Comprehensive Study Guide for Atkins' Physical Chemistry (8th/9th Edition)
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Course
Physical chemistry
Institution
University Of Limpopo (UL)
Book
Atkins\' Physical Chemistry
This study guide offers comprehensive coverage of Atkins' Physical Chemistry, focusing on the 8th or 9th edition of the textbook. It provides clear explanations, step-by-step solutions, and abundant examples to aid understanding of core concepts in thermodynamics, quantum mechanics, kinetics, and s...
University of Limpopo
Faculty of Sciences & Agriculture
School of Physical and Mineral Sciences
Department of Chemistry
SCHA031
Physical Chemistry 3
Study Guide for SCHA031
16 Credits
First Semester
Prepared by Prof T Magadzu, University of Limpopo
Content evaluated by Dr LE Macevele, University of Limpopo
,TABLE OF CONTENT
Study Guide for SCHA031 ....................................................................................................................... 1
MODULE INFORMATION ......................................................................................................................... 6
Chemical kinetics .................................................................................................................................... 9
1. Introduction ........................................................................................................................................ 9
1.1 Application of the techniques ....................................................................................................... 9
1.1.1 Quenching methods ............................................................................................................... 9
1.2 The rates of chemical reaction...................................................................................................... 9
1.2.1 Rate laws and rate constants ............................................................................................... 10
1.2.2 Reaction order ..................................................................................................................... 10
1.2.3 The determination of the rate law....................................................................................... 11
1.3 Integrated rate laws .................................................................................................................... 13
1.3.1 First-order reactions ............................................................................................................ 13
1.3.2 Half-lives and time constants ............................................................................................... 14
1.3.3 Second-order reactions ........................................................................................................ 15
1.4 Reactions approaching equilibrium ............................................................................................ 18
1.4.1 First-order reactions close to equilibrium ........................................................................... 18
1.4.2 The temperature dependence of reaction rates ................................................................. 19
1.5 Exercise ....................................................................................................................................... 21
Catalysis ................................................................................................................................................ 22
2. Introduction ...................................................................................................................................... 22
2.1 Heterogeneous Catalysis............................................................................................................. 22
2.2 Molecular motion in gases .......................................................................................................... 23
2.2.1 The kinetic model of gases ................................................................................................... 23
2.2.2 The collision frequency ........................................................................................................ 24
2.2.3 The mean free path.............................................................................................................. 24
2.2.4 Collisions with walls and surfaces ........................................................................................ 26
2.3 The growth and structure of solid surfaces ................................................................................ 27
2.3.1 Flat surface of solid .............................................................................................................. 27
2.3.2 Kinds of defects .................................................................................................................... 28
2.3.3 Atoms on a surface (top layer)............................................................................................. 28
, 2.3.4 The extent of adsorption ..................................................................................................... 29
2.4 The importance of pore structure and surface area................................................................... 35
2.4.1 Pore Structure ...................................................................................................................... 36
2.4.2 Experimental Methods of Estimating Surface Areas. .......................................................... 36
2.5 Exercise ....................................................................................................................................... 40
Quantum Theory: Introduction and Principles ..................................................................................... 41
3.1 Classical mechanics ..................................................................................................................... 41
3.2 Quantum mechanics ................................................................................................................... 41
3.3 The origins of quantum mechanics ............................................................................................. 41
3.4 The failures of classical physics ................................................................................................... 43
3.4.1 Blackbody radiation ............................................................................................................. 43
3.4.2 Heat capacities ..................................................................................................................... 48
3.4.3 Atomic and molecular spectra ............................................................................................. 49
3.5 Wave-particle duality .................................................................................................................. 49
3.5.1 The particle character of electromagnetic radiation ........................................................... 50
3.5.2 The wave character of particles ........................................................................................... 52
3.6 The dynamics of microscopic systems ........................................................................................ 53
3.6.1 The Born interpretation of the wavefunction...................................................................... 54
3.6.2 Normalization....................................................................................................................... 55
3.6.3 Quantization......................................................................................................................... 56
3.6.4 Operators, eigenvalues, and eigenfunctions ....................................................................... 56
3.6.5 The uncertainty principle ..................................................................................................... 57
3.6.6 The postulates of quantum mechanics ................................................................................ 58
3.7 Exercise ....................................................................................................................................... 59
Quantum theory: Techniques and Applications ................................................................................... 61
4.1 Translational motion ................................................................................................................... 61
4.1.1 A particle in a box................................................................................................................. 61
4.2 Motion in two and more dimensions ......................................................................................... 66
4.2.1 Separation of variables ........................................................................................................ 66
4.2.2 Degeneracy .......................................................................................................................... 67
4.3 Tunnelling.................................................................................................................................... 67
4.4 Vibrational motion ...................................................................................................................... 69
, 4.4.1 The energy levels ................................................................................................................. 69
4.4.2 The wavefunctions ............................................................................................................... 71
4.5 Rotational motion ....................................................................................................................... 72
4.5.1 Rotation in two dimensions: a particle on a ring ................................................................. 72
4.5.2 Rotation in three dimensions: the particle on a sphere ...................................................... 73
4.6 Exercise ....................................................................................................................................... 76
Solids and X-ray diffraction ................................................................................................................... 77
5.1 Structures of Solids ..................................................................................................................... 77
5.1.1 Lattice and Unit cells ............................................................................................................ 77
5.2 X-ray diffraction .......................................................................................................................... 79
5.2.1 The Basics ............................................................................................................................. 79
5.2.2 The Interplanar Spacing, d(hkl)............................................................................................... 80
5.2.3 The investigation of Structure ............................................................................................. 81
5.2.4 Indexing the Reflections....................................................................................................... 83
5.2.5 Intensity of X-ray Diffraction patterns ................................................................................. 85
5.3 Exercise ....................................................................................................................................... 86
Atomic spectra and atomic structure ................................................................................................... 87
6.1 The structure and spectra of hydrogenic atoms ......................................................................... 87
6.1.1 Radial wave equation ........................................................................................................... 88
6.2 Atomic orbitals and their energies.............................................................................................. 90
6.2.1 The energy levels ................................................................................................................. 90
6.2.2 Ionization energies ............................................................................................................... 91
6.2.3 Shells and subshells.............................................................................................................. 93
6.2.4 Atomic orbitals ..................................................................................................................... 93
6.2.5 Boundary surface ................................................................................................................. 94
6.2.6 Radial distribution functions ................................................................................................ 94
6.2.7 Spectroscopic transition and selection rules ....................................................................... 97
6.3 Exercise ....................................................................................................................................... 99
Molecular spectroscopy: Rotational and Vibrational Spectra ............................................................ 100
7. Introduction .................................................................................................................................... 100
7.1 General features of spectroscopy ............................................................................................. 100
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