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Raffi Hovasapian

Raffi Hovasapian

The Ideal Gas Law

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
00:50
Convention for Heat
02:40
Convention for Work
04:24
Schematic Representation
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
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
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
02:16
N is the Number of Particles in the System
03:27
The Molecular Partition Function
05:06
Quantum States & Degeneracy
07:46
Thermo Property in Terms of ln Q
10:09
Example: Thermo Property in Terms of ln Q
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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Lecture Comments (25)

1 answer

Last reply by: Professor Hovasapian
Sat Sep 10, 2016 2:30 AM

Post by Saeed Alshahrani on September 4, 2016

Hello Professor Hovasapian,

Here is my chemistry thermodynamics course table of contents.

Are all the material in the table covered in your course? If not, what's your advice for the material that you didn't cover.

Thanks in advance, and sorry for the long massage.


Week 1
B. Ideal Gas and the Equation of State
Things to know and do
Equilibrium and Temperature
The Equation of State
Units
Canceling Units
Boyles Law
Gay-Lussac’s Law
The Gas Constant and the Mole
Avagadro’s hypothesis
Avagadro’s number
Daltons Law of Partial Pressure
Graham’s Law of Effusion
C. Kinetic Theory of Gases
The Kinetic Theory of Gases
Boyle’s Law (from first principles)
Kinetic energy
Equate the Empirical and the Derived
Implications
The Boltzmann Constant
Molecular Speeds
Root Mean Square
D. Collision Frequency
Molecular Collisions
Collision Frequency
Collision Density
Refinement
Mean Free Path
Viscosity of Gases
The Coefficient of Viscosity
Real Gases
E. Viscosity
Viscosity of Gases
The Coefficient of Viscosity
Real Gases
Compressibility Factor
Equations of State for Real Gases
Attractive Forces
Molecular Size
Topics. CH3510 Fall 2015
Week 2
F. Real Gases
van der Waals Equation
The Critical Point
van der Waals Isotherms
vdW and the Critical Point
The Constants
The Law of corresponding states
G. Thermodynamics
Systems
Definitions
Boundaries and Processes
Zeroth Law
First Law of Thermodynamics
The Sign Convention
State Functions
Work
H. Heat Capacity
Reversibility
Special Cases; Constant Volume
Special Cases: Constant Pressure
Enthalpy
Enthalpy and Internal Energy
Heat Capacity
I. CP and CV
Heat Capacity CV
Heat Capacity CP
How CP and CV are related
Equipartition of Energy
J. Isothermal and Adiabatic Expansion
Equipartition of Energy
Special cases – Isothermal Expansion
Reversible Isothermal Expansion
Irreversible Isothermal Expansion
Adiabatic Expansion
Reversible Adiabatic Expansion
Irreversible Adiabatic Expansion …
Thermochemistry
Stoichiometry
Topics CH3510 Fall 2016
Week 3
K. Hess’s Law and Calorimetry
Extent of Reaction
Bomb Calorimeter Experiment
Hess’s Law
L. Joule Thompson Experiment
Relationship between ?U and ?H
Enthalpies of Formation
Standard States
Enthalpies for Solutions
Enthalpy of Neutralization
The Joule- Thomson Experiment
µ the Joule – Thomson Coefficient
M. The Second Law and the Carnot Cycle
The Second Law of Thermodynamics
Heat and Work
The Carnot Cycle
Overall ?U
Overall q
Overall w
Interpretation
Efficiency
N. Entropy
Efficiency
Work done by the System
Work done on the System
Net Work
Efficiency in Terms of Heat
Entropy
Entropy and Internal Energy
Entropy Changes
Changes of State
Topics. CH3510 Fall 2015
Week 4
O. Practical Entropy
Ice Calorimeter
Irreversible Changes
Supercooling and Superheating
Entropy and Ideal gases
Entropy as a Function of T and P
P. Entropy of Mixing
Entropy of Mixing
Trouton’s Rule
The Third Law
Reaction Entropy
The Magnitude of Entropy
Q. Gibbs Free Energy
Conditions for Equilibrium
Entropy of Equilibrium
The Gibbs (Free) Energy
Gibbs Energy of Formation
R. Maxwell’s Demon
Free Energy of Reaction
Gibbs Energy of Formation
Gibbs Energy and Work
Gibbs and Non PV Work
The Helmholtz Energy
Helmholtz Energy – the Work Function
Spontaneity and Equilibrium
Properties of a System
Fundamental Equations
Week 5
S. Gibbs – Helmholtz Equation
Fundamental Equations
Maxwell’s Relations
Gibbs Helmholtz Equation
The Effect of Pressure on G
Fugacity and Chemical Potential
Topics CH3510 Fall 2016
T. Chemical Potential
Fugacity and Chemical Potential
Fugacity
Activity
Chemical Potential
Implications of µ
Chemical Equilibria
Law of Mass Action
U. Thermodynamic Equilibria
Thermodynamic Equilibrium Constant
Equilibrium
In terms of Concentration
Characteristics
Condensed Phases
Le Chatelier’s Principle
V. Equilibria Composition
Equilibrium Composition
A Very Unpleasant Problem
The Behavior of G as Function of ?
Week 6
W. Why do Equilibria Happen?
Phases and Solutions
Phase Diagram of Water
The Clapeyron Equation
The Clausius Clapeyron Equation
Phase Transitions
Phase Diagram of Water
Triple Point
Phase Diagram of CO2
X. Phases and Solutions
A Note on Equilibria Units
Mixtures and Solutions
Partial Molar Properties
Molar Volumes
Free Energy of Mixing
Entropy of mixing
Enthalpy of Mixing
Y. Raoults Law
Raoult’s Law
Liquid Vapor Composition

