ENMA 300

Homework 1

Due: Monday Feb 6, 2012

1. Predict the type of bonding that holds the atoms/molecules together in the following solid materials. Explain why you have made the prediction for each material. Where appropriate include calculations. The Sargent-Welsh % ionic character table was used to calculate the % ionicity instead of the formula from the book. You will get similar values using equation in the book. It is important to calculate percent ionicity not just EN. CaO: We need to do a % ionic character calculation for CaO because it is a compound with a metallic and a non-metallic element. (EN=2.5 so %ionic bonding is ~ 79% from S-W table and equation 2.2). Thus, the bonding in CaO is highly ionic and we need to use ionic radii in any calculations. CdS: We need to do a % ionic character calculation for CdS because it is a compound with a metallic and a non-metallic element. (EN=2.5 -1.7= 0.8, so %ionic bonding ~ 15% ). Thus, we would expect covalent bonding to be dominant and we need to use covalent radii (if you are using the table in the front of your text use the atomic radius) for any calculations. FeO: We need to do a % ionic character calculation for FeO because it is a compound with a metallic and a non-metallic element. (EN=1.7 so %ionic bonding ~ 51%). Thus, we would expect ionic bonding to be dominant and we need to use ionic radii. However, it is covalent enough that we need to consider electronic as well as ionic conductivity if we are interested in electrical behavior. Bronze (a copper rich copper-tin alloy): Cu and Sn are both metals so we would expect the bonding to be metallic. Solid Ne: Ne is an inert gas so it already has a stable electron configuration. Thus the bonding in solid Ne is van der Waals bonding. This is why its melting point is -248.7C or 24.3K. Polyisoprene (a type of rubber): For rubber, the bonding is covalent with some van der Waals. (Rubber is composed primarily of carbon and hydrogen atoms.) More later in chapter 4. AlP: The positions of Al and P in the periodic table indicate that it is a compound with a metallic and a non-metallic element so we should do a % ionic character calculation (EN=0.6 so %ionic bonding ~ 10%). Thus, the bonding is predominantly covalent although it has a small amount of ionic character. You would use covalent radii for this material. Note: The percent ionicity (ionic character) calculation allows you to determine if a bond is highly ionic, ionic or strongly covalent. This is useful in determining the appropriate radii (ionic or covalent) to use in calculations. It also gives us information regarding appropriate model materials and whether we might anticipate semiconducting behavior, etc. When the % ionic character is less than 100% (as it is in all cases) it does not mean that some bonds in the material are ionic and some are covalent. Rather it means that the character of each bond is mixed. The

percent ionicity calculation doesnt apply when the bonding is metallic, hydrogen or Van der Waals bonding. 2a) Make a table with the melting point, elastic modulus, CTE, and density for Sn, Au and W. Reference your source(s) for the information. Briefly discuss how these properties relate to bonding. Melting Point C (K) Elastic Modulus (GPa) CTE (1/C) Density @RT (g/cm3) Sn (tin) 232 (505 44.3 23.8 x10-6 7.27 Au (gold) 1064 (1337) 77 14.2 x10-6 19.32 W (tungsten) 3410 (3683) 400 4.5 x10-6 19.3 Reference Table in front cover of text Table B.2 page 834-835 of text Table B.6 page 846 of text Table in front cover of text

Notes: 1. The Elastic Modulus is mainly dependent on bonding so that it doesnt change much with microstructure or even crystal structure. Composition can have an effect since it can modify the bonding character. 2. While the textbook has values of common and important properties for many materials, it is good to be familiar with other sources for data. MatWeb is a good web source for data on many materials, especially commercial materials. (http://www.matweb.com). The CRC Handbook of Chemistry and Physics is another good, standard reference for many basic properties. The melting point is related to the bond strength since stronger bonds require more energy to break them so melting can occur. Elastic modulus or stiffness is related to bonding since solids that are more strongly bonded will be more difficult to bend or stretch. The coefficient of thermal expansion is related to bond strength since it is related to how tightly atoms are held in their equilibrium positions and also in how close a material is to its melting point. Atoms in more strongly bonded materials are going to stay closer to their equilibrium positions. Atoms in low melting materials are relatively more energetic since they are closer to their melting point at any given temperature (homologous T=T/Tmp in K) so they can move about their equilibrium position more. Density is not strongly related to bonding. While covalency tends to expand the lattice so that a material with the zincblende structure because of radius ratio will have an atomic packing factor and thus a density greater than one with it because of a covalent nature favoring sp3 bonds, the atomic mass and crystal structure play much larger roles in density. Density is included as an interesting contrasting property since it is not strongly related to bonding. Note: the first part of this paragraph will make more sense once we have covered bonding type and crystal structures. b) On the same nested schematic diagram sketch potential well diagrams for Sn, Au and W. Give a brief explanation for the relative location and shape of each curve.

Notes: All the curves should be asymptotically approaching zero and smooth like figure 2.8b on page 25 of the text. However, I am not very good at drawing on the computer. The depth of well is related to Tmp. Note that the well is deepest for W, followed by Au. It is shallowest for Sn. The slope of the curve near r~r0 (i.e. as you come to and leave r0) is related to the stiffness/elastic modulus. Thus, the sharper the well, the larger the elastic modulus will be. The coefficient of thermal expansion (CTE) is related to the symmetry of the well close to r0. You need to look at the r for a given T or energy when you are determining the symmetry. I have exaggerated the differences in the equilibrium spacing r0 to help you to see the curves more easily. I have also tried to indicate how to look at symmetry. c) Briefly indicate how this schematic diagram could help you select a material for a specific application. The graph is a visual way to represent some of the differences between the materials. If critical materials selection factors were melting point, elastic modulus or coefficient of thermal expansion it could help you choose a material or visually support your choice in a presentation. However, a table would be just as useful. This exercise is largely intended to help you identify properties that are not strongly dependent on structure since most properties are a strong function of microstructure and crystal structure.