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Raffi Hovasapian

Raffi Hovasapian

Example Problems II

Slide Duration:

Table of Contents

I. Classical Thermodynamics Preliminaries
The Ideal Gas Law

46m 5s

Intro
0:00
Course Overview
0:16
Thermodynamics & Classical Thermodynamics
0:17
Structure of the Course
1:30
The Ideal Gas Law
3:06
Ideal Gas Law: PV=nRT
3:07
Units of Pressure
4:51
Manipulating Units
5:52
Atmosphere : atm
8:15
Millimeter of Mercury: mm Hg
8:48
SI Unit of Volume
9:32
SI Unit of Temperature
10:32
Value of R (Gas Constant): Pv = nRT
10:51
Extensive and Intensive Variables (Properties)
15:23
Intensive Property
15:52
Extensive Property
16:30
Example: Extensive and Intensive Variables
18:20
Ideal Gas Law
19:24
Ideal Gas Law with Intensive Variables
19:25
Graphing Equations
23:51
Hold T Constant & Graph P vs. V
23:52
Hold P Constant & Graph V vs. T
31:08
Hold V Constant & Graph P vs. T
34:38
Isochores or Isometrics
37:08
More on the V vs. T Graph
39:46
More on the P vs. V Graph
42:06
Ideal Gas Law at Low Pressure & High Temperature
44:26
Ideal Gas Law at High Pressure & Low Temperature
45:16
Math Lesson 1: Partial Differentiation

46m 2s

Intro
0:00
Math Lesson 1: Partial Differentiation
0:38
Overview
0:39
Example I
3:00
Example II
6:33
Example III
9:52
Example IV
17:26
Differential & Derivative
21:44
What Does It Mean?
21:45
Total Differential (or Total Derivative)
30:16
Net Change in Pressure (P)
33:58
General Equation for Total Differential
38:12
Example 5: Total Differential
39:28
II. Energy
Energy & the First Law I

1h 6m 45s

Intro
0:00
Properties of Thermodynamic State
1:38
Big Picture: 3 Properties of Thermodynamic State
1:39
Enthalpy & Free Energy
3:30
Associated Law
4:40
Energy & the First Law of Thermodynamics
7:13
System & Its Surrounding Separated by a Boundary
7:14
In Other Cases the Boundary is Less Clear
10:47
State of a System
12:37
State of a System
12:38
Change in State
14:00
Path for a Change in State
14:57
Example: State of a System
15:46
Open, Close, and Isolated System
18:26
Open System
18:27
Closed System
19:02
Isolated System
19:22
Important Questions
20:38
Important Questions
20:39
Work & Heat
22:50
Definition of Work
23:33
Properties of Work
25:34
Definition of Heat
32:16
Properties of Heat
34:49
Experiment #1
42:23
Experiment #2
47:00
More on Work & Heat
54:50
More on Work & Heat
54:51
Conventions for Heat & Work
1:00:50
Convention for Heat
1:02:40
Convention for Work
1:04:24
Schematic Representation
1:05:00
Energy & the First Law II

1h 6m 33s

Intro
0:00
The First Law of Thermodynamics
0:53
The First Law of Thermodynamics
0:54
Example 1: What is the Change in Energy of the System & Surroundings?
8:53
Energy and The First Law II, cont.
11:55
The Energy of a System Changes in Two Ways
11:56
Systems Possess Energy, Not Heat or Work
12:45
Scenario 1
16:00
Scenario 2
16:46
State Property, Path Properties, and Path Functions
18:10
Pressure-Volume Work
22:36
When a System Changes
22:37
Gas Expands
24:06
Gas is Compressed
25:13
Pressure Volume Diagram: Analyzing Expansion
27:17
What if We do the Same Expansion in Two Stages?
35:22
Multistage Expansion
43:58
General Expression for the Pressure-Volume Work
46:59
Upper Limit of Isothermal Expansion
50:00
Expression for the Work Done in an Isothermal Expansion
52:45
Example 2: Find an Expression for the Maximum Work Done by an Ideal Gas upon Isothermal Expansion
56:18
Example 3: Calculate the External Pressure and Work Done
58:50
Energy & the First Law III

1h 2m 17s

Intro
0:00
Compression
0:20
Compression Overview
0:34
Single-stage compression vs. 2-stage Compression
2:16
Multi-stage Compression
8:40
Example I: Compression
14:47
Example 1: Single-stage Compression
14:47
Example 1: 2-stage Compression
20:07
Example 1: Absolute Minimum
26:37
More on Compression
32:55
Isothermal Expansion & Compression
32:56
External & Internal Pressure of the System
35:18
Reversible & Irreversible Processes
37:32
Process 1: Overview
38:57
Process 2: Overview
39:36
Process 1: Analysis
40:42
Process 2: Analysis
45:29
Reversible Process
50:03
Isothermal Expansion and Compression
54:31
Example II: Reversible Isothermal Compression of a Van der Waals Gas
58:10
Example 2: Reversible Isothermal Compression of a Van der Waals Gas
58:11
Changes in Energy & State: Constant Volume

1h 4m 39s

Intro
0:00
Recall
0:37
State Function & Path Function
0:38
First Law
2:11
Exact & Inexact Differential
2:12
Where Does (∆U = Q - W) or dU = dQ - dU Come from?
8:54
Cyclic Integrals of Path and State Functions
8:55
Our Empirical Experience of the First Law
12:31
∆U = Q - W
18:42
Relations between Changes in Properties and Energy
22:24
Relations between Changes in Properties and Energy
22:25
Rate of Change of Energy per Unit Change in Temperature
29:54
Rate of Change of Energy per Unit Change in Volume at Constant Temperature
32:39
Total Differential Equation
34:38
Constant Volume
41:08
If Volume Remains Constant, then dV = 0
41:09
Constant Volume Heat Capacity
45:22
Constant Volume Integrated
48:14
Increase & Decrease in Energy of the System
54:19
Example 1: ∆U and Qv
57:43
Important Equations
1:02:06
Joule's Experiment

16m 50s

Intro
0:00
Joule's Experiment
0:09
Joule's Experiment
1:20
Interpretation of the Result
4:42
The Gas Expands Against No External Pressure
4:43
Temperature of the Surrounding Does Not Change
6:20
System & Surrounding
7:04
Joule's Law
10:44
More on Joule's Experiment
11:08
Later Experiment
12:38
Dealing with the 2nd Law & Its Mathematical Consequences
13:52
Changes in Energy & State: Constant Pressure

43m 40s

Intro
0:00
Changes in Energy & State: Constant Pressure
0:20
Integrating with Constant Pressure
0:35
Defining the New State Function
6:24
Heat & Enthalpy of the System at Constant Pressure
8:54
Finding ∆U
12:10
dH
15:28
Constant Pressure Heat Capacity
18:08
Important Equations
25:44
Important Equations
25:45
Important Equations at Constant Pressure
27:32
Example I: Change in Enthalpy (∆H)
28:53
Example II: Change in Internal Energy (∆U)
34:19
The Relationship Between Cp & Cv

32m 23s

Intro
0:00
The Relationship Between Cp & Cv
0:21
For a Constant Volume Process No Work is Done
0:22
For a Constant Pressure Process ∆V ≠ 0, so Work is Done
1:16
The Relationship Between Cp & Cv: For an Ideal Gas
3:26
The Relationship Between Cp & Cv: In Terms of Molar heat Capacities
5:44
Heat Capacity Can Have an Infinite # of Values
7:14
The Relationship Between Cp & Cv
11:20
When Cp is Greater than Cv
17:13
2nd Term
18:10
1st Term
19:20
Constant P Process: 3 Parts
22:36
Part 1
23:45
Part 2
24:10
Part 3
24:46
Define : γ = (Cp/Cv)
28:06
For Gases
28:36
For Liquids
29:04
For an Ideal Gas
30:46
The Joule Thompson Experiment

39m 15s

Intro
0:00
General Equations
0:13
Recall
0:14
How Does Enthalpy of a System Change Upon a Unit Change in Pressure?
2:58
For Liquids & Solids
12:11
For Ideal Gases
14:08
For Real Gases
16:58
The Joule Thompson Experiment
18:37
The Joule Thompson Experiment Setup
18:38
The Flow in 2 Stages
22:54
Work Equation for the Joule Thompson Experiment
24:14
Insulated Pipe
26:33
Joule-Thompson Coefficient
29:50
Changing Temperature & Pressure in Such a Way that Enthalpy Remains Constant
31:44
Joule Thompson Inversion Temperature
36:26
Positive & Negative Joule-Thompson Coefficient
36:27
Joule Thompson Inversion Temperature
37:22
Inversion Temperature of Hydrogen Gas
37:59
Adiabatic Changes of State

35m 52s

Intro
0:00
Adiabatic Changes of State
0:10
Adiabatic Changes of State
0:18
Work & Energy in an Adiabatic Process
3:44
Pressure-Volume Work
7:43
Adiabatic Changes for an Ideal Gas
9:23
Adiabatic Changes for an Ideal Gas
9:24
Equation for a Fixed Change in Volume
11:20
Maximum & Minimum Values of Temperature
14:20
Adiabatic Path
18:08
Adiabatic Path Diagram
18:09
Reversible Adiabatic Expansion
21:54
Reversible Adiabatic Compression
22:34
Fundamental Relationship Equation for an Ideal Gas Under Adiabatic Expansion
25:00
More on the Equation
28:20
Important Equations
32:16
Important Adiabatic Equation
32:17
Reversible Adiabatic Change of State Equation
33:02
III. Energy Example Problems
1st Law Example Problems I

42m 40s

Intro
0:00
Fundamental Equations
0:56
Work
2:40
Energy (1st Law)
3:10
Definition of Enthalpy
3:44
Heat capacity Definitions
4:06
The Mathematics
6:35
Fundamental Concepts
8:13
Isothermal
8:20
Adiabatic
8:54
Isobaric
9:25
Isometric
9:48
Ideal Gases
10:14
Example I
12:08
Example I: Conventions
12:44
Example I: Part A
15:30
Example I: Part B
18:24
Example I: Part C
19:53
Example II: What is the Heat Capacity of the System?
21:49
Example III: Find Q, W, ∆U & ∆H for this Change of State
24:15
Example IV: Find Q, W, ∆U & ∆H
31:37
Example V: Find Q, W, ∆U & ∆H
38:20
1st Law Example Problems II

1h 23s

Intro
0:00
Example I
0:11
Example I: Finding ∆U
1:49
Example I: Finding W
6:22
Example I: Finding Q
11:23
Example I: Finding ∆H
16:09
Example I: Summary
17:07
Example II
21:16
Example II: Finding W
22:42
Example II: Finding ∆H
27:48
Example II: Finding Q
30:58
Example II: Finding ∆U
31:30
Example III
33:33
Example III: Finding ∆U, Q & W
33:34
Example III: Finding ∆H
38:07
Example IV
41:50
Example IV: Finding ∆U
41:51
Example IV: Finding ∆H
45:42
Example V
49:31
Example V: Finding W
49:32
Example V: Finding ∆U
55:26
Example V: Finding Q
56:26
Example V: Finding ∆H
56:55
1st Law Example Problems III

44m 34s

Intro
0:00
Example I
0:15
Example I: Finding the Final Temperature
3:40
Example I: Finding Q
8:04
Example I: Finding ∆U
8:25
Example I: Finding W
9:08
Example I: Finding ∆H
9:51
Example II
11:27
Example II: Finding the Final Temperature
11:28
Example II: Finding ∆U
21:25
Example II: Finding W & Q
22:14
Example II: Finding ∆H
23:03
Example III
24:38
Example III: Finding the Final Temperature
24:39
Example III: Finding W, ∆U, and Q
27:43
Example III: Finding ∆H
28:04
Example IV
29:23
Example IV: Finding ∆U, W, and Q
25:36
Example IV: Finding ∆H
31:33
Example V
32:24
Example V: Finding the Final Temperature
33:32
Example V: Finding ∆U
39:31
Example V: Finding W
40:17
Example V: First Way of Finding ∆H
41:10
Example V: Second Way of Finding ∆H
42:10
Thermochemistry Example Problems

