1.

9 Advanced subtopic: The effect of substituents on the strength of acid and base Note to the
teachers:

Advanced subtopic is only compulsory for students who will do certification. It is advisable for students
who will not do certification to study this subtopic as well if they want to increase their understanding of
the strengths of acids and bases.

Acetic acid as shown in Figure 1.5 is a weak acid. The acidity of this acid is due to the presence of one
acidic hydrogen bonds to oxygen atoms. In aqueous solution this acidic hydrogen may be released as
hydrogen ion (H *).

Three hydrogen atoms bond to carbon atoms are non-acidic hydrogens. They can't be released as
hydrogen ions. These hydrogen atoms can be replaced with electron withdrawing substituents such as
halogens (F, CI, Bror I). Halogen behaves as electron withdrawing substituent because it is more
electronegative than hydrogen, Halogen substituent will decrease electron cloud or electron density of
O-H bonds. This may be weaken and lengthen the O-H bond. Because of this, the acidic hydrogen atom
is easier to release and the strength of acid increases. Replacement one non-acidic hydrogena with
chlorine atom gives chloroacetic acid as shown in Fi 1.6.

Chloroacetic acid is about 80 times stronger than acetic acid Further replacement of non-acidic
hydrogen atoms with chlorine increases the strength of acid formed. For example the strength of
CCICOOH> CHCI, COOH> CH, CICOOH> CH, COOH. Replacement of non-acidic hydrogen atoms with
fluorine atom also gives stronger acids than the acetic acid. Since electronegativity of fluorine is higher
than that of chlorine substituted acetic acid is stronger than chlorine substituted acetic acid. For
example trifluoroacetic acid (CF COOH) is stronger than trichloroacetic acid (CCI, COOH).

Formic acid, as shown in Figure 1.7, is also a weak acid. One hydrogen atom that bonds to carbon
atoms in this acid can be replaced with electron donating substituents such as methyl groups (CH,) to
give acetic acid.

Replacement of one non-acidic hydrogen atom of formic acid with methyl group will increase electron
cloud or electron density of O-H bonds. This will strengthen and shorten the H bond. Because of this,
the acidic hydrogen atom is difficult to release and the strength of acid decreases. Acete acid is weaker
than formic acid.

Exercise 10: Compare the strengths of trifluoroacetic acid, acetic acid, and formic acid.

Based on Bronsted-Lowry theory, base such as ammonia (NH) is a proton acceptor, One of its hydrogen
atoms can be replaced with electron donating substrates such as methyl groups (CH) to give
methylamine (CH NH.) As shown in Figure 1.8.

Replacement of one hydrogen atom with methyl group will increase the availability of electron clouds
or electron density at the nitrogen atom. This increases the power of the nitrogen atom to attract
protons. Methylamine is stronger basic compare to ammonia. Replacement of three hydrogen atoms in
the ammonia with electron withdrawing substituents such as fluorine atoms will give trifluoroammine.
This replacement will decrease the availability of electron or electron density at the nitrogen atom. This
decreases the power of the atomic nitrogen to attract protons. Trifluoroammine is weaker compared to
ammonia.

Exercise 11: Compare the basic strengths of methylamine, ammonia and trifluoroammine.

1.10 Advanced subtopic: The effect of solvent on the strength of acid and base

Note to the teachers: Advanced subtopic is only compulsory for students who will do certification. It is
advisable for students who will not do certification to study this subtopic as well if they want to increase
their understanding of the strengths of acids and bases.

In acid-base chemistry the solvent used is not limited to water. There are many other solvents used
such as liquid ammonia and glacial acetic acid. Glacial acetic acid is nearly pure acetic acid. It contains
less than 1% water.

You have studied that in ammonia water is a weak base, whereas acetic acid is a weak acid.

CH3COOH + H2O <–––> H2O+ + CH3COO- (26)

NH3 + H20 <–––>NH4+ + OH- (27)

Based on equations (26) and (27) we can conclude that the strength to donate protons of CH COOH> H,
0> NH, or the strength to accept protons of CH COOH <H, O <NH. If we replace water with ammonia in
equation (26) we will get the following equation.

CH3COOH + NH3 <–––> NH4+ + CH3COO- (28)

Solvent

Since NH, is a stronger proton acceptor than H, O, in NH, solvent, CH COOH is more easily to donate its
protons. Therefore the strength of CH. COOH increases in NH, solvent. Since NH, is a stronger base than
HO or NH, is more basic than H, O, the strength of CH, COOH increases in a solvent which is more basic
than water In general, the strength of acid increases in basic solvent.

NH, is a weak base in water. If we replace water with glacial acetic acid in equation (27) we will get the
following equation.

NH,3 + CH3COOH <–––> NH4 + + CH3CO0- (29)

Solvent

Since CH, COOH is a stronger proton donor than H, O, in CH, COOH solvent, NH, is more easily to accept
protons. Therefore the strength of NH, increases in CH, COOH solvent, Since CH, COOH is a stronger acid
than H, O or CH, COOH is more acidic than H, O, the strength of NH, increases in a solvent which is more
acidic than water In general, the strength of base increases in acidic solvents
The strength of base increases in acidic solvents

Exercises 12: Why is acetic acid or ethanoic acid a stronger acid in liquid methylamine than in water?

1.11 The strengths of hydrohalic acids

Hydrohalic acids are HF, HCI, HBr, and HI. All of them are polar molecules. with the halogen atom being
electron rich and the hydrogen atom being electron poor. The strength of these acids depends on two
things: polarity of H-X bonds and the strength of H-X bonds (X = F, C, Br, I).

The polarity of H-X bonds increases with an increase in the electronegativity of the halogen. The
polarity of H-F bonds> H-CI bonds> H-Br bonds> H-I bonds. The polarity of H-X bonds is related to the
ease of electron transfer from hydrogen atoms to halogen atoms to give H and X. Based on the polarity
of H-X bonds, the acid strength of HF> HCl> HBr> HI. The strength of H-Xbond Affects the ease of the
hydrohalic acids to release H. The weaker the H-X bond the easier the H to be released and the stronger
the hydrohalic acid. The strength of covalent bond in H-F> H-Cl> H-Br> HI.

HI is the easiest hydrohalic acid to release H ", while HF is the most difficult. Based on the strength of HX
bond the acid strength of HF <HCI <HBr <HI. Experimental results show that the strength of HF <HCl
<HBr < HI This indicates that the effect of bond strength is greater than the effect of bond polarity HX (X
= F, Cl, Bror l) is one of many binary acids (acids consists of two elements) .In general, for binary acias of
elements in the same groun the periodic table, the bond strength is the more determinant factor than
the polarity of the bond in determining the acid strength. in