ELECTRONEGATIVITY

This page explains what electronegativity is, and how and why it varies around the Periodic Table. It looks at the way that electronegativity differences affect bond type and explains what is meant by polar bonds and polar molecules.

What is electronegativity
Electronegativity is the relative ability of an atom to attract electrons in a covalent bond. The electronegativity of an atom depends on its ability to attract electrons and its ability to hold onto electrons. Electronegativity increases across a period as the nuclear charge on the atoms increases but the shielding stays the same, so the electrons are more strongly attracted to the atom. Electronegativity decreases down a group as the number of shells increases, so shielding increases and the electrons are less strongly attracted to the atom. An atom which has a high electronegativity is said to be electronegative; an atom which does not have a high electronegativity is said to be electropositive. Electronegativities are relative; electronegativity has no units and is measured on a scale from 0.7 to 4.0. The electronegativities of some elements in the periodic table are shown below:
H 2.1 Li 1.0 Na 0.9 K 0.8 Be 1.5 Mg 1.2 Ca 1.0 B 2.0 Al 1.5 Ga 1.6 C 2.5 Si 1.8 Ge 1.8 N 3.0 P 2.1 As 2.0 O 3.5 S 2.5 Se 2.4 F 4.0 Cl 3.0 Br 2.8 Ne Ar Kr He

Sc 1.3

Ti 1.5

V 1.6

Cr 1.6

Mn 1.5

Fe 1.8

Co 1.8

Ni 1.8

Cu 1.9

Zn 1.6

Note that the noble gases cannot be ascribed an electronegativity since they do not form bonds. Electronegativity is a very useful concept for predicting whether the bonding between two atoms will be ionic, covalent or metallic. Consider a covalent bond between two atoms A and B.
A x o B

If both atoms have a similar electronegativity, both atoms attract the electrons with similar power and the electrons will remain midway between the two. The bond will thus be covalent - the electrons are shared between the two atoms.

Eg H (2.1) and H (2.1)

H x o
H

a covalent bond

If one atom is significantly more electronegative than the other, it attracts the electrons more strongly than the other and the electrons are on average closer to one atom than the other. The electrons are still shared, but one atom has a slight deficit of electrons and thus a slight positive charge and the other a slight surplus of electrons and thus a slight negative charge. Such a bond is said to be polar covalent. Eg H (2.1) and O (3.0)
- x +

O o

a polar covalent bond

A slight positive charge or negative charge on an atom is represented by a or a symbol respectively. If the difference between the two atoms is large, then the sharing of electrons is so uneven that the more electronegative atom has virtually sole possession of the electrons. The electrons are, in effect, not shared at all but an electron has essentially between transferred from one atom to the other. The more electropositive atom is positively charged and the more electronegative atom is negatively charged. The bonding is thus ionic. Eg Na (0.9) and Cl (3.0)
+ Na x Cl o -

an ionic bond If both atoms are electropositive, neither has a great ability to attract electrons and the electrons do not remain localised in the bond at all. They are free to move, both atoms gain a positive charge and the bonding is metallic. Eg Mg (1.2) and Mg (1.2)
2+

Mg

x o x o

2+

Mg

a metallic bond

Differences in electronegativity can be used to predict how much ionic or metallic character a covalent bond will have.

Given suitable electronegativity data, it is thus possible to predict whether a bond between two atoms will be ionic, polar covalent, covalent or metallic. If both atoms have electronegativities less than 1.6 - 1.9 then the bond is metallic. If either atom has an electronegativity greater than 1.9 and the difference is less than 0.5 then the bond is covalent. If either atom has an electronegativity greater than 1.9 and the difference is more than 0.5 but less than 2.1 then the bond is polar covalent. If the difference is greater than 2.1 then the bond is ionic. These rules are not perfect and there are notable exceptions; for example the bond between Si (1.8) and Si (1.8) is covalent but the bond between Cu (1.9) and Cu (1.9) is metallic. The bond between Na (0.9) and H (2.1) is ionic but the bond between Si (1.8) and F (4.0) is polar covalent. However as basic giudelines they are very useful provided that their limitations are appreciated.

