Chapter 14

CHAPTER 14
Acid and Base Equilibria
Indicators are used to monitor changes in pH. The pH of a solution can be monitored using an
acid–base indicator, a substance that undergoes a color change within a specific pH range that is
characteristic of that indicator. In the example above, the color of red cabbage juice from pH 2 to
pH 13 is shown. (By V. Belkhir, site de l'Académie de Nantes - Site de l'académie de Nantes, CC
BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=2742825)
Many vital chemical and physical processes take place exclusively in

aqueous solution, including the complex biochemical reactions that occur in
living organisms and the reactions that rust and corrode steel objects, such as
bridges, ships, and automobiles. Among the most important reactions in
aqueous solution are those that can be categorized as acid–base reactions. So
far, our discussions of these reactions have been largely qualitative. In this
chapter we take a more quantitative approach to understanding such reactions,
using the concept of chemical equilibrium that we developed in Chapter 12. We
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will begin by revisiting acid–base reactions in a qualitative fashion and then
develop quantitative methods to describe acid–base equilibriums.
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14.1
Definitions of Acids and Bases
LEARNING OBJECTIVES
• To be able to identify acids and bases based on definitions
Previously we defined acids as substances that dissolve in water to

produce hydrogen (H+) ions, whereas bases were defined as substances that
dissolve in water to produce hydroxide (OH−) ions. In fact, this is only one
possible set of definitions. Although the general properties of acids and bases
have been known for more than a thousand years, the definitions
of acid and base have changed dramatically as scientists have learned more
about them. In ancient times, an acid was any substance that had a sour taste
(e.g., vinegar or lemon juice), caused
consistent color changes in dyes
derived from plants (e.g., turning
blue litmus paper red), reacted with
certain metals to produce hydrogen
gas and a solution of a salt containing
a metal cation, and dissolved
carbonate salts such as limestone
(CaCO3) with the evolution of carbon
dioxide. Although these definitions
were useful, they didn’t address the
underlying chemistry.
The Arrhenius Definition of Acids and Bases

The first person to define acids and bases in detail was the Swedish
chemist Svante Arrhenius (1859–1927; Nobel Prize in Chemistry, 1903).
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According to the Arrhenius definition, an acid is a substance like hydrochloric
acid that dissolves in water to produce H+ ions (protons), and a base is a
substance like sodium hydroxide that dissolves in water to produce hydroxide
(OH−) ions. Therefore HCl is an acid since it makes H+ ions in solution and
NaOH is a base since it makes hydroxide ions
−
(1) HCl (aq) → H+ (aq) + Cl (aq)
(2) NaOH (aq) → Na+ (aq) + OH− (aq)
For a lot of common acids and bases this definition works well, but for
others such as ammonia it is insufficient and other definitions were created.
The Brønsted–Lowry Definition of Acids and Bases

Because of some limitations of the Arrhenius definition, a more general
definition of acids and bases was needed. One was proposed independently in
1923 by the Danish chemist J. N. Brønsted (1879–1947) and the British
chemist T. M. Lowry (1874–1936), who defined acid–base reactions in terms of
the transfer of a proton (H+ ion) from one substance to another.
According to Brønsted and Lowry, an acid is any substance that can

donate a proton, and a base is any substance that can accept a proton. Because
of its more general nature, the Brønsted–Lowry definition will be used in this
text unless otherwise specified. There is a third common definition—Lewis
acids and bases—but that is beyond the scope of this course.
Let’s look at an example of a Brønsted–Lowry acid and base. The generic

form for an acid is typically written as HA and would react as follows:
(3) HA (aq) +H2O (l) → H3O+ (aq) + A− (aq)
You can see that the acid HA is donating a proton to water and forming the
hydronium ion, H3O+. We often simplify this by leaving out the water and
using H+ instead of the hydronium ion. You can always assume when you see
an H+ (aq) in an acid-base reaction that it is really H3O+.
(4) HA (aq) → H+ (aq) + A− (aq)
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The generic base we typically use is B. In our Brønsted–Lowry definition,
it will react in water as a base to gain a proton like this.
(5) B (aq) +H2O (l) → HB+ (aq) + OH− (aq)
You can see from Equation 4 and Equation 5, why the Arrhenius and Brønsted–
Lowry definitions are mostly the same as we end up making H+ with the acid
and OH− with the base. There are, however, some cases where they don’t
overlap. Let’s consider how ammonia reacts with acetic acid in a
neutralization reaction to form NH4+ and CH3COO–.
(6) NH3 (aq) + CH3COOH (aq) → NH4+ (aq) + CH3COO- (aq)
NH3 is therefore Brønsted–Lowry base as it accepts a proton and

CH3COOH is a Brønsted–Lowry acid for donating a proton. Furthermore, if
the reaction were to go the other way, we can see that once a Brønsted–Lowry
base (NH3) accepts a proton, it becomes a Brønsted–Lowry acid that could
donate that proton to return to its original state. We therefore call the NH4+
the conjugate acid of NH3 and likewise, CH3COO– is the conjugate base of
CH3COOH. The conjugate pair of any acid is simply the acid and it’s basic form
created from the loss of a proton. The conjugate pair of a base is therefore the
base and the acidic form created from the addition of the proton. It is
important that you be able to recognize a conjugate of an acid or base.
(7) NH3 (aq) + CH3COOH (aq) → NH4+ (aq) + CH3COO- (aq)