59m 7s

Intro
0:00
Example I: Find ∆H° for the Following Reaction
0:42
Example II: Calculate the ∆U° for the Reaction in Example I
5:33
Example III: Calculate the Heat of Formation of NH₃ at 298 K
14:23
Example IV
32:15
Part A: Calculate the Heat of Vaporization of Water at 25°C
33:49
Part B: Calculate the Work Done in Vaporizing 2 Mols of Water at 25°C Under a Constant Pressure of 1 atm
35:26
Part C: Find ∆U for the Vaporization of Water at 25°C
41:00
Part D: Find the Enthalpy of Vaporization of Water at 100°C
43:12
Example V
49:24
Part A: Constant Temperature & Increasing Pressure
50:25
Part B: Increasing temperature & Constant Pressure
56:20
IV. Entropy
Entropy

49m 16s

Intro
0:00
Entropy, Part 1
0:16
Coefficient of Thermal Expansion (Isobaric)
0:38
Coefficient of Compressibility (Isothermal)
1:25
Relative Increase & Relative Decrease
2:16
More on α
4:40
More on κ
8:38
Entropy, Part 2
11:04
Definition of Entropy
12:54
Differential Change in Entropy & the Reversible Path
20:08
State Property of the System
28:26
Entropy Changes Under Isothermal Conditions
35:00
Recall: Heating Curve
41:05
Some Phase Changes Take Place Under Constant Pressure
44:07
Example I: Finding ∆S for a Phase Change
46:05
Math Lesson II

33m 59s

Intro
0:00
Math Lesson II
0:46
Let F(x,y) = x²y³
0:47
Total Differential
3:34
Total Differential Expression
6:06
Example 1
9:24
More on Math Expression
13:26
Exact Total Differential Expression
13:27
Exact Differentials
19:50
Inexact Differentials
20:20
The Cyclic Rule
21:06
The Cyclic Rule
21:07
Example 2
27:58
Entropy As a Function of Temperature & Volume

54m 37s

Intro
0:00
Entropy As a Function of Temperature & Volume
0:14
Fundamental Equation of Thermodynamics
1:16
Things to Notice
9:10
Entropy As a Function of Temperature & Volume
14:47
Temperature-dependence of Entropy
24:00
Example I
26:19
Entropy As a Function of Temperature & Volume, Cont.
31:55
Volume-dependence of Entropy at Constant Temperature
31:56
Differentiate with Respect to Temperature, Holding Volume Constant
36:16
Recall the Cyclic Rule
45:15
Summary & Recap
46:47
Fundamental Equation of Thermodynamics
46:48
For Entropy as a Function of Temperature & Volume
47:18
The Volume-dependence of Entropy for Liquids & Solids
52:52
Entropy as a Function of Temperature & Pressure

31m 18s

Intro
0:00
Entropy as a Function of Temperature & Pressure
0:17
Entropy as a Function of Temperature & Pressure
0:18
Rewrite the Total Differential
5:54
Temperature-dependence
7:08
Pressure-dependence
9:04
Differentiate with Respect to Pressure & Holding Temperature Constant
9:54
Differentiate with Respect to Temperature & Holding Pressure Constant
11:28
Pressure-Dependence of Entropy for Liquids & Solids
18:45
Pressure-Dependence of Entropy for Liquids & Solids
18:46
Example I: ∆S of Transformation
26:20
Summary of Entropy So Far

23m 6s

Intro
0:00
Summary of Entropy So Far
0:43
Defining dS
1:04
Fundamental Equation of Thermodynamics
3:51
Temperature & Volume
6:04
Temperature & Pressure
9:10
Two Important Equations for How Entropy Behaves
13:38
State of a System & Heat Capacity
15:34
Temperature-dependence of Entropy
19:49
Entropy Changes for an Ideal Gas

25m 42s

Intro
0:00
Entropy Changes for an Ideal Gas
1:10
General Equation
1:22
The Fundamental Theorem of Thermodynamics
2:37
Recall the Basic Total Differential Expression for S = S (T,V)
5:36
For a Finite Change in State
7:58
If Cv is Constant Over the Particular Temperature Range
9:05
Change in Entropy of an Ideal Gas as a Function of Temperature & Pressure
11:35
Change in Entropy of an Ideal Gas as a Function of Temperature & Pressure
11:36
Recall the Basic Total Differential expression for S = S (T, P)
15:13
For a Finite Change
18:06
Example 1: Calculate the ∆S of Transformation
22:02
V. Entropy Example Problems
Entropy Example Problems I

43m 39s

Intro
0:00
Entropy Example Problems I
0:24
Fundamental Equation of Thermodynamics
1:10
Entropy as a Function of Temperature & Volume
2:04
Entropy as a Function of Temperature & Pressure
2:59
Entropy For Phase Changes
4:47
Entropy For an Ideal Gas
6:14
Third Law Entropies
8:25
Statement of the Third Law
9:17
Entropy of the Liquid State of a Substance Above Its Melting Point
10:23
Entropy For the Gas Above Its Boiling Temperature
13:02
Entropy Changes in Chemical Reactions
15:26
Entropy Change at a Temperature Other than 25°C
16:32
Example I
19:31
Part A: Calculate ∆S for the Transformation Under Constant Volume
20:34
Part B: Calculate ∆S for the Transformation Under Constant Pressure
25:04
Example II: Calculate ∆S fir the Transformation Under Isobaric Conditions
27:53
Example III
30:14
Part A: Calculate ∆S if 1 Mol of Aluminum is taken from 25°C to 255°C
31:14
Part B: If S°₂₉₈ = 28.4 J/mol-K, Calculate S° for Aluminum at 498 K
33:23
Example IV: Calculate Entropy Change of Vaporization for CCl₄
34:19
Example V
35:41
Part A: Calculate ∆S of Transformation
37:36
Part B: Calculate ∆S of Transformation
39:10
Entropy Example Problems II

56m 44s

Intro
0:00
Example I
0:09
Example I: Calculate ∆U
1:28
Example I: Calculate Q
3:29
Example I: Calculate Cp
4:54
Example I: Calculate ∆S
6:14
Example II
7:13
Example II: Calculate W
8:14
Example II: Calculate ∆U
8:56
Example II: Calculate Q
10:18
Example II: Calculate ∆H
11:00
Example II: Calculate ∆S
12:36
Example III
18:47
Example III: Calculate ∆H
19:38
Example III: Calculate Q
21:14
Example III: Calculate ∆U
21:44
Example III: Calculate W
23:59
Example III: Calculate ∆S
24:55
Example IV
27:57
Example IV: Diagram
29:32
Example IV: Calculate W
32:27
Example IV: Calculate ∆U
36:36
Example IV: Calculate Q
38:32
Example IV: Calculate ∆H
39:00
Example IV: Calculate ∆S
40:27
Example IV: Summary
43:41
Example V
48:25
Example V: Diagram
49:05
Example V: Calculate W
50:58
Example V: Calculate ∆U
53:29
Example V: Calculate Q
53:44
Example V: Calculate ∆H
54:34
Example V: Calculate ∆S
55:01
Entropy Example Problems III

57m 6s

Intro
0:00
Example I: Isothermal Expansion
0:09
Example I: Calculate W
1:19
Example I: Calculate ∆U
1:48
Example I: Calculate Q
2:06
Example I: Calculate ∆H
2:26
Example I: Calculate ∆S
3:02
Example II: Adiabatic and Reversible Expansion
6:10
Example II: Calculate Q
6:48
Example II: Basic Equation for the Reversible Adiabatic Expansion of an Ideal Gas
8:12
Example II: Finding Volume
12:40
Example II: Finding Temperature
17:58
Example II: Calculate ∆U
19:53
Example II: Calculate W
20:59
Example II: Calculate ∆H
21:42
Example II: Calculate ∆S
23:42
Example III: Calculate the Entropy of Water Vapor
25:20
Example IV: Calculate the Molar ∆S for the Transformation
34:32
Example V
44:19
Part A: Calculate the Standard Entropy of Liquid Lead at 525°C
46:17
Part B: Calculate ∆H for the Transformation of Solid Lead from 25°C to Liquid Lead at 525°C
52:23
VI. Entropy and Probability
Entropy & Probability I

54m 35s

Intro
0:00
Entropy & Probability
0:11
Structural Model
3:05
Recall the Fundamental Equation of Thermodynamics
9:11
Two Independent Ways of Affecting the Entropy of a System
10:05
Boltzmann Definition
12:10
Omega
16:24
Definition of Omega
16:25
Energy Distribution
19:43
The Energy Distribution
19:44
In How Many Ways can N Particles be Distributed According to the Energy Distribution
23:05
Example I: In How Many Ways can the Following Distribution be Achieved
32:51
Example II: In How Many Ways can the Following Distribution be Achieved
33:51
Example III: In How Many Ways can the Following Distribution be Achieved
34:45
Example IV: In How Many Ways can the Following Distribution be Achieved
38:50
Entropy & Probability, cont.
40:57
More on Distribution
40:58
Example I Summary
41:43
Example II Summary
42:12
Distribution that Maximizes Omega
42:26
If Omega is Large, then S is Large
44:22
Two Constraints for a System to Achieve the Highest Entropy Possible
47:07
What Happened When the Energy of a System is Increased?
49:00
Entropy & Probability II

35m 5s

Intro
0:00
Volume Distribution
0:08
Distributing 2 Balls in 3 Spaces
1:43
Distributing 2 Balls in 4 Spaces
3:44
Distributing 3 Balls in 10 Spaces
5:30
Number of Ways to Distribute P Particles over N Spaces
6:05
When N is Much Larger than the Number of Particles P
7:56
Energy Distribution
25:04
Volume Distribution
25:58
Entropy, Total Entropy, & Total Omega Equations
27:34
Entropy, Total Entropy, & Total Omega Equations
27:35
VII. Spontaneity, Equilibrium, and the Fundamental Equations
Spontaneity & Equilibrium I

28m 42s

Intro
0:00
Reversible & Irreversible
0:24
Reversible vs. Irreversible
0:58
Defining Equation for Equilibrium
2:11
Defining Equation for Irreversibility (Spontaneity)
3:11
TdS ≥ dQ
5:15
Transformation in an Isolated System
11:22
Transformation in an Isolated System
11:29
Transformation at Constant Temperature
14:50
Transformation at Constant Temperature
14:51
Helmholtz Free Energy
17:26
Define: A = U - TS
17:27
Spontaneous Isothermal Process & Helmholtz Energy
20:20
Pressure-volume Work
22:02
Spontaneity & Equilibrium II

34m 38s

Intro
0:00
Transformation under Constant Temperature & Pressure
0:08
Transformation under Constant Temperature & Pressure
0:36
Define: G = U + PV - TS
3:32
Gibbs Energy
5:14
What Does This Say?
6:44
Spontaneous Process & a Decrease in G
14:12
Computing ∆G
18:54
Summary of Conditions
21:32
Constraint & Condition for Spontaneity
21:36
Constraint & Condition for Equilibrium
24:54
A Few Words About the Word Spontaneous
26:24
Spontaneous Does Not Mean Fast
26:25
Putting Hydrogen & Oxygen Together in a Flask
26:59
Spontaneous Vs. Not Spontaneous
28:14
Thermodynamically Favorable
29:03
Example: Making a Process Thermodynamically Favorable
29:34
Driving Forces for Spontaneity
31:35
Equation: ∆G = ∆H - T∆S
31:36
Always Spontaneous Process
32:39
Never Spontaneous Process
33:06
A Process That is Endothermic Can Still be Spontaneous
34:00
The Fundamental Equations of Thermodynamics