1 answer

Last reply by: Professor Hovasapian
Sat Apr 23, 2016 7:33 PM

Post by Bernhard Retzl on April 21, 2016

Is there a possibility  to reduce the Buffering of the videos?

1 answer

Last reply by: Professor Hovasapian
Fri Mar 25, 2016 10:53 PM

Post by Jupil Youn on March 12, 2016

During the lecture, you explained that any fundamental property of a system should never depend on how much is there. It applies to nano-scale system?  

1 answer

Last reply by: Professor Hovasapian
Wed Nov 11, 2015 4:18 AM

Post by Jeffrey Tao on November 9, 2015

I just looked through the table of contents, and it seems that this course requires multivariable calculus (partial derivatives). Would you say that I should take your course in multivariable calculus first before starting this one (I've already taken AP Calculus BC)?

1 answer

Last reply by: Professor Hovasapian
Fri Feb 27, 2015 1:44 AM

Post by David Löfqvist on February 25, 2015

How long time would you recommend for this course?

1 answer

Last reply by: Professor Hovasapian
Wed Nov 19, 2014 5:48 AM

Post by Scott Beck on November 17, 2014

Hi you are a very excellent teacher and I love your use of words. Do you have an estimate to when your AP Calculus AB course will be released?

1 answer

Last reply by: Professor Hovasapian
Mon Oct 13, 2014 5:46 PM

Post by Okwudili Ezeh on October 12, 2014

Please could you post the transcription for all your lectures.

1 answer

Last reply by: Professor Hovasapian
Mon Oct 13, 2014 5:43 PM

Post by manu vats singh on October 11, 2014

which textbook would you recommend for this course

2 answers

Last reply by: Noah Jakson
Fri Oct 10, 2014 4:00 PM

Post by Noah Jakson on October 9, 2014

Thank you for the quick and informative response.  We are doing Classical Thermodynamics in the fall and in the spring we will be doing QM.  So Thermo now, QM later.

The syllabus is a bit screwy, I just realized because there are titles that are the same, so I apologize for the error of listing McQuarrie twice.

Our official book is #3, however, many students and faculty are not very fond of it, including myself, and we are still sampling many texts to find one that is a good fit, which is why the syllabus states "other books that could be used for this class."

I have heard many good things about McQuarrie, so I will have to borrow it and see.  

Thank you very much Professor Hovasapian.

