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Physical Chemistry for Biological Sciences

Chemistry

Author: Carey Southern
Publisher: DePaul University
Source: LibreTexts
Language: EN
Category: Basic Sciences

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Contents· 165 sections

01: The Dawn of the Quantum Theory
1.01: Blackbody Radiation Cannot Be Explained Classically
1.02: Quantum Hypothesis Used for Blackbody Radiation Law
1.03: Photoelectric Effect Explained with Quantum Hypothesis
1.04: The Hydrogen Atomic Spectrum
1.05: The Rydberg Formula and the Hydrogen Atomic Spectrum
1.06: Matter Has Wavelike Properties
1.07: de Broglie Waves can be Experimentally Observed
1.08: The Bohr Theory of the Hydrogen Atom
1.09: The Heisenberg Uncertainty Principle
1.E: The Dawn of the Quantum Theory (Exercises)
02: Waves and the Schrodinger Equation
2.01: The One-Dimensional Wave Equation
2.02: The Schrodinger Equation
2.03: Linear Operators in Quantum Mechanics
2.04: The Schrodinger Equation is an Eigenvalue Problem
03: Postulates and Principles of Quantum Mechanics
3.01: The Wavefunction Specifies the State of a System
3.02: Wavefunctions Have a Probabilistic Interpretation
3.03: Wavefunctions Must Be Normalized
3.04: Quantum Operators Represent Classical Variables
3.05: Observable Quantities Must Be Eigenvalues of Quantum Mechanical Operators
3.06: The Time-Dependent Schrodinger Equation
3.E: Postulates and Principles of Quantum Mechanics (Exercises)
04: The Particle in a Box
4.01: The Energy of a Particle in a Box is Quantized
4.02: The Average Momentum of a Particle in a Box is Zero
4.03: The Uncertainty Principle - Estimating Uncertainties from Wavefunctions
4.04: A Particle in a Three-Dimensional Box
4.E: The Schrodinger Equation and a Particle in a Box (Exercises)
05: The Harmonic Oscillator and the Rigid Rotor
5.01: A Harmonic Oscillator Obeys Hooke's Law
5.02: The Equation for a Harmonic-Oscillator Model of a Diatomic Molecule Contains the Reduced Mass of the Molecule
5.03: The Harmonic Oscillator Approximates Molecular Vibrations
5.04: The Harmonic Oscillator Energy Levels
5.05: The Harmonic Oscillator Wavefunctions involve Hermite Polynomials
5.06: Hermite Polynomials are either Even or Odd Functions
5.07: The Harmonic Oscillator and Infrared Spectra
5.08: The Rigid Rotator is a Model for a Rotating Diatomic Molecule
5.09: The Energy Levels of a Rigid Rotor
5.E: The Harmonic Oscillator and the Rigid Rotor (Exercises)
06: The Hydrogen Atom
6.01: The Schrodinger Equation for the Hydrogen Atom Can Be Solved Exactly
6.02: The Wavefunctions of a Rigid Rotator are Called Spherical Harmonics
6.03: Hydrogen Atomic Orbitals Depend upon Three Quantum Numbers
6.04: s-orbitals are Spherically Symmetric
6.05: Orbital Angular Momentum and the p-Orbitals
6.06: The Helium Atom Cannot Be Solved Exactly
6.E: The Hydrogen Atom (Exercises)
07: Multielectron Atoms
7.01: Perturbation Theory and the Variational Method for Helium
7.02: Hartree-Fock Equations are Solved by the Self-Consistent Field Method
7.03: An Electron has an Intrinsic Spin Angular Momentum
7.04: Wavefunctions must be Antisymmetric to Interchange of any Two Electrons
7.05: Hartree-Fock Calculations Give Good Agreement with Experimental Data
7.E: Multielectron Atoms (Exercises)
08: Chemical Bonding in Diatomic Molecules
8.01: The Born-Oppenheimer Approximation Simplifies the Schrodinger Equation for Molecules
8.02: The H Prototypical Species
8.03: The Overlap Integral
8.04: Chemical Bond Stability
8.05: Bonding and Antibonding Orbitals
8.06: A Simple Molecular-Orbital Treatment of H Places Both Electrons in a Bonding Orbital
8.07: Molecular Orbitals Can Be Ordered According to Their Energies
8.08: Molecular-Orbital Theory Does not Predict a Stable Diatomic Helium Molecule
8.09: Electrons Populate Molecular Orbitals According to the Pauli Exclusion Principle
8.10: SCF-LCAO-MO Wavefunctions are Molecular Orbitals formed from a Linear Combination of Atomic Orbitals and Whose Coefficients Are Determined Self-Consistently
8.11: Most Molecules Have Excited Electronic States
8.E: Chemical Bond in Diatomic Molecules (Exercises)
09: Molecular Spectroscopy
9.01: The Electromagnetic Spectrum
9.02: Electronic Spectra Contain Electronic Vibrational and Rotational Information
9.03: The Franck-Condon Principle
9.04: What Causes Molecules to Absorb UV and Visible Light
9.05: Fluorescence and Phosphorescence
9.06: Jablonski diagram
9.E: Molecular Spectroscopy (Exercises)
10: The First Law of Thermodynamics
10.01: Overview of Classical Thermodynamics
10.02: All Dilute Gases Behave Ideally
10.03: van der Waals and Redlich-Kwong Equations of State
10.04: Pressure-Volume Work
