Electron affinity

From Wikipedia, the free encyclopedia

The electron affinity, Eea, of an atom or molecule is the energy required to detach an electron from a singly charged negative ion, i.e., the energy change for the process

X- → X + e-

An equivalent definition is the energy released (Einitial − Efinal) when an electron is attached to a neutral atom or molecule. It should be noted that the sign convention for Eea is the opposite to most thermodynamic quantities: a positive electron affinity indicates that energy is released on going from atom to anion.

All elements have a positive electron affinity, but older texts mistakenly report that some elements such as inert gases have negative Eea, meaning they would repel electrons. This is not recognised by modern chemists. Atoms whose anions are relatively more stable than neutral atoms have a smaller Eea. Chlorine most strongly attracts extra electrons; mercury most weakly attracts an extra electron. Eea of noble gases are close to 0.

Although Eea vary in a chaotic manner across the table, some patterns emerge. Generally, nonmetals have more positive Eea than metals.

Contents

The following data are quoted in kJ/mole. Elements marked with an asterisk are expected to have electron affinities close to zero on quantum mechanical grounds.

Group → 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
↓ Period
1 H
73

He
*
2 Li
60
Be
*

B
27
C
122
N
*
O
141
F
328
Ne
*
3 Na
53
Mg
*

Al
42
Si
134
P
72
S
200
Cl
349
Ar
*
4 K
48
Ca
2
Sc
18
Ti
8
V
51
Cr
65
Mn
*
Fe
15
Co
64
Ni
112
Cu
119
Zn
*
Ga
41
Ge
119
As
79
Se
195
Br
343
Kr
*
5 Rb
47
Sr
5
Y
30
Zr
41
Nb
86
Mo
72
Tc
*
Ru
101
Rh
110
Pd
54
Ag
126
Cd
*
In
39
Sn
107
Sb
101
Te
190
I
295
Xe
*
6 Cs
46
Ba
14
*
Hf
 
Ta
31
W
79
Re
*
Os
104
Ir
150
Pt
205
Au
223
Hg
*
Tl
36
Pb
35
Bi
91
Po
 
At
 
Rn
*
7 Fr
 
Ra
 
**
Rf
 
Db
 
Sg
 
Bh
 
Hs
 
Mt
 
Ds
 
Rg
 
Uub
 
Uut
 
Uuq
 
Uup
 
Uuh
 
Uus
 
Uuo
 

* Lanthanides La
45
Ce
92
Pr
 
Nd
 
Pm
 
Sm
 
Eu
 
Gd
 
Tb
 
Dy
 
Ho
 
Er
 
Tm
99
Yb
 
Lu
33
** Actinides Ac
 
Th
 
Pa
 
U
 
Np
 
Pu
 
Am
 
Cm
 
Bk
 
Cf
 
Es
 
Fm
 
Md
 
No
 
Lr
 
Chemical series of the periodic table
Alkali metals Alkaline earth metals Lanthanides Actinides Transition metals
Poor metals Metalloids Nonmetals Halogens Noble gases

Eea increases across a period (row) (since the radius slightly decreases, because of the increased attraction from the nucleus, and the number of electrons in the top shell increases, helping the atom reach maximum stability) in the periodic table and decrease going down a group (family) (because of a large increase in radius and number of electrons that decrease the stability of the atom, repulsing each other).

Eea is not limited to the elements but also applies to molecules. For instance the electron affinity for benzene is positive, that of naphthalene also positive and that of anthracene,phenanthrene and pyrene is negative. In silico experiments show that the electron affinity of hexacyanobenzene surpasses that of fullerene [1].

  1. ^ Remarkable electron accepting properties of the simplest benzenoid cyanocarbons: hexacyanobenzene, octacyanonaphthalene and decacyanoanthracene Xiuhui Zhang, Qianshu Li, Justin B. Ingels, Andrew C. Simmonett, Steven E. Wheeler, Yaoming Xie, R. Bruce King, Henry F. Schaefer III and F. Albert Cotton Chemical Communications, 2006, 758 - 760 Abstract

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