PART CHAPTER2. Atomic Bonding

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PART O N E APTER2 Atomic Bonding The scanning tunneling microscope (Section 4.7) allows the imaging of individual atoms bonded to a material surface.

1 PART O N E APTER2 Atomic Bonding The scanning tunneling microscope (Section 4.7) allows the imaging of individual atoms bonded to a material surface. In this case, the microscope was also used to manipulate the atoms into a simple pattern. Four lead atoms are shown forming a rectangle on the surface of a copper crystal. (From G. Meyer and K.. Rieder, MRS Bulletin [1998].)

2 Outer orbital (with four sp 3 hybrid bonding electrons) Inner orbital (with two 1s electrons) Nucleus (with six protons and six neutrons) Figure 2-1 Schematic of the planetary model of a 12 atom.

3 I A Li Na K Rb s Fr (223) II A III A IV A V A VI A VII A 4 Be Mg a Sr Ba Ra VIII III B IV B V B VI B VII B I B 21 Sc Y La Ac (227) 22 Ti Zr f V Nb Ta r Mo W Mn Tc Re Fe Ru Os o Rh Ir Ni Pd Pt u Ag Au II B 30 Zn d g B Al Ga In Tl Si Ge Sn Pb N P As Sb Bi O S Se Te Po (210) 9 F l Br I At (210) 0 2 e Ne Ar Kr Xe Rn (222) 58 e Th Pr Pa Nd U Pm (145) 93 Np Sm Pu (244) 63 Eu Am (243) 64 Gd m (247) 65 Tb Bk (247) 66 Dy f (251) 67 o Es (254) 68 Er Fm (257) 69 Tm Md (258) 70 Yb No (259) 71 Lu Lw (260) Figure 2-2 Periodic table of the elements indicating atomic number and atomic mass (in amu).

4 (sp 3 ) Energy (ev) s Figure 2-3 Energy-level diagram for the orbital electrons in a 12 atom. Notice the sign convention. An attractive energy is negative. The 1s electrons are closer to the nucleus (see Figure 2 1) and more strongly bound (binding energy = ev). The outer orbital electrons have a binding energy of only 6.5 ev. The zero level of binding energy corresponds to an electron completely removed from the attractive potential of the nucleus.

5 Electron transfer Na l Ionic bond Na + l Figure 2-4 Ionic bonding between sodium and chlorine atoms. Electron transfer from Na to l creates a cation (Na + ) and an anion (l ). The ionic bond is due to the coulombic attraction between the ions of opposite charge.

6 l Na+ Figure 2-5 Regular stacking of Na + and l ions in solid Nal. This is indicative of the nondirectional nature of ionic bonding.

7 Na + l a 4 F c 10 9 (N) a (nm) Figure 2-6 Plot of the coulombic force (Equation 2.1) for a Na + l pair.

8 Na + l a F c (coulombic force of attraction) 2 F (net bonding force) 1 Fc 10 9 (N) a (nm) 2 F R (repulsive force) 3 4 Figure 2-7 Net bonding force curve for a Na + l pair showing an equilibrium bond length of a 0 = 0.28 nm.

9 Na + l Bonding force + 0 a Bonding energy + 0 a a 0 Figure 2-8 omparison of the bonding force curve and the bonding energy curve for a Na + l pair. Since F = de/da, the equilibrium bond length (a 0 ) occurs where F = 0 and E is a minimum (see Equation 2.5).

10 (a) (b) (c) r Na + r l a 0 Figure 2-9 omparison of (a) a planetary model of a Na + l pair with (b) a hard-sphere model and (c) a soft-sphere model.

11 Na l Na + Figure 2-10 Formation of an ionic bond between sodium and chlorine in which the effect of ionization on atomic radius is illustrated. The cation (Na + ) becomes smaller than the neutral atom (Na), while the anion (l ) becomes larger than the neutral atom (l). l

12 R = 1.0 r = 0.2 N = 1 possible N = 2 possible N = 3 maximum N = 4 unstable Figure 2-11 The largest number of ions of radius R that can coordinate an atom of radius r is 3 when the radius ratio, r/r = 0.2. (Note: The instability for N = 4 can be reduced but not eliminated by allowing a three-dimensional, rather than a coplanar, stacking of the larger ions.)