Base Acid Conjugate Conjugate
Acid Base
One of the biggest difficulties for a beginning chemistry student learning

about acids and bases is being able to use these definitions to reliably identify
whether a substance is an acid or a base. Memorizing the strong acids and
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bases in the section below will help, as will learning a couple of common
functional groups that reliably predict whether the substance will be an acid or
a base.
N o t e t h e Pa t t e r n
Common groups that make a molecule acidic or basic
• Any amine group (–NH2) will act as a base and gain a proton just like
ammonia in Equation 1.
• Any carboxylic acid group (–COOH or sometimes written as –CO2H)
will be an acid and lose the hydrogen that is attached to the oxygen.
• Any ionic compound with a hydroxide (metal hydroxide) will be a base
and donate an OH–.
A few more general pointers:
• Remove H and decrease the charge by one on an acid to get the
conjugate base
• Add H and increase the charge by one on an base to get the conjugate
acid
• Hydrogens attached to carbon atoms will not dissociate and can’t be
acidic.
• Hydrogens attached to very electronegative elements except for
nitrogen tend to be acidic.
• In order to gain a proton as a base, a nonmetal will have a lone pair of
electrons and often a negative charge.
STUDY TIP
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Strengths of Acids and Bases
Acids can donate one proton (monoprotic acids), two protons (diprotic
acids), or three protons (triprotic acids). The strength of the acid is not
determined by how many protons the acid could donate, but rather how many
are actually dissociated into a solution which needs to be measured by
considering the equilibrium between the acid and it’s products (H+ and the
conjugate base). Strong acids have an equilibrium that lies so far towards
products that they react essentially completely with water to give H+ and the
corresponding anion. Similarly, strong bases dissociate essentially completely
in water to give OH− and the corresponding cation. Therefore, whenever we
have a strong acid or strong base in solution, we can assume that it is 100%
dissociated into ions. When we write the dissociation, we won’t therefore need
to write it as an equilibrium. The general form for a strong acid (where HA can
be any acid from table 14.1) is shown below:
(8) HA (aq) → H+ (aq) + A− (aq)
In contrast, only a fraction of the molecules of weak acids and

weak bases react with water to produce ions, so weak acids and weak bases are
also weak electrolytes. Typically less than 5% of a weak acid dissociates into
ions in solution, whereas more than 95% is present in undissociated form. The
equation for a weak acid is therefore represented as being an equilibrium (and
would require using an equilibrium constant to find the equilibrium
concentration):
(9) HA (aq) ⇌ H+ (aq) + A− (aq)
In practice, only a few strong acids are commonly encountered: HCl, HBr,
HI, HNO3, HClO4, and H2SO4. Therefore acids not on this list are considered
weak acids. In order to be able to classify acids as strong or weak, these 6 need
to be memorized! The most common strong bases are ionic compounds of
alkali metals and Ca, Ba, and Sr with the hydroxide ion as the anion.
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TABLE 14.1 The common strong acids and bases in aqueous solution
Strong Acids Strong Bases

HCl hydrochloric acid Alkali metal
HI hydroiodic acid MOH hydroxides (Na, K, Li,
HBr hydrobromic acid etc)
HClO4 perchloric acid Alkaline earth metal
H2SO4 sulfuric acid M(OH)2 hydroxides (only Ca,
HNO3 nitric acid Ba, Sr)
MEMORIZE
MEMORIZE
EXAMPLE 14.1
Classify each compound as a strong acid, a weak acid, a strong base, a weak
base, or none of these.
a. CH3CH2COOH
b. CH3CH2OH
c. Sr(OH)2
d. CH3CH2NH2
e. HBrO
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SOLUTION
a) This compound is propionic acid. It contains a carboxylic acid group
analogous to that in acetic acid, so it must be a weak acid.
b) A CH3CH2OH is ethanol, an organic compound that contains the −OH

group. As a covalent compound, it does not dissociate to form a
hydroxide ion. Because it does not contain a carboxylic acid, ethanol
also cannot dissociate to form H+(aq) ions. Thus we predict that in
aqueous solution ethanol is a poor enough acid to consider not really
either an acid or base.
c) Sr(OH)2 is an ionic compound that contains one Sr2+ and two OH− ions

per formula unit. We therefore expect it to be a base, and since it is on
our memorization list, it is a strong base.
d) CH3CH2NH2 is an amine (ethylamine), an organic compound in which

one hydrogen of ammonia has been replaced by an R
group. Consequently, we expect it to behave similarly to ammonia,
reacting with water to produce small amounts of the OH− ion.
Ethylamine is therefore a weak base.
e) HBrO is hypobromous acid. We can guess it is an acid as it has an H

bonded to more electronegative elements. It is not listed in Table 14.1
as one of the common strong acids and therefore we would classify it as
a weak acid.
PRACTICE PROBLEM 14.1

Classify each compound as a strong acid, a weak acid, a strong base, a weak
base, or none of these.
a. Ba(OH)2
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b. HIO4
c. CH3CH2CH2COOH
d. (CH3)2NH
e. CH2O
Answer: a. strong base b. strong acid c. weak acid d. weak base e. neither
EXAMPLE 14.2
a. Write the conjugate base for the acid H2S
b. Write the conjugate acid for the base CH3NH2
SOLUTION
a) Since we are told that H2S is acting as an acid and it is not on our list of
strong acids, we can write the equilibrium reaction for it as follows:
H2S ⇌ H+ + HS−
Since HS− is what is formed from the loss of the proton, we know that
HS− is the conjugate base which could accept a proton to reform H2S.
b) A CH3NH2 is methylamine, a weak base. When it reacts therefore, it

