...
15:45 - what does this mean?
16:17 - ok, make sense. What about...
17;36 - ...refresher on...("from Chem 1...")
18:54 - returning to our plot, we can say...
20:01 - example: A mixture of CO(g)...
21:41 - Diagram: our reaction looks like this...
24:10 - answer: 2) write an expression for...
24:39 - answer: 3) Calculate K:
25:29 - we know Q and K - what happens?
25:47 - Calculate
26:35 - ...means reaction, at this temperature and with this mix...
27:28 - example: What if, instead of...
28:26 - "we will make a little more methanol...by adding more..."
29:26 - example: Consider the following reaction...
36:48 - answer
39:58 - Henry Louis Le Chatelier (1850 - 1936)
40:19 - (cont) "I let the discovery of the ammonia synthesis slip through my hands..."
42:35 - the most influential persons of the 20th century?
44:17 - where did fixed nitrogen come from before 1920?
45:48 - Le Chatelier's Principle says, for example...that with an increase...
47:22 - Example: Can we determine the relationship between...
47:44 - answer: " we have to calculate the mole fraction of each of these two components..."
Lecture 19
Observational Chemical Kinetics
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Observational Chemical Kinetics
Recorded on May 16, 2012.

00:06 - Introduction: Observational chemical kinetics
00:17 - Henry Louis Chatelier (1850 - 1936)
00:25 - Henry Louis Le Chatelier..."I let the discovery of the ammonia sythesis slip..."
02:21 - Le Chatelier's Principle says, for example, that with an increase in the total...
02:47 - example: Can we determine the relationship between...
03:06 - answer:
06:30 - what about the influence of temperature on K?
08:12 - That's it for Thermodynamics (Topic discussed in Chapter 17)
10:11 - Diagram: where are we?
12:30 - the first chemical subjected to kinetic analysis?
13:12 - some notation & jargon...a stoichiometric reaction...
17:30 - so an elementary reaction is one in which the indicated products...
17:53 - we discussed the extent of reaction...
18:52 - this is not as confusing as it looks. Here's an example...
20:19 - in terms of the extent of reaction...
22:44 - ...for this generation reaction...
23:20 - in terms of the extent of reaction...
23:30 - A rate law relates the concentration of reactants...
28:23 - for stoichiometric reactions, the rate law can not be deduced by inspection.
30:08 - Often, reactions are significantly reversible and both the forward and backward...
32:10 - be reminded that these simple expressions apply only because...
33:35 - what are the units of the rate constant in this case?
34:46 - Method 1. Method of Initial Rates
40:05 - Method 2. Use an integrated rate law.
43:59 - Method 2. (continued) Half-life
45:17 - Graph: (length of half of line is constant.)
45:55 - How do we experimentally determine the rate of law
Lecture 20
The Integrated Rate Law
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The Integrated Rate Law
Recorded on May 18, 2012.

Slide Information
00:09 - Introduction: Integrated Law
00:18 - today...
00:41 - Two types of reactions: take for example the following:
02:19 - stoichiometric
03:12 - for elementary reactions...
04:09 - this is another bimolecular reaction
07:14 - How do we experimentally determine the rate law?
17:48 - Method 3 - Use the integrated rate law to define the half-life of the reaction.
20:30 - vs time for a 2nd order reaction...
21:10 - Method 2: Use an integrated rate law.
21:56 - we've mentioned 1st order and 2nd order reactions...zero order reaction.
23:15 - [A] vs time for a 0 order reaction
23:56 - what kind of reaction does this?
24:36 - the microscopic view of "heterogeneous" catalysis
26:00 - some common integrated rate laws.
27:06 - so in reality, we have three methods for classifying a reaction...
28:30 - Method 3. Measuring the influence of initial reactant concentration...
29:08 - example: what % will decompose after one hour?
30:34 - For reversible reactions, we mentioned...
31:34 - Let's start with the simplest reversible reaction
Lecture 21
The Steady State Approximation
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The Steady State Approximation
Recorded on May 21, 2012.

