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Free Energy Example Problems I

Slide Duration:

Section 1: 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
Section 2: 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

35m 52s

Intro
0:00
0:10
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
18:08
18:09
21:54
22:34
Fundamental Relationship Equation for an Ideal Gas Under Adiabatic Expansion
25:00
More on the Equation
28:20
Important Equations
32:16
32:17
Reversible Adiabatic Change of State Equation
33:02
Section 3: 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
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
Section 4: 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
Section 5: 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
Section 6: 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
Section 7: 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
Section 8: 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
Section 9: 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
Section 10: Quantum Mechanics Preliminaries
Complex Numbers

34m 25s

Intro
0:00
Complex Numbers
0:11
Representing Complex Numbers in the 2-Dimmensional Plane
0:56
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
Schrӧdinger 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
Schrӧdinger 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 Schrӧdinger 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
Section 11: 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
Section 12: 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
Section 13: 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
Section 14: 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
Section 15: 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
Section 16: 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
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
Section 17: 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
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
28:02
Example: 1s Orbital
28:34
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
Section 18: 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
Section 19: 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
Section 20: 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
Section 21: 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
Section 22: 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
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
Section 23: 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
Section 24: 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
Section 25: 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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### Free Energy Example Problems I

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 0:11
• Example I: Deriving a Function for Entropy (S)
• Example I: Deriving a Function for V
• Example I: Deriving a Function for H
• Example I: Deriving a Function for U
• Example II 15:18
• Example III 21:52
• Example IV 26:12
• Example IV: Part A
• Example IV: Part B
• Example IV: Part C
• Example V 33:45
• Example VI 40:46
• Example VII 43:43
• Example VII: Part A
• Example VII: Part B
• Example VII: Part C

### Transcription: Free Energy Example Problems I

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

Today, we are going to start our example problem sets for free energy.0004

let us just jump right on in.0009

Our first example it says given that G of TP = G super 0 T + nRT + LN T for an ideal gas,0013

use the fundamental equations and the definitions of the composite functions to derive functions for S, V, H, and U.0024

This is a really important problem.0034

It is a more important problem theoretically than is practically but I think it just depends on the particular situation you run across.0039

Remember, we said when we are talking about free energy in the last lesson that if you know the functional form of the free energy expression,0046

If you know what the function looks like, in this case we have this,0054

that we can derive all the other thermodynamic functions from this using the basic equations that we had at our disposal.0061

From this expression for free energy, we can derive the entropy, the volume, the enthalpy, and the actual energy of the system.0067

Again, this is really great way to play with the mathematics to get a sense of what is going on and just become comfortable with it.0077

A lot of the problems in the problem sets for free energy are going to involve a lot of mathematical manipulation.0087

The manipulations themselves are not difficult but they are mathematical manipulations.0095

Again, this is just the way of getting you comfortable with handling the equations0101

not just seeing them on a page but actually using them to derive other relations.0106

None of them are going to be very long, it is just you have to be very careful because of all mathematics there is going to be a lot of symbolism on the page.0110

It is just a question of busyness that is going to be the biggest problem here.0119

In any case, let us go ahead and jump right on in.0123

Let us go ahead and rewrite this.0128

We have G of TP = Z0 of T + nRT nat log of P.0130

This G with a superscript 0, this is just a standard free energy.0143

My free energy at a given temperature and pressure is going to equal the standard free energy + nRT ×0147

log of the new pressure whatever the pressure happens to be that is raised to 2 from the 1 atm.0155

Using the fundamental equations of the definitions of a composite function,0162

our fundamental equations for G is this.0166

We had DG = - S DT + V DP so we know that DG DT,0170

That made us slow down a little bit just to make sure we have all of our variables correctly, is equal to –S.0186

We know this already from that or we can just read it out from here, this is the total differential expression.0192

This is going to be the DG DT holding this variable constant.0198

From the equation above, from this equation, if I actually take DG DT holding P constant,0205

