Chapter 2: Atomic Structure & Interatomic Bonding

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1 Chapter 2: Atomic Structure & Interatomic Bonding ISSUES TO ADDRESS... What promotes bonding? What types of bonds are there? What properties are inferred from bonding? Chapter 2-1

2 Atomic Structure (Freshman Chem.) atom electrons 9.11 x kg protons } neutrons 1.67 x kg atomic number = # of protons in nucleus of atom = # of electrons of neutral species A [=] atomic mass unit = amu = 1/12 mass of 12 C Atomic wt = wt of x molecules or atoms 1 amu/atom = 1g/mol C H etc. Chapter 2-2

3 Atomic Structure Valence electrons determine all of the following properties 1) Chemical 2) Electrical 3) Thermal 4) Optical Chapter 2-3

4 Electronic Structure Electrons have wavelike and particulate properties. This means that electrons are in orbitals defined by a probability. Each orbital at discrete energy level is determined by quantum numbers. Quantum # n = principal (energy level-shell) Designation K, L, M, N, O (1, 2, 3, etc.) l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,, n -1) m l = magnetic m s = spin ½, -½ 1, 3, 5, 7 (-l to +l) Chapter 2-4

5 Electrons... Electron Energy States have discrete energy states tend to occupy lowest available energy state. 4d 4p N-shell n = 4 3d 4s Energy 3p M-shell n = 3 3s 2p 2s Adapted from Fig. 2.4, Callister & Rethwisch 8e. L-shell n = 2 1s K-shell n = 1 Chapter 2-5

6 Chapter 2-6

7 Chapter 2-7

8 SURVEY OF ELEMENTS Most elements: Electron configuration not stable. Element Hydrogen Helium Lithium Beryllium Boron Carbon... Neon Sodium Magnesium Aluminum... Argon... Krypton Atomic # Electron configuration 1s 1 1s 2 (stable) 1s 2 2s 1 1s 2 2s 2 1s 2 2s 2 2p 1 1s 2 2s 2 2p s 2 2s 2 2p 6 (stable) 1s 2 2s 2 2p 6 3s 1 1s 2 2s 2 2p 6 3s 2 1s 2 2s 2 2p 6 3s 2 3p s 2 2s 2 2p 6 3s 2 3p 6 (stable)... 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable) Adapted from Table 2.2, Callister & Rethwisch 8e. Why? Valence (outer) shell usually not filled completely. Chapter 2-8

9 Electron Configurations Valence electrons those in unfilled shells Filled shells more stable Valence electrons are most available for bonding and tend to control the chemical properties example: C (atomic number = 6) 1s 2 2s 2 2p 2 valence electrons Chapter 2-9

10 Electronic Configurations ex: Fe - atomic # = 26 1s 2 2s 2 2p 6 3s 2 3p 6 3d 6 4s 2 4d 4p 3d 4s N-shell n = 4 valence electrons Energy 3p M-shell n = 3 3s 2p 2s Adapted from Fig. 2.4, Callister & Rethwisch 8e. L-shell n = 2 1s K-shell n = 1 Chapter 2-10

11 The Periodic Table Columns: Similar Valence Structure give up 1e - give up 2e - give up 3e - inert gases H Li Be Na Mg K Rb Ca Sr Sc Y accept 2e - accept 1e - O S Se Te F Cl Br I He Ne Ar Kr Xe Adapted from Fig. 2.6, Callister & Rethwisch 8e. Cs Ba Po At Rn Fr Ra Electropositive elements: Readily give up electrons to become + ions. Electronegative elements: Readily acquire electrons to become - ions. Chapter 2-11

12 Electronegativity Ranges from 0.7 to 4.0, Large values: tendency to acquire electrons. Smaller electronegativity Larger electronegativity Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University. Chapter 2-12

13 Chapter 2-13

14 Chapter 2-14

15 Ionic bond metal + nonmetal donates electrons accepts electrons Dissimilar electronegativities ex: MgO Mg 1s 2 2s 2 2p 6 3s 2 O 1s 2 2s 2 2p 4 [Ne] 3s 2 Mg 2+ 1s 2 2s 2 2p 6 O 2-1s 2 2s 2 2p 6 [Ne] [Ne] Chapter 2-15

16 Ionic Bonding Occurs between + and - ions. Requires electron transfer. Large difference in electronegativity required. Example: NaCl Na (metal) unstable electron Cl (nonmetal) unstable Na (cation) stable + - Coulombic Attraction Cl (anion) stable Chapter 2-16

17 Ionic Bonding Energy minimum energy most stable Energy balance of attractive and repulsive terms A E N = E A + E R = - + r B r n Repulsive energy E R Interatomic separation r Net energy E N Adapted from Fig. 2.8(b), Callister & Rethwisch 8e. Attractive energy E A Chapter 2-17

18 Chapter 2-18

19 Chapter 2-19

20 Examples: Ionic Bonding Predominant bonding in Ceramics NaCl MgO CaF 2 CsCl Give up electrons Acquire electrons Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University. Chapter 2-20

21 Covalent Bonding similar electronegativity share electrons bonds determined by valence s & p orbitals dominate bonding Example: CH 4 shared electrons C: has 4 valence e -, needs 4 more CH 4 H from carbon atom H: has 1 valence e -, needs 1 more Electronegativities are comparable. H C H H shared electrons from hydrogen atoms Adapted from Fig. 2.10, Callister & Rethwisch 8e. Chapter 2-21

22 Chapter 2-22

23 Chapter 2-23

24 Primary Bonding Metallic Bond -- delocalized as electron cloud Ionic-Covalent Mixed Bonding % ionic character = 1- e - (X A -X B ) 4 x ( 100 %) where X A & X B are Pauling electronegativities Ex: MgO X Mg = 1.2 X O = ( % ionic character 1 e ) x (100%) 73.4% ionic Chapter 2-24

25 Chapter 2-25

26 Arises from interaction between dipoles Fluctuating dipoles Permanent dipoles-molecule induced -general case: -ex: liquid HCl SECONDARY BONDING asymmetric electron clouds secondary bonding H Adapted from Fig. 2.13, Callister & Rethwisch 8e. H secondary bonding H Cl secondary bonding ex: liquid H 2 H 2 H 2 H Cl H secondary bonding H Adapted from Fig. 2.15, Callister & Rethwisch 8e. -ex: polymer secondary bonding Chapter 2-26

27 Type Ionic Summary: Bonding Bond Energy Comments Large! Nondirectional (ceramics) Covalent Metallic Secondary Variable large-diamond small-bismuth Variable large-tungsten small-mercury smallest Directional (semiconductors, ceramics polymer chains) Nondirectional (metals) Directional inter-chain (polymer) inter-molecular Chapter 2-27

28 Properties From Bonding: T m Bond length, r r Melting Temperature, T m Energy Bond energy, E o Energy r o smaller T m r unstretched length r o r E o = bond energy larger T m T m is larger if E o is larger. Chapter 2-28

29 Properties From Bonding : a Coefficient of thermal expansion, a length, L o coeff. thermal expansion unheated, T 1 heated, T 2 D L D L L o = a ( T 2 - T 1 ) a ~ symmetric at r o Energy E unstretched length r o larger a r a is larger if E o is smaller. o E smaller a o Chapter 2-29

30 Summary: Primary Bonds Ceramics (Ionic & covalent bonding): Metals (Metallic bonding): Large bond energy large T m large E small a Variable bond energy moderate T m moderate E moderate a Polymers (Covalent & Secondary): Directional Properties Secondary bonding dominates small T m small E large a Chapter 2-30

31 Chapter 2-31

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