will gain a proton and become CH3NH3+. Therefore, CH3NH3+ is the
conjugate acid.
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Classify each as an acid or base and write it’s conjugate.
a. CH3COOH
b. BrO−
c. SO42−
Answer: a. acid; CH3COO− is conj. base b. base; HBrO is conj. acid c. base; HSO4− is
conj. acid
LINK TO HOMEWORK PROBLEMS
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14.2
pH
LEARNING OBJECTIVES
• To be able to use pH to measure quantitatively the acidity of a solution
The pH Scale
One of the key factors affecting reactions that occur in dilute solutions of
acids and bases is the concentration of H+ and OH− ions. The pH scale
provides a convenient way of expressing the hydrogen ion (H+) concentration
of a solution and enables us to describe acidity or basicity in quantitative
terms. Note that in aqueous solution, we will often write the hydrogen ion
concentration as [H+], but we are really measuring the hydronium ion
concentration [H3O+] as water molecules will bond the free H+ ions.
The pH of a solution is the negative logarithm of the H+ ion concentration:
(10) pH = − log[H +]
If you aren’t familiar with logarithmic functions yet, don’t worry! In terms
of calculations, all you need to know is that “log” is a function just like a square
root, so using the log button on your calculator will apply that function to the
number you input. To “undo” the log function and solve for [H+] given the
pH, you will use the following equation:
[H ] = 10
+ −pH
(11)
Because the hydrogen ion concentration is 1.0 × 10−7 M in pure water at

25°C, the pH of pure liquid water (and, by extension, of any neutral solution) is
(12) pH = −log[1.0 × 10−7] = 7.00
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Acidic solutions have a pH < 7, and basic solutions have a pH>7. Adding an
acid to a solution of pure water will increase the concentration of H+ ions, and
cause the pH to decrease. Hence, concentration of H+ and the value of pH
move in opposite directions. Keep in mind that the pH scale is logarithmic, so
a change of 1.0 in the pH of a solution corresponds to a tenfold change in the
hydrogen ion concentration. When calculating pH, it is important to remember
that your input is going to be in molarity, but pH itself is unitless! The pH of
some common substances is shown in Figure 14.1.
FIGURE 14.1 The pH of Some Common Substances
Some common substances and their pH on the pH scale. (From: Slower -

Own work, CC BY-SA 3.0, https://commons.wikimedia.org/w/
index.php?curid=1985227)
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Autoionization of Water
Pure liquid water actually exists in an equilibrium between liquid water
and extremely low but measurable concentrations of H3O+ ions (synonymous
with H+ in aqueous solutions) and OH− ions produced via an autoionization
reaction, in which one water molecule acts as an acid and another as a base:
(13) H2O (l) + H2O (l) ⇌ H3O+ (aq) + OH− (aq)
Sometimes this is just written as:
(14) H2O (l) ⇌ H+ (aq) + OH− (aq)
The equilibrium expression for this can be found the same way as any
other aqueous reaction except in this case, we denote the equilibrium constant
Kw as it has a constant value at 25˚C we will use often.
(15) Kw = [H+][OH−] = 1.0 × 10−14
From here we can find the relationship between [H+] and [OH−].
1.0 × 10−14
[H ] =
+
(16)
[OH ]
−
Note what this means for the [H+] when adding a base. Since Kw is a
constant, increasing the [OH−] will decrease the [H+]. Hence when we add
base to a neutral solution, the [H+] drops below 1.0 × 10−7 M and the pH is
going to be greater than 7! Look up at Equation 14.13 and think about
LeChatelier’s principle to see why this makes sense. Another observation that
can be made from this is that every acidic solution still has some OH− present,
and every basic solution still has some H+ present, they may just be at
extremely low concentrations.
Sometimes, we will have the [OH−] of a solution because of some amount

of base added and we will want to measure the pH of the solution. In these
cases we could use Equation 16 to convert to [H+] and then find the pH.
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Alternately, it can be easier to use the relationship shown here which can be
derived by taking the negative log of both sides of Equation 15:
(17) 14 = pH + pOH
To convert to the pOH you use the same method as pH, only we use the
[OH−] instead:
(18) pOH = − log[OH−]
EXAMPLE 14.3
What is the pH of a 2.1 × 10−2 M aqueous solution of HClO4?
SOLUTION
HClO4 is a strong acid, so it dissociates completely into H+ ions and
ClO4− ions:
HClO4(aq) → H+(aq) + ClO4−(aq)
The H+ ion concentration is therefore the same as the initial perchloric acid
concentration since every 1 perchloric acid makes 1 H+. The pH of the
perchloric acid solution is thus
pH = − log[H +] = − log(2.1 × 10−2) = 1.68
Note: Significant figures rules here have you use the same number of decimal
points as significant figures we put into the function.
Note: The assumption that [H+] is the same as the concentration of the acid
is valid for only strong acids.
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What is the pH of a 3.0 × 10−5 M aqueous solution of HNO3?
Answer: 4.52
EXAMPLE 14.4
The pH of a vinegar sample is 3.80. What is its hydrogen ion concentration?
SOLUTION
We are given the pH and asked to calculate the hydrogen ion concentration.
From Equation 14.11
[H ] = 10
+ −pH
Thus
[H ] = 10
+ −3.80
= 1.6 × 10−4 M

What is the hydrogen ion concentration of turnip juice, which has a pH of
5.41?
Answer: 3.9 × 10−6 M
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EXAMPLE 14.5
What is the pH of a 0.55 M solution of NaOH?
SOLUTION
NaOH is a strong base, so it dissociates completely into Na+ and OH− ions:
NaOH(aq) → Na+(aq) + OH−(aq)
The OH− ion concentration is therefore the same (0.55 M) as the initial base
concentration. In order to find pH, we can either convert to [H+] and then
pH or find pOH and then convert to pH. Both will be shown here:
Method 1: Find [H+] and convert to pH
We know that
[H ][OH ] = 1.0 × 10

+ − −14
Rearranging, gives us:
1.0 × 10−14
[H ] =
+
[OH −]
Since we know that 0.55 M NaOH makes 0.55 M [OH−], we can find [H+]:
1.0 × 10−14
[H ] =
+
= 1.8 × 10−14 M
[0.55 M]
Now plug in and solve for pH:
pH = − log[H +] = − log(1.8 × 10−14) = 13.74
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Method 2: Find pOH and convert to pH
Since we know the [OH−] is equal to 0.55 M, we can find the pOH easily:
pOH = − log[OH −] = − log(0.55) = 0.26
Now we can use the relationship between pH and pOH to solve for pH:
14 = pH + pOH
14 − 0.26 = pH = 13.74
As you can see, we get the same answer either way!