30m 50s

Intro
0:00
The Fundamental Equations of Thermodynamics
0:44
Mechanical Properties of a System
0:45
Fundamental Properties of a System
1:16
Composite Properties of a System
1:44
General Condition of Equilibrium
3:16
Composite Functions & Their Differentiations
6:11
dH = TdS + VdP
7:53
dA = -SdT - PdV
9:26
dG = -SdT + VdP
10:22
Summary of Equations
12:10
Equation #1
14:33
Equation #2
15:15
Equation #3
15:58
Equation #4
16:42
Maxwell's Relations
20:20
Maxwell's Relations
20:21
Isothermal Volume-Dependence of Entropy & Isothermal Pressure-Dependence of Entropy
26:21
The General Thermodynamic Equations of State

34m 6s

Intro
0:00
The General Thermodynamic Equations of State
0:10
Equations of State for Liquids & Solids
0:52
More General Condition for Equilibrium
4:02
General Conditions: Equation that Relates P to Functions of T & V
6:20
The Second Fundamental Equation of Thermodynamics
11:10
Equation 1
17:34
Equation 2
21:58
Recall the General Expression for Cp - Cv
28:11
For the Joule-Thomson Coefficient
30:44
Joule-Thomson Inversion Temperature
32:12
Properties of the Helmholtz & Gibbs Energies

39m 18s

Intro
0:00
Properties of the Helmholtz & Gibbs Energies
0:10
Equating the Differential Coefficients
1:34
An Increase in T; a Decrease in A
3:25
An Increase in V; a Decrease in A
6:04
We Do the Same Thing for G
8:33
Increase in T; Decrease in G
10:50
Increase in P; Decrease in G
11:36
Gibbs Energy of a Pure Substance at a Constant Temperature from 1 atm to any Other Pressure.
14:12
If the Substance is a Liquid or a Solid, then Volume can be Treated as a Constant
18:57
For an Ideal Gas
22:18
Special Note
24:56
Temperature Dependence of Gibbs Energy
27:02
Temperature Dependence of Gibbs Energy #1
27:52
Temperature Dependence of Gibbs Energy #2
29:01
Temperature Dependence of Gibbs Energy #3
29:50
Temperature Dependence of Gibbs Energy #4
34:50
The Entropy of the Universe & the Surroundings

19m 40s

Intro
0:00
Entropy of the Universe & the Surroundings
0:08
Equation: ∆G = ∆H - T∆S
0:20
Conditions of Constant Temperature & Pressure
1:14
Reversible Process
3:14
Spontaneous Process & the Entropy of the Universe
5:20
Tips for Remembering Everything
12:40
Verify Using Known Spontaneous Process
14:51
VIII. Free Energy Example Problems
Free Energy Example Problems I

54m 16s

Intro
0:00
Example I
0:11
Example I: Deriving a Function for Entropy (S)
2:06
Example I: Deriving a Function for V
5:55
Example I: Deriving a Function for H
8:06
Example I: Deriving a Function for U
12:06
Example II
15:18
Example III
21:52
Example IV
26:12
Example IV: Part A
26:55
Example IV: Part B
28:30
Example IV: Part C
30:25
Example V
33:45
Example VI
40:46
Example VII
43:43
Example VII: Part A
44:46
Example VII: Part B
50:52
Example VII: Part C
51:56
Free Energy Example Problems II

31m 17s

Intro
0:00
Example I
0:09
Example II
5:18
Example III
8:22
Example IV
12:32
Example V
17:14
Example VI
20:34
Example VI: Part A
21:04
Example VI: Part B
23:56
Example VI: Part C
27:56
Free Energy Example Problems III

45m

Intro
0:00
Example I
0:10
Example II
15:03
Example III
21:47
Example IV
28:37
Example IV: Part A
29:33
Example IV: Part B
36:09
Example IV: Part C
40:34
Three Miscellaneous Example Problems

58m 5s

Intro
0:00
Example I
0:41
Part A: Calculating ∆H
3:55
Part B: Calculating ∆S
15:13
Example II
24:39
Part A: Final Temperature of the System
26:25
Part B: Calculating ∆S
36:57
Example III
46:49
IX. Equation Review for Thermodynamics
Looking Back Over Everything: All the Equations in One Place

25m 20s

Intro
0:00
Work, Heat, and Energy
0:18
Definition of Work, Energy, Enthalpy, and Heat Capacities
0:23
Heat Capacities for an Ideal Gas
3:40
Path Property & State Property
3:56
Energy Differential
5:04
Enthalpy Differential
5:40
Joule's Law & Joule-Thomson Coefficient
6:23
Coefficient of Thermal Expansion & Coefficient of Compressibility
7:01
Enthalpy of a Substance at Any Other Temperature
7:29
Enthalpy of a Reaction at Any Other Temperature
8:01
Entropy
8:53
Definition of Entropy
8:54
Clausius Inequality
9:11
Entropy Changes in Isothermal Systems
9:44
The Fundamental Equation of Thermodynamics
10:12
Expressing Entropy Changes in Terms of Properties of the System
10:42
Entropy Changes in the Ideal Gas
11:22
Third Law Entropies
11:38
Entropy Changes in Chemical Reactions
14:02
Statistical Definition of Entropy
14:34
Omega for the Spatial & Energy Distribution
14:47
Spontaneity and Equilibrium
15:43
Helmholtz Energy & Gibbs Energy
15:44
Condition for Spontaneity & Equilibrium
16:24
Condition for Spontaneity with Respect to Entropy
17:58
The Fundamental Equations
18:30
Maxwell's Relations
19:04
The Thermodynamic Equations of State
20:07
Energy & Enthalpy Differentials
21:08
Joule's Law & Joule-Thomson Coefficient
21:59
Relationship Between Constant Pressure & Constant Volume Heat Capacities
23:14
One Final Equation - Just for Fun
24:04
X. Quantum Mechanics Preliminaries
Complex Numbers

34m 25s

Intro
0:00
Complex Numbers
0:11
Representing Complex Numbers in the 2-Dimmensional Plane
0:56
Addition of Complex Numbers
2:35
Subtraction of Complex Numbers
3:17
Multiplication of Complex Numbers
3:47
Division of Complex Numbers
6:04
r & θ
8:04
Euler's Formula
11:00
Polar Exponential Representation of the Complex Numbers
11:22
Example I
14:25
Example II
15:21
Example III
16:58
Example IV
18:35
Example V
20:40
Example VI
21:32
Example VII
25:22
Probability & Statistics

59m 57s

Intro
0:00
Probability & Statistics
1:51
Normalization Condition
1:52
Define the Mean or Average of x
11:04
Example I: Calculate the Mean of x
14:57
Example II: Calculate the Second Moment of the Data in Example I
22:39
Define the Second Central Moment or Variance
25:26
Define the Second Central Moment or Variance
25:27
1st Term
32:16
2nd Term
32:40
3rd Term
34:07
Continuous Distributions
35:47
Continuous Distributions
35:48
Probability Density
39:30
Probability Density
39:31
Normalization Condition
46:51
Example III
50:13
Part A - Show that P(x) is Normalized
51:40
Part B - Calculate the Average Position of the Particle Along the Interval
54:31
Important Things to Remember
58:24
SchrÓ§dinger Equation & Operators

42m 5s

Intro
0:00
Schrӧdinger Equation & Operators
0:16
Relation Between a Photon's Momentum & Its Wavelength
0:17
Louis de Broglie: Wavelength for Matter
0:39
Schrӧdinger Equation
1:19
Definition of Ψ(x)
3:31
Quantum Mechanics
5:02
Operators
7:51
Example I
10:10
Example II
11:53
Example III
14:24
Example IV
17:35
Example V
19:59
Example VI
22:39
Operators Can Be Linear or Non Linear
27:58
Operators Can Be Linear or Non Linear
28:34
Example VII
32:47
Example VIII
36:55
Example IX
39:29
SchrÓ§dinger Equation as an Eigenvalue Problem

30m 26s

Intro
0:00
Schrӧdinger Equation as an Eigenvalue Problem
0:10
Operator: Multiplying the Original Function by Some Scalar
0:11
Operator, Eigenfunction, & Eigenvalue
4:42
Example: Eigenvalue Problem
8:00
Schrӧdinger Equation as an Eigenvalue Problem
9:24
Hamiltonian Operator
15:09
Quantum Mechanical Operators
16:46
Kinetic Energy Operator
19:16
Potential Energy Operator
20:02
Total Energy Operator
21:12
Classical Point of View
21:48
Linear Momentum Operator
24:02
Example I
26:01
The Plausibility of the SchrÓ§dinger Equation

21m 34s

Intro
0:00
The Plausibility of the Schrӧdinger Equation
1:16
The Plausibility of the Schrӧdinger Equation, Part 1
1:17
The Plausibility of the Schrӧdinger Equation, Part 2
8:24
The Plausibility of the Schrӧdinger Equation, Part 3
13:45
XI. The Particle in a Box
The Particle in a Box Part I

56m 22s

Intro
0:00
Free Particle in a Box
0:28
Definition of a Free Particle in a Box
0:29
Amplitude of the Matter Wave
6:22
Intensity of the Wave
6:53
Probability Density
9:39
Probability that the Particle is Located Between x & dx
10:54
Probability that the Particle will be Found Between o & a
12:35
Wave Function & the Particle
14:59
Boundary Conditions
19:22
What Happened When There is No Constraint on the Particle
27:54
Diagrams
34:12
More on Probability Density
40:53
The Correspondence Principle
46:45
The Correspondence Principle
46:46
Normalizing the Wave Function
47:46
Normalizing the Wave Function
47:47
Normalized Wave Function & Normalization Constant
52:24
The Particle in a Box Part II

45m 24s

Intro
0:00
Free Particle in a Box
0:08
Free Particle in a 1-dimensional Box
0:09
For a Particle in a Box
3:57
Calculating Average Values & Standard Deviations
5:42
Average Value for the Position of a Particle
6:32
Standard Deviations for the Position of a Particle
10:51
Recall: Energy & Momentum are Represented by Operators
13:33
Recall: Schrӧdinger Equation in Operator Form
15:57
Average Value of a Physical Quantity that is Associated with an Operator
18:16
Average Momentum of a Free Particle in a Box
20:48
The Uncertainty Principle
24:42
Finding the Standard Deviation of the Momentum
25:08
Expression for the Uncertainty Principle
35:02
Summary of the Uncertainty Principle
41:28
The Particle in a Box Part III

48m 43s

Intro
0:00
2-Dimension
0:12
Dimension 2
0:31
Boundary Conditions
1:52
Partial Derivatives
4:27
Example I
6:08
The Particle in a Box, cont.
11:28
Operator Notation
12:04
Symbol for the Laplacian
13:50
The Equation Becomes…
14:30
Boundary Conditions
14:54
Separation of Variables
15:33
Solution to the 1-dimensional Case
16:31
Normalization Constant
22:32
3-Dimension
28:30
Particle in a 3-dimensional Box
28:31
In Del Notation
32:22
The Solutions
34:51
Expressing the State of the System for a Particle in a 3D Box
39:10
Energy Level & Degeneracy
43:35
XII. Postulates and Principles of Quantum Mechanics
The Postulates & Principles of Quantum Mechanics, Part I