If I take the derivative of this directly I’m going to end up with DG DT.0223

This is just a function of temperature so it is a regular derivative not a partial derivative +0235

the derivative of this with respect to T holding P constant is going to be nR LN P.0241

From the fundamental equation I have this, from taking a derivative of this equation which is the equation they gave us I have this.0253

I’m going to set these equal to each other.0260

I have - S = D 0 DT + nR LN P but this, that, this thing right here this DG DT is just - S for the standard conditions.0262

DG DT under constant P = - S so DG standard DT is just - S standard, that is all it is.0295

We get - S = - S standard + nR LN P.0306

I can go ahead and I can leave it like that or I just can go ahead and rearrange things, multiply by -1.0316

S = S standard - nR LN P, there we go.0321

From this equation which is the equation for the free energy of the system,0330

I was able to do derive an equation for the entropy of the system.0338

It is equal to the standard entropy - nR LN P, that is what we are doing here.0344

That takes care of the S.0352

Let us go ahead and let us see what is next.0357

Once again, let me go ahead and write the equation DG = - S DT + V DP.0361

I know that DG DP under constant T = volume.0372

Let us see from the equation of the equation that they gave us, the functional form of the equation which is this one,0384

+ nRT LN P, if I take the derivative directly, let me see if I do the DG DP under constant T.0393

If I take the derivative of this holding temperature constant and take it with respect to pressure,0412

I get nRT × the derivative of LN P which is 1/ P.0419

I get nRT/ P.0427

I have this equal to nRT/ P from the fundamental equation I have the same thing is equal to V.0430

I will just go ahead and set them equal to each other so I get V = nRT/ P which we knew already.0437

We actually ended deriving it from the functional form of the free energy as a function of temperature and pressure V= nRT/ P.0446

This is just PV = nRT, this is the ideal gas law, this confirms it.0454

I have derived a thermodynamic property of volume from the free energy using these other equations that I have.0460

Using this equation and this equation.0468

Let us see what we can do, we have taken care of the S, we have taken care of the V, let us see if we can do something for the enthalpy.0474

The composite functions let us just go ahead and recap our definition for composite functions.0484

The enthalpy = the energy + PV.0490

Our Helmholtz energy which does not concern us in this particular problem but I will go ahead and write it down anyway as the definition.0495

G = DU + PV - TS which is equal to G= H – TS.0501

These are the definitions of the composite functions, enthalpy A this.0513

Let us go ahead and deal with this one because again they gave us G in the problem and now we want to find H.0517

Let us go ahead and take this, bring it over here.0526

We will rearrange this and we will write H = G + TS.0529

H = G is just G is this thing so we are going to write G of T + nRT LN P + T × S.0536

H = G standard of T + nRT LN P + T × we already know what S is, we just found it.0561

In the previous page that is just is equal to S standard of T – nR LN P.0574

I get H = G standard of T + nRT LN P + T S standard T – nRT LN P.0584

That cancels with that and I am left with the enthalpy of my system = the standard free energy of the system + the temperature × the standard entropy.0602

This is interesting.0625

I have G standard + T S standard.0627

You remember the definition of H was just G + TS.0632

G standard + T S standard is nothing more than H standard.0641

This is my equation, this is what I was looking for.0647

I was able to derive the functional value for the enthalpy of the system based strictly on the fact that0654

I was given the functional form of the free energy of the system and ends up being the standard free energy +0663

the temperature I happen to be at that moment × the standard entropy.0671

This just happens to equal the standard enthalpy.0679

In other words, the enthalpy of the system under standard conditions.0689

Again, because H = G + TS that is the definition of a composite function, we just rearranged.0694

H standard = G standard + S standard.0709

This is the functional form but it just happens to equal that.0716

Let us go ahead and see if we can derive something for U.0727

They also want U.0730

We have H = U + pressure × volume so U = enthalpy - pressure × volume.0732

U = enthalpy – we are dealing with an ideal gas so it is going to be H – nRT.0745