What is the pH of a 1.2 × 10−4 M aqueous solution of KOH?
Answer: 10.08
EXAMPLE 14.6
What is the [OH−] in a solution with a pH of 9.65?
SOLUTION
Similar to Example 14.4, we have two ways we can solve this. Using the pOH
is usually easier in terms of dealing with numbers, so we’ll do that way for
simplicity here.
Starting with the pH, we can solve for pOH:
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14 = pH + pOH
14 − 9.65 = pOH = 4.35
Now we will be able to go from pOH to [OH−]:
[OH ] = 10
− −pOH
Thus
[OH ] = 10
− −4.35
= 4.5 × 10−5 M

What is the hydroxide ion concentration of a sample of seawater, which has a
pH of 8.03?
Answer: [OH−] = 1.1 × 10−6 M
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14.3
Weak Acid Equilibrium
LEARNING OBJECTIVES
• To be able to do calculations of equilibrium for weak acids
The Magnitude of the Equilibrium Constant

The magnitude of the equilibrium constant for an ionization reaction can
be used to determine the relative strengths of acids and bases. Remember the
general equation for the ionization of a weak acid in water, where HA is the
parent acid and A− is its conjugate base, is as follows:
(19) HA (aq) + H2O (l) ⇌ H3O+ (aq) + A− (aq)
Or to simplify further (recalling that H3O+ = H2O + H+):
(20) HA (aq) ⇌ H+ (aq) + A− (aq)
From what we learned about equilibrium in Chapter 12, we can therefore

write out the equilibrium constant expression for this as follows:
[H ][A ]
+ −
(21) Ka =
[HA]
This is known as the acid dissociation constant and while it is measured in

concentration, just as a Kc would be, it is given the subscript “a” to clarify that
it is the constant for the ionization of an acid.
It should be clear from the equation above that the larger the value of Ka
is, the stronger the acid is as the concentration of H+ is higher at equilibrium.
Since A− is the conjugate base of HA, it also means that the larger the value of
Ka is, the weaker the conjugate base A− is as it is present in a high amount. In
order to calculate the conditions created by these acids, we therefore need to
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be given the Ka of the various acids. Table 14.2 gives us the Ka values of some
common weak acids we will encounter.
TABLE 14.2 Values of Ka for selected weak acids (HA)
Acid HA Ka
sulfuric acid * HSO4− 1.0 × 10−2
hydrofluoric acid HF 6.3 × 10−4
nitrous acid HNO2 5.6 × 10−4
formic acid HCOOH 1.8 × 10−4

benzoic acid C6H5COOH 6.3 × 10−5
acetic acid CH3COOH 1.7 × 10−5
pyridinium ion C5H5NH+ 5.9 × 10−6
hypochlorous acid HOCl 4.0 × 10−8
hydrocyanic acid HCN 4.9 × 10−10
ammonium ion NH4+ 5.6 × 10−10
water H2O 1.0 × 10−14

*This is the Ka for HSO4− ⇌ H+ + SO42−. The first proton from H2SO4 is considered
to dissociate completely as it is a strong acid.
Calculating pH for a Weak Acid

Since a weak acid reaches equilibrium in aqueous solution, as long as we
know the Ka and the initial concentration, we can solve for the [H+] at
equilibrium and then convert to pH. Unlike a strong acid, where we simply use
the initial concentration and stoichiometry, we will need to create a RICE chart
for the equilibrium of the weak acid. Let’s consider how we would find the pH
of a 0.10 M solution of a weak acid, HA, that has a Ka = 1.8×10−4.
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First, we need to make our RICE chart with the equation and initial
concentrations.
R HA (aq) ⇌ H+ (aq) A− (aq)

I 0.10 M 0 0
C
E
Next, we need to fill in the change, which will just follow the 1:1 ratios.

I 0.10 M 0 0
C −x +x +x
E 0.10 − x x x
Adding up the initial and change, we can then find the equilibrium

I 0.10 M 0 0
C −x +x +x
E 0.10 − x x x
To solve this as we did equilibrium problems, we can just plug this into
Equation 21, set the appropriate window in our calculator and solve for x (see
Section 12.5 for review of this method). Alternately, we can use an
approximation method and verify after solving that the approximation is valid.
Because it is so much faster to solve with the approximation and the majority
of the time it is fine to use, we often use this method. The approximation relies
on the fact that Ka is small, so as long as the dissociation is very small we can
assume that x is quite small and therefore will not change 0.10−x by very
much. So, we can approximate the value for the equilibrium concentration of
HA to be ≈ 0.10. Putting these values into Equation 21, you can see that we have
[H ][A ]
+ −
[x][x] [x][x]
(22) Ka = 1.8 × 10−4 = = ≈
[HA] [0.10-x] [0.10]
Now, to solve, we just need to multiply both sides by 0.10 and take the square
root.
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(23) (0.10) · (1.8 × 10−4) = x2
(24) x= 1.8 × 10−5 = 0.0042 M
Solving this the graphical way yielded a result of 0.0043 M when

rounding. To verify that we can use this, we need the percent ionization of the
acid to be less than 5%. The percent ionization is a common measure of acid
strength found by comparing the percent of the initial concentration of acid
that is turned into H+.
[H ]eq
+
(25) Percent ionization = × 100