46m 18s

Intro
0:00
Postulate I
0:31
Probability That The Particle Will Be Found in a Differential Volume Element
0:32
Example I: Normalize This Wave Function
11:30
Postulate II
18:20
Postulate II
18:21
Quantum Mechanical Operators: Position
20:48
Quantum Mechanical Operators: Kinetic Energy
21:57
Quantum Mechanical Operators: Potential Energy
22:42
Quantum Mechanical Operators: Total Energy
22:57
Quantum Mechanical Operators: Momentum
23:22
Quantum Mechanical Operators: Angular Momentum
23:48
More On The Kinetic Energy Operator
24:48
Angular Momentum
28:08
Angular Momentum Overview
28:09
Angular Momentum Operator in Quantum Mechanic
31:34
The Classical Mechanical Observable
32:56
Quantum Mechanical Operator
37:01
Getting the Quantum Mechanical Operator from the Classical Mechanical Observable
40:16
Postulate II, cont.
43:40
Quantum Mechanical Operators are Both Linear & Hermetical
43:41
The Postulates & Principles of Quantum Mechanics, Part II

39m 28s

Intro
0:00
Postulate III
0:09
Postulate III: Part I
0:10
Postulate III: Part II
5:56
Postulate III: Part III
12:43
Postulate III: Part IV
18:28
Postulate IV
23:57
Postulate IV
23:58
Postulate V
27:02
Postulate V
27:03
Average Value
36:38
Average Value
36:39
The Postulates & Principles of Quantum Mechanics, Part III

35m 32s

Intro
0:00
The Postulates & Principles of Quantum Mechanics, Part III
0:10
Equations: Linear & Hermitian
0:11
Introduction to Hermitian Property
3:36
Eigenfunctions are Orthogonal
9:55
The Sequence of Wave Functions for the Particle in a Box forms an Orthonormal Set
14:34
Definition of Orthogonality
16:42
Definition of Hermiticity
17:26
Hermiticity: The Left Integral
23:04
Hermiticity: The Right Integral
28:47
Hermiticity: Summary
34:06
The Postulates & Principles of Quantum Mechanics, Part IV

29m 55s

Intro
0:00
The Postulates & Principles of Quantum Mechanics, Part IV
0:09
Operators can be Applied Sequentially
0:10
Sample Calculation 1
2:41
Sample Calculation 2
5:18
Commutator of Two Operators
8:16
The Uncertainty Principle
19:01
In the Case of Linear Momentum and Position Operator
23:14
When the Commutator of Two Operators Equals to Zero
26:31
XIII. Postulates and Principles Example Problems, Including Particle in a Box
Example Problems I

54m 25s

Intro
0:00
Example I: Three Dimensional Box & Eigenfunction of The Laplacian Operator
0:37
Example II: Positions of a Particle in a 1-dimensional Box
15:46
Example III: Transition State & Frequency
29:29
Example IV: Finding a Particle in a 1-dimensional Box
35:03
Example V: Degeneracy & Energy Levels of a Particle in a Box
44:59
Example Problems II

46m 58s

Intro
0:00
Review
0:25
Wave Function
0:26
Normalization Condition
2:28
Observable in Classical Mechanics & Linear/Hermitian Operator in Quantum Mechanics
3:36
Hermitian
6:11
Eigenfunctions & Eigenvalue
8:20
Normalized Wave Functions
12:00
Average Value
13:42
If Ψ is Written as a Linear Combination
15:44
Commutator
16:45
Example I: Normalize The Wave Function
19:18
Example II: Probability of Finding of a Particle
22:27
Example III: Orthogonal
26:00
Example IV: Average Value of the Kinetic Energy Operator
30:22
Example V: Evaluate These Commutators
39:02
Example Problems III

44m 11s

Intro
0:00
Example I: Good Candidate for a Wave Function
0:08
Example II: Variance of the Energy
7:00
Example III: Evaluate the Angular Momentum Operators
15:00
Example IV: Real Eigenvalues Imposes the Hermitian Property on Operators
28:44
Example V: A Demonstration of Why the Eigenfunctions of Hermitian Operators are Orthogonal
35:33
XIV. The Harmonic Oscillator
The Harmonic Oscillator I

35m 33s

Intro
0:00
The Harmonic Oscillator
0:10
Harmonic Motion
0:11
Classical Harmonic Oscillator
4:38
Hooke's Law
8:18
Classical Harmonic Oscillator, cont.
10:33
General Solution for the Differential Equation
15:16
Initial Position & Velocity
16:05
Period & Amplitude
20:42
Potential Energy of the Harmonic Oscillator
23:20
Kinetic Energy of the Harmonic Oscillator
26:37
Total Energy of the Harmonic Oscillator
27:23
Conservative System
34:37
The Harmonic Oscillator II

43m 4s

Intro
0:00
The Harmonic Oscillator II
0:08
Diatomic Molecule
0:10
Notion of Reduced Mass
5:27
Harmonic Oscillator Potential & The Intermolecular Potential of a Vibrating Molecule
7:33
The Schrӧdinger Equation for the 1-dimensional Quantum Mechanic Oscillator
14:14
Quantized Values for the Energy Level
15:46
Ground State & the Zero-Point Energy
21:50
Vibrational Energy Levels
25:18
Transition from One Energy Level to the Next
26:42
Fundamental Vibrational Frequency for Diatomic Molecule
34:57
Example: Calculate k
38:01
The Harmonic Oscillator III

26m 30s

Intro
0:00
The Harmonic Oscillator III
0:09
The Wave Functions Corresponding to the Energies
0:10
Normalization Constant
2:34
Hermite Polynomials
3:22
First Few Hermite Polynomials
4:56
First Few Wave-Functions
6:37
Plotting the Probability Density of the Wave-Functions
8:37
Probability Density for Large Values of r
14:24
Recall: Odd Function & Even Function
19:05
More on the Hermite Polynomials
20:07
Recall: If f(x) is Odd
20:36
Average Value of x
22:31
Average Value of Momentum
23:56
XV. The Rigid Rotator
The Rigid Rotator I

41m 10s

Intro
0:00
Possible Confusion from the Previous Discussion
0:07
Possible Confusion from the Previous Discussion
0:08
Rotation of a Single Mass Around a Fixed Center
8:17
Rotation of a Single Mass Around a Fixed Center
8:18
Angular Velocity
12:07
Rotational Inertia
13:24
Rotational Frequency
15:24
Kinetic Energy for a Linear System
16:38
Kinetic Energy for a Rotational System
17:42
Rotating Diatomic Molecule
19:40
Rotating Diatomic Molecule: Part 1
19:41
Rotating Diatomic Molecule: Part 2
24:56
Rotating Diatomic Molecule: Part 3
30:04
Hamiltonian of the Rigid Rotor
36:48
Hamiltonian of the Rigid Rotor
36:49
The Rigid Rotator II

30m 32s

Intro
0:00
The Rigid Rotator II
0:08
Cartesian Coordinates
0:09
Spherical Coordinates
1:55
r
6:15
θ
6:28
φ
7:00
Moving a Distance 'r'
8:17
Moving a Distance 'r' in the Spherical Coordinates
11:49
For a Rigid Rotator, r is Constant
13:57
Hamiltonian Operator
15:09
Square of the Angular Momentum Operator
17:34
Orientation of the Rotation in Space
19:44
Wave Functions for the Rigid Rotator
20:40
The Schrӧdinger Equation for the Quantum Mechanic Rigid Rotator
21:24
Energy Levels for the Rigid Rotator
26:58
The Rigid Rotator III

35m 19s

Intro
0:00
The Rigid Rotator III
0:11
When a Rotator is Subjected to Electromagnetic Radiation
1:24
Selection Rule
2:13
Frequencies at Which Absorption Transitions Occur
6:24
Energy Absorption & Transition
10:54
Energy of the Individual Levels Overview
20:58
Energy of the Individual Levels: Diagram
23:45
Frequency Required to Go from J to J + 1
25:53
Using Separation Between Lines on the Spectrum to Calculate Bond Length
28:02
Example I: Calculating Rotational Inertia & Bond Length
29:18
Example I: Calculating Rotational Inertia
29:19
Example I: Calculating Bond Length
32:56
XVI. Oscillator and Rotator Example Problems
Example Problems I

33m 48s

Intro
0:00
Equations Review
0:11
Energy of the Harmonic Oscillator
0:12
Selection Rule
3:02
Observed Frequency of Radiation
3:27
Harmonic Oscillator Wave Functions
5:52
Rigid Rotator
7:26
Selection Rule for Rigid Rotator
9:15
Frequency of Absorption
9:35
Wave Numbers
10:58
Example I: Calculate the Reduced Mass of the Hydrogen Atom
11:44
Example II: Calculate the Fundamental Vibration Frequency & the Zero-Point Energy of This Molecule
13:37
Example III: Show That the Product of Two Even Functions is even
19:35
Example IV: Harmonic Oscillator
24:56
Example Problems II

46m 43s

Intro
0:00
Example I: Harmonic Oscillator
0:12
Example II: Harmonic Oscillator
23:26
Example III: Calculate the RMS Displacement of the Molecules
38:12
XVII. The Hydrogen Atom
The Hydrogen Atom I

40m

Intro
0:00
The Hydrogen Atom I
1:31
Review of the Rigid Rotator
1:32
Hydrogen Atom & the Coulomb Potential
2:50
Using the Spherical Coordinates
6:33
Applying This Last Expression to Equation 1
10:19
Angular Component & Radial Component
13:26
Angular Equation
15:56
Solution for F(φ)
19:32
Determine The Normalization Constant
20:33
Differential Equation for T(a)
24:44
Legendre Equation
27:20
Legendre Polynomials
31:20
The Legendre Polynomials are Mutually Orthogonal
35:40
Limits
37:17
Coefficients
38:28
The Hydrogen Atom II

35m 58s

Intro
0:00
Associated Legendre Functions
0:07
Associated Legendre Functions
0:08
First Few Associated Legendre Functions
6:39
s, p, & d Orbital
13:24
The Normalization Condition
15:44
Spherical Harmonics
20:03
Equations We Have Found
20:04
Wave Functions for the Angular Component & Rigid Rotator
24:36
Spherical Harmonics Examples
25:40
Angular Momentum
30:09
Angular Momentum
30:10
Square of the Angular Momentum
35:38
Energies of the Rigid Rotator
38:21
The Hydrogen Atom III

36m 18s

Intro
0:00
The Hydrogen Atom III
0:34
Angular Momentum is a Vector Quantity
0:35
The Operators Corresponding to the Three Components of Angular Momentum Operator: In Cartesian Coordinates
1:30
The Operators Corresponding to the Three Components of Angular Momentum Operator: In Spherical Coordinates
3:27
Z Component of the Angular Momentum Operator & the Spherical Harmonic
5:28
Magnitude of the Angular Momentum Vector
20:10
Classical Interpretation of Angular Momentum
25:22
Projection of the Angular Momentum Vector onto the xy-plane
33:24
The Hydrogen Atom IV

33m 55s

Intro
0:00
The Hydrogen Atom IV
0:09
The Equation to Find R( r )
0:10
Relation Between n & l
3:50
The Solutions for the Radial Functions
5:08
Associated Laguerre Polynomials
7:58
1st Few Associated Laguerre Polynomials
8:55
Complete Wave Function for the Atomic Orbitals of the Hydrogen Atom
12:24
The Normalization Condition
15:06
In Cartesian Coordinates
18:10
Working in Polar Coordinates
20:48
Principal Quantum Number
21:58
Angular Momentum Quantum Number
22:35
Magnetic Quantum Number
25:55
Zeeman Effect
30:45
The Hydrogen Atom V: Where We Are