3 answers

Last reply by: Noah Jakson
Thu Oct 9, 2014 3:45 PM

Post by Noah Jakson on October 8, 2014

Hello Professor Hovasapian,

I was wondering if you could recommend a physical chemistry text.  My syllabus has seven books, but the professor told us to pick one, and I am not sure which one would be best.

The choices:

Physical Chemistry, Atkins/DePaula
Physical Chemistry: A Molecular Approach: D. A. McQuarrie & J. D. Simon
Physical Chemistry, Engel & Reid
Physical Chemistry: Berry, Rice & Ross
Molecular Thermodynamics: R. E. Dickerson
Statistical Thermodynamics: D. A. McQuarrie
Rates & Mechanism of Reactions: W. G. Cardiff
Kinetics & Mechanism: J. W. Moore & R. G. Pearson
Physical Chemistry: A Molecular Approach: D. A. McQuarrie & J. D. Simon

1 answer

Last reply by: Professor Hovasapian
Sat Sep 6, 2014 9:32 PM

Post by Tom Glow on September 6, 2014

Amazing!  Thank you Professor, I have been excited about this course since it was announced!

Related Articles:

The Ideal Gas Law

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
  • Course Overview 0:16
    • Thermodynamics & Classical Thermodynamics
    • Structure of the Course
  • The Ideal Gas Law 3:06
    • Ideal Gas Law: PV=nRT
    • Units of Pressure
    • Manipulating Units
    • Atmosphere : atm
    • Millimeter of Mercury: mm Hg
    • SI Unit of Volume
    • SI Unit of Temperature
    • Value of R (Gas Constant): Pv = nRT
  • Extensive and Intensive Variables (Properties) 15:23
    • Intensive Property
    • Extensive Property
    • Example: Extensive and Intensive Variables
  • Ideal Gas Law 19:24
    • Ideal Gas Law with Intensive Variables
  • Graphing Equations 23:51
    • Hold T Constant & Graph P vs. V
    • Hold P Constant & Graph V vs. T
    • Hold V Constant & Graph P vs. T
    • Isochores or Isometrics
    • More on the V vs. T Graph
    • More on the P vs. V Graph
    • Ideal Gas Law at Low Pressure & High Temperature
    • Ideal Gas Law at High Pressure & Low Temperature

Transcription: The Ideal Gas Law

Hello and welcome to www.educator.com.0000

Welcome to the first lesson of Physical Chemistry.0002

Before I actually launch into the Physical Chemistry, I want to talk a little bit about the course as a whole so0006

that you have an idea of what is that you are in for and what is there to expect.0011

Physical chemistry is taught in two ways.0018

We teach classical thermodynamics first and then we could quantum mechanics and then we go back and teach statistical thermodynamics.0023

In other words, we go back and we use quantum mechanics to explain what we learned in thermodynamics.0032

The other way that is taught, it seems to be becoming more and more popular these days, its quantum mechanics first0039

and then statistical and classical thermodynamics are done simultaneously.0046

This particular course does classical thermodynamics first, so I go with the first method.0052

Classical thermodynamics first then it goes on to quantum mechanics, spectroscopy next, and then finally, statistical thermodynamics.0057

Many choices have to be made in AP Chemical course about which topics to cover.0067

The more topics one covers, the less time one has to cultivate it for understanding of the fundamentals.0072

In other words, time is finite if I spend more time on this, it is more topics, but it gives me less time to assimilate what it is that I have learned before.0079

I have always been one who believes that it is more fruitful to read three novels closely and deeply than to have read 20 novels,0091

and for the sake of impressing be able to enumerate 20 novels.0098

You get a lot more out of doing less but doing it very well, that is always the case.0102

If you ever run across a situation where you have to make a choice, I promise you, if you make the choice of doing fewer things0109

but doing them well and deeply, it will be a lot better than having done multiple things.0115

It is just the way the mind works, it is just the way discipline works, is just a way to true deep learning which actually works.0121

I have chosen what I consider to be the most important topics for a strong foundation.0129

If, after further reflection, I feel that what I have left out deserves to be covered or if there is a clear demand for topic that I have left out,0134

I will absolutely be happy to add that topic of the course, however many topics that might be.0142

