5.

01x Lecture Summary #10

PERIODIC TRENDS IN ELEMENTAL PROPERTIES
PERIODIC TABLE
Assembled by Mendeleev (1869) and others based on similar chemical and physical
properties of elements. For example,
• Li, Na, K originally grouped together in a column because they are all soft,
malleable, reactive metals
• He, Ne, Ar grouped together because of their inertness
Elements in same column have related valence e– configurations
• Li, Na, K have a single valence e– in a s state
• He, Ne, Ar have filled shells
An atom’s bonding properties and chemical behavior result from configuration of its
valence electrons.

IONIZATION ENERGY DEFINITIONS

B(1s22s22p1) B+ (1s22s2) + e– ∆E = Epro – Ereact = IE

IE ≡ first ionization energy - energy to remove e– from HOAO or most weakly bound e–

B+(1s22s2) B+2 (1s22s1) + e– ∆E = IE2

IE2 ≡ second ionization energy

B+2(1s22s1) B+3 (1s2) + e– ∆E = IE3

IE3 ≡ third ionization energy

B+3(1s2) B+4 (1s1) + e– ∆E = IE4

IE4 ≡ fourth ionization energy

B+4(1s1) B+5 + e– ∆E = IE5

IE5 ≡ fifth ionization energy

10.1
Are these two ∆E’s equal?
B+(1s22s2) B+2 (1s22s1) + e– ∆E

B(1s22s22p1) B+ (1s22s12p1) + e– ∆E

PERIODIC TRENDS IN IONIZATION ENERGY

Increase IE

Decrease IE
But some glitches due to subshell
structure, for example, IEB < IEBe IEO < IEN

The amount of BE gained by increased Z in The amount of BE gained by increased Z in

B doesn't compensate for extra energy O doesn't compensate for repulsion
required to reach p state, so IE of B lower between 2e–s in same state, so IE of O
than expected. lower than expected.

Down a column, IE decreases. Although Z increases as go down a column, so does n. Shells

are well-separated in space, so e–s in larger n are farther away from nucleus. Large
distance from nucleus dominates over the increased Z, making e– bound less strongly and
therefore decreasing IE.

ELECTRON AFFINITY

Cl + e– Cl– ∆E = –349 kJ/mole

energy released — ion is more stable than atom

10.2
but electron affinity, EA, is defined as

EA = –∆E

So, EA for Cl is EA = 349 kJ/mole

Unlike IE, EA can be positive or negative……
N + e– N– ∆E = 7 kJ/mole

So EA = –7 kJ/mole for N
ion less stable than atom
1/2 filled subshell
Noble gases have negative electron affinities. Halogens have largest EA's because extra
e– fills a hole in p subshell to give a complete shell.

Increase EA

Decrease EA

ELECTRONEGATIVITY

1
electronegativity = (IE + EA) empirical
2

proportional to average of IE and EA

10.3
ATOMIC SIZES

value of r below which 90% of electron density is contained ≡ radius

In a crystal of identical nuclei,

Decrease r

Increase r
ISOELECTRONIC - having same electron configuration
example, all 1s2 2s2 2p6

Radius of Li (white, 152 pm) vs. Li+ (red, 90 pm) Radius of I (white, 133 pm) vs I- (blue, 206 pm)

10.4