[HA]init
In our example above, the percent ionization is therefore

0.0042 M
(26) × 100 = 4.2%
0.10 M
As long as the percent ionization is below 5% you can use the

approximation. You can generally assume this to be the case for problems in
this course so starting with the approximation as the default is the best course
of action. Now, to finish the problem, we will need to find the pH using the
[H+] at equilibrium.
(27) pH = − log[H+] = − log(.0042) = 2.38
EXAMPLE 14.7
Find the percent ionization and pH of a 0.35 M solution of HOCl.
SOLUTION
First we need to determine whether this is an acid or base and then decide
whether it is weak or strong. It is safe to assume that this is an acid as it has
a hydrogen listed at the front and doesn’t have a negative charge or nitrogen.
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We then remember the strong acid list which does not have this so it is a
weak acid. We will therefore need to write a Ka expression and make a RICE
chart.
−
HOCl (aq) ⇌ H+ (aq) + OCl (aq)
R HOCl (aq) ⇌ H+ (aq) OCl− (aq)

I 0.35 M 0 0
C −x +x +x
E 0.35 − x x x
[H ][OCl ]
+ −
Ka =
[HOCl]
Next, we will use the approximation method to solve for the [H+]. We look at
table 14.2 to get the value of Ka for HOCl. Then substitute that and the
equilibrium values into the equilibrium expression for this acid.
[x][x] [x][x]
4.0 × 10−8 = ≈
[0.35-x] [0.35]
Now, solving for x will give us the equilibrium concentrations of H+
(0.35) · (4.0 × 10 )
−8
x=
x = 1.2 × 10−4
To find the percent ionization, we need to divide the concentration of

hydrogen ions at equilibrium by the initial concentration of acid:
1.2 × 10−4
% ionization = · 100 = 0.034%
0.35
This is a very small percent ionization so the approximation is fine. Now we

can use the equilibrium concentrations of H+ to find the pH
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pH = − log[H +] = − log(1.2 × 10−4) = 3.92

A solution of hydrofluoric acid has a concentration of 2.5 M. What is the
percent ionization and pH of the solution?
Answer: 1.6% and pH=1.4
We can also find the Ka of a weak acid by knowing the initial molarity of
the acid and either the pH or percent ionization. You can imagine why this
would be useful—measuring the Ka of a weak acid can be done in the lab with
only a scale, beakers, and a pH probe. Let’s look at a quick example of how this
would work.
EXAMPLE 14.8
What is the Ka of a 0.20 M solution of a weak acid if the pH is measured to be
5.20?
SOLUTION
First we need to write our Ka expression and make a RICE chart. Let HA be
our generic weak acid.
HA (aq) ⇌ H+ (aq) + A− (aq)
[H ][A ]
+ −
Ka =
[HA]
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I 0.20 M 0 0
C −x +x +x
E 0.20 − x x x
Next, we will use the pH value we are given to solve for the [H+].
pH = − log[H +] so [H +] = 10−pH
plugging in our value of pH:
[H ] = 10
+ −5.20
= 6.3 × 10−6
Now, looking back at our RICE chart, we can see that x=[H+], so we can plug
this value in as x in our Ka expression.
[x][x] [6.3 × 10−6][6.3 × 10−6]

Ka = = = 2.0 × 10−10
[0.20-x] [0.20-6.3 × 10−6]

What is the Ka of a 0.45 M solution of a weak acid if the pH is measured to be
4.22?
Answer: 8.0×10−9
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14.4
Polyprotic Acids
LEARNING OBJECTIVES
• To write out the equilibrium steps for polyprotic acids
• To calculate final concentrations in solution for polyprotic acids
In the previous sections we learned about the equilibrium of weak

monoprotic acids—that is acids that only lose one proton. Remember that for
such an acid, the equilibrium reaction looks like this:
(28) HA (aq) ⇌ H+ (aq) + A− (aq)
Some acids can ionize more than one proton, however. Such acids are
said to be polyprotic acids. The common acids that we deal with contain
diprotic acids—carbonic and sulfuric acid—which lose two protons, and
triprotic acids—phosphoric acid—which lose three protons. These are written
in a stepwise fashion where the first proton is lost and some of that product
then reacts again to lose another. Let’s look at the dissociation of sulfuric acid
here as an example. Remember that H2SO4 is a strong acid.
Step 1: H2SO4 (aq) → H+ (aq) + HSO4− (aq)
(29)
Step 2: HSO4− (aq) ⇌ H+ (aq) + SO42− (aq)
You can see why we write these as stepwise, in order for the second reaction to
occur, the first has to have already happened.
As you can imagine, the multiple stepwise reactions make the calculations
here a bit more complicated. Turns out, it isn’t that much more complicated, it
just requires us to do two sequential RICE charts and think a bit carefully
about the initial concentrations of the second.
711
EXAMPLE 14.9
Write the stepwise dissociation reactions for carbonic acid, H2CO3.
SOLUTION
First we need to remember this is an acid, so each of these reactions will lose
an H+. As carbonic acid is a diprotic acid, we have two reactions. (Usually
hydrogens that can be lost are written up front or after oxygens)
Step 1: H2CO3 (aq) ⇌ H+ (aq) + HCO3− (aq)
Step 2: HCO3− (aq) ⇌ H+ (aq) + CO32− (aq)
Note here that we have formed carbonate in the end. Many of the polyprotic
acids we will see will form common polyatomic ions.