10.05: Work and Heat are not State Functions
10.06: Work and Heat Have a Simple Molecular Interpretation
10.07: Energy is a State Function
10.08: Heat Capacity is a Path Function
10.09: An Adiabatic Process is a Process in which No Energy as Heat is Transferred
10.10: The Temperature of a Gas Decreases in a Reversible Adiabatic Expansion
10.11: Enthalpy is a State Function
10.12: Relative Enthalpies Can Be Determined from Heat Capacity Data and Heats of Transition
10.13: Enthalpy Changes for Chemical Equations are Additive
10.14: Heats of Reactions Can Be Calculated from Tabulated Heats of Formation
10.15: The Temperature Dependence of H
10.E: The First Law of Thermodynamics (Exercises)
11: Entropy and The Second Law of Thermodynamics
11.01: Energy Does not Determine Spontaneity
11.02: Nonequilibrium Isolated Systems Evolve in a Direction That Increases Their Energy Dispersal
11.03: Unlike heat Entropy is a State Function
11.04: The Second Law of Thermodynamics
11.05: The Famous Equation of Statistical Thermodynamics is Sk ln W
11.06: We Must Always Devise a Reversible Process to Calculate Entropy Changes
11.07: Thermodynamics Provides Insight into the Conversion of Heat into Work
11.E: Entropy and The Second Law of Thermodynamics (Exercises)
12: Helmholtz and Gibbs Energies
12.01: Helmholtz Energy
12.02: Gibbs Energy Determines the Direction of Spontaneity at Constant Pressure and Temperature
12.03: The Maxwell Relations
12.04: The Enthalpy of an Ideal Gas is Independent of Pressure
12.05: Thermodynamic Functions have Natural Variables
12.06: The Standard State for a Gas is an Ideal Gas at 1 Bar
12.07: The Gibbs-Helmholtz Equation
12.E: Helmholtz and Gibbs Energies (Exercises)
13: Chemical Equilibrium
13.01: Equilibrium Results when Gibbs Energy is Minimized
13.02: An Equilibrium Constant is a Function of Temperature Only
13.03: Standard Gibbs Energies of Formation Can Be Used to Calculate Equilibrium Constants
13.04: Gibbs Energy of a Reaction vs. Extent of Reaction is a Minimum at Equilibrium
13.05: Reaction Quotient and Equilibrium Constant Ratio Determines Reaction Direction
13.06: The Sign of G and not G Determines the Direction of Reaction Spontaneity
13.07: The van 't Hoff Equation
13.08: Thermodynamic Equilibrium Constants Are Expressed in Terms of Activities
13.09: Activities are Important for Ionic Species
13.10: Homework Problems
14: Solutions I - Volatile Solutes
14.01: A Mixture is a Combination of Two or More Substances
14.02: The Gibbs-Duhem Equation Relates Chemical Potential and Composition at Equilibrium
14.03: Chemical Potential of Each Component Has the Same Value in Each Phase in Which the Component Appears
14.04: Ideal Solutions obey Raoult's Law
14.05: Most Solutions are Not Ideal
14.06: Vapor Pressures of Volatile Binary Solutions
14.07: Activities of Nonideal Solutions
14.08: Activities are Calculated with Respect to Standard States
14.09: Gibbs Energy of Mixing of Binary Solutions in Terms of the Activity Coefficient
14.E: Solutions I- Liquid-Liquid Solutions (Exercises)
15: Solutions II - Nonvolatile Solutes
15.01: Standard State of Nonvolatile Solutions
15.02: The Activities of Nonvolatile Solutes
15.03: Colligative Properties Depend only on Number Density
15.04: Osmotic Pressure can Determine Molecular Masses
15.05: Electrolytes Solutions are Nonideal at Low Concentrations
15.06: The Debye-Huckel Theory
15.07: Extending Debye-Huckel Theory to Higher Concentrations
15.08: Homework Problems
16: Chemical Kinetics I - Rate Laws
16.01: The Time Dependence of a Chemical Reaction is Described by a Rate Law
16.02: Rate Laws Must Be Determined Experimentally
16.03: First-Order Reactions Show an Exponential Decay of Reactant Concentration with Time
16.04: Different Rate Laws Predict Different Kinetics
16.05: Reactions can also be Reversible
16.E: Chemical Kinetics I - Rate Laws (Exercises)
17: Chemical Kinetics II- Reaction Mechanisms
17.01: A Mechanism is a Sequence of Elementary Reactions
17.02: The Principle of Detailed Balance
17.03: Multiple Mechanisms are often Indistinguishable
17.04: The Steady-State Approximation
17.05: Rate Laws Do Not Imply Unique Mechanism
17.06: The Lindemann Mechanism
17.07: Some Reaction Mechanisms Involve Chain Reactions
17.08: A Catalyst Affects the Mechanism and Activation Energy
17.09: The Michaelis-Menten Mechanism for Enzyme Catalysis
17.E: Chemical Kinetics II- Reaction Mechanisms (Exercises)
18: Kinetics- Temperature Dependence and Relaxation Methods
18.01: Rate Constants Are Usually Strongly Temperature Dependent
18.02: The Rate Constants of a Reversible Reaction Can Be Determined Using Relaxation Techniques
18.03: Transition-State Theory Can Be Used to Estimate Reaction Rate Constants