51m 53s

Intro
0:00
The Hydrogen Atom V: Where We Are
0:13
Review
0:14
Let's Write Out ψ₂₁₁
7:32
Angular Momentum of the Electron
14:52
Representation of the Wave Function
19:36
Radial Component
28:02
Example: 1s Orbital
28:34
Probability for Radial Function
33:46
1s Orbital: Plotting Probability Densities vs. r
35:47
2s Orbital: Plotting Probability Densities vs. r
37:46
3s Orbital: Plotting Probability Densities vs. r
38:49
4s Orbital: Plotting Probability Densities vs. r
39:34
2p Orbital: Plotting Probability Densities vs. r
40:12
3p Orbital: Plotting Probability Densities vs. r
41:02
4p Orbital: Plotting Probability Densities vs. r
41:51
3d Orbital: Plotting Probability Densities vs. r
43:18
4d Orbital: Plotting Probability Densities vs. r
43:48
Example I: Probability of Finding an Electron in the 2s Orbital of the Hydrogen
45:40
The Hydrogen Atom VI

51m 53s

Intro
0:00
The Hydrogen Atom VI
0:07
Last Lesson Review
0:08
Spherical Component
1:09
Normalization Condition
2:02
Complete 1s Orbital Wave Function
4:08
1s Orbital Wave Function
4:09
Normalization Condition
6:28
Spherically Symmetric
16:00
Average Value
17:52
Example I: Calculate the Region of Highest Probability for Finding the Electron
21:19
2s Orbital Wave Function
25:32
2s Orbital Wave Function
25:33
Average Value
28:56
General Formula
32:24
The Hydrogen Atom VII

34m 29s

Intro
0:00
The Hydrogen Atom VII
0:12
p Orbitals
1:30
Not Spherically Symmetric
5:10
Recall That the Spherical Harmonics are Eigenfunctions of the Hamiltonian Operator
6:50
Any Linear Combination of These Orbitals Also Has The Same Energy
9:16
Functions of Real Variables
15:53
Solving for Px
16:50
Real Spherical Harmonics
21:56
Number of Nodes
32:56
XVIII. Hydrogen Atom Example Problems
Hydrogen Atom Example Problems I

43m 49s

Intro
0:00
Example I: Angular Momentum & Spherical Harmonics
0:20
Example II: Pair-wise Orthogonal Legendre Polynomials
16:40
Example III: General Normalization Condition for the Legendre Polynomials
25:06
Example IV: Associated Legendre Functions
32:13
The Hydrogen Atom Example Problems II

1h 1m 57s

Intro
0:00
Example I: Normalization & Pair-wise Orthogonal
0:13
Part 1: Normalized
0:43
Part 2: Pair-wise Orthogonal
16:53
Example II: Show Explicitly That the Following Statement is True for Any Integer n
27:10
Example III: Spherical Harmonics
29:26
Angular Momentum Cones
56:37
Angular Momentum Cones
56:38
Physical Interpretation of Orbital Angular Momentum in Quantum mechanics
1:00:16
The Hydrogen Atom Example Problems III

48m 33s

Intro
0:00
Example I: Show That ψ₂₁₁ is Normalized
0:07
Example II: Show That ψ₂₁₁ is Orthogonal to ψ₃₁₀
11:48
Example III: Probability That a 1s Electron Will Be Found Within 1 Bohr Radius of The Nucleus
18:35
Example IV: Radius of a Sphere
26:06
Example V: Calculate <r> for the 2s Orbital of the Hydrogen-like Atom
36:33
The Hydrogen Atom Example Problems IV

48m 33s

Intro
0:00
Example I: Probability Density vs. Radius Plot
0:11
Example II: Hydrogen Atom & The Coulombic Potential
14:16
Example III: Find a Relation Among <K>, <V>, & <E>
25:47
Example IV: Quantum Mechanical Virial Theorem
48:32
Example V: Find the Variance for the 2s Orbital
54:13
The Hydrogen Atom Example Problems V

48m 33s

Intro
0:00
Example I: Derive a Formula for the Degeneracy of a Given Level n
0:11
Example II: Using Linear Combinations to Represent the Spherical Harmonics as Functions of the Real Variables θ & φ
8:30
Example III: Using Linear Combinations to Represent the Spherical Harmonics as Functions of the Real Variables θ & φ
23:01
Example IV: Orbital Functions
31:51
XIX. Spin Quantum Number and Atomic Term Symbols
Spin Quantum Number: Term Symbols I

59m 18s

Intro
0:00
Quantum Numbers Specify an Orbital
0:24
n
1:10
l
1:20
m
1:35
4th Quantum Number: s
2:02
Spin Orbitals
7:03
Spin Orbitals
7:04
Multi-electron Atoms
11:08
Term Symbols
18:08
Russell-Saunders Coupling & The Atomic Term Symbol
18:09
Example: Configuration for C
27:50
Configuration for C: 1s²2s²2p²
27:51
Drawing Every Possible Arrangement
31:15
Term Symbols
45:24
Microstate
50:54
Spin Quantum Number: Term Symbols II

34m 54s

Intro
0:00
Microstates
0:25
We Started With 21 Possible Microstates
0:26
³P State
2:05
Microstates in ³P Level
5:10
¹D State
13:16
³P State
16:10
²P₂ State
17:34
³P₁ State
18:34
³P₀ State
19:12
9 Microstates in ³P are Subdivided
19:40
¹S State
21:44
Quicker Way to Find the Different Values of J for a Given Basic Term Symbol
22:22
Ground State
26:27
Hund's Empirical Rules for Specifying the Term Symbol for the Ground Electronic State
27:29
Hund's Empirical Rules: 1
28:24
Hund's Empirical Rules: 2
29:22
Hund's Empirical Rules: 3 - Part A
30:22
Hund's Empirical Rules: 3 - Part B
31:18
Example: 1s²2s²2p²
31:54
Spin Quantum Number: Term Symbols III

38m 3s

Intro
0:00
Spin Quantum Number: Term Symbols III
0:14
Deriving the Term Symbols for the p² Configuration
0:15
Table: MS vs. ML
3:57
¹D State
16:21
³P State
21:13
¹S State
24:48
J Value
25:32
Degeneracy of the Level
27:28
When Given r Electrons to Assign to n Equivalent Spin Orbitals
30:18
p² Configuration
32:51
Complementary Configurations
35:12
Term Symbols & Atomic Spectra

57m 49s

Intro
0:00
Lyman Series
0:09
Spectroscopic Term Symbols
0:10
Lyman Series
3:04
Hydrogen Levels
8:21
Hydrogen Levels
8:22
Term Symbols & Atomic Spectra
14:17
Spin-Orbit Coupling
14:18
Selection Rules for Atomic Spectra
21:31
Selection Rules for Possible Transitions
23:56
Wave Numbers for The Transitions
28:04
Example I: Calculate the Frequencies of the Allowed Transitions from (4d) ²D →(2p) ²P
32:23
Helium Levels
49:50
Energy Levels for Helium
49:51
Transitions & Spin Multiplicity
52:27
Transitions & Spin Multiplicity
52:28
XX. Term Symbols Example Problems
Example Problems I

1h 1m 20s

Intro
0:00
Example I: What are the Term Symbols for the np¹ Configuration?
0:10
Example II: What are the Term Symbols for the np² Configuration?
20:38
Example III: What are the Term Symbols for the np³ Configuration?
40:46
Example Problems II

56m 34s

Intro
0:00
Example I: Find the Term Symbols for the nd² Configuration
0:11
Example II: Find the Term Symbols for the 1s¹2p¹ Configuration
27:02
Example III: Calculate the Separation Between the Doublets in the Lyman Series for Atomic Hydrogen
41:41
Example IV: Calculate the Frequencies of the Lines for the (4d) ²D → (3p) ²P Transition
48:53
XXI. Equation Review for Quantum Mechanics
Quantum Mechanics: All the Equations in One Place

18m 24s

Intro
0:00
Quantum Mechanics Equations
0:37
De Broglie Relation
0:38
Statistical Relations
1:00
The Schrӧdinger Equation
1:50
The Particle in a 1-Dimensional Box of Length a
3:09
The Particle in a 2-Dimensional Box of Area a x b
3:48
The Particle in a 3-Dimensional Box of Area a x b x c
4:22
The Schrӧdinger Equation Postulates
4:51
The Normalization Condition
5:40
The Probability Density
6:51
Linear
7:47
Hermitian
8:31
Eigenvalues & Eigenfunctions
8:55
The Average Value
9:29
Eigenfunctions of Quantum Mechanics Operators are Orthogonal
10:53
Commutator of Two Operators
10:56
The Uncertainty Principle
11:41
The Harmonic Oscillator
13:18
The Rigid Rotator
13:52
Energy of the Hydrogen Atom
14:30
Wavefunctions, Radial Component, and Associated Laguerre Polynomial
14:44
Angular Component or Spherical Harmonic
15:16
Associated Legendre Function
15:31
Principal Quantum Number
15:43
Angular Momentum Quantum Number
15:50
Magnetic Quantum Number
16:21
z-component of the Angular Momentum of the Electron
16:53
Atomic Spectroscopy: Term Symbols
17:14
Atomic Spectroscopy: Selection Rules
18:03
XXII. Molecular Spectroscopy
Spectroscopic Overview: Which Equation Do I Use & Why

50m 2s

Intro
0:00
Spectroscopic Overview: Which Equation Do I Use & Why
1:02
Lesson Overview
1:03
Rotational & Vibrational Spectroscopy
4:01
Frequency of Absorption/Emission
6:04
Wavenumbers in Spectroscopy
8:10
Starting State vs. Excited State
10:10
Total Energy of a Molecule (Leaving out the Electronic Energy)
14:02
Energy of Rotation: Rigid Rotor
15:55
Energy of Vibration: Harmonic Oscillator
19:08
Equation of the Spectral Lines
23:22
Harmonic Oscillator-Rigid Rotor Approximation (Making Corrections)
28:37
Harmonic Oscillator-Rigid Rotor Approximation (Making Corrections)
28:38
Vibration-Rotation Interaction
33:46
Centrifugal Distortion
36:27
Anharmonicity
38:28
Correcting for All Three Simultaneously
41:03
Spectroscopic Parameters
44:26
Summary
47:32
Harmonic Oscillator-Rigid Rotor Approximation
47:33
Vibration-Rotation Interaction
48:14
Centrifugal Distortion
48:20
Anharmonicity
48:28
Correcting for All Three Simultaneously
48:44
Vibration-Rotation

59m 47s

Intro
0:00
Vibration-Rotation
0:37
What is Molecular Spectroscopy?
0:38
Microwave, Infrared Radiation, Visible & Ultraviolet
1:53
Equation for the Frequency of the Absorbed Radiation
4:54
Wavenumbers
6:15
Diatomic Molecules: Energy of the Harmonic Oscillator
8:32
Selection Rules for Vibrational Transitions
10:35
Energy of the Rigid Rotator
16:29
Angular Momentum of the Rotator
21:38
Rotational Term F(J)
26:30
Selection Rules for Rotational Transition
29:30
Vibration Level & Rotational States
33:20
Selection Rules for Vibration-Rotation
37:42
Frequency of Absorption
39:32
Diagram: Energy Transition
45:55
Vibration-Rotation Spectrum: HCl
51:27
Vibration-Rotation Spectrum: Carbon Monoxide
54:30
Vibration-Rotation Interaction

46m 22s

Intro
0:00
Vibration-Rotation Interaction
0:13
Vibration-Rotation Spectrum: HCl
0:14
Bond Length & Vibrational State
4:23
Vibration Rotation Interaction
10:18
Case 1
12:06
Case 2
17:17
Example I: HCl Vibration-Rotation Spectrum
22:58
Rotational Constant for the 0 & 1 Vibrational State
26:30
Equilibrium Bond Length for the 1 Vibrational State
39:42
Equilibrium Bond Length for the 0 Vibrational State
42:13
Bₑ & αₑ
44:54
The Non-Rigid Rotator