Write the stepwise dissociation reactions for sulfurous acid (H2SO3).
Answer: H2SO3⇌H++HSO3− ; HSO3− ⇌H++SO32−
Calculating pH and Final Concentrations of a Polyprotic Acid

Let’s look at how we would deal with finding the pH and concentrations of
all species in a 0.2 M sulfuric acid solution to see how this works. Looking at
Equation 29 we can see the two stepwise dissociations. We will need to address
these separately and sequentially, so let’s start with the first dissociation:
R H2SO4 (aq) → H+ (aq) HSO4− (aq)

I 0.20 M 0 0
C −x +x +x
E 0.20 − x x x
712
We know that H2SO4 is a strong acid, so this dissociates completely and
therefore the value of “x” in the chart will be 0.20 M as shown below:
R H2SO4 (aq) → H+ (aq) HSO4− (aq)

I 0.20 M 0 0
C −0.20 M + 0.20 M + 0.20 M
E 0M 0.20 M 0.20 M
Now that we have carried out the first dissociation, we have to carry out
the second dissociation. We are going to use a second RICE chart here, but we
don’t usually need to do this as the second dissociation is so small compared to
the first that you will often get a concentration at equilibrium equal to the Ka.
Note that we are essentially starting a new problem here where the initial
concentration of HSO4− is equal to the final concentration of HSO4− made in
the first step. The other difference is that we have been assuming that the
concentration of H+ is essentially 0 M, but now we need to also include the H+
R HSO4− (aq) ⇌ H+ (aq) SO42− (aq)

I 0.20 M 0.20 M 0
C −y +y +y
E 0.20 − y M 0.20 + y M yM
made from the first dissociation.
Now we can set up the equilibrium expression and solve for “y”. Looking back
at Table 14.2, we can see that the Ka for HSO4− is 1.0 × 10−2.
[H ][SO4 ] [0.20+y][y]
+ 2−
−2
(30) Ka = 1.0 × 10 = =
[HSO4−] [0.20-y]
Solving this equation for “y” using the intersection method graphing yields an
answer of 9.1 × 10−3. Note that this is very close to the Ka — this is often the
case because the y is so small that (1+y)/(1−y) is essentially 1 and y ≈ Ka.
Now that we have solved for y, we can finish off our analysis. The
equilibrium concentration of H2SO4 is 0 because it was all used up. The others
are found by the equilibrium column at the bottom of the second RICE chart.
713
[HSO4 ] = 0.19M
−
[SO4 ] = 9.1 × 10 M
2− −3
(31)
[H ] = 0.21M
+
(32) pH = − log[.21] = 0.68
In order to carry out these calculations, you therefore need to have the Ka
for all of the different dissociations to calculate the concentrations of species
from each reaction. This is listed below in Table 14.3. Often times, the
equilibrium constants of the steps are referred to as Ka1 for the first
dissociation, Ka2 for the second and so on.
TABLE 14.3 Values of Ka for polyprotic acids
Acid HA Ka1 Ka2 Ka3

sulfuric acid H2SO4 Large* 1.0 × 10−2
sulfurous acid H2SO3 1.5 × 10−2 1.0 × 10−7
carbonic acid H2CO3 4.3 × 10−7 5.6 × 10−11
phosphoric acid H3PO4 7.5 × 10−3 6.2 × 10−8 ~3.0 × 10−13
ascorbic acid HC5H7O6 8.0 x 10−5 1.6 × 10−12

malonic acid H2C3H2O4 1.5 x 10−3 2.0 x 10−6
pyrophosphoric
H4P2O7 3.0 x 10−2 4.4 x 10−3
acid
periodic acid H5IO6 2.8 x 10−2 5.3 x 10−9
*Considered to dissociate completely as it is a strong acid.
714
EXAMPLE 14.10
Find the pH and the concentration of all species present at equilibrium for a
0.45 M solution of carbonic acid.
SOLUTION
First, let’s begin writing out the stepwise dissociations.
Step 1: H2CO3 (aq) ⇌ H+ (aq) + HCO3− (aq)
Step 2: HCO3− (aq) ⇌ H+ (aq) + CO32− (aq)
We will start with the first reaction and need to write out the RICE chart:
R H2CO3 (aq) ⇌ H+ (aq) HCO3− (aq)

I 0.45 M 0 0
C −x +x +x
E 0.45 − x x x
Now we can look on Table 14.3 and find the value of Ka1 for carbonic acid.
We’ll use this to solve for “x” with the equilibrium expression.
R HCO3− (aq) ⇌ H+ (aq) CO32− (aq)
I 4.4 × 10−4 M 4.4 × 10−4 0
C −y +y +y
4.4 × 10−4 −
E 4.4 × 10−4 + y y
y
[H ][HCO3 ]
+ −
[x][x]
Ka1 = 4.3 × 10−7 = =
[H2CO3] [0.45-x]
Solving for x using the approximation yields an x value of 4.4 × 10−4. (A

quick check of this shows that the approximation is fine)
Now, we can find the second reaction by writing out the RICE chart:
715
Looking up Ka2 on Table 14.3 and using the equilibrium expression will allow
us to solve for “y.”
[H ][CO3 ] [4.4 × 10−4 + y][y]

+ 2−
Ka2 = 5.6 × 10−11 = =
[HCO3−] [4.4 × 10−4 − y]
y = 5.6 × 10−11
Now we can evaluate the concentrations of everything:
[H2CO3] = 0.45 − 4.4 × 10 = 0.45M

−4
[HCO3 ] = 4.4 × 10
− −4
− 5.6 × 10−11 = 4.4 × 10−4 M
[CO3 ] = 5.6 × 10
2− −11
[H ] = 4.4 × 10
+ −4
+ 5.6 × 10−11 = 4.4 × 10−4 M
Too small to worry about so it

can be ignored in most cases
Now, to find the pH. We should note that the [H+] did not change after the
first dissociation. This is true for all species except H2SO4 and you only need
to do the first RICE chart in these cases. To find the pH, we take the −log of
the [H+] we calculated from the first reaction:
pH = − log[4.4 × 10−4] = 3.36
716
Find all the species present and the pH of a 0.65 M solution of carbonic acid:
Answer: pH= 3.28; [H2CO3]=0.65M, [HCO3−]=5.3 × 10−4, [CO32−]=5.6 × 10−11,

