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Lecture 20: Periodic Trends. Reading: Zumdahl 12.14-12.15 Outline Periodic Trends Ionization Energy, Electron Affinity, and Radii A Case Example. Periodic Trends. The valence electron structure of atoms can be used to explain various properties of atoms.
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Lecture 20: Periodic Trends • Reading: Zumdahl 12.14-12.15 • Outline • Periodic Trends • Ionization Energy, Electron Affinity, and Radii • A Case Example
Periodic Trends • The valence electron structure of atoms can be used to explain various properties of atoms. • In general, properties correlate down a group of elements. • A warning: such discussions are by nature very generalized…exceptions do occur.
Periodic Trends: Ionization • If we put in enough energy, we can remove an electron from an atom. • The electron is completely “removed” from the atom (potential energy = 0).
Periodic Trends: Ionization • Generally done using photons, with energy measured in eV (1 eV = 1.6 x 10-19 J). • The greater the propensity for an atom to “hold on” to its electrons, the higher the ionization potential will be. • Koopmans’ Theorem: The ionization energy of an electron is equal to the energy of the orbital from where the electron came.
Periodic Trends: Ionization • One can perform multiple ionizations: first Al(g) Al+(g) + e- I1 = 580 kJ/mol second Al+(g) Al2+(g) + e- I2 = 1815 kJ/mol third Al2+(g) Al3+(g) + e- I3 = 2740 kJ/mol fourth Al3+(g) Al4+(g) + e- I4 = 11,600 kJ/mol
Which reaction represents the ionization of F? A. 1s22s22p5 1s22s22p6 B. 1s22s22p5 1s22s22p43s1 C. 1s22s22p5 1s22s22p4 D. 1s22s22p5 1s22s12p6
Periodic Trends: Ionization • First Ionization Potentials: Column 8 Column 1
Periodic Trends: Ionization • First Ionization Potentials: • Increases as one goes from left to right. • Reason: increased Z+ • Decrease as one goes down a group. • Reason: increased distance from nucleus
Periodic Trends: Ionization • Removal of valence versus core electrons Na(g) Na+(g) + e- I1 = 495 kJ/mol (removing “valence” electron) [Ne]3s1 [Ne] Na+(g) Na2+(g) + e- I2 = 4560 kJ/mol [Ne] 1s22s22p5 (removing “core” electron) • Takes significantly more energy to remove a core electron….tendancy for core configurations to be energetically stable.
Which atom would you expect to have the lowest ionization energy? 1s22s22p3 B. 1s22s22p63s23p5 C. 1s22s22p63s23p64s2 D. 1s22s22p63s23p64s23d104p65s1
Periodic Trends: Electron Affinity • Electron Affinity: the energy change associated with the addition of an electron to a gaseous atom.
Periodic Trends: Electron Affinity • We will stick with our thermodynamic definition, with energy released being a negative quantity. Wow!
Periodic Trends: Electron Affinity • Elements that have high electron affinity: • Group 7 (the halogens) and Group 6 (O and S specifically).
Periodic Trends: Electron Affinity • Some elements will not form ions: N? • Orbital configurations can explain both observations.
Periodic Trends: Electron Affinity • Why is EA so great for the halogens? F(g) + e- F-(g) EA = -327.8 kJ/mol [Ne] 1s22s22p5 1s22s22p6 • Why is EA so poor for nitrogen? N(g) + e- N-(g) EA > 0 (unstable) 1s22s22p3 1s22s22p4 (e- must go into occupied orbital)
Periodic Trends: Electron Affinity • How do these arguments do for O? O(g) + e- O-(g) EA = -140 kJ/mol 1s22s22p4 1s22s22p5 Bigger Z+ overcomes e- repulsion. • What about the second EA for O? O-(g) + e- O2-(g) EA > 0 (unstable) 1s22s22p5 1s22s22p6 [Ne] configuration, but electron repulsion is just too great.
Which diagram indicates the evolution in electron affinity from high affinity to low affinity?
Atomic Radii • Atomic Radii are defined as the covalent radii, and are obtained by taking 1/2 the distance of a bond: r = atomic radius
Atomic Radii • Decrease to right due due increase in Z+ • Increase down column due to population of orbitals of greater n.
Looking Ahead • We can partition the periodic table into general types of elements. Metals: tend to give up e- non-Metals: tend to gain e- Metalloids: can do either