13 R r cos 30 = = = r + R R 30 Figure 2-12 The minimum radius ratio, r/r, that can produce threefold coordination is

14 (a) (b) l l (c) l (d) l Figure 2-13 The covalent bond in a molecule of chlorine gas, l 2, is illustrated with (a) a planetary model compared with (b) the actual electron density and (c) an electron-dot schematic and (d) a bond-line schematic.

15 Ethylene molecule (a) Ethylene mer Polyethylene molecule (b)... Figure 2-14 (a) An ethylene molecule ( 2 4 ) is compared with (b) a polyethylene molecule ( 2 4 ) n that results from the conversion of the = double bond into two single bonds.

16 Figure 2-15 Two-dimensional schematic representation of the spaghettilike structure of solid polyethylene.

17 Figure 2-16 Three-dimensional structure of bonding in the covalent solid, carbon (diamond). Each carbon atom () has four covalent bonds to four other carbon atoms. (This geometry can be compared with the diamond cubic structure of Figure 3 23.) In this illustration, the bondline schematic of covalent bonding is given a perspective view to emphasize the spatial arrangement of bonded carbon atoms.

18 Si 4+ O 2 Figure 2-17 The SiO 4 4 tetrahedron represented as a cluster of ions. In fact, the Si O bond exhibits both ionic and covalent character.

19 E + 0 a Bond energy Bond length Figure 2-18 The general shape of the bond energy curve as well as associated terminology applies to covalent as well as ionic bonding. (The same is true of metallic and secondary bonding.)

20 109.5 Figure 2-19 Tetrahedral configuration of covalent bonds with carbon. The bond angle is

21 l

22 l l l mer l l

23 l

24 Electron cloud from valence electrons u 2+ ion core (cutaway view) Figure 2-20 Metallic bond consisting of an electron cloud, or gas. An imaginary slice is shown through the front face of the crystal structure of copper, revealing u 2+ ion cores bonded by the delocalized valence electrons.

25 I A Li Na K Rb s Fr 0.7 II A III A IV A V A VI A VII A 4 Be Mg a Sr Ba Ra 0.9 VIII III B IV B V B VI B VII B I B 21 Sc Y La-Lu Ac-No Ti Zr f V Nb Ta r Mo W Mn Tc Re Fe Ru Os o Rh Ir Ni Pd Pt u Ag Au 2.4 II B 30 Zn d g B Al Ga In Tl Si Ge Sn Pb N P As Sb Bi O S Se Te Po F l Br I At e 10 Ne 18 Ar 36 Kr 54 Xe 86 Rn Figure 2-21 The electronegativities of the elements. (After Linus Pauling, The Nature of the hemical Bond and the Structure of Molecules and rystals; An Introduction to Modern Structural hemistry, 3rd ed., ornell University Press, Ithaca, New York, 1960)

26 Isolated Ar atom Magnitude of dipole moment Isolated Ar atom + Secondary bond + enter of negative (electron) charge enter of positive charge (nucleus) Figure 2-22 Development of induced dipoles in adjacent argon atoms leading to a weak, secondary bond. The degree of charge distortion shown here is greatly exaggerated.

27 O = + + Dipole Figure 2-23 ydrogen bridge. This secondary bond is formed between two permanent dipoles in adjacent water molecules. (From W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. 1: Structures, John Wiley & Sons, Inc., New York, 1964.)

28 covalent Semiconductors Polymers metallic secondary Metals ionic eramics and glass Figure 2-24 Tetrahedron representing the relative contribution of different bond types to the four fundamental categories of engineering materials (the three structural types plus semiconductors).

29 a Reference ion

30 n 3 3 n

31 n O n

32 F F F F

33 F F

34 F F F F F F

35 Na (solid) l 2 (g) Na (g) + l (g) f Nal (solid) Na + (g) + l (g)

The Periodic Table. Periodic Properties. Can you explain this graph? Valence Electrons. Valence Electrons. Paramagnetism

The Periodic Table. Periodic Properties. Can you explain this graph? Valence Electrons. Valence Electrons. Paramagnetism Periodic Properties Atomic & Ionic Radius Energy Electron Affinity We want to understand the variations in these properties in terms of electron configurations. The Periodic Table Elements in a column