That is kind of interesting.0756

Actually, we want it, here we go.0760

U = H – nRT, we already found H.0762

H is this nRT so you already found that.0766

Here which happens to equal the energy of the system under standard conditions because U = H – nRT.0774

Therefore, U standard = H standard – nRT.0795

Therefore, let us see, I got U = H – nRT.0806

Under standard conditions, the H happens to equal H standard so this is just H.0812

Basically, I have got from here, I can stop here because I already got everything else.0822

If I want to continue, U = H – nRT, H = H standard nRT.0827

Therefore, U = H standard - nRT but that is equal to U standard.0835

Everything is falling into place nicely here.0843

U = H which is G standard T + TS standard T – nRT.0847

I can use the short version of it or I can use this version of it which is expressed in terms of the actual standard free energy.0866

Given the functional form of the standard free energy I was able to derive expressions for the entropy.0876

I was able to find the entropy, the change in entropy.0881

I was able to find the volume of the system.0883

I was able to find the change in enthalpy of the system.0885

I was able to find the change in energy of the system strictly from having the functional form of the free energy.0888

This procedure is the same, this is the general procedure, it will always work.0900

If you are given the functional form for free energy, what we did here will always allow you to derive the entropy change,0904

the enthalpy change, the volume and the energy change.0910

Using the thermodynamic equation of state and the Van Der Waals equation find DU DV sub T for the Van Der Waals gas.0921

DU DV sub T for the Van Der Waals gas, not the ideal gas.0931

Let us go ahead and let us write the thermodynamic equation of state.0936

In this particular case, we have got P = T × DP DT constant volume - DU DV T.0944

I’m going to rearrange this because now I'm looking for that.0961

I have got DU DV sub T = T × DP DT under constant volume – P.0966

The Van Der Waals equation P = nRT/ V - nV - AN²/ V².0983

Therefore, I have got this and I have got this so I'm going to find this DP DT.0998

I have P so now I’m going to take DP DT and I’m going to hold volume constant.1005

When I do that, when I take the derivative of this expression holding volume constant,1013

I'm going to end up with derivative with respect to T, it is just going to be this.1019

I'm going to get nR/ V –NB.1029

Again, constant and constant, NV is a constant so the derivative ends up going to 0.1033

I take this value and I plug it into there so I get DU DV constant T = T × nR/ V - NB – P.1038

P is just this, the whole thing, just put back in here - nRT / V - NB – N² A/ V².1058

That is going to equal nRT/ V - NB - nRT/ V - NB + N² A/ V².1072

That cancels and what I’m left with is DU DV constant T for the Van Der Waals gas = N² × A/ V², this is what we wanted.1088

Notice, this does not equal to 0 like the ideal gas.1106

Recall, when we had DU = CV DT + DU DV under constant T DV, this is the expression for the differential change in energy of the system.1111

It is going to be a function of temperature and the function of volume.1133

The DU DV, the Joules law for an ideal gas, this DU DV sub T that was equal to 0.1135

Because it was equal to 0, this term went away and the energy just became a function of temperature based on the constant volume heat capacity.1146

That was for an ideal gas, in this particular case this is a Van Der Waals gas.1153

For the Van Der Waals gas, this is no longer equal to 0.1158

When we use this equation for a Van Der Waals gas we actually have to include it.1161

When we integrate this, we have to integrate this term and we have to integrate this term, in order to find our δ U, our change in energy.1168

δ U is no longer just DU = the integral of CV DT from T1 to T2.1182

For a Van Der Waals gas, now you have δ U = the integral of this one which is CV DT from T1 to T2 +1198

the integral from volume 1 to volume 2 of this Du DV which in this case is N² A² / V² DV.1210

If we have an isothermal process for a Van Der Waals gas, isothermal means that this term can go to 0.1224