All bonds are assumed to be covalent in principle: differences in electronegativity can be used to predict how much ionic or metallic character a covalent bond will have. Electronegativity differences show that bonds between non-identical atoms are all essentially intermediate in character between ionic and covalent. No bond is completely ionic, and only bonds between identical atoms are completely covalent. Bonds between identical atoms cannot be ionic as there is no difference in electronegativity. They will therefore be either covalent or metallic.

Patterns of electronegativity in the Periodic Table

The most electronegative element is fluorine. If you remember that fact, everything becomes easy, because electronegativity must always increase towards fluorine in the Periodic Table

Trends in electronegativity across a period As you go across a period the electronegativity increases. The chart shows electronegativities from sodium to chlorine - you have to ignore argon. It doesn't have an electronegativity, because it doesn't form bonds.

Trends in electronegativity down a group As you go down a group, electronegativity decreases. (If it increases up to fluorine, it must decrease as you go down.) The chart shows the patterns of electronegativity in Groups 1 and 7.

Explaining the patterns in electronegativity The attraction that a bonding pair of electrons feels for a particular nucleus depends on:

the number of protons in the nucleus; the distance from the nucleus; the amount of screening by inner electrons.

Why does electronegativity increase across a period? Consider sodium at the beginning of period 3 and chlorine at the end (ignoring the noble gas, argon). Think of sodium chloride as if it were covalently bonded.

Both sodium and chlorine have their bonding electrons in the 3-level. The electron pair is screened from both nuclei by the 1s, 2s and 2p electrons, but the chlorine nucleus has 6 more protons in it. It is no wonder the electron pair gets dragged so far towards the chlorine that ions are formed. Electronegativity increases across a period because the number of charges on the nucleus increases. That attracts the bonding pair of electrons more strongly. Why does electronegativity fall as you go down a group? Think of hydrogen fluoride and hydrogen chloride.

The bonding pair is shielded from the fluorine's nucleus only by the 1s2 electrons. In the chlorine case it is shielded by all the 1s22s22p6 electrons. In each case there is a net pull from the centre of the fluorine or chlorine of +7. But fluorine has the bonding pair in the 2-level rather than the 3-level as it is in chlorine. If it is closer to the nucleus, the attraction is greater. As you go down a group, electronegativity decreases because the bonding pair of electrons is increasingly distant from the attraction of the nucleus. Diagonal relationships in the Periodic Table What is a diagonal relationship? At the beginning of periods 2 and 3 of the Periodic Table, there are several cases where an element at the top of one group has some similarities with an element in the next group. Three examples are shown in the diagram below. Notice that the similarities occur in elements which are diagonal to each other - not side-by-side.

For example, boron is a non-metal with some properties rather like silicon. Unlike the rest of Group 2, beryllium has some properties resembling aluminium. And lithium has some properties which differ from the other elements in Group 1, and in some ways resembles magnesium. There is said to be a diagonal relationship between these elements. There are several reasons for this, but each depends on the way atomic properties like electronegativity vary around the Periodic Table. So we will have a quick look at this with regard to electronegativity - which is probably the simplest to explain.

Explaining the diagonal relationship with regard to electronegativity Electronegativity increases across the Periodic Table. So, for example, the electronegativities of beryllium and boron are: Be 1.5

2.0

Electronegativity falls as you go down the Periodic Table. So, for example, the electronegativities of boron and aluminium are: B 2.0 Al 1.5 So, comparing Be and Al, you find the values are (by chance) exactly the same. The increase from Group 2 to Group 3 is offset by the fall as you go down Group 3 from boron to aluminium. Something similar happens from lithium (1.0) to magnesium (1.2), and from boron (2.0) to silicon (1.8). In these cases, the electronegativities aren't exactly the same, but are very close. Similar electronegativities between the members of these diagonal pairs means that they are likely to form similar types of bonds, and that will affect their chemistry. You may well come across examples of this later on in your course.