Chapter 16 Text

gecause the oxidation number of the central atom increases as the number of
attached O atoms increases, this correlation can be stated in an equivalent way:
In a series of oxyacids, the acidity increases as the oxidation number of the central
atom increases,
16.10 Acid-Base Behavior and Chemical Structure 647
SAMPLE EXERCISE 16.19
Arrange the compounds in each of the following series in order of increasing acid
strength: (a) AsH3/ HI, NaH, H2O; (b) H2SeO3, H2SeO4, H2O.
Solution
Analyze: We are asked to arrange two sets of compounds in order from weakest acid
to strongest acid.
Plan: For the binary acids in part (a), we will consider the electronegativities of As, I,
Ma, and O, respectively. For the oxyacids in part (b), we will consider the number of
oxygen atoms bonded to the central atom and the similarities between the Se-containing
compounds and some more familiar acids.
Solve: (a) The elements from the left side of the periodic table form the most basic
binary hydrogen compounds because the hydrogen in these compounds carries a negative
charge. Thus NaH should be the most basic compound on the list. Because arsenic
is less electronegative than oxygen, we might expect that AsH3 would be a weak base
toward water. That is also what we would predict by an extension of the trends shown
in Figure 16.13. Further, we expect that the binary hydrogen compounds of the halogens,
as the most electronegative element in each period, will be acidic relative to
water. In fact, HI is one of the strong acids in water. Thus the order of increasing acidity
is NaH < AsH3 < H2O < HI.
(b) The acidity of oxyacids increases as the number of oxygen atoms bonded to the
central atom increases. Thus, H2SeC>4 will be a stronger acid than H2SeO3; in fact, the
Se atom in H2SeO4 is in its maximum positive oxidation state, and so we expect it to
be a comparatively strong acid, much like H2SO4. H2SeO3 is an oxy acid of a nonmetal
that is similar to H2SO3. As such, we expect that H2SeO3 is able to donate a proton to
H2O, indicating that H2SeO3 is a stronger acid than H2O, Thus, the order of increasing
acidity is H2O < H2SeO3 < H2SeO4.
PRACTICE EXERCISE
In each of the following pairs choose the compound that leads to the more acidic (or
less basic) solution: (a) HBr, HF; (b) FH3, H2S; (c) HNO2, HNO3; (d) H2SO3, H2SeO3.
Answers; (a) HBr; (b) H2S; (c) HNO3; (b) H2SO3
Carboxylic Acids
Another large group of acids is illustrated by acetic acid
H :0:
I II ..
H—C—C—O—H
H
The portion of the structure shown in blue is called the carboxyl group, which is
often written as COOH. Thus, the chemical formula of acetic acid is often written
as CH3COOH, where only the hydrogen atom in the carboxyl group can be
ionized. Acids that contain a carboxyl group are called carboxylic acids, and
they form the largest category of organic acids. Formic acid and benzoic acid,
whose structures are drawn in the margin, are further examples of this large and
important category of acids.
Acetic acid (CH3COOH) is a weak acid (Ka = 1.8 X 1(T5). Methanol
(CH3OH), on the other hand, is not an acid in water. Two factors contribute to
the acidic behavior of carboxylic acids. First, the additional oxygen atom attached
to the carboxyl group carbon draws electron density from the O—H bond,
increasing its polarity and helping to stabilize the conjugate base. Second, the
conjugate base of a carboxylic acid (a carboxylate union) can exhibit resonance
Carboxylic acids are organic
compounds that have the general
formula R — COOH, where R is either
a hydrogen or a chain of carbonbased
groups.
H—C—O—H
Formic acid
Benzoic acid