MSE 280: Introduction to Engineering Materials

Atomic structure and Bonding
Reading: Chapter 2 g p

Overview
•Electrons, protons and neutrons in atoms (Bohr and QM models). •IP, EA, χ, and periodic trends. •Bonding between atoms. •Intermolecular forces. •Relation to macroscopic properties.
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© 2007, 2008 Moonsub Shim, University of Illinois

MSE280

Electrons in atoms
orbital electrons: n = principal quantum number
n=3 2

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Adapted from Fig. 2.1, Callister 6e.

Nucleus: Z = # protons N = # neutrons

Atomic mass A ≈ Z + N

Electrons in discrete orbitals. Bohr atom: 1) electrons are particles that revolve around the nucleus. 2) quantized angular momentum. Quantum Mechanics: Wave or matrix mechanics → Probability. 2
MSE280

© 2007, 2008 Moonsub Shim, University of Illinois

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2008 Moonsub Shim.. • tend to occupy lowest available energy state. University of Illinois MSE280 Atomic orbitals dxy dyz s px py pz Electrons.3 from Callister 6 ed.. • have discrete energy states (Quantized).Comparison of Bohr and QM models Figs.2 and 2. University of Illinois dxz dx2 y2 - dz2 4 MSE280 2 . 3 © 2007. © 2007. 2. 2008 Moonsub Shim.

Quantum numbers • Principal: n = 1. ms = 1/2 Which atom is this? Be 5 n = 2. 2008 Moonsub Shim. d. 1. e. eg 2s 1s n = 2. ms = 1/2 n = 1. ±3… . 3. ±l Determines the number of states in a given l subshell (2l +1 total) • Spin: ms = ±1/2 e. 2008 Moonsub Shim. University of Illinois MSE280 Electron Configuration . ms = -1/2 © 2007. . n – 1 = s. ml = 0. ml = 0. l = 0. 3….Shorthand notation to represent which states electrons occupy in an atom (without specifying electron spin). f = fundamental • Magnetic: ml = 0.g.for degenerate levels (e. ml = 0. f… s = sharp. University of Illinois MSE280 3 .g. Carbon 2p 2s 1s Electron configuration: 1s22s22p2 Note . ml = 0. 2. d = diffuse. ±1.g. l = 0.each energy level can only hold two electrons of opposite spin (Pauli exclusion principle). each orbital is filled with one electron before electrons are paired up. p = principal. l = 0. 6 © 2007. 2p-orbitals). p. ±2. ms = -1/2 n = 1. 4… • Angular momentum: l = 0. 2. l = 0.

2 2s 2 2p 6 1s 1s 2 2s 2 2p 6 3 s 2 3p 6 1s 2 2s 2 2p 6 3 s 2 3p 6 3d 10 4 s 2 4p 6 8 © 2007. K. Na. Br Partially filled d-orbital: Transition metals e.Electron configuration 1 electron in the s-orbital: Alkali metals Li.2.. Co… Valence electrons determine which group atoms belong to. Se… Filled s-orbital and 5 electrons in p-orbital: Halogens F. Rb… 2 electrons in the s-orbital: Alkaline earths Be. 7 © 2007. Cl Br… F Cl.. Callister 6e. 2008 Moonsub Shim. Mg. • have complete s and p subshells • t d t be i t tend to b inert. Mn. S. 2008 Moonsub Shim. University of Illinois MSE280 Stable configuration Stable electron configurations. Fe. Z Element 2 He 10 Ne 18 Ar 36 Kr Noble gases Configuration 1s 2 Adapted from Table 2. Ca… Filled s-orbital and 4 electrons in p-orbital: Chalcogens O. University of Illinois MSE280 4 .g.

9 © 2007.Valence electrons 3s 2p p 2s 1s Na Valence electron 3s 2p 2s 1s Na+ } Filled shell leads to stability. 2008 Moonsub Shim. University of Illinois MSE280 How much energy does it require to take an electron out of an atom? Energy of an electron in vacuum Energy IP Valence electron • Ionization potential (IP): Energy required to pull out a valence electron (in vacuum).e. need to put in energy to pull out the electron). © 2007. University of Illinois 10 MSE280 5 . 2008 Moonsub Shim. By convention. IP is positive (i. Lose an electron Valence electrons 3p 3s 3 2p 2s 1s Cl Gain an electron 3p 3s 2p 2s 1s Cl- } Filled shell leads to stability.