Slide Information
00:05 - some announcements...
02:37 - today...
03:36 - Svante Arrhenius
04:20 - Arrhenius discovered the greenhouse effect in 1896
04:39 - Article Arrhenius wrote about climate change
05:59 - experimentally we often observe an acceleration...Arrhenius Equation.
10:25 - consecutive reactions are sequences of reactions...
11:49 - an understanding of consecutive reactions is important...
12:44 - consider this generic consecutive reaction:
14:28 - what do these equations predict about [B] versus time?
18:02 - Ok, now let's look at the other possibility:
18:36 - what if...
20:23 - this suggests an expedient method for dealing with...steady-state approximation
25:50 - So - how does this compare with the exact solution?
27:08 - ...Let's first examine a case where we expect that it will work well...
28:40 - now we'll make...
29:16 - now a case where we expect...
30:32 - ...and this is a complete disaster - just as expected.
31:16 - the Steady-State Approximation:
33:43 - REMEMBER: this works if...
33:58 - Irvine Langmuir
35:00 - a page from G.N. Lewis's lab notebook...
35:26 - Photo: How does this work (tungsten bulb)?
37:35 - until 1906, all lightbulbs had carbon filaments. These bulbs were also evacuated
42:20 - the Lindeman-Hinshelwood mechanism...
48:18 - let's apply the steady-state approximation...
Lecture 22
Midterm Exam Review
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Midterm Exam Review
Slide Information

00:05 - some announcements
00:44 - Chem 131 C Quiz 6
03:23 - Youtube search for Chem Lectures
03:34 - chemistry lecture page with YouTube link
03:53 - what does Midterm Exam 2 cover?
04:46 - "what does Midterm Exam 2 cover?"
06:12 - Papers about La Chatellier Principle
06:52 - what was I thinking about? The ammonia synthesis reaction is:
08:10 - what was I thinking about? Iron is a catalyst for this reaction in the Haber-Bosch process...
13:38 - Problem I - entropy and the Carnot cycle (see especially Lecture 13)
14:13 - entropy - statistical definition:
14:32 - Diagram: now, there are three flavors of systems:
15:05 - The Carnot Cycle
15:16 - a heat engine extracts work from a temperature gradient.
15:37 - Graph: The Carnot Cycle
16:22 - Graph: ...ANY process can be decomposed into...
18:12 - Graph: What do we know for sure?
19:47 - how efficient is the heat engine?
20:21 - Diagram (work over heat)
20:39 - how efficient is a Carnot Cycle?
22:47 - Graph: ...now this pair...
23:49 - let's prove this...
24:03 - so the total work is:
24:51 - Problem: What is the entropy change...
25:08 - Since S is a state function we can write...
26:08 - so represented in a Temperature-Entropy diagram, a Carnot cycle looks like this...
26:33 - What if one or more steps of the process are irreversible?
27:37 - and a more general statement of this is called the Claussius Inequality
28:19 - This equation makes predictions about 3 types of processes:
28:41 - some simple but important examples:
29:18 - some simple but important examples: example - a reversible phase transition.
29:51 - example - reversible heating/cooling of a gas.
30:48 - rev. expansion/compression of a gas.
31:45 - Calculating entropy changes for reversible processes on ideal gases:
32:26 - because S is a state function...
33:20 - Because S, like U, is a state function, you can add up...
33:53 - Calculate the entropy change when...
36:47 - Problem 2
37:09 - chemical potential of species...
37:38 - really? yes, think about this way ("...partial derivative")
38:24 -...you should know...
Lecture 23
Lindemann-Hinshelwood Part I
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Lindemann-Hinshelwood Part I
Recorded on May 30, 2012