29m 24s

Intro
0:00
The Non-Rigid Rotator
0:09
Pure Rotational Spectrum
0:54
The Selection Rules for Rotation
3:09
Spacing in the Spectrum
5:04
Centrifugal Distortion Constant
9:00
Fundamental Vibration Frequency
11:46
Observed Frequencies of Absorption
14:14
Difference between the Rigid Rotator & the Adjusted Rigid Rotator
16:51
Adjusted Rigid Rotator
21:31
Observed Frequencies of Absorption
26:26
The Anharmonic Oscillator

30m 53s

Intro
0:00
The Anharmonic Oscillator
0:09
Vibration-Rotation Interaction & Centrifugal Distortion
0:10
Making Corrections to the Harmonic Oscillator
4:50
Selection Rule for the Harmonic Oscillator
7:50
Overtones
8:40
True Oscillator
11:46
Harmonic Oscillator Energies
13:16
Anharmonic Oscillator Energies
13:33
Observed Frequencies of the Overtones
15:09
True Potential
17:22
HCl Vibrational Frequencies: Fundamental & First Few Overtones
21:10
Example I: Vibrational States & Overtones of the Vibrational Spectrum
22:42
Example I: Part A - First 4 Vibrational States
23:44
Example I: Part B - Fundamental & First 3 Overtones
25:31
Important Equations
27:45
Energy of the Q State
29:14
The Difference in Energy between 2 Successive States
29:23
Difference in Energy between 2 Spectral Lines
29:40
Electronic Transitions

1h 1m 33s

Intro
0:00
Electronic Transitions
0:16
Electronic State & Transition
0:17
Total Energy of the Diatomic Molecule
3:34
Vibronic Transitions
4:30
Selection Rule for Vibronic Transitions
9:11
More on Vibronic Transitions
10:08
Frequencies in the Spectrum
16:46
Difference of the Minima of the 2 Potential Curves
24:48
Anharmonic Zero-point Vibrational Energies of the 2 States
26:24
Frequency of the 0 → 0 Vibronic Transition
27:54
Making the Equation More Compact
29:34
Spectroscopic Parameters
32:11
Franck-Condon Principle
34:32
Example I: Find the Values of the Spectroscopic Parameters for the Upper Excited State
47:27
Table of Electronic States and Parameters
56:41
XXIII. Molecular Spectroscopy Example Problems
Example Problems I

33m 47s

Intro
0:00
Example I: Calculate the Bond Length
0:10
Example II: Calculate the Rotational Constant
7:39
Example III: Calculate the Number of Rotations
10:54
Example IV: What is the Force Constant & Period of Vibration?
16:31
Example V: Part A - Calculate the Fundamental Vibration Frequency
21:42
Example V: Part B - Calculate the Energies of the First Three Vibrational Levels
24:12
Example VI: Calculate the Frequencies of the First 2 Lines of the R & P Branches of the Vib-Rot Spectrum of HBr
26:28
Example Problems II

1h 1m 5s

Intro
0:00
Example I: Calculate the Frequencies of the Transitions
0:09
Example II: Specify Which Transitions are Allowed & Calculate the Frequencies of These Transitions
22:07
Example III: Calculate the Vibrational State & Equilibrium Bond Length
34:31
Example IV: Frequencies of the Overtones
49:28
Example V: Vib-Rot Interaction, Centrifugal Distortion, & Anharmonicity
54:47
Example Problems III

33m 31s

Intro
0:00
Example I: Part A - Derive an Expression for ∆G( r )
0:10
Example I: Part B - Maximum Vibrational Quantum Number
6:10
Example II: Part A - Derive an Expression for the Dissociation Energy of the Molecule
8:29
Example II: Part B - Equation for ∆G( r )
14:00
Example III: How Many Vibrational States are There for Br₂ before the Molecule Dissociates
18:16
Example IV: Find the Difference between the Two Minima of the Potential Energy Curves
20:57
Example V: Rotational Spectrum
30:51
XXIV. Statistical Thermodynamics
Statistical Thermodynamics: The Big Picture

1h 1m 15s

Intro
0:00
Statistical Thermodynamics: The Big Picture
0:10
Our Big Picture Goal
0:11
Partition Function (Q)
2:42
The Molecular Partition Function (q)
4:00
Consider a System of N Particles
6:54
Ensemble
13:22
Energy Distribution Table
15:36
Probability of Finding a System with Energy
16:51
The Partition Function
21:10
Microstate
28:10
Entropy of the Ensemble
30:34
Entropy of the System
31:48
Expressing the Thermodynamic Functions in Terms of The Partition Function
39:21
The Partition Function
39:22
Pi & U
41:20
Entropy of the System
44:14
Helmholtz Energy
48:15
Pressure of the System
49:32
Enthalpy of the System
51:46
Gibbs Free Energy
52:56
Heat Capacity
54:30
Expressing Q in Terms of the Molecular Partition Function (q)
59:31
Indistinguishable Particles
1:02:16
N is the Number of Particles in the System
1:03:27
The Molecular Partition Function
1:05:06
Quantum States & Degeneracy
1:07:46
Thermo Property in Terms of ln Q
1:10:09
Example: Thermo Property in Terms of ln Q
1:13:23
Statistical Thermodynamics: The Various Partition Functions I

47m 23s

Intro
0:00
Lesson Overview
0:19
Monatomic Ideal Gases
6:40
Monatomic Ideal Gases Overview
6:42
Finding the Parition Function of Translation
8:17
Finding the Parition Function of Electronics
13:29
Example: Na
17:42
Example: F
23:12
Energy Difference between the Ground State & the 1st Excited State
29:27
The Various Partition Functions for Monatomic Ideal Gases
32:20
Finding P
43:16
Going Back to U = (3/2) RT
46:20
Statistical Thermodynamics: The Various Partition Functions II

54m 9s

Intro
0:00
Diatomic Gases
0:16
Diatomic Gases
0:17
Zero-Energy Mark for Rotation
2:26
Zero-Energy Mark for Vibration
3:21
Zero-Energy Mark for Electronic
5:54
Vibration Partition Function
9:48
When Temperature is Very Low
14:00
When Temperature is Very High
15:22
Vibrational Component
18:48
Fraction of Molecules in the r Vibration State
21:00
Example: Fraction of Molecules in the r Vib. State
23:29
Rotation Partition Function
26:06
Heteronuclear & Homonuclear Diatomics
33:13
Energy & Heat Capacity
36:01
Fraction of Molecules in the J Rotational Level
39:20
Example: Fraction of Molecules in the J Rotational Level
40:32
Finding the Most Populated Level
44:07
Putting It All Together
46:06
Putting It All Together
46:07
Energy of Translation
51:51
Energy of Rotation
52:19
Energy of Vibration
52:42
Electronic Energy
53:35
XXV. Statistical Thermodynamics Example Problems
Example Problems I

48m 32s

Intro
0:00
Example I: Calculate the Fraction of Potassium Atoms in the First Excited Electronic State
0:10
Example II: Show That Each Translational Degree of Freedom Contributes R/2 to the Molar Heat Capacity
14:46
Example III: Calculate the Dissociation Energy
21:23
Example IV: Calculate the Vibrational Contribution to the Molar heat Capacity of Oxygen Gas at 500 K
25:46
Example V: Upper & Lower Quantum State
32:55
Example VI: Calculate the Relative Populations of the J=2 and J=1 Rotational States of the CO Molecule at 25°C
42:21
Example Problems II

57m 30s

Intro
0:00
Example I: Make a Plot of the Fraction of CO Molecules in Various Rotational Levels
0:10
Example II: Calculate the Ratio of the Translational Partition Function for Cl₂ and Br₂ at Equal Volume & Temperature
8:05
Example III: Vibrational Degree of Freedom & Vibrational Molar Heat Capacity
11:59
Example IV: Calculate the Characteristic Vibrational & Rotational temperatures for Each DOF
45:03
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Example Problems II

Lecture Slides are screen-captured images of important points in the lecture. Students can download and print out these lecture slide images to do practice problems as well as take notes while watching the lecture.

  • Intro 0:00
  • Example I: Find the Term Symbols for the nd² Configuration 0:11
  • Example II: Find the Term Symbols for the 1s¹2p¹ Configuration 27:02
  • Example III: Calculate the Separation Between the Doublets in the Lyman Series for Atomic Hydrogen 41:41
  • Example IV: Calculate the Frequencies of the Lines for the (4d) ²D → (3p) ²P Transition 48:53

Transcription: Example Problems II

Hello and welcome back to www.educator.com, welcome back to Physical Chemistry.0000

Today, we are going to do another set of example problems for the term symbols and for atomic spectra.0004

Let us get started.0011

This next one, find the term symbols for the ND2 configuration.0014

We are doing the same thing that we did before, just more practice.0020

ND2, we know that D orbital has 5 suborbitals.0024

There are 2 spin orbitals for every suborbital, we had a total of 10.0035

ND2 that means 10 and we have 2 electrons, that is going to be 10 choose 2 viable microstates.0041

That is equal to 10!/ 8! is 2!, what you end up with is 90/ 2 = 45.0051

There are 45 microstates, 45 viable microstates.0061

This tends to get very complex very quickly.0066

45 viable microstates but again it is reasonably easy to handle.0071

It is tedious but it is reasonably easy to handle.0077

We have the D which is 12345, m sub l is 2, 1, 0, -1, -2.0080

Remember the quantum numbers represent the locations.0095

The largest ML achievable, we start with the same way.0098

Find the viable microstates and then find the largest ML.0103

The largest ML achievable is ML is equal to 4.0108

1, 2, 3, 4, 5, that is achievable if we put both electrons in the m sub l = 2.0117

Here, because we put them both for the same suborbital, they have to have opposite spin, ½ and -1/2.0125

Here, the largest MS, the largest M sub S is going to equal 0.0137

We have M sub L = 4, M sub S = 0, this implies that L = 4, this implies that S = 0.0147

It implies that 2S + 1 which is the spin multiplicity is equal to 1.0159

The 4 gives us a G term symbol and the 1.0165

We have a singlet G state.0168

The singlet G state, let us go ahead and do our 2L + 1 × 2S + 1.0173

2L + 1 is equal to, L is 4, 2 × 4 is 8, 8 + 1 is 9, 9 × 1.0198

9 × 1, we have 9 microstates that belong to the singlet G state.0204

ML is equal to 4, 3, 2, 1, 0, -1, -2, -3, -4 and MS is equal to 0.0212

We have 4 0, 3 0, 2 0, 1 0, 0 0.0225

That that, that that, that accounts for the 9 microstates.0229

Let us explicitly list what those microstates are.0232

12345, 12345, 12345, 12345, 12345, 12345, 12345, 12345, 12345, there we go.0236

We started off with this and this, let us just run through this entire.0258

This is 4 0, we need to go 3 0, 2 0, 1 0, 0 0, -1 0, -2 0, -3 0, -4 0.0265

We run through them, this is just the beginning.0274

That is there, that is that one, that is that one, that is that one.0278

For example, if I take this one, here the m sub l is 2.0290

Here, the m sub l is -1.0296

2 -1 is 1, up spin downspin is 0.0299

This microstate represents the 1 0 combination.0303

We work our way down this way which is going to be this this, this this, this this, and this this.0312

These are the 10 microstates that have the same energy.0323

The degeneracy of this singlet G is 10.0331

The next largest ML, the next largest M sub L is equal to 3.0340

Mind you, just because I have the next largest ML = 4, the next largest ML = 3, I just do not work my way down.0351

I do, but I still have to be careful because I still might have another state where the ML can be the same.0361

And it is the same if there is another configuration that I can come up with that has not been accounted for.0369