[H+]=5.3 × 10−4
717
14.5
Weak Base Equilibrium
LEARNING OBJECTIVES
• To be able to calculate the pH and Kb for weak base equilibria
• To quantify and use the relationship between Ka and Kb
The Base Equilibrium Constant

A weak base reaches an equilibrium in aqueous solutions, just as weak
acids do. In the case of a weak base however, the equilibrium does not
increase H+, but rather OH−, requiring us to go through an additional step to
calculate the pH. In order to look at this more closely, let’s first start with the
general equation for the ionization of a weak base in water, where B is a weak
base and HB+ is its conjugate acid, is as follows:
(33) B (aq) + H2O (l) ⇌ HB+ (aq) + OH− (aq)
Given this reaction, we can therefore write out the equilibrium constant
expression for this as follows (remember the H2O is a pure liquid and not part
of the expression):
[OH ][HB]
−
(34) Kb =
[B ]
−
This is known as the base dissociation constant and just like the acid
dissociation constant is measured in concentration. The base dissociation
constant is given the subscript “b” to clarify that it is the constant for the
ionization of a base.
Just like it's counterpart Ka, the larger the value of Kb is, the stronger the
base. In this case, it causes the pH to increase since the creation of OH− drives
the concentration of H+ down.
718
Calculating pH for a Weak Base
Just as with Ka for weak acids, we can look up the Kb for a weak base and
use this to calculate the pH of the base. Table 14.4 shows the Kb for some
common bases. Many of these are the conjugates of the weak acids we looked
at in section 14.3. In a few pages we will learn exactly how the Ka and Kb of a
conjugate pair are related, but first let’s look at an example of using Kb and an
initial concentration to solve for pH.
TABLE 14.4 Values of Kb for selected weak bases
Base B Kb
sulfate SO42− 9.8 × 10−13
fluoride ion F− 1.6 × 10−11
nitrite NO2− 1.8 × 10−11
formate ion HCOO− 5.6 × 10−11
benzoate C6H5COO− 1.6 × 10−10
acetate CH3COO− 5.8 × 10−10
pyridine C5H5N 1.7 × 10−9
hypochlorite OCl− 2.5 × 10−7
cyanide CN− 2.0 × 10−5
ammonia NH3 1.8 × 10−5
trimethylamine (CH3)3N 6.3 × 10−5
methylamine CH3NH2 4.6 × 10−4
719
EXAMPLE 14.11
Find the percent ionization and pH of a 0.54 M solution of ammonia.
SOLUTION
We will tackle the percent ionization first as it will help us decide whether we
can use the approximation method. First we need to identify that ammonia is
a weak base and write a reaction, Kb expression, and make a RICE chart.
NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH− (aq)
[NH4 ][OH ]
+ −
Kb =
[NH3]
R NH3 (aq) ⇌ NH4+ (aq) OH− (aq)

I 0.54 M 0 0
C
E
Remember that we can leave the water out of the equilibrium expression and
RICE chart because it is a pure liquid and therefore has essentially a constant
concentration for the purposes of this equilibrium.
Next, we will in the RICE chart to show the equilibrium concentrations in
R NH3 (aq) ⇌ NH4+ (aq) OH− (aq)

I 0.54 M 0 0
C −x +x +x
E 0.54 − x x x
terms of x.
720
Now, we need to look up the value of Kb for NH3 in Table 14.4 and plug in the
equilibrium values from the RICE chart into the Kb expression we wrote
above.
[x][x] [x][x]
Kb = 1.8 × 10−5 = ≈
[0.54-x] [0.54]
(0.54) · (1.8 × 10 )
−5
x=
x = 3.1 × 10−3
Similar to with weak acids we can use the approximation assuming a small x
as long as the percent ionization is less than 5%.
3.1 × 10−3
% ionization = · 100 = 0.57%
0.54
This is a very small percent ionization so the approximation is fine. Now we

need to find the pH. Look back at the RICE chart and you can see that the
value of x=[OH−] so we need to convert this to pH. In this case, we’ll use the
pOH to do so.
pOH = − log[OH −] = − log(3.1 × 10−3) = 2.51
Now we convert this to pH
pOH + pH = 14
pH = 14 − pOH
pH = 14 − 2.51 = 11.49
721
A solution of fluoride ion has a concentration of 0.21 M. What is the percent
ionization and pH of the solution?
Answer: 8.6×10−4% and pH=8.26

The Relationship between Ka and Kb
We can relate Ka and Kb by looking at the two reactions from an acid and
conjugate base pair. Let’s look at our generic B as the base and HB+ as our
conjugate acid. The first reaction is just the generic base reaction:
(35) B (aq) + H2O (l) ⇌ HB+ (aq) + OH− (aq)
The second reaction is now the acid reaction for the HB+ that we formed
(36) HB+ (aq) ⇌ H+ (aq) + B (aq)
In order to see how the two relate to each other, we can look at the sum of the
two reactions, which would be:
(37) B(aq) + H2O (l) + HB+ (aq) ⇌ HB+ (aq) + OH− (aq) + H+ (aq) + B (aq)
Simplifying this by crossing out the common terms on both sides (B and HB+)
gets us the following:
(38) H2O (l) ⇌ OH− (aq) + H+ (aq)
Since this is the equation for the autoionization of water, we can say that
the sum of an acid or base ionization and that of it’s conjugate is equal to the
reaction of the autoionization of water. Further, when we add two reactions
together, the equilibrium constant of the sum is equal to the multiplication of
the two separate equilibrium constants added together —try it for the reactions
above to see for yourself. In this case, the equilibrium constant for Equation 37
is equal to Ka×Kb and for Equation 38 it is equal to Kw.
(39) Kw = Ka × Kb
722
TABLE 14.5 Values of Ka and Kb for selected weak acids (HA) and conjugate bases
Acid HA Ka A−/B Kb
sulfuric acid HSO4− 1.0 × 10−2 SO42− 9.8 × 10−13
hydrofluoric
HF 6.3 × 10−4 F− 1.6 × 10−11
acid
nitrous acid HNO2 5.6 × 10−4 NO2− 1.8 × 10−11
formic acid HCOOH 1.8 × 10−4 HCOO− 5.6 × 10−11