Slide Information
00:06- Lindemann-Hinshelwood
01:22- Announcements
3:19- Today: Steady-State Approximation, Lindemann-Hinshelwood Mechanism
03:46- The Steady-State Approximation
07:58- Graph: Concentration, Time
08:25- Solve the Simplified Equations that Result
09:37- How Does This Compare with the Exact Solution?
10:25- How Well the Steady State Works- Graph of Concentration, Time
11:18- The Steady-State Approximation is Breaking Down
12:30- Example: Apply the Steady-State Approximation to the Following Reaction Mechanism
18:06- Simplifying Further
21:26- Two Limiting Experimentally Observed Rate Laws
24:40- Most Elementary Reactions are Either Unimolecular or Biomolecular
25:44- Biomolecular Reactions Have an Obvious Mechanism in the Gas Phase
26:17- Transition State Graph
26:42- But How Does a Unimolecular Reaction Occur?
27:06- Unomolecular Reactions- Isomerization
27:31- Unimolecular Reacions- Decomposition Reactions
28:05- How Does this Happen? The Lindemann-Hinshelwood Mechanism Provides an Explanation
30:10- Applying the Steady-Sate Approximation to the Lindemann-Hinshelwood Mechanism
31:10- The Strong Collision Assumption
13:35- Can We Apply the Steady-State Approximation to the Mechanism?
34:14- What Does it Predict?
37:26- What Does This Mean Mechanistically?
38:04- The Kinetics of Pressure-Dependent Reactions
41:19- We Can Write the LH Rate in This Form
43:29- Does it Work? Plot
44:09- It Doesn't Work So Well
45:44- Reactions Where a Pre-Equilibrium is Established
47:45- Test the Lindemann-Hinshelwood Mechanism for the Isomerization of Cyclopropane
49:02- The Data is Not Convincing- Plot
50:18- Use the Steady State Approximation Again
Lecture 24
Lindemann-Hinshelwood Part II
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Lindemann-Hinshelwood Part II
Recorded on June 1, 2012

Slide Information
00:06- Enzymes
00:14- Midterm II Results
01:12- How Am I Doing?
06:36- Today: Lindemann-Hinshelwood Mechanism, Enzyme Kinetics
07:58- Most Elementary Reactions are Either Unimolecular or Biomolecular
09:45- The Lindmann-Hinshelwood Mechanism Provides an Explanation
11:22- Can We Apply the Steady-State Approximation to this Mechanism?
12:52- What Does it Predict?
14:28- What Does This Mean Mechanistically?
16:20- Let's Apply the Steady-State Approximation
16:53- The Kinetics of Pressure-Dependent Reactions
20:08- If the LH Mechanism is Operating...Plot
20:45- Plot: Does it Work?
21:16- LH Mechanism: A Mechanism for Which a Pre-Equilibrium is Established
22:03- The Reaction Will Have an Apparent Second Order
22:34- Apply Mathematics to the Enzyme
24:42- Schematic Illustration of Enzyme Kinetics
26:35- Kinetic Scheme/Steady State Approximation Applied
28:52- Solving for [(ES)]
30:05- Obtaining the Michaelis -Menten Equation
Lecture 25
Enzymes Pt. II
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Enzymes Pt. II
Recorded on June 4, 2012.

Slide Information
00:06- Enzymes (Second & Final Attempt)
00:45- Announcements
02:42- Chem 1 Students...
04:47- Today: Enzyme Kinetics, Enzyme Inhibition
5:00- How Enzymes Catalyze Reactions
07:27- Equations Specific to Enzyme Catalysis, Rate of Reaction
12:36- The Michaelis-Menten Equation
13:04- Simplifying the Rate of Reaction
15:20- Making the Michaelis-Menten Equation Useful
15:46- What's Happening if K2 is big?
16:56- If K2 is Big, if [S] is Big
17:56- And if [S] is Big, Then...
19:49- IF [S] is Small
20:27- Plot of Reaction Rate vs. Concentration of S
23:57- K2=Kcat=Turnover Number
24:30- Ratio Between V and Vmax
25:34- Basis for the Lineweaver-Burk Plot
27:15- The Lineweaver-Burk Plot
28:30- Problem From Last Year's Final Exam
31:28- What Could Possibly Happen to Mess This Up?
32:56- Classifying Inhibitors Based Upon Their Effect on the Lineweaver-Burk Plot
34:46- Three Flavors of Enzyme Inhibition: Competitive Inhibition
35:10- Out Competing a Competitive Inhibitor: Plot
37:10- What Influence Does Vmax Have on the Lineweaver-Burk Plot?
37:57- Noncompetitive Inhibition
39:28- Uncompetitive Inhibition
40:26- Derive the Math For the Plots
43:13- No Inhibitor/Inhibitor Equations
44:07- Table of Inhibition
45:18- The Classical Case of Competitive Inhibition: Malonate and SD
46:09- Succinate
46:15- Fumarate
46:36- Competitive Inhibitors Generally Resemble the Substrate of the Protein to which They Bind
Lecture 26
Transition State Theory
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Transition State Theory
Recorded June 6, 2012.