If what I have presented in the course is understood to a reasonable degree then any topic that I have left out,0148

but your particular course does cover, it should be reasonably easy to follow.0155

That should be very easy to follow.0159

I have presented as a solid, good, foundational course.0161

This course is a very important part of your scientific literacy.0168

It is a first exposure to pulling back the curtain and exposing what is actually going on.0171

I hope that you find it as beautiful as I do.0178

Best wishes and let us jump right on in.0180

We are going to start with the ideal gas law.0186

Mostly, what we will be talking about is gases.0191

We will talk about liquid and solids and we will see a couple of them in the problems but gas is going to be what we are most concerned with.0195

Let us begin with the ideal gas law.0203

The ideal gas law, you know it as PV = NRT, the pressure given a gas, the pressure × volume = the number of mol × the gas constant × the temperature in Kelvin.0207

That is it, nothing more than that.0218

It is an equation state.0232

It is an equation state and you are going to hear that term a lot as an equation of state.0235

What that means is the four variables, pressure, volume, temperature, and the number of mol.0241

Describe completely the state of our gases in at a given moment.0259

Describe the state of the gas.0265

Let us talk about units, units are going to be very important in this course.0275

In fact, probably, the single most annoying thing that you would have when you do with your problems is remembering to deal with the units and covering the units.0279

It just makes all this crazy but there it is.0289

Let us talk about units, the SI unit of pressure is a Pascal, symbolized as Pa.0294

Pressure is defined as force per unit area.0318

When I have the amount of force, if I divide it by the particular area over which I’m applying the force, I get the pressure, pressure = f/a.0325

Even force is a Newton and the unit of area is a square meter so 1 Pa = 1 N/sq m.0336

From here, we can go ahead and manipulate the units to serve our purposes.0353

From here, we can manipulate units as necessary to move between equivalent unit expressions.0363

If you ever lose your way in the problem, I have to talk about this more while I actually do the problems.0394

If you ever lose your way to the problem.0398

Let us think about the units and that will help you solve the problem in many of the cases, particularly in classical thermodynamics.0402

It will let you move between equivalent unit expressions.0409

Let us go ahead and do not stick to the page here.0414

We have 1 N/ sq m, in Newton is a kg m/s² /m².0417

We have 1kg m² s, there we go.0434

1 N/ m², which is a Pascal, is equal to 1 kg m/s² /m².0449

If I multiply by m/ m, I end up with 1 kg m²/ s² / m³ and that is equal to 1 J/ m³.0463

1 N/ m² which is 1 Pa is also equal to 1 kg /ms² = 1 J / m³.0482

That is it, I’m just manipulating units.0491

I have 1 atmosphere of pressure is equal to 1.01325 × 10⁵ Pa, this exact.0497

I have 1 atmosphere is equal to 760 tors, that is also exact.0519

The mm of mercury Hg, is actually bigger than the tors by a factor of 14 parts or 10⁸ which is clearly insignificant.0529

We take 1 mm of mercury equal to 1 tors.0560

The SI unit of volume, as I have said is a unit of pressure, now we will do it as a unit of volume is actually the cubic meter not the cubic centimeter.0574

In practice, we use cubic centimeters and we use liters.0589

1 liter is 1 cubic decimeter = 1000 cubic centimeters = 10⁻³ cubic meters.0604

1 liter is 10⁻³ cubic meters, this is exact.0619

In the next page, the SI unit of temperature is the Kelvin.0630

The value of r, the gas constant, pv= nrt, r = pv/ nt, p0 v0/ n0 t0.0654

If I take the pressure to be 1 atmosphere.0678

Let us do it this way, I will just write out what does we still have here.0689

P0, if we take 1 atmosphere as our base which we said as 1.01325 × 10⁵ Pa.0699

If I take my initial volume or basic volume to be 22.41383 L, and if I take N to be 1 mol which is going to be 22.41383 × 10⁻³ m³/ mol.0712

We are trying to stick with SI units, temperature = 273.15 Kelvin.0745

Therefore, if I put all of these in values for p0 v0 n0 t0, sticking with m³/mol Pa, I end up with r= 8.31441 Pa m³/ mol Kelvin.0754