But now, the change in energy is not equal to 0.1232

For an ideal gas and isothermal process involves that there is no change in energy and it implies that δ U = 0 but only for an ideal gas.1236

Do not just automatically assume that just because we are talking about an isothermal process, the δ U = 0, it does not.1245

For an ideal gas and isothermal process this is 0 and this is 0 so δ U = 0.1256

Not for a Van Der Waals gas, for Van Der Waals you have to evaluate this integral right here.1262

An isothermal process implies that δ U = 0 only for an ideal gas.1271

That thing is, you get so many problems and questions that involve ideal gases.1284

A lot of students automatically equate isothermal with δ U = 0, that is not the case.1287

It is never the case.1294

This is the equation you want to know.1296

Let the equation tell you what is what.1299

Are you dealing with an ideal gas, solid, liquid, Van Der Waals gas, are you dealing with a different kind of gas, whatever it is.1301

Let us go ahead and take a look at example 3.1314

Calculate δ U for the isothermal expansion of 1 mol of nitrogen as a Van Der Waals gas from 10 dm³/ mol to 100 dm³/ mol.1317

It should be just 1 dm³ to 10 dm³.1330

Let us see what we have got, 10 to 100.1334

A, in this particular case is 0.141 so let us see what we have.1337

We always start with our basic equation, those are the ones that we want to use.1342

Those are the one that tell us what we are doing.1347

DU = CV DT + DU DV at constant T DV.1350

This is an isothermal process so isothermal means the DT is 0 so we can take that to 0.1362

We have got DU = this thing, DU now equal this thing, that is what we are going to integrate.1366

We got δ U = the integral from v1 to v2 of N² A/ V² DV = N² A × the integral DV/ V from v1 to v2.1381

Let us put our v², there we go.1403

δ U = 1 mol, this is 1 × A is 0.141 × the integral, 10 × 10⁻³ to 100 × 10⁻³.1406

The reason it is 10 dm³ to 100 dm³, A is expressed in Pascal’s.1431

When you are working with Pascal’s you have to work in m³.1441

Recall, volume must be in m³ when working in Pascal.1445

Again, it is pesky and it is annoying but you have to keep track of your units.1464

Take a look at what units you are actually given in the case of the Van Der Waals gas,1469

this particular unit is 0.141 using the Pascal and meters so it has to be in cubic meters.1473

The volume was given cubic decimeters so you have to convert to m³.1482

10 dm³ is 10 × -3 m³ when working with Pascal.1487

It is going to be the DV/ V² so we end up with δ U = 1² × 0.141 × 1/ V.1498

It is minus because this is going to be when we integrate this, the negative sign is going to be 1/ V -1/ V.1516

I'm just going to bring the negative over here 10 × 10⁻³ to 100 × 10⁻³.1522

When I evaluate this, I get δ U = 12.69 J.1530

An isothermal expansion of 1 mol of nitrogen as a Van Der Waals gas from 10 dm³ to 100 dm³ isothermally you end up with 12.69 J as your δ U.1544

Van Der Waals gas δ U is not equal to 0, it is equal to 12.69.1563

Let us see what we have got.1571

Derive an expression for the change in entropy with respect to volume under a constant temperature for a Van Der Waals gas.1577

Find an expression for δ S for the isothermal expansion of the Van Der Waals gas from v1 to v2.1586

Comparing the expression in part B with the analogous expression for the ideal gas, for the same increase in volume,1592

will the change in entropy be greater for the Van Der Waals gas or for the ideal gas?1600

Let us see what we can do.1608

Part A, I’m going to do this in red.1613

Part A, the equation for the Van Der Waals gas is nRT/ V – NB.1618

Let us make V a little bit better, - N² A/ V².1629

From one of Maxwell's relations said that DS DV at T = DP DT under constant V.1638

We are looking for DS DV and Maxwell's relations said the DS DV = the change in pressure with respect to temperature holding the volume constant.1661

