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CHEM * 4620 - Fall 2020

Solid State Chemistry

The course held in Fall-2020 is now concluded. Happy and safe holidays!
Instructor: Prof. Dmitriy Soldatov     SSC-2503;  x 53548;  soldatov @
Assistant: Farukh Ali     SSC-2503;  x 53548;  fali @
  Mon Tue Wed Thu Fri
Classes: Virtual - 13:00-14:20 - 13:00-14:20 -
Office hrs: Virtual       18:00-19:00  
Outline   Lecture Notes V.07   Textbook   Virtual Room
Some online resources
Textbook Online  Point symmetry   Crystal structures 1   Crystal structures 2   Miller indices
Schedule of Classes
September   October   November   December
Mon Tue Wed Thu Fri Mon Tue Wed Thu Fri Mon Tue Wed Thu Fri Mon Tue Wed Thu Fri
  1 2 3 4       1 2 2 3 4 5 6   1 2 3 4*
7 8 9 10' 11 5 6 7 8 9 9 10 11 12 13 7 8 9 10 11
14 15' 16 17 18 12 13" 14 15 16 16 17 18 19 20 14 15 16 17 18
21 22 23 24 25 19 20 21 22 23 23 24 25 26 27 21 22 23 24 25
28 29 30     26 27 28 29 30 30         28 29 30 31  
' No class    " Fall Study Break Day; class moved to Thu, Dec 3    * Last day to drop courses
 Asnt 1 Due 9 Oct 2020 Review 15 Oct 2020 Part I
 Asnt 2 Due 16 Oct 2020 Review 22 Oct 2020 Part I
 Asnt 3 Due 23 Oct 2020 Review 29 Oct 2020 Part I
 Asnt 4 Due 6 Nov 2020 Review 12 Nov 2020 Part II
 Asnt 5 Due 20 Nov 2020 Review 26 Nov 2020 Part II
 Asnt 6 Due 27 Nov 2020 Review 3 Dec 2020 Part III
 Asnt 7** Due 15 Dec 2020 No review Parts III, II, I
** Replaces Final Exam scheduled for 15 Dec 2020

Course Contents
Part I Solid state structure: Types of solids. Crystals and crystal chemistry. Crystallinity in bulk materials.  
  After taking this part of the course, you will understand how the ions, atoms and molecules build solids. You will learn the basic concepts used to describe the crystal structure, what will make it easy for you to read the literature reporting crystal structure data. You will learn the principles that govern the formation crystals, from those of noble gases and viruses to ionic compounds and silicates. You will see that crystallinity is ubiquitous in various materials that surround us, and even present in almost every tissue of our body.  
  INTRODUCTION: The aggregate states of matter. The solids. Solid state chemistry. CRYSTAL STRUCTURES: Crystals. Symmetry. (Translational symmetry. Space symmetry.) Unit cell. Crystal systems. Crystal lattice. (Crystal lattice types. Bravais lattice. Indices of directions.) Lattice planes and Miller indices. d-Spacing formula. Crystal density formula. Closed packed structures. Polytypes formed by cp layers. Some other packing arrangements. Crystal structures of metals / alloys. Crystal structures of noble gases. Crystal structures of approximately spherical molecules. Crystal structures of ionic compounds. (Important structure types based on ccp and hcp arrangements of ions. Structure type CsCl.) Crystal structures of silicates. (Quartz vs olivine: a comparison.) CRYSTALLINITY IN BULK MATERIALS: Crystalline vs amorphous materials. Polymers. (Crystallites and crystallinity. Crystallization in polymers. Example: cis-, trans- and saturated fatty acids in fat. Example: crystal structure of Nylon-66. Example: elastin vs collagen. Example: crystallinity of starch granules. Texture.) Polycrystalline materials. Nanocrystalline materials.  
Part II Physical chemistry of solids: Bonding and stability. Heterogeneous equilibria. Phase diagrams of one- and two-component systems.  
  In this part you will learn why only certain solids form while others do not exist and how relative stability of solids may be predicted. You will see how ignoring basic thermodynamics by some pharmaceutical companies resulted in their million dollar losses. You will also see how easy it is to read and draw phase diagrams and what rules control the formation and transformations of solid phases. A number of examples to practice reading and drawing phase diagrams will be provided to make it easy for you to read scientific and technical literature reporting phase equilibria data.  
  BONDING IN SOLIDS: Types of solids by bonding. (Ionic vs covalent bonding in crystals.) Ionic compounds. (Properties of ions. Ionic radii. Structure of ionic crystals. The radius ratio rule. Lattice energy. Thermochemical radii. The Born-Haber cycle.) PHASE DIAGRAMS: The phase rule. Stability and equilibrium. One-component systems and polymorphism. (Monotropic and enantiotropic polymorphous transitions. Relative thermodynamic stability of polymorphs vs T and P. Selected examples of polymorphism.) Phase transitions. (Reversible vs irreversible. First vs second order. Glass transitions.) Two-component (binary) systems. (Simple eutectic system: PTX-diagram. Simple eutectic system. Lever rule. System with a congruently melting compound. System with an incongruently melting compound. Syntectic and monotectic reactions. Exothermic and endothermic compounds. Polymorphous transitions. Degenerated phase diagrams.) Binary systems with solid solutions. (Complete solid solutions and fractional crystallization. Partial solid solutions.) Phase diagrams: additional exercises. (Phase transformation reactions: summary. Drawing phase diagrams. De-icing salts.)  
Part III Properties and applications: Electronic structure and defects. Physical properties: electrical, magnetic, optical. Chemical reactivity in the solid state.  
  After taking basics in the two previous parts, it will be easy to understand many useful properties of solids, such as mechanical, electrical, magnetic and optical. Why are metals plastic but not transparent, while most ionic crystals are hard and transparent? Why is all electronics based on semiconductors even though they are much poorer conductors than metals? How does the lithium battery work? What is the difference between a regular lamp (such as a fluorescent lamp), lightemitting diode (such as in the traffic lights) and laser diode (such as in a laser pointer)? Finally, you will see how chemical reactions occur in solids and why solid state organic synthesis can replace the traditional "wet" chemistry in future.  
  BAND STRUCTURE OF SOLIDS. CRYSTAL DEFECTS: Classification of defects. Point defects. (Color centers in NaCl. Color centers in diamond. Impurities as point defects.) Line defects. ELECTRICAL PROPERTIES OF SOLIDS: Conductivity. Superconducting materials. Semiconductors and doping. (Ga-Doped Si. As-Doped Si. pn-Junction and diode. Examples of other devices based on pn-junctions.) Ionic conductors. (Ionic conductivity in NaCl. Ionic conductivity in AgCl. Properties of ionic conductors. Lithium battery.) Ferroelectric and related materials. (Ferroelectric vs antiferroelectric vs ferrielectric materials. Pyroelectric materials. Piezoelectric materials.) MAGNETIC PROPERTIES OF SOLIDS: Magnetism. Effect of temperature on magnetic materials. Overview of selected magnetic materials. (Five transition elements from Cr to Ni. Metal alloys. Lanthanides. Spinels and garnets.) Applications. OPTICAL PROPERTIES OF SOLIDS: Color and transparency. Luminescence. (Fluorescent lamp.) Lasers. (Ruby laser. Laser diode.) CHEMICAL REACTIVITY IN THE SOLID STATE: Solid state reaction. (Topotactic and epitactic reactions.) Solid state organic synthesis. (Polymerization of diacetylenes. Photochemical cycloaddition. Intramolecular elimination: conformational effects. Reactions in clays.) Conclusion.