That still gives me that same ML.0375

The next largest ML is equal to 3, achievable as 1, 2, 3, 4, 5.0378

This is achievable as this, 2, 1, 3.0397

This particular microstate has not been accounted for.0406

It was not in the previous 10 that I listed, this is fine.0410

Here, the MS for this is equal to 1 +½ +½.0413

I have an ML equal to 3 and have an MS equal to 1, that implies that L = 3,0420

this implies that S = 1 and implies that 2S + 1 which is the spin multiplicity is equal to 3.0431

L = 3 gives me an F.0439

That was the triplet S state.0442

2L + 1 × 2S + 1, 2 × 3 is 6, 6 + 1 = 7, 2S + 1 that is this, × 3 we have 21 microstates.0446

21 microstates for this level.0463

We have the ML values, ML3 which means 3, 2, 1, 0, -1, -2, -3.0474

MS 1, 0, -1, 3 × 7 = 21.0484

I need to arrange, I need to list 21 microstates that give me0491

all possible combinations 3 1, 2 1, 1 1, 0 1, all the way down 3 0, 2 0, 1 0, all the way down.0496

Here is how it looks.0510

We have 12345, 12345, 12345, 12345, 12345, 12345, 12345, 12345, 12345, 12345, 7.0515

12345, 12345, 12345, 6 7.0537

You see the fact of the matter is one procedure is not necessarily better than another.0558

At some point, you have to list the microstates.0563

I prefer this particular procedure working with the largest ML0565

and with each term symbol that I find will listing the microstates, because I like the list microstates explicitly like this.0568

I do not like that whole 1 + 0 – symbolism, that confuses me after all these years, I still get confused.0577

I’m going to do the next problem like that one because the problem is going to be slightly different.0584

That is a problem that you often see and you probably want to do one of them.0590

Your actual homework assignment but in general I really prefer this particular method.0592

Finding the term symbol based on the largest ML and the largest MS from a basic configuration and0597

then using that basic configuration to generate all the microstates for that particular term symbol.0603

I just think it works out better.0608

It is tedious.0610

12345, 12345, 12345, this is our basic.0614

I think I’m going to go to red here.0627

Let us go up and up, that is that one, that is that one.0633

When we go down up, down up, down up, down up, down up, down up, down up.0649

There is a symmetry when you are listing these microstates, find a pattern, follow that pattern.0663

We have down and down, down and down, down and down, down down, down down, down down, down and down.0670

There we go, those are our 21 microstates here.0684

Let us go back to black.0691

The next largest value of ML is equal to 2 and this is achievable as I can either do a 2 and 0, both up spin.0705

Or I can do a 1 and 1 up spin down spin.0734

This one has been accounted for already.0739

I just need to find one that has not been accounted for as my basis and0744

then use my ML and MS for that one to generate my term symbol.0750

This one has not been accounted for, that is the one that I'm going to use.0755

In this particular case, here MS is equal to 0.0760

I have an ML = 2, I will go ahead and write the MS.0765

MS is equal to 0 and ML = 2 implies the L = 2, implies that S = 0, implies that 2S + 1 is equal to 1.0769

L = 2 gives me the D, the 1.0780

I have a singlet D state.0783

Therefore, my 2L + 1, my degeneracy for this basic term symbol 2S + 1 is equal to 5 × 10786

which is 5 microstates in the singlet D.0796

ML = 2, 1, 0, -1, -2, I hope by now, the basic pattern that I’m doing is what is that0801

we are doing is starting to come together.0810

MS = 0, I'm going to have 12345, 12345, 12345, 12345, 12345.0814

Let us go ahead and go to red.0829

We picked this as our standard, we will go here.0833

The next one is going to go, I will leave 1 and electron here.0837

I will leave an electron here.0841

Notice, in this case my basic is here.0853

I have come over here already, I'm not occupied with the left side anymore and not occupied here.0857

I do not take this over to this, I bring this here.0864

These are the 5 microstates.0873

The individual M sub L is needed to add to these numbers and the individual M sub S need to add to this number.0876

That takes care of that, let us go back to black.0887

The next value of M sub L can take, if you make a mistake in any of this,0897

you will find out because what is going to end up happening is you are going to end up0922

using all your microstates before your term symbols run out.0928

You are going to end up using, you are going to run out of microstates.0933

Where you have too many or not enough, believe me, if you have made a mistake it will show up.0937

It may not show up right away but it will show up eventually.0943

You are going to end up short on either terms symbols or in microstates, that is what is going to happen.0946

Let us see, the next largest value ML can take is ML is equal to 1.0954

And that is achievable 12345, this or,0964

this is achievable as I can put on both up spin like that or I can do up spin down spin like that.0973

This one has already been accounted for.0982

It is already taken care of.0986

This one has not been accounted for, that is the one that I use.0987

Here, MS is equal to 1.0991

I have got ML is equal to 1, I have got MS is equal to 1.0993

That implies that L = 1, that implies that S = 1, that implies that 2S + 1 which is the spin multiplicity = 3.0997

That is going to give me a triplet P state.1012

2L + 1 × 2S + 1 is equal to 3 × 3, I have 9 microstates.1017

ML = 1, 0, -1.1031

MS = 1, 0, -1, 3 × 3 is equal to 9 microstates.1034

I have got 12345, 12345, and 12345, 12345, 12345, 12345, 12345, 12345, 12345.1040

The state that I picked was this and this.1064

I have this this, I have this, I have this.1069

I can go this way, that way, this way, that way, this way, that way.1074

I can go down, this way that way, this way that way, this way this way.1082

M sub L is 1, 1 + 0 is 1.1096

Up spin up spin is 1.1101

1 + 0 is 1 downspin up spin 0.1108

1 + 0 is 1 down spin down spin -1.1114

1 + -1 is 0 up spin up spin 1.1122

1 + 1 m sub l + m sub l.1129

1 + -1 is 0 down spin up spin 0, that is 0 0.1133

0 -1 -1 downspin up spin 0, that is it.1142

That is all that is going on here.1148

Let us see what we have got.1153

We just have taken care of 9 + 21 + 5 + 9 = 44 microstates.1158

We have accounted for 44 of the 45 microstates.1171

There is 1 microstate left.1174

The next largest ML is equal to 0.1181

Achievable as that, this state is not an accounted for.1191

Yes, this is the one that we use.1200

And the MS here is equal to 0.1202

We have ML is equal to 0, we have MS is equal to 0.1205

It implies that L is equal to 0, it implies that S is equal to 0.1209

It implies that 2S + 1 is equal to 1.1215

2L + 1 × 2S + 1 is equal to 1 × 1 = to 1 microstate.1224

It corresponds and this particular microstate, we have ML = 0, we have MS = 0.1231

The only way that this is achievable is that.1239

We have singlet G, triplet F, singlet D, triplet P, singlet S.1247

Our singlet G, L + S = 4 + 0 = 4.1264

The absolute value of L - S = the absolute value of 4 -0 = 4.1273

J is equal to 4.1281

What we have is a singlet G 4 state.1284

Let me go ahead and put degeneracy in there.1293

Once again, the degeneracy of the complete term symbol is equal to 2J + 1.1297

This 2L + 1 × the 2S + 1 that is equal to the degeneracy of the basic term symbol without the J value.1305

The degeneracy of the actual full term symbol is 2J + 1.1313

In this particular case, I will put a parentheses, it is equal to 9.1318

Triplet S state, L + S = 3 + 1 = 4.1336

The absolute value of L - S = absolute value of 3 -1 is equal to 2.1345

Therefore, J = 4, 3, 2.1353

Start here and work your way down there by increments of 1.1357

We have a triplet F 4, we have a triplet F 3, and we have a triplet F 2.1361

The degeneracy are 9, 7, and 5.1370

9 + 7 + 5 is 21.1376

We have a singlet D state.1387

L + S is equal to 2 + 0 is equal to 2.1391

The absolute value of L – S, the absolute value of 2 -0 is equal 2.1395

Therefore, the J is equal to 2 so we have a singlet D2 state degeneracy of 5.1402

And we have our triplet P.1411

Let me go ahead do on the next page here.1418

I have a triplet P, L + S = 1 + 1 is equal 2.1426

The absolute value of L - S = 1 -1 = 0.1444

Therefore, J is equal to 2, 1, 0.1451

I have a triplet P2, I have a triplet P1, and I have a triplet P0 state.1455

The degeneracy are 5, 3, and 1 for total of 9.1462

Remember, the total degeneracy, the basic term symbol.1470

The triplet P was 9, these are individual breakdowns.1472

5 microstates in the triplet P2, 3 microstates in the triplet P1, 1 microstate in the triplet P0 state.1475

Final state here, we have singlet S.1485

L +S is equal to 0 + 0 is equal to 0.1492

The absolute of L - S = absolute 0 -0 = 0.1498

J = 0, we have a singlet S0 and the degeneracy is 1.1503

Ground state, we are looking for the one with the largest S value.1512

The largest S is equal to 3.1523

Let us try this again.1537

We have a singlet G, we had a triplet F, we have a singlet D, we had a triplet P, and we had a singlet S.1545

The largest S is going to be 3.1559

The largest S is equal to 3 that means that triplet F or the triplet P.1563

The next is the largest L value.1574

The largest L between F and the P is the F, the triplet F.1577

Because we are talking about the D2 which is less than half filled, we are going to take the smallest J value.1583

Less than half means the smallest J value.1593

We had a triplet F4, triplet F3, triplet F2.1598

Our triplet F2 is our ground state for that particular electron configuration of the D2.1605

Let us see what is next.1623

Find the term symbols for the NS1 ND1 configuration.1625

I am a little bit of a typo here, this should actually the NP1 configuration not ND1 configuration.1639

NS1 NP1 configuration, this is an excited configuration.1650

You have 1 electron in the S and 1 electron in the P.1655

I d o not want to write this.1670

I do not think I wrote this the way that I actually wanted to write this.1671

Let me do this.1674

I’m going to be real specific about it.1679

Let me go ahead and do it this way.1690

Let me go ahead and rewrite this configuration.1692

Let us do it as NS1 and we will do N prime.1695

This is crazy, I’m going to pick a specific one.1705

The 1S1 and 2P1.1709

We had the 1S2 excited, when the electron has been excited to the P level.1714

The primary quantum numbers do not really matter.1719

Ultimately, what we are concerned with is this S1 P1, that is what really matters.1721

For excited states where electrons are in different suborbital, I think it is best to do a table or write out the configuration explicitly.1727

What I have done here, I have actually done a table.1781

However, like I said I'm not a big fan of tables.1797

If I'm going to do the microstates, I much rather just write them all up explicitly.1803

At least that way I can see what it is that I'm actually dealing with.1808

I’m going to go ahead and do that.1811

I’m going to modify what it is that I have done.1811

I’m going to write out the possible microstates, the 1S1, 2P1.1814

First of all, we are going to do the same thing and find out the number of viable microstates here.1821

First of all, let us see what we are looking at.1828

Let me go ahead and do this in blue.1829

We are looking at this, the S and then some P.1832

Because they are in different orbitals, here you have the 1 and here you have the 2, basically the S and P,1837

because they are in separate, you have to treat them differently.1852

Here you have 1 electron has two different ways of being in this S orbital.1855

1 electron in the P has 6 different ways.1861

Basically, here you have 2 choose 1.1864

We are going to multiply that by the 6 choose 1.1867

It is going to be 2 × 6, we are going to end up with 12 viable microstates.1871

Because the electrons are in different orbitals S and P,1877

I have to take the number of ways of finding the electron in one orbital × the number of ways of finding the P in the other orbital,1883

and I have to multiply those numbers.1890

There are 12 viable microstates.1893

I’m going to go ahead and list out those 12 microstates.1897

Maybe I should just use a table.1902

I’m going to go ahead and use a table here.1904

For excited states where electrons are in different suborbitals, the largest ML,1910

the largest M sub L achievable is if you put one here.1923

Here the ML is, the m sub l is 0, here the m sub l is 1, 0, -1.1935

If I do this, the largest M sub L possible is if an electron goes into this orbital and this orbital, that is going to equal 1.1941

