Ch. 8.
3: Periodic Variation in Effective Nuclear Charge, Atomic Radius, Ionic Radius
• Periodic Table
o Elements in same column have similar properties
§ Column # (IA-VIIIA) gives # valence electrons
§ All elements in column end in same nsx npy configuration
o Ion Formation
§ Metals lose electrons to form noble gas core:
• Na → Na+ + e–: [Ne]3s1 → [Ne]
• Al → Al3+ + 3e–: [Ne]3s23p1 → [Ne]
§ Nonmetals gain electrons to form next noble gas:
• F + e– → F: 1s22s22p5 → 1s22s22p6 or [Ne]
• Se + 2e– → Se2–: [Ar]4s23d104p4 → [Ar]4s23d104p6 or [Kr]
o Special Ion Formation
§ Transition metals lose ns2 electrons before (n–1)dx:
• Fe → Fe3+ + 3e–: [Ar]4s23d6 → [Ar]3d5
• Ni → Ni2+ + 2e–: [Ar]4s23d8 → [Ar]3d8
• Populated (n–1)d orbitals shield ns electrons, ns higher in energy, easier to remove
• Will see evidence in 2nd lesson from now
§ Post-transition metals can lost ns2 npx or just npx electrons:
• Sn → Sn2+ + 2e–: [Kr]5s24d105p2 → [Kr]5s24d10
• Sn → Sn4+ + 4e–: [Kr]5s24d105p2 → [Kr]4d10
• Full (n–1)d10 called “pseudo-noble gas” configuration
• Shielding & Effective Nuclear Charge
o Outermost (valence) electrons shielded from full nuclear charge (Z) by inner core electrons:
§ Trade-off between coulombic attraction to nucleus and repulsion by core electrons
§ In all elements with n≥2, the effective nuclear charge, Zeff, is approximated by Zeff = Z – σ
• Where σ is the shielding factor, repulsion of core electrons
o σ = number of core electrons
• This is not exact but gives a good qualitative understanding of the phenomenon
• = # Valence Electrons, where σ = # of core electrons
Atomic Radius-Ionic Radius [Link] p.2
o Within a period, Zeff increases as Z increases across and σ remains constant:
§ Within a group, Zeff remains constant as Z and σ both increase as n increases
• Zeff = #Valence Electrons (outermost electrons with greatest n)
• Atomic Radius Depends on Zeff & n:
o Radius is smallest where Zeff is largest, increases to left as
Zeff decreases Radius Increases
§ Electron attraction depends on Zeff
§ Stronger attraction pulls electrons closer to nucleus
§ Electron cloud, radius smaller
o Radius increases as n increases
§ Electrons in higher energy levels more shielded,
Radius Increases
farther from nucleus
§ Electron orbitals larger, radius larger
o Periodic Variations & Patterns in Radius
§ Within period see same general patterns
• Large decreases in radius for Group I (alkali metals) and II (alkaline earth metals), smaller decreases
until Group VII (halogens)
• Group I always largest, Group VII smallest (Group VIII, noble gases on prior chart
• Variation within transition and inner transition metals complex
§ From one period to next, all elements in same group slowly increase
Atomic Radius-Ionic Radius [Link] p.3
• Ionic Radius (see right)
o Metals lose electrons: Na → Na+ + e–
§ positive ion smaller than atom: less electron-electron
repulsion, remaining electrons experience more
electrostatic attraction to nucleus
o Nonmetals gain electrons
§ negative ion larger than atom: more electron-electron
repulsion, electrons experience less electrostatic attraction
to nucleus
• Periodic Trend:
o Ionic radius increases down a group
§ Same trend as seen in atomic radius
§ Higher energy electrons more shielded, less attracted
to nucleus, so farther away.
o Ionic radius increases from right to left
§ Anion size increases until reach cations, then size starts
low and increases again
§ Anions filling higher energy level than cations
o Isoelectronic ions have same electron configuration
§ E.g. N3–, O2–, F–, (Ne), Na+, Mg2+, Al3+: All have [Ne]
configuration
§ In isoelectronic series, radius decreases
as Z (hence Zeff) increases: [Ne]
• As Z increases, ions’ nuclei exert
stronger electrostatic attraction for the same
number of electrons [Ar]
• Read about MP and BP in text.
[Kr]