benzoic acid C6H5COOH 6.3 × 10−5 C6H5COO− 1.6 × 10−10
acetic acid CH3COOH 1.7 × 10−5 CH3COO− 5.8 × 10−10
pyridinium ion C5H5NH+ 5.9 × 10−6 C5H5N 1.7 × 10−9
hypochlorous
HOCl 4.0 × 10−8 OCl− 2.5 × 10−7
acid
hydrocyanic 4.9 × 10−1
HCN CN− 2.0 × 10−5
acid 0
ammonium 5.6 × 10−1
NH4+ NH3 1.8 × 10−5
ion 0
tri-
(CH3)3NH+ 1.6 × 10−10 (CH3)3N 6.3 × 10−5
methylamine
methylamine CH3NH3+ 2.2 × 10−11 CH3NH2 4.6 × 10−4
This table shows Ka and Kb for conjugate pairs of acid and base. Note that the stronger an
acid a substance is, the weaker its conjugate base is.
Note the implication here, if we know the Ka of an acid, we can use Kw to

find the Kb for its conjugate base and vice versa! This relationship explains
why a stronger acid has a weaker conjugate base and vice versa. If we look
again at the table of weak acids and weak bases, we can merge them together to
see the relationship between a conjugate pair as shown in Table 14.5.
723
• The stronger an acid is, the weaker it’s conjugate base is.
• The Ka and Kb that are related by the equation Ka×Kb = Kw are those of
the conjugate pair. Sometimes you will need to use this relationship to
find the correct equilibrium constant for the problem you are doing. Do
not assume you are given the one you need to directly solve a problem!
• Be careful that you use the correct reaction depending on whether you
have an acid or base and whether it is weak or strong. Determine this
first and then set up your equations as follows:
STUDY TIP
o Strong acid: HA (aq) → H+ (aq) + A− (aq)

o Weak acid: HA (aq) ⇌ H+ (aq) + A− (aq)
o Strong base: M(OH) (aq) → M+ (aq) + OH− (aq)
o Weak base: B (aq) + H2O (l) ⇌ HB+ (aq) + OH− (aq)
EXAMPLE 14.12
If the Kb for aniline (C6H5NH2) is 7.4×10−10. What is the formula of the
conjugate acid? What is the corresponding Ka for that conjugate?
SOLUTION
First we need to figure out the formula for the conjugate. Since we are given
the Kb for aniline, we recognize that it is a base and therefore will gain a
proton. So, writing out the reaction with water we would have:
724
C6H5NH2 (aq) + H2O (l) ⇌ C6H5NH3+ (aq) + OH− (aq)
Therefore, the conjugate acid of aniline is anilinium, which is C6H5NH3+.
Now, we can use the relationship between Ka and Kb to solve for the Ka for
anilinium.
Kw = Ka × Kb
Kw
Ka =
Kb
1.0 × 10−14 −5
Ka = = 1.4 × 10
7.4 × 10−10

A weak acid (HA) has a Ka of 8.0×10−9. What is the conjugate base and what
is the Kb of that conjugate?
Answer: A–; 8.0×10−9
725
TABLE 14.6 Ka Chart in Alphabetical Order
Acid HA Ka1 Ka2 Ka3

acetic acid CH3COOH 1.7 × 10−5
ammonium ion NH4+ 5.6 × 10−10
ascorbic acid HC5H7O6 8.0 x 10−5 1.6 × 10−12
benzoic acid C6H5COOH 6.3 × 10−5
carbonic acid H2CO3 4.3 × 10−7 5.6 × 10−11
formic acid HCOOH 1.8 × 10−4
hypochlorous
HOCl 4.0 × 10−8
acid
hydrocyanic
HCN 4.9 × 10−10
acid
hydrofluoric
HF 6.3 × 10−4
acid
malonic acid H2C3H2O4 1.5 x 10−3 2.0 x 10−6
nitrous acid HNO2 5.6 × 10−4
periodic acid H5IO6 2.8 x 10−2 5.3 x 10−9
phosphoric acid H3PO4 7.5 × 10−3 6.2 × 10−8 ~3.0 × 10−13

pyridinium ion C5H5NH+ 5.9 × 10−6
pyrophosphoric
H4P2O7 3.0 x 10−2 4.4 x 10−3
acid
Sulfuric acid H2SO4 Large* 1.0 × 10−2
sulfurous acid H2SO3 1.5 × 10−2 1.0 × 10−7

water H2O 1.0 × 10−14
726
TABLE 14.7 Kb Chart in Alphabetical Order
Base B Kb
acetate CH3COO− 5.8 × 10−10
ammonia NH3 1.8 × 10−5
benzoate C6H5COO− 1.6 × 10−10
cyanide CN− 2.0 × 10−5
fluoride ion F− 1.6 × 10−11
formate ion HCOO− 5.6 × 10−11
hypochlorite OCl− 2.5 × 10−7
methylamine CH3NH2 4.6 × 10−4
nitrite NO2− 1.8 × 10−11
pyridine C5H5N 1.7 × 10−9
sulfate SO42− 9.8 × 10−13
trimethylamine (CH3)3N 6.3 × 10−5
727
14.6
Acid-Base Properties of Salt Solutions
LEARNING OBJECTIVES
• To identify the effect of salt dissolution on the acid–base properties of a
solution
• To be able to find the pH of a salt solution given the concentration
Salt Solