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Greenwood & Earnshaw

This chapter discusses the halogens (fluorine, chlorine, bromine, iodine, and astatine). It provides molecular orbital diagrams for F2, Cl2, Br2, and I2 showing how hybridization allows for inversion of the σ and π molecular orbitals for the heavier halogens. Bond energies are provided showing fluorine's bond is weak due to lone pair repulsions. Interhalogens and trihalide anions are discussed along with iodine oxides and oxoacids.

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222 views3 pages

Greenwood & Earnshaw

This chapter discusses the halogens (fluorine, chlorine, bromine, iodine, and astatine). It provides molecular orbital diagrams for F2, Cl2, Br2, and I2 showing how hybridization allows for inversion of the σ and π molecular orbitals for the heavier halogens. Bond energies are provided showing fluorine's bond is weak due to lone pair repulsions. Interhalogens and trihalide anions are discussed along with iodine oxides and oxoacids.

Uploaded by

Tanisha Harris
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Greenwood & Earnshaw

2nd Edition

Chapter 17 The Halogens Fluorine, Chlorine, Bromine, Iodine and Astatine

Molecular Orbital Diagram F2


F2
*

2p

2p

2s & 2p atomic orbitals are too widely separated in energy to allow significant mixing (hybridization) to occur.
2s

*
2s

Bond Energies for the Halogens, kJ/mol

Fluorine bond energies are anomalous. The F-F bond is very weak due to lone-pair/lone-pair repulsions (cf. O-O, N-N). Fluorine has tightly held, non-polarizable electrons, the atoms are small and no low-lying d atomic orbitals exist. The fluorine lone pairs are strong -donors to atoms having low-lying empty orbitals. Fluorine forms strong, polar bonds to carbon, hydrogen and many other elements. Fluorine is very electrophilic and strongly oxidizing.

Molecular Orbital Diagram Cl2, Br2, I2


* *

3,4,5 p
3s & 3p and higher atomic orbitals are not so widely separated in energy and allow significant mixing (hybridization) to occur. 3, 4,5 s

3,4,5 p
This mixing causes the inversion of the and molecular orbitals energy.

* 3,4,5 s

Y is the heavier halogen!

diatomic

F
-

F Br F F F
-

Br F Br F

-X-

YX

+XX2

YX2

Br F

YX2

-X-

YX3
X2

+X-

YX4

F F F F F I F F

F F Br F F F F

YX4 F I F F F

-X-

YX5
X2

+X-

YX6

F YX7
+XYX8 Cs+IF8-

+ YX6

-X-

F F Br F F F

F I F F

F F

square antiprismatic?

Interhalogens

Trihalide Anions
The heavier halogen is invariably in the center position. The anion is linear or near linear. One Deviation is for Br3- which is 171Emost 176E or higher. The bonding is almost certainly 3c-4e bonding. The two bonds in YX2 species need not be equivalent and may vary with the cation. The bond length is longer than the single bond covalent radii. The formal bond order is 0.5. In BrI2- the Br-I bond is longer than the I-I bond. Iodine forms an extensive set of polyiodine anions: In- n = odd; In2- n = even, I164- . (see page 837).

Iodine Oxides and Oxoacids of Iodine


195 pm 183 pm

139.2E 179 pm

192 pm

I O

O
178 pm

HO HO

O I OH

178 pm

OH
189 pm

Dimer
- H2O -2 H2O

O I2O5 O

177 pm

OH

HEf = -158.1 kJ I 4O9 & I2O4 also known

ortho-periodic acid

Trimer

H5IO6 O
178 pm

O O

3-

O O I O O
ortho-periodate

5-

178 pm

95E

I O NaIO4 periodate O O I O OH O O I O OH O O

O I
177 pm

O
185 pm

O K3IO5
4-

O K5IO6 O I O O
4-

O O O I

O O O

O O

meso-periodate (edge-sharing)

meso-periodate (face-sharing)

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