Lectures in Advanced Inorganic Chemistry

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1 Republic of Iraq The Ministry of Higher Education & Scientific Research University:Karbala College:Science Department:Chemistry Stage:M.Sc Lectures in Advanced Inorganic Chemistry By Assist.Prof. Dr. Hayder H. Al-Hmedawi

3 The MSc. syllabus of Advanced Inorganic Chemistry ( semester 1) Instructional Objectives 1- To study in depth about periodic table, bonding and structure. 2- To gain knowledge about the main group chemistry. 3- To acquire knowledge about coordination chemistry. 4- To study in detail about the reaction mechanism of complexes. UNIT I Periodic Table for elements, arrangement of elements in Groups in the Periodic Table- s-block, p-block, d-block and f- block elements; atomic states and term symbols. Slater s rules for the determination of screening constants; periodic properties(ionic radii, ionization potential, electron affinity, electronegativity (Pauling, Mulliken and Aflred-Rochnow scales), UNIT II Bonding and Structure: ionic compounds, Ionic Model-Lattice energy Born- Lande equation, polarizing power and polarizability and Fajan s rules ionic, covalent bonding,, Lewis Structures, Calculation of number of bonds in covalent molecules, octet rule, Concept of resonance,concept of hybridization accordig to VBT and VSEPR,concept in MOT. UNIT III Main Group Chemistry: General characteristics,hydrides, Boranes, Carboranes, Silicones, Silicates, Boron nitride, Borazines and Phosphazenes and cyclophosphazenes. S-N compounds S 4 N 4, (SN)x., oxides, Oxidation-reduction reactions. UNIT IV Coordination chemistry: Stereoisomerism- Chirality, optical activity- CD, ORD, Cotton effect, absolute configuration of metal complexes, magnetic circular dichroism. Theories of Metal-Ligand bond: VBT and Crystal field theory - splitting of d-orbitals under various geometries Factors affecting splitting CFSE and evidences for CFSE (Structural and thermodynamic effects) Spectrochemical series Jahn Teller distortion Spectral and magnetic properties

4 of complexes Site preferences - Successes of Crystal Field Theory, MOT, sigma and pi-bonding in complexes Nephelauxetic effect The angular overlap model. UNIT V Reaction Mechanism of complexes Coordination Chemistry Reaction Mechanism: Kinetics and mechanism of reactions in solution labile and inert complexes Ligand displacement reactions in octahedral and square planar complexes acid hydrolysis, base hydrolysis and anation reactions Trans effect theory and applications. Electron transfer reactions electron exchange reactions complementary and non-complementary types inner sphere and outer sphere processes Application of Electron transfer reactions in inorganic complexes - isomerization and racemization reactions of complexes Molecular rearrangement reactions of four and six- coordinate complexes Interconversion between stereoisomers. Reactions of coordinated ligands Template effect and its application for the synthesis of Macrocyclic ligands Unique properties Textbooks and references books 1) Inorganic Chemistry, 5th Edition; Gary. L. Miessler and Donald. A. Tarr (2014). 2) Inorganic Chemistry by Catherine. E. Housecroft and Alan G. Sharpe, Prentice Hall (4th Edition (2012). 3) Basic Inorganic Chemistry, 3 rd ed., by F. A. Cotton et al., Wiley (2007). 4) Inorganic Chemistry principles of structure and reactivity 4th ed, by James E. Huhhey et al, Harper Collins college Puplishers (1993) 5) Shriver & Atkins'Inorganic Chemistry,by Atkins, Overton, Rourke, Weller, Armstrong, 5th Edition. Oxford (2010). 6) Inorganic Chemistr, by D. F. Shriver, P.W. Atkins and C. H. Langford, Oxford (1990).

5 Periodic Table The periodic table is a classification system for the elements. Each element has unique properties and you can predict an element's physical and chemical properties based on its position in the periodic table.

6 Periodic Law: When elements are arranged in order of increasing atomic number, there is a periodic repetition of their physical and chemical properties.

8 Numbering of groups

9 Naming of periods First period: n=1, l=0, i.e. there are one orbital in this period is 1s, therefore number of elements in this period are only two elements H and He,1s 1 for H and 1s 2 for He.

10 Second period n=2, l= 0,1, i.e. there are two orbitals in this period is 2s and 2p therefore number of elements in this period are only eights elements: Li, Be, B, C, N, O, F and Ne : 3Li, [He] 2s 1, 4Be, [He] 2s 2, 5B, [He] 2s 2 2p 1 6C, [He] 2s 2 2p 2, 7N, [He] 2s 2 2p 3, 8O, [He] 2s 2 2p 4 9F, [He] 2s 2 2p 5, 10Ne, [He] 2s 2 2p 6

11 Third period n=3, l= 0, 1, 2, i.e. there are three orbitals in this period is 3s, 3p and 3d therefore number of elements in this period are eighteen(18) elements,but actually number of elements in this period are only eight(8) elements because 3d orbitals is high energy, i.e. It can be said that the electrons enter the orbitals which have energy equal to number of period n or n+1, i.e in third period the electrons enter the orbitals 3s and 3p only because these orbital have energy 3 in 3s and 4 in 3p. Therefore number of elements in this period are only eight: Na, Mg, Al, Si, P, S, Cl and Ar :

12 Fourth period n=4, l= 0, 1, 2, 3, i.e. there are fourth orbitals in this period is 4s, 4p, 4d and 4f therefore number of elements in this period are 32 elements,but actually number of elements in this period are only eighteen(18) elements because 4d and 4f orbitals are high energy. i.e in fourth period the electrons enter the orbitals 4s, 4p and 3d (from third period)only because these orbital energetic allowed,4s 3d 4p. Therefore number of elements in this period are only eighteen(18) elements: n=4

13 Fifth period n=5, l= 0, 1, 2, 3,4, i.e. there are fifth orbitals in this period is 5s, 5p, 5d, 5f and 5g. Number of elements in this period are only eighteen(18) elements: the orbitals of energetic allowed are 5s 4d 5p :

14 Sixth period n=6, l= 0, 1, 2, 3,4,5, i.e. there are sixth orbitals in this period is 6s, 6p, 6d, 6f, 6g and 6h. Number of elements in this period are only (32) elements: the orbitals of energetic allowed are 6s 4f 5d 6p :

15 Seventh period n=7, l= 0, 1, 2, 3,4,5,6, i.e. there are seventh orbitals in this period is 7s, 7p, 7d, 7f, 7g, 6h and 7i. Number of elements in this period are only (32) elements: the orbitals of energetic allowed are 7s 5f 6d 7p :

16 Classification of elements Firs: Based on their general properties

17 Second: Classifying Elements by Electron Configuration

1. Course Description. 2. Course Objectives

1. Course Description. 2. Course Objectives College of Science Department of Chemistry Course Code: CHEM 4411 Course Title: Inorganic Chemistry II General Information Number of Credits: 3 Instructional Format: 3 hours lectures Contact Hours/Week: