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Inorganic Spectroscopic Chemistry

Time : Thursday 9:00 - 11:45 Classroom : Chem 430 Textbooks : F.A. Cotton Chemical Applications of Group Theory, 3rd ed., 1990, Wiley. E.A.V. Ebsworth, D.W.H. Rankin, S. Cradock Structural Methods in Inorganic Chemistry, 2nd ed., 1991, CRC. R.S. Drago Physical Methods for Chemists, 2nd ed., 1992, Saunders. A.K. Brisdon Inorganic Spectroscopic Methods 1998, Oxford. Contents : UV-visible (electronic) spectroscopy
Cotton Chapter 9 Ebsworth/Rankin/Cradock Chapter 6 Brisdon Chapter 4

IR/Raman (vibrational) spectroscopy

Cotton Chapter 10 Ebsworth/Rankin/Cradock Chapter 5 Brisdon Chapter 2

Mass Spectrometry
Ebsworth/Rankin/Cradock Chapter 9 Drago Chapter 16 Brisdon Chapter 5

NMR Spectroscopy
Ebsworth/Rankin/Cradock Chapter 2 Drago Chapter 7, 8 Brisdon Chapter 3

ESR Spectroscopy
Ebsworth/Rankin/Cradock Chapter 3 Drago Chapter 9 Brisdon Chapter 3

Grade :

Mid-term 40%

Final 40%

Quiz 20%

Introduction
Determining structure
contain any known compound? is it pure? what functional group it contains? what is its composition and molecular weight? how the functional groups linked together? what is molecular symmetry? what are the bond lengths and bond angles? what is its electronic structure?

Some physical techniques in determining structure

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Group present

Molecular symmetry

Bond lengths and angles Electronic structure

excited state

electronic transition

vibrational transition rotational transition ground state E = Eelectronic + Evibration + Erotation + Etranslation population distribution Nupper = exp(-DE/kT) k =1.381 10-23 J/K Nlower radiation unit E = hu = hc/l
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1 nm = 10-9 m 1 cm-1 = 11.98 J/mol = 2.86 cal/mol 1 eV = 96500 J/mol = 23060 cal/mol

spectrum of electromagnetic radiation

Nuclear energies Chemical energies Molecular energies Spin energies XRF Electronic Rotational Mssbauer XPS UPS Vibrational ESR NMR NQR
GED XRD

timescales associated with some spectroscopic techniques

Technique NMR (solution) ESR (solution) rotational spectroscopy (gas) vibrational spectroscopy (gas) electronic spectroscopy (solution) Mssbauer spectroscopy (solid) Energy of excited state (Hz) 108 1010 1011 1014 1016 1019 Typical relaxation time (seconds) 10 10-5 10-4 10-8 10-15 10-8 Typical linewidth (Hz) 10-1 105 104 108 1015 108
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glossary of spectroscopic and structural techniques

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Symmetry group theory

symmetry operation identity inversion reflection rotation rotation and reflection
E i

s
C S

point group character table ex. What is the point group for [PtCl4]2-? Cl Cl Pt Cl Cl symmetry element: E, C4, C2, i, sh, sv, sd, S4 point group: D4h

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character table of D4h

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