I have the equation, the Van Der Waals equation.1676

If I hold the volume constant and if I take the derivative of P with respect to T this is just equal to nR/ V – NB.1678

There you go, that is my first part.1695

The rate of change of entropy as I change the volume for a Van Der Waals gas is nR/V – NB.1698

That is all, nothing strange is happening here.1704

It is just mathematics, simple derivatives.1706

Now, they want us to find an expression for the δ S.1712

Let us start with our basic equation again for DS = CV/ T DT + DS DV under constant T DV.1715

They say that this process is isothermal.1732

Isothermal so that goes to 0, DT is 0.1734

All I have is DS = this thing.1738

For the Van Der Waals gas, I just derived this thing, it is nR/ V – NB.1743

It was equal to nR/ V - NB × DV.1747

I just integrate this and I get δ S = nR × integral from v1 to v2 of DV V – NB.1755

I get nR × log of V -NB from V1 to V2.1773

I get my expression, I get nR × the LN of V2 – NB.1790

They just want the expression over v1 – NB.1798

For Van Der Waals gas, my δ S is this based on the fact that the DS DV is this.1803

That comes from this, the basic equation.1811

They want us to compare this with that for the ideal gas.1820

Let us go ahead and do that.1825

We can go ahead and just recall what the expression is for the ideal gas or we can go ahead and derive it.1828

Let us go ahead and derive it because I think it is always good to recall the things.1835

We cannot remember everything that is going on.1839

Maxwell's relations says the DS DV under constant T = DP DT under constant V.1843

For an ideal gas P = nRT/ V.1853

Therefore, this DP DT under constant V this thing is just equal to nR/ V.1858

DS = CV/ T DT this is our basic equation + DS DV under constant T DV.1872

We are dealing with an isothermal process so that goes to 0.1886

DS DV = DP DT, DP DT = nR/ V.1889

Therefore, DS = nR/ V DV.1895

When we integrate this, we end up with δ S.1903

For the ideal gas = n × R × the log of V2/ V1.1914

We just calculated that the δ S of the Van Der Waals gas = nR × the nat log of V2 - NB/ V1 – NB.1923

We can compare these two, between these two, the δ S of the Van Der Waals gas is going to be bigger than the δ S of the ideal gas.1939

The change in entropy of a Van Der Waals gas is going to be bigger than the change in entropy of the ideal gas.1956

When you subtract the same value, V2/ V1 V2 – NB V1 – NB.1964

You are subtracting the same value from numerator and denominator.1975

When you subtract the same value from numerator and denominator of a ratio, the value of the quotient goes up.1978

The value of the quotient actually rises.1996

The log of the bigger number is bigger.2000

Therefore, the δ S of the Van Der Waals, this expression is greater than this expression.2002

The value of the quotient rises as just a basic mathematical fact.2011

Let us see if we can make our way through this ocean of mathematics that we happen to be swimming through.2020

I’m starting to lose my own way here.2025

Example number 5, to a first approximation the compressibility factor Z of the Van Der Waals gas is Z = PV/ RT.2030

The compressibility factor of any gas is just the pressure × the volume/ R × T.2037

It is equal this thing, from this and the thermodynamic equation of state to demonstrate that the change in molar enthalpy2045

with respect to pressure under constant temperature for a Van Der Waals gas = B – 2A / RT.2054

Again, this is nothing more than mathematical manipulation.2060

Let us see what we can do.2064

Let us go ahead and rewrite this again.2067

We go ahead and go back to blue.2072

I have got PV and again when this line over it just means molar, it just means V is nothing more than this V line, this V bar is nothing more than V/ N.2074

That said so, if I just want to multiply everything by N, I end up getting V.2086

