Periodic Trends in the

Strenghts of Acids
Trends in the Strenghts of Binary Acids
Many (but not all) of the binary compounds between
hydrogen and nonmetals, which we may represent by
HX and H2X, are acidic and are called binary acids
The relative strenghts of binary acids correlate
with the periodic table in two ways
• The strenghts of the binary acids increase
from left to right within the same period
• The strenghts of the binary acids increase
from top to bottom within the same group
Two factors can account for these variations.
• The electronegativity of the nonmetal X
• The strength of the H-X bond
The electronegativity of the nonmetal X
Variations in electronegativity of the atom X
alter the polarity of the H-X bond, so as X
becomes more electronegative, the partial
positive charge (δ+) on H becomes greater.
This makes it easier for the hydrogen to
separate as H+, so the molecule becomes a
better proton donor.
The strength of the H-X bond
A major influence on acidity is the strength
of the H-X bond. Breaking this bond is
essential for the hydrogen to separate as an
H+ ion, so anything that contributes to
variations in bond strength will also affect
variations in acid strength.
Within same period
Going from left to right across a period, atomic size varies little, so the strengths of the H-X bonds are
nearly the same. The major influence is the variation in the electronegativity of X, which increases from
left to right.
• Within Period 3, H2S < HCl
• Within Period 2, H2O <HF

Within same group

Going from top to bottom in the same group, there are two opposing factors.
• The electronegativity decreases, so the H-X bonds become less polar.
• At the same time, the atoms X become much larger, and this leads to a large drop in the H-X bond
strength.
The variation in polarity tends to make the acids weaker, but the variation in bond strength tends to
make them stronger. Changes in bond strength seem to win out, because the acids HnX become stronger
as we go down a group.

HF < HCl < HBr < HI

 Trends in the Strenghts of Oxoacids
Acids composed of hydrogen, oxygen, and some other
elements are called oxoacids
A feature common to the structures of all
oxoacids is the presence of O-H groups
bonded to some central atom. For example,
the structures of two oxoacids of the Group
6A elements are
If the group of atoms, G, attached to the O-H group is able to draw electron density from the O atom, the O
will pull electron density from the O-H bond, thereby making the bond more polar

There are two principal factors that determine how the polarity of the O-H bond is affected:

Effect of the Electronegativity of When the central atoms of oxoacids hold

the Central Atom the same number of oxygen atoms, the acid
strength increases from bottom to top
within a group and from left to right within
a period

As the electronegativity of X increases, electron

density is drawn away from O, which draws electron
density away from the O-H bond. This makes the bond
more polar and makes the molecule a better proton
donor
There are two principal factors that determine how the polarity of the O-H bond is affected:

Effect of the Number of Oxygens Bound to the Central Atom

In an oxoacid, lone oxygens pull electron density away from
the central atom, which increases the central atom’s ability
to draw electron density away from the O-H bond

HClO < HClO2 < HClO3 < HClO4

For a given central atom, the acid strength of an oxoacid increases with the number of oxygens held by
the central atom
Strengths of Organic Acids
The ability of lone oxygens to affect acid strength extends to organic compounds

The greater ability of oxygen to pull electron density from the carbon produces a greater polarity of the
O-H bond, which is one factor that causes acetic acid to be a better proton donor than ethanol

The acidity of the molecule can be increased further if other electronegative

groups such as halogens are bonded to carbon atoms near the -CO2H group
of the acid
CH3CO2H < CH2ClCO2H < CHCl2CO2H < CCl3CO2H