Recall that 1 Pa = 1 J/ m³, so 1 Pa m³ = 1 J.0782

Pa m is a Joules, therefore, r = 8.31441 Js/mol Kelvin.0801

That is where all that stuff comes from, J/ mol Kelvin.0811

If I wanted it in liters/ atmosphere/ mol Kelvin, I get 0.08206.0817

I will give the number here 0.058, that is liter atmosphere/ mol Kelvin.0824

If you want an equivalent expression for J at liter atmosphere, just use this conversion factor right here.0835

If you want an equivalent between J and liter atmosphere, and you will, then 8.31441 J/ mol Kelvin × 1 mol Kelvin is 0.08206 liter atmosphere mol Kelvin.0844

It will cancel mol Kelvin and I’m left with 101.3 j/ liter atmosphere.0894

That is the conversion factor.0905

Keep a very close eye on units and conversions.0913

It is going to be very important in this course.0915

Let us talk about, I will go to the left here.0920

Let us talk about extensive and intensive variables.0925

Extensive and intensive variables or properties.0931

Let us start off with the ideal gas law, pv = nrt, intensive property.0946

The two intensive properties in this are pressure and temperature.0958

The reason they are intensive is that they do not depend on the amount of the substance present.0965

An intensive property and intensive variable is the one that does not depend on the amount of it present.0984

An extensive properties here are volume and the number of moles, they do depend on amount.0991

Let us see, mass is another extensive property because the amount of mass depends on how much you have.1013

You have 3g or 4g, it is going to make it a difference.1026

Mass is an extensive property.1028

If I take 1 mass of iron, if I take 1 g of iron and 10 g of iron both sitting on a table, the temperature is going to be the same.1031

If I measure the temperature of the 1 g or 10 g, it does not matter how much s there.1039

The temperature is intensive, it has nothing to do with how much iron is there but the mass does, volume does, number of moles does.1044

That is the difference between the two.1053

Let us see, this is very important now.1057

The ratio of 2 extensive variables always gives an intensive variable.1065

For example, our example is going to be, if I have mass which is an extensive variable and if I have volume which is an extensive variable,1101

if I take the ratio of the mass to the volume I get the density.1118

The density is an intensive variable.1128

1 g of iron, 10 g of iron, the density of iron stays.1131

1 g of iron has a certain volume, 10 g of iron has a certain volume, that is our extensive but if I take the ratio of 2 extensive, I will end up with intensive variable.1138

That is very deep, very profound, and very important, density intensive.1148

I repeat, the ratio of 2 extensive variables always gives an intensive variable.1156

We would often do that.1160

Let us go ahead and take a look at pv = nrt.1165

We have pv = nrt and we are going to divide both sides but n.1170

I end up with pv / n = rt.1184

I'm going to rewrite this as, basically what I am going to do is take this.1188

I’m going to take whatever volume, which is an extensive variable, I’m going to divided by n, which is also an extensive variable.1193

They are both extensive, the ratio of 2 extensive is an intensive.1203

I’m going to rewrite this as pv ̅ = rt, where V ̅ Is just equal to v/n.1206

I have taken the volume and divide it by n.1216

It is called the molar volume, volume per mol.1220

The ideal gas law written that way consists of all intensive variables.1226

We can discuss gases and their properties without worrying about whether there is 1 or 50 mol.1261

Now the amount does not matter.1267

When amounts do not matter, that is where we begin to uncover and elucidate underlying truths.1270

Now, we can discuss gases and their properties without worrying about whether we have 5 mol or 50 mol.1277

It is not going to make any difference.1312

Any fundamental property of the system should never depend on how much is there.1315

As I said, we wish to elucidate general truths in any specific case we might deal with the amount.1348

But when we talk about generalities, we never talk about the amount.1368

We should have to talk about the amount.1370

We should plot it in every situation across the board.1372

In general, volume is not the only thing that you will see with a line over it.1382

In general, any variable with a line over it is a molar quantity.1388

In other words, it is been divided by the number of moles that are present.1403

Molar quantity meaning it has been divided by n, the number of moles.1407

Let us talk about being able to graph equations.1431

Graphing equations, we will clearly graph an equation is just insanely important in science.1435