It is not a problem, this is just the molar volume instead of the volume.2088

PV/ RT = 1 + B - A/ RT × P/ RT.2095

Let us see here, they want this thing.2109

The thermodynamic equation of state is the following.2115

Thermodynamic equation of state says that DH/ DP = V - T × DV DT.2119

I will put these over, it does not really matter, DT under constant P.2136

This is equal to this so I need to find DV DT from this equation and plug it into here and see what I end up with.2144

I’m going to rearrange this equation and solve for V.2153

Let me go ahead and do that over here.2157

I get PV =, I’m going to multiply everything by RT.2160

I’m going to get RT + B - A/ RT × P.2165

I’m going to go ahead and divide by P so I'm going to get V = RT/ P + B - A/ RT.2173

Once again, rewrite the DH DP = V - T × DV DT that is the thermodynamic equation of state.2188

Now, I have this so let me go ahead and find DV DT while holding P constant.2207

I’m going to find this from this equation, holding P constant I end up with R/ P - -A R/ RT².2217

When I take the derivative of this with respect to T, this derivative is 0 and I'm going to get - and – that is going to be +.2245

We are good.2254

This - and this -, when I take the derivative of this with respect to T, I get this -.2256

It is going to equal R/ P + AR/ R² T².2262

I’m just going to go ahead and cancel the R so I will just do it now.2273

A/ RT², 1 R cancels 1 R leaving just 1 R on the bottom.2275

My DH DP T = V - T × DV DT which is this R/ P + A/ RT².2283

This is equal to V, V is equal to this whole thing so I’m going to put that back in.2310

It is going to be RT/ P + B - A/ RT –,2315

I’m going to go ahead and distribute, this is RT/ P - A/ RT².2326

RT/ P cancels RT/ P and I get the DH/ DP under constant T = this - that - that = B -2A/ RT².2339

What happened here?2373

I think I have lost my way in this mathematics.2373

Let us see what is going on.2376

Let us see if I copy everything correctly here.2377

There is our T – T, I'm sorry this is here and I distribute the T.2379

I forgot to distribute the T over this one.2389

This is T there, sorry about that.2391

There we go, let me go ahead and erase this part and let me do this part again.2397

This RT/ P cancels this RT/ P.2400

We have B - A/ RT and this T cancels that - A/ RT.2403

There we go, -2A/ RT.2410

There you go, that takes care of the first one.2417

The change in molar enthalpy with respect to a change in pressure at constant temperature for a Van Der Waals gas = B – 2A/ RT.2424

Example 6, using the same expression from example 5 for the compressibility Z of2448

the Van Der Waals gas which was this thing, show that DS DP sub T = this thing.2457

By one of Maxwell's relations, we have the following – DS DP sub T which is actually what we want.2473

That is actually equal to DV DT sub P.2486

This is the same thing that we did before, we are going to take this equation.2503

We want to take the derivative of V with respect to T so we are going to rearrange this equation2516

just like we did before in the previous example.2523

We ended up with the following, we ended up with V = RT/ P + B - A/ RT.2526

When we take the derivative of this with respect to T holding P constant so that DV DT holding P constant we end up with R/ P + AR/ RT².2538

We go ahead and put this in for here and we are going to end up with DS DP under constant T =...2571

Let me just rewrite this again, DT under constant P which is actually equal to – R/ P + AR/ RT².2593

This one was not that bad, this was just using Maxwell's relation and taking the derivative of the Van Der Waals equation.2611

That was nice and simple.2618

Example 7, this one is a little interesting.2624

Using the results from the previous two problems for DH DP and DS DP, calculate δ H and δ S2630

for the isothermal pressure increase of CO₂ as a Van Der Waals gas from 1 mPa to 15 mPa at 298°K.2639

These are the values for the Van Der Waals constants for CO₂ and they ask us to run the same calculation of 598.2649

They say compare the values you calculated for 298 to those obtained for an ideal gas.2658