The largest M sub S, if they both have an up spin ½ and ½, it is going to be that.1952

Our table, the ML is going to be 1, 0, -1.1960

The MS is going to be 1, 0, -1.1963

We are going to have 1, 0, -1.1968

We would have 1, 0, -1.1971

This is M sub S, this is M sub L.1978

The different ways of getting an ML value of 1 is 0, 1.1986

This is going to be 0 0, this is going to be 0 -1.1995

A spin of ½ are both going to be + ½.1999

This is going to be both + ½ and both + ½.2002

Here, this is going to be 0 0.2011

It is going to be 1, it is going to be 0 1 and this is going to be + and this is going to be -.2018

I can also do it with 0 - and 1 +.2031

I can have an M sub L value of 0 and 1.2036

0 and 1 add to 1, + and - add to 0.2039

0 and 1 add to 1, - and + add to 0.2042

This is going to be 0 + 0 - or 0 -0 +, these are not the same.2048

These are not the same because we are in different orbitals.2056

Because the electrons are in different orbital.2060

1 is in the S and one is in the P, very different.2062

These are not equivalent orbitals.2066

And this is going to be 0 -1 + -, 0 -1 - +.2069

And over here, I will do -1, this is going to be 0 -1, 0 -1.2077

0 0, 0 1, 0 – 1, this is going to be - -, - -, - -.2093

There we go, these are 9 microstates.2105

Yes, these are all the possible microstates that are available.2111

The largest ML is 1 which means 1, 0, -1 and the largest MS that has a viable microstate is 1.2115

It is going to be 1, 0, -1.2123

ML is going to be 1, 0, -1.2131

MS is 1, 0, -1.2135

For every combination, I will knock one out.2138

1 1 knock one out , 1 0 knock one out, 1 -1 knock one out, 0 1, 0 0, 0 -1, 0 1, 0 0, 0 -1 knock them out.2141

And it does not matter which one I choose.2165

-1 1, -1 0, -1 -1, -1 1, -1 0, -1 -1 knock one out.2168

For this ML = 1 MS = 1 that implies that L = 1, that implies that S = 1.2179

It implies that 2S + 1 = 3.2189

Here, I am looking at the triplet P state, I think.2195

Yes, triplet P and that has 9 microstates.2201

I know that already, 9 microstates.2207

And I do not know that is the 2L + 1.2211

Let me go ahead and stick with the same procedure.2212

2L + 1 × 2S + 1 should be 6 microstates.2217

123456789, 9 microstates.2222

2 L + 1 = 3 × 3 is equal to 9 microstates and here they are.2225

The only difference is this is 0 1 symbolism instead of the actual writing out the specific explicit orbital configuration.2236

The triplet P state, after I have done this, the table I'm left with is going to be the following.2249

I still have the 1, 0, and the -1 and I have the 1, 0, and -1, except all I have left now is 0, 1.2256

This is - this is +, this is 0 0 - +, and this is 0 -1 - +.2271

This is what is left over.2280

Here, the largest M sub L with a viable microstate is again, notice 1.2286

Here the largest M sub L is 1.2293

The largest M sub S is 0.2297

You notice in both cases, I ended up with a largest ML possible of 1.2302

I did not just go down to 0.2308

In this case, we have ML = 1, MS = 0.2311

That implies that L = 1, that implies that S = 0, that implies that 2S + 1 is equal to 1.2319

And this is going to be a single P state.2327

2L + 1 × 2S + 1, that is equal to 3 × 1 = 3 microstates.2335

These are your 3 microstates, we knock them out because ML = 1, 0, -1 and MS is equal to 0.2348

1 0, 0 0, -1 0, we knock them out.2362

We are left with that.2373

Let us go ahead and deal with our triplet P state.2375

Triplet P, L + S is equal to 1 + 1 is equal 2.2378

The absolute value of L - S is equal to 1 -1 is equal to 0.2388

Therefore, J is equal to 2, 1, 0.2394

I have a triplet P2, I have a triplet P1, I have a triplet P0.2398

The degeneracies are 5, 3, and 1.2405

I have a singlet P, it is going to be L + S = 1 + 0 is equal to 1.2416

L – S, absolute value is equal to 1 -0 = 1.2427

Therefore, J is equal to 1.2431

Therefore, I have a singlet P1 state and its degeneracy is equal to 3.2434

Which is the ground state?2444

The largest S between the triplet P and the singlet P, it is going to be the triplet P.2450

And then I have the largest L value, that does not matter because they are all P.2459

Triplet P2, triplet P1, triplet P0 and it is less than half filled.2467

Therefore, we are going to pick the smallest J which means we are going to pick the triplet P0 as the ground state.2479

That really is exhausting.2494

Let us do a little bit some of spectra.2500

Use the table below to calculate the separation between the doublet in the Lyman series for atomic hydrogen go up to N = 4.2503

You remember, our discussion a couple of lessons ago2520

when we are talking about the Lyman series and we are talking about the fine structure.2523

We said that the fine structure consist of doublets.2530

Each of those lines actually split into two because the P level, the 2P, 3P, 4P2536

it consists of a doublet P 3/2 and a doublet P ½.2542

We see them right here.2549

For the 2P, we have a doublet P 3/2 so that is a double line, that is a double line, that is a double line.2551

And where is the 4P, that is the double line and so on.2565

I want to go to N = 4.2575

We are going to do N = 2, N = 3, N = 4.2577

I do not want you to find a separation between the doublets.2580

The separation between those doublet, one of those is going to be a transition from here to here.2583

It is going to be a transition from here to here.2591

The separation between those is just the difference in energy between this and this.2595

The difference in energy between this and this.2601

The difference in energy this and this.2605

This can take a higher number and subtract the lower number, that is all.2607

Let us go ahead and write all this out.2614

Recall the Lyman series is for the NP 1 down to 1S1 transition.2623

The table shows NP1 with 2 states, doublet P 3/2 and a doublet P ½.2651

Again, the problem is to find the separation between the two.2676

We just take the difference between energy is higher - the lower.2678

I will write everything.2687

The problem asks us to find a separation between the lines for NP12692

and doublet P 3/2 down to 1S1 which is a doublet S 1/2 and NP1 doublet P 1/2 down to 1S1 doublet S ½.2726

We need to find the difference in energy.2750

For N = 2, we have 82259.28501 - 82258.9191, the difference in energy is 0.3659 wave numbers.2757

For N =3, we have 97.2795

We are just taking that – that, that is all we are doing.2800

97492.3196 - 97482.2112 the δ E = 0.1084 inverse cm.2805

N = 4, we have 102823.8942 - 102823.8486 δ E = 00.0457 inverse cm.2834

This probably is something that I should have told you a little bit earlier, I will go ahead and tell you now, I apologize.2863

I decided to use energy tables that I got off of the NIST web site.2869

They are the most up to date, as far as I know.2873

Very recent, the spectra and energy values were calculated within the last 45 years, if I'm not mistaken the last time I checked.2876

Your book making a different tables, tables that have different values.2887

The values are very close to these, but again as the years go on, as our techniques improve, our values improve.2892

Do not worry about if you will get 0.0457, if you are using different values from different tables.2899

Perhaps, your book was printed a long time ago.2905

You are going to be using table that have different values.2909

Do not worry about it, go with the values in the table you are given.2911

The table itself is not that important.2915

It is the process that is important.2916

I just wan to you to know that.2918

You do not have to get that same numbers I'm getting, you are probably using older tables.2920

The ones that are in your book, that is not a problem at all.2924

They are very minor differences.2929

Let us go ahead and round this out.2933

Using the table below for atomic sodium, this time it is atomic sodium.2936

Calculate the frequencies in inverse cm, all the lines for the 4D transitions.2939

This time we are going to calculate the frequencies of the spectral lines for the transition from the 4D to 3P level.2951

The 4D has a doublet D and the 3P has doublet P.2961

Let us go ahead and we will see what we have got.2968

The 4D, let us look at 4D here for sodium.2970

For sodium, you are looking at 1S2, 2S2, 2P6, 3S1 configuration.2975

This is the grounds state right here, the 2P6 3S1 configuration.2983

Its term symbol is a doublet S ½.2988

We know that, the S1 configuration is always a doublet S ½.2993

The primary quantum number is irrelevant.2999

We are going up to, we are going from 4D to 3P.3003

First of all, let us find the 3P if we can, it is right here.3007

The 3P configuration, we are going to have those two.3013

Let us look for the 4D configuration.3022

For D, we have that.3024

We have two possible levels in the D.3027

We have a doublet D 5/2 and a doublet P 3/2 and it could go down to a doublet a P 1/2 and doublet a P 3/2.3030

This is the transition is taking place.3039

The doublet D to singlet P represents one line.3042

The fine structure of that line shows this one going to this one.3047

The doublet D 5/2 to the doublet P ½.3053

The doublet P 5/2 to the doublet P 3/2.3058

The doublet P 3/2 to the doublet P ½.3063

The doublet P 3/2 to the doublet P 3/2.3066

There are 4 possible transitions.3068

The fine structure could show up to 4 possible lines.3070

Let us see which one of those lines, which of those transitions is actually allowed and which is not allowed.3073

Let us go ahead and do this one.3082

Our doublet D has doublet D 5/2 and it has a doublet D 3/2.3088

Our doublet P has a doublet P 3/2 and a doublet P ½.3101

There are 4 possible transitions.3110

Here to here, here to here, here to here, and here to here.3119

We have the doublet D 5/2 down to the doublet P 3/2.3126

I have got the doublet D 5/2 down to the doublet P ½.3137

I have got the doublet D 3/2 down to the doublet P 3/2.3147

Let me go ahead and put the other one right here.3158

I have got the doublet D 3/2 down to the doublet P ½.3161

Let us calculate some values here.3166

Here our δ L, for this one right here, our δ L = -1 DP.3169

Our δ S, doublet and doublet = 0.3179

Our δ J, 5/2 to 3/2 = -1.3182

This one is allowed.3187

Here we have a δ L = -1, we have a δ S = 0, we have δ J 5/2 to ½, it is -2.3190

This is not allowed.3199

Here we have δ L is equal to -1, δ S = 0 and we have δ J is equal to 0.3202

Yes, this one is allowed.3212

Here we have δ L = D to P-1, δ S = 0, and δ J = 0.3213

This one is allowed.3222

The 4 possibilities that is allowed, that is allowed, and that is allowed.3224

This transition is not allowed.3231

We are going to see 3 lines in the fine structure of this particular transition.3233

The rest is just working out the numbers.3239

I'm going to go ahead and do the doublet D 5/2 down to the doublet P 3/2.3243

That is going to be 34548.729 - 16973.366 = 17575.363 inverse cm.3254

That is where I’m going to see one of my lines.3276

The doublet P 3/2 down to the doublet P 3/2, we are going to have 34548.764 - 16973.366 = 17575.398 inverse cm.3281

That is going to be the second of the 3 lines.3318

Of course, the last one is doublet D 3/2 down to a doublet P ½.3323

That is going to be 34548.764 - 16956.170.3332

I think I hate most about quantum mechanics is the computational part.3344

The theoretical part in quantum mechanics is great, all the symbols not these tedious calculation.3348

But it is a necessity.3354

= 17592.594 inverse cm, this is that line.3357

The fine structure of this particular transition will show 3 unevenly spaced lines, the differences between these numbers.3369

This and this, and this and this, it is not even.3378

You will get something that looks like that, the separation.3383

That is it, there we go.3388

Thank you so much for joining us here at www.educator.com.3391

We will see you next time.3393

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