Let us go ahead and start with our pv= rt.1448

This is a relation among 3 variables, pressure, a molar volume, and temperature.1457

It is a relation among 3 variables.1468

If any 2 or none, the 3rd is automatically known.1477

Let us solve for each variable separately.1499

We are going to solve for p, v, and we are going to solve for t.1501

Let us start by solving for p.1506

P= rt/( v) ̅ , I’m going to write it as rt × 1 / V ̅.1509

This is 1/V ̅, these are hyperbolas.1521

I’m going to hold temperature constant and I’m going to graph pressure vs. Volume.1529

Holding t constant is very important.1539

We will graph p vs. V ̅, in other words, p is on the y axis and V ̅ Is the x axis.1549

As the molar volume changes, it gets bigger.1569

What happens to the pressure or as the pressure gets bigger, what happens to the volume?1573

Here is what we get.1579

This is the pressure, it is going to be at atmospheres, the axis is going to be molar volume, it is going to be deci³/ mol.1588

Molar volume what you get when you graph this equation by holding t constant, you have to put this.1602

You will end up with hyperbolas.1619

This is the one for 100 Kelvin, this is one for 200 Kelvin, again, I get different graphs, lines, curves, one for each temperature that I’m holding constant.1623

I am holding temperature constant and I’m changing v and let us see what happens to p.1641

This might be 400 Kelvin.1647

Clearly, the whole thing, there is an infinite number of these.1650

For a given v or volume, higher temperature means a higher pressure.1662

You already know this from General Chemistry that a higher t means a higher p, that is it what is going on.1691

Let us go forward again.1701

Every point of the PD graph or the PD plane, every single point of that two dimensional plane represents a particular state of the gas.1710

In other words, it represents a particular pressure, a particular volume, and a particular temperature.1735

It represents a particular state of the gas by holding the temperature constant, by holding the t constant.1742

I can strain the states to follow the curve.1773

Here is my p, here is my v, and I have a bunch of different temperatures.1788

Now as I change pressure, as I change volume, the change is going to follow that curve.1795

It is just going to bounce around, it is going to follow that curve for different temperatures.1805

It is going to be another curve for another temperature.1809

When I make changes, it goes up and down along the curve.1813

These curves for this particular graph holding temperature constant, these curves are called isotherms.1819

Isotherms just mean equal heat.1830

That is all it means, equal heat or in other words, holding temperature constant.1837

In thermodynamics, when you hear the term isothermal that means I'm keeping the temperature constant, that is all it means.1842

These curves are called isotherms when t is held constant.1848

Let us start again with pv = rt, this time let us go ahead and solve for volume.1868

V is equal to rt/p, I can write this as r/p × t.1877

That is interesting, this is linear.1890

I’m going to hold pressure constant.1894

Now let us hold pressure constant, this is constant and r is already a constant.1900

I’m going to graph v vs. T and express v as a function of t.1910

Here is the graph that I get.1929

This is my volume, this is my temperature in Kelvin, and this is linear.1934

And I hold p as a constant at different pressures, this is what looks like.1941

This one might be 3 atmospheres, let us say this one is 2 of atmospheres, let us say this one is 1 atmosphere.1952

What I have done is I have expressed this pv= nrt, now I have graphed the volume vs. Temperature.1965

At different pressures that I choose, the hold constant, I have these lines.1974

When I hold pressure constant, these lines are called isobars.1982

If I pick it as pressure 3 atmospheres, if I raise the temperature, the volume is going to travel along this line.1986

This is going to be everywhere.1994

At 2 atmospheres, if I change the volume, if I change the temperature the volume is going to travel along that line.1996

It will go backwards.2000

If at 1 atmosphere, it is going to travel along this line.2003

This is a state and a state for a given volume, for a given temperature, and for a given pressure.2006

These lines are called isobars.2016

When pressure is held constant, the lines that you get are called isobars.2023

When pressure is held constant and you have volume vs. Temperature those are called isobars.2027

As pressure rise, of course r with p, the slope decreases.2047

That is why from your perspective, as the pressure rises, the line gets closer.2063