-Larger Δχ more ionic bond. electron goes from higher energy state in vacuum to lower energy state in atom).How much energy does it require to place an electron in an atom? Energy of electron in vacuum Energy EA Lowest available state Valence electrons • Electron Affinity (EA): Energy gained by putting an electron in (from vacuum). 12 IP + EA 2 © 2007. EA is negative (i. the atom with larger χ will have higher electron density around its nucleus. 2008 Moonsub Shim.e. 2008 Moonsub Shim. By convention. 11 © 2007. University of Illinois MSE280 How do we determine when an atom will accept an electron or give one up? Vacuum level Energy y EA IP Lowest available state Valence electrons χ • Electronegativity (χ): a measure of how likely an atom will take up or give up an electron A simple (and intuitive) definition: x~ -When two atoms are brought together. University of Illinois MSE280 6 .

2008 Moonsub Shim. University of Illinois MSE280 Bonding Primary Ionic Covalent Metallic E Secondary Dipole-dipole H-bonds H bonds Dipole-induced-dipole Fluctuating dipoles Equilibrium bond length 14 © 2007.13 © 2007. University of Illinois MSE280 7 . 2008 Moonsub Shim.

In many cases n ~ 8. University of Illinois MSE280 Ionic Bonding Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable + Coulombic Attraction - Cl (anion) stable z1 z 2 e 2 EA = 4πε o r Since z1 = +1 for Na+ and z2 = -1 for Cl2 Negative energy means attraction only. Example: NaCl 3p 3s Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable + Coulombic Attraction - Cl (anion) stable 3p 3s Na (χ = 0. e-e repulsion) ER = B and n depend on atoms involved.ions. University of Illinois MSE280 8 .g. Large difference in electronegativity required. there is also repulsive energy (e. Requires electron transfer.9) Cl (χ = 3. 2008 Moonsub Shim. 2008 Moonsub Shim. A Will the atoms collapse on themselves? o E =− e 4πε r B rn =− A r No.0) 15 © 2007.Ionic Bonding • • • • Occurs between + and . 16 © 2007.

7 Fr 0. 2008 Moonsub Shim.8 Zn 1.6 Fe 1.5 Cr 1.5 Mg 1. Copyright 1960 by Cornell University.9 Ra 0.0 Sr 1. 2.0 O 3. 2008 Moonsub Shim.8 Rb 0.5 At 2. 3rd edition.7 is adapted from Linus Pauling. Copyright 1939 and 1940. University of Illinois MSE280 Ionic Bonding: examples • Predominant bonding in Ceramics H 2.9 K 0.7 Be 1.8 I 2.7.8 NaCl MgO M O CaF 2 Cs Cl Ni 1.2 Ca 1. 18 © 2007.2 He Ne Ar Kr Xe Rn - Give up electrons Acquire electrons From Callister 6e resource CD.0 Ba 0.8 Cs 0. 2.0 Na 0. (Fig. Callister 6e.1 Li 1. 3rd edition. University of Illinois MSE280 9 .9 Ti 1.8 As 2.Ionic Bonding E ER = B rn r Bond energy gy EA = − Equilibrium bond length A r Note: Other types of bonds can also be described in a similar manner17 © 2007.5 F 4. Adapted from Fig.0 Br 2. The Nature of the Chemical Bond.0 Cl 3.

10. needs 1 more CH 4 H H shared electrons from carbon atom C H shared electrons from hydrogen atoms Adapted from Fig. needs 4 more H: has 1 valence e. 2. Callister 6e. 2008 Moonsub Shim. University of Illinois H 19 MSE280 atomic orbitals for carbon: 2p 2s 1s Atomic Orbitals an s-orbital z y x 4 valence electrons but two different types orbitals. 2008 Moonsub Shim. University of Illinois MSE280 10 . px three p orbitals py pz Hybridization y 1s + 1p = sp-orbitals 1s + 2p = sp2-orbitals sp3 hybridization for C in CH4 1s + 3p = sp3-orbitals z y x x z z 60° y 60° x y 20 © 2007. H’s on CH4 should be equivalent.Covalent Bonding • “Sharing” of electrons • Why do some atoms want to share electrons? H Molecular orbitals H 1s • Example1: H2 Atomic orbitals 1s H H H H • Example2: CH4 C: has 4 valence e. © 2007. Electronegativities are same or comparable.

8 Cl 2 As 2.9 Ra 0. 3rd edition.8 I 2. 3rd edition.8 Rb 0.0 Ba 0. University of Illinois more ionic MSE280 11 .2 Ca 1.0 Na 0.8 Ge 1. Copyright 1939 and 1940.7.8 Sn 1.8 Pb 1.0 Sr 1.8 Cs 0.6 Cr 1.8 C 2.0 Adapted from Fig.5 Mg 1.7 Fr 0.5 Si 1. GaAs • • • • Molecules with nonmetals Molecules with metals and nonmetals Elemental solids (RHS of Periodic Table) Compound solids (about column IVA) 21 © 2007. 2.5 At 2.7 c column IVA H2 O C(diamond) Be 1.7 is p g .9 K 0. 2008 Moonsub Shim.6 Ni 1.1 21 Li 1. % ionic character = {1 − exp[−0.5 Fe 1. University of Illinois MSE280 % ionic character Most bonds between two different types of atoms are somewhere in between ionic and covalent. ( g adapted from Linus Pauling. The Nature of the Chemical Bond.9 F2 He O 2.0 F 4.0 Br 2.25( χ A − χ B ) 2 ]} χj = electronegativity of atom j KEY POINT: Larger electronegativity difference © 2007. (Fig.8 Zn 1.0 Cl 3. Copyright 1960 by Cornell University.8 Ga 1. Callister 6e. 2.2 Ne Ar Kr Xe Rn - Si C Ti 1.EXAMPLES: COVALENT BONDING H2 H 2. 2008 Moonsub Shim.

24 © 2007. 2008 Moonsub Shim. t l tt ti i 1) ZnS.Example problem • Order the following semiconductors from most covalent to most ionic. ZnSe. University of Illinois MSE280 What’s so important about ionicity of bonds? • Chemical properties – NaCl (highly ionic solid) dissolves readily in water but Si (covalent solid) does not. University of Illinois MSE280 12 . CuCl 2) ZnS. 2008 Moonsub Shim. ZnO 23 © 2007. GaP. • All properties of materials are largely determined by the types and strength of bonds between the constituent atoms. • Electronic properties – Ionicity of the bonds will have a strong influence on the band gap and other electronic properties.

• Large atomic radius and small IP will more likely lead to metallic bonding. University of Illinois MSE280 13 . Callister 6e. H Cl second a H Cl ry bon ding From Callister 6e resource CD. • Primary bond for metals and their alloys. Callister 6e. 2. 2008 Moonsub Shim.14. 2. 25 © 2007. Callister 6e. Adapted from Fig.14. • Hydrogen bonding H O H O H H O H H 26 © 2007. 2. 2008 Moonsub Shim.Metallic Bonding • Arises from a sea of donated valence electrons + + + + + + + + + Fixed ion cores (nuclei and inner electrons) “sea” of electrons Adapted from Fig.11. University of Illinois MSE280 Secondary Bonds: Intermolecular Forces Van der Waals • Dipole-dipole interaction: secondary bond between molecules with permanent dipole moments -general case: -ex: liquid HCl -ex: polymer + - secondary bonding secondary bonding + - Adapted from Fig.

University of Illinois MSE280 14 . University of Illinois MSE280 SUMMARY: BONDING Type Ionic Covalent Bond Energy Large! Variable large-Diamond small-Bismuth Variable large-Tungsten small-Mercury smallest Comments Nondirectional (ceramics) Directional (semiconductors.• Dipole-induced-dipole interaction: secondary bond between molecules with permanent dipole moments + + + polar Nonpolar (e. 2008 Moonsub Shim.13.g. Callister 6e. © 2007. 2.secondary bonding + - H H H H secondary bonding 27 Adapted from Fig. 2008 Moonsub Shim. atom) secondary bonding • Fluctuating dipoles asymmetric electron clouds ex: liquid H 2 H2 H2 + . ceramics polymer chains) Nondirectional (metals) Directional inter-chain (polymer) inter-molecular From Callister 6e resource CD. Metallic Secondary 28 © 2007.

University of Illinois 30 MSE280 15 . From Callister 6e resource CD. Tm F Energy (r) r • Bond energy. Eo ro r smaller T m Energy (r) ro u st etc ed e gt unstretched length r Eo = “bond energy” larger T m Tm is larger if Eo is larger. smaller Elastic Modulus larger Elastic Modulus © 2007. Lo PROPERTIES FROM BONDING: E cross sectional area A o Elastic modulus F ΔL =E Ao Lo undeformed deformed ΔL F • E ~ curvature at ro Energy unstretched length ro r E is larger if curvature at ro is larger. University of Illinois MSE280 • Elastic modulus. From Callister 6e resource CD. r F • Melting Temperature. 2008 Moonsub Shim. E length. 2008 Moonsub Shim. 29 © 2007.PROPERTIES FROM BONDING: TM • Bond length.

University of Illinois MSE280 16 . 2008 Moonsub Shim. 31 © 2007.SUMMARY: BONDING and Materials’ properties Ceramics (Ionic & covalent bonding): Large bond energy large Tm large E small α Metals (Metallic bonding): Variable bond energy moderate Tm moderate E moderate α Polymers (Covalent & Secondary): second ary bo nding Directional Properties Secondary bonding dominates small T small E large α From Callister 6e resource CD.