Slide Information
00:06- Transition State Theory
00:13- Announcements
01:24- Where Are We?
02:54- Where Does the Arrhenius Equation Come From?
03:54- Joke
04:34- Transition State Theory, Introduction
05:08- History of the Transition State Theory
06:54- Transition Sate Theory For a Gaseous Biomolecular Reaction
09:00- Notation applied to TST
11:16- Activated Complex
11:52- Working Out The Reaction Rate
14:30- Flashback to Ch. 17: Calculating Equilibrium Constants from Partition Functions
16:08- Difference Between Zero-Point Energies
16:34- Gibbs Free Energy as a Function of Reaction Coordinate
18:13- Generic Equilibrium applied to TST
19:15- TST Equilibrium
20:37- Frequency
21:17- Setting Two Expressions for the Reaction Rate Equal to One Another
23:25- Calculating the Partition Function for the Transition State
25:50- What is the Partition Function for AB++?
26:28- Vibration Along the Reaction Coordinate
27:24- Super Soft Mode
29:26- Partition Function
30:54- Rewriting K++
32:06- The Eyring Equation
35:38- Calculating the Pre-Exponential Factor in the Arrhenius Equation
36:17- Applying to a Reaction that Occurs in Water
39:27- Equilibrium Constants in Solutions are Defined in Terms of Activities
40:26- Debye-Huckel Limiting Law
41:11- What D-H Predicts
42:02- Thermodynamic Equilibrium Constant
42:31- Comparing K and K'
44:31- Question: Adding NaCl to a Solution of Acetic Acid
46:32- Applying this Logic to TST
47:25- Equation for the Kinetic Salt Effect
48:00- What Does it Mean?
Lecture 27
The Final Exam
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The Final Exam
Recorded on June 12, 2012.

Slide Information:

00:22- The Final Exam
05:36- TST For Ionic Reactions in Solution
07:26- How does the Ionic Content of a Solution Influence the Reaction Rate when Reactants are Charged?
08:52- How Equilibrium is Influenced by Ions in Solution and the Debye-Huckel Limiting law
11:06- Graphing what the Debye-Huckel Limiting Law Predicts
13:00- What We Want to Know About the Plot of the Graph
14:40- How the Equilibrium Constant is Affected by the Ionic Strength
15:33- The Thermodynamic Equilibrium Constant and the Concentration Equilibrium Constant
16:40- Comparing The Thermodynamic Equilibrium Constant and the Concentration Equilibrium Constant
18:28- Question: Adding NaCl to a Solution of Acetic Acid
21:46- Question: Solubility of the Above Problem
24:58- Why Does This Happen? Oppositely Charge Ions Attract...
25:37- Freely Arranging Ions In Order to Lower Their Energy
27:58- Favoring the Most Ionic State of the System
28:23- Applying this Logic to the TST Treatment of the Reaction
29:52- Equations at Infinite Dilution
30:36- Master Equation for Transition State Theory and What it Predicts
31:02- Plotting What is Predicted
34:05- The 131C Final Exam
35:57- Review Problem: Calculating The Michaelis Constant, Km, Vmax, Turnover Number, Catalytic Efficiency of an Enzyme
36:33- In Enzyme Kinetics, This is the Mechanism that Operates
37:32- Michaeilis-Menten Kinetics Graph: Reaction Rate/Substrate Concentration
38:24- The Lineweaver-Burk Plot
39:19- What Your Plot Should Look Like Qualitatively
40:11- Example Problem: Chemical Kinetics: Steady State Reaction
46:18- More Kinetic Issues- Rules for Reaction Rate
47:06- Method 1 for Experimentally Determining the Rate Law
48:25- Method 2 for Experimentally Determining the Rate Law
48:41- Example of Method 2
49:00- Method 3: Measuring the Influence of the Initial Reactant Concentration of the Reaction Half-Life
49:36- Summary of Three Methods
49:39- The Arrhenius Equation