It becomes more flat closer to the x axis.2069

Let us start again with pv ×rt, this time let us go ahead.2083

Let us try this, let us go p = r/ vt.2102

Let me shift one thing and make sure that.2124

P = rt, pressure = rt/ v.2133

What we did is we took our t and we held temperature constant.2143

I’m going to take r/ v × t, I’m going to take r/ v separate × t.2152

Again, we get a linear graph and now I’m going to graph pressure vs. Temperature but I'm going to hold the volume constant.2159

And what I get here is this a linear graph.2170

Pressure, temperature, different volumes, so again, we get something linear2178

This one might be 30 deci³/ mol, this one might be 20 deci³/ mol, this one might be 10 deci³/ mol.2191

Again, we are talking about molar volume.2210

Whenever I have these, whenever I have a pressure, temperature, graph for a particular volume,2215

if I change the temperature my pressure is going to move along this line.2221

These lines are called isochors or isometrics.2226

For a constant volume, for constant molar volume, we get things called isochors or isometrics.2234

Lines of constant volume, that is it.2257

Let us go ahead and draw this all out here.2262

I have got p = rt / V ̅.2265

I have got p and v = r/ p × t and I got p = r/ v × t.2280

This graph I ended up with hyperbolas.2302

This t was held constant and these were called isotherms.2307

Here we have v along this axis, this is p along that axis and this is going to be v along that axis.2321

This is v along this is axis and this is t along this axis.2335

I ended up getting these things, these were called isobars.2337

In this case, I held p as a constant.2343

Basically, the thing that you are taking with the gas constant here are t/ v, these are the variables, hold that thing called constant.2348

V and t are variables, hold the other variable constant.2355

Here it is p and t, we will hold the other variable constant.2358

We are going to hold this constant and again here we have pressure, here we have temperature, and we ended up with a bunch of v and this are called isochors.2361

Let me take a look at this one right here, this was molar volume vs. Temperature.2376

This equation here which was molar volume= r/ p × t.2399

This equation, when I look at these pictures, this equation and graph is easier to see, as temperature drops to 0 it is telling me that the volume is going to drop to 0.2409

This equation and graph, they imply that at t = 0, the molar volume = 0.2433

OK this does not happen to real gases and here is why.2447

Gases as t decreases, at some value of t the gas actually liquefies, it turns into liquid.2466

The gas liquefies so a further drop in temperature does not change the volume.2485

When something is liquid, the temperature in that stays at that volume.2499

A further drop in t does not change the volume.2505

It does not increase the volume.2511

In other words, this is an ideal gas would behave this way that real gases liquefy at low temperatures.2514

Therefore, the graph itself real gases, they do not go to 0.2519

OK now first equation that we did was this one where we have pressure and where we had the molar volume.2529

This equation and this graph which was p = rt/ v.2543

1/v or v was the x axis, these imply that as pressure increases, as I go up in pressure it implies that the volume actually go down to 0.2553

As p increases, the volume goes to 0 but again, that does not happen.2579

At a certain pressure, at a certain p, the gas liquefies.2589

Let us say you are just squeezing all the gas particles at some point they will just turn into liquid.2598

The gas liquefies.2603

No further increase in p reduces the molar volume.2606

This is called isothermal compression.2635

It is isothermal because you are moving along isotherm.2636

These are called isotherms because you are compressing it.2639

In other words, you will be increasing the pressure.2641

As you increasing the pressure, what is going to end up happening is the volume is going to get closer and closer to 0.2644

But at some point, it is going to liquefy and it is not going to go any further.2652

Hence, the ideal gas that is why it is called the ideal gas law.2656

It is never a real gas law, hence, an ideal gas.2660

At low pressures and high temperatures, the ideal gas law is actually very accurate.2670

The ideal gas law is quite accurate at describing gases behavior.2691

Deviations from ideal behavior occur at high pressures and or low temperatures.2721

In other words, as the molecules starts to get really close to each other.2750

We will talk about that more in subsequent sections.2755

Thank you for joining us here at www.educator.com, we will see you next time for our continuation of classical thermodynamics.2758

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