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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.
+Z
Z-
+Z
(Z-1)-
e-
Energy
• 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:
Al(g) Al+(g) + e- I1 = 580 kJ/mol first
Al+(g) Al2+(g) + e- I2 = 1815 kJ/mol second
Al2+(g) Al3+(g) + e- I3 = 2740 kJ/mol third
Al3+(g) Al4+(g) + e- I4 = 11,600 kJ/mol fourth
Which reaction represents the ionization of F?
A. 1s22s22p5
B. 1s22s22p5
1s22s22p6
1s22s22p43s1
C. 1s22s22p5 1s22s22p4
D. 1s22s22p5 1s22s12p6
Periodic Trends: Ionization
• First Ionization Potentials:
Column 1
Column 8
Periodic Trends: Ionization
• First Ionization Potentials:
• Increases as one goes from left to right.
• Decrease as one goes down a group.
• Reason: increased Z+
• Reason: increased distance from nucleus
Periodic Trends: Ionization
• Removal of valence versus core electrons
Na(g) Na+(g) + e- I1 = 495 kJ/mol
Na+(g) Na2+(g) + e- I2 = 4560 kJ/mol
[Ne]3s1 [Ne]
[Ne] 1s22s22p5
(removing “valence” electron)
(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?
A. 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.
+Z
Z-
+Z
(Z+1)-
e-
Energy
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:
• Orbital configurations can explain both observations.
N?
Periodic Trends: Electron Affinity
• Why is EA so great for the halogens?
F(g) + e- F-(g) EA = -327.8 kJ/mol
1s22s22p5 1s22s22p6 [Ne]
• 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
• 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.
Bigger Z+ overcomes e- repulsion.
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