We just found expressions for a Van Der Waals gas for the change in enthalpy with respect to pressure,2666

the change in entropy with respect to pressure, we could integrate these expressions to get expressions for the actual change in enthalpy and2671

the change in entropy and when you compare that to the ideal gas.2679

Let us see what we have got.2688

We know what δ H is and we want to know what δ S is.2690

Let us go ahead and write down what we got.2697

Our CO₂ gas, we are taking it from 1 mPa, we are taking it to 15 mPa and we have our value of.2709

A = 0.366 m 6 Pa/ mol² and B = 42.9 × 10⁻⁶ m³/ mol.2720

From the previous example, we found that DH DP at constant T = B - 2A/ RT.2742

Therefore, I have got DH = V -2A / RT DP.2755

When I go ahead and integrate this expression, I’m going to get δ H = B - 2 A/ RT × the integral from P1 to P2 of DP and it is going to = B -2A/ RT × δ P.2768

Our δ H is going to equal, again this is molar.2801

We have got D – 2A.2808

Let us just plug in all of our values so we have B which is going to be 42.9 × 10⁻⁶ -2 × 0.366/ 8.314 × 298 × δ P.2810

It is going to be 15 -1, I’m going to do × 10⁶ because this is mPa.2837

We are working in Pascal’s in order to make sure that the units match.2847

15 -1 is 14 mPa, it is 14 × 10⁶ Pa.2855

When I do this, I get δ H of -3536 J/ mol that is all this line means molar.2861

There we go, that is the δ H based on what we calculated for DH DP and integrated it.2874

For the DS, we work out that DS DP under constant T = - R/ P + RA/ RT².2886

Therefore, DS = when I move P over I integrate the expression, I'm going to get from P1 to P2 of this thing.2906

This thing R/ P + R A/ RT² DP.2919

DS = - R × the integral from P1 to P2 of DP/ P.2932

This - comes out so this becomes a - and this becomes a - that distributes over both.2943

- A / RT² and I cancel one of the R × the integral P1 to P2 DP.2949

Therefore, our DS = - R LN P2/ P1 - A/ RT² × δ P.2967

We put the values in, δ S = -8.314 × the nat log of 15/ 1.2984

The mPa cancels mPa, the units cancel, I can leave the numbers alone.2996

-0.366/ 8.314 × 298² × 15 - 1.3003

And again, this one × 10⁶ and there is no cancellation here.3017

I’m going to do these separately, - 22.5 - 6.9.3024

Therefore, the entropy change is -29.4 J/°K mol.3033

That takes care of the δ S.3047

Let us see what is next, they ask us to run the same calculations part B under a new temperature.3052

It is the same exact process same, same exact thing we just did the only difference is instead of 298 for the T, we are going to put 598 for the T.3061

What we end up with are δ H, I will go ahead and put 598.3068

It is going to equal- 1460 J/ mol and δ S = - δ S at 598 = -24.22 J/mol °K.3076

Let us go ahead and compare the two values.3118

Let us see, C wants us to compare the values for the ideal gas and the Van Der Waals gas.3125

The δ S for an ideal gas = - R LN P2/ P1 that was the first term.3130

We will do it in just a second.3144

It is - 22.5 J/°K mol3147

The δ H for the ideal gas = 0.3158

It is 0 because DH/ DP T = 0 for an ideal gas, remember Joule Thompson coefficient for an ideal gas.3168

I will put Joule Thompson.3185

In case you are wondering where this came from, right here for the ideal gas, just look back on lesson 21.3193

Lesson 21 which is the entropy changes for an ideal gas.3207

Notice, this expression right here this was the first half of the expression for the Van Der Waals equation that we just did in part A.3218

The Van Der Waals expression, remember I did into -22.5 - another value.3228

That -22.5, that takes care of the ideal gas portion of the Van Der Waals gas.3235

Because it is a Van Der Waals gas, there is actually an additional term.3240

It is no different than the Van Der Waals equation.3244

Thank you so much for joining us here at www.educator.com.3253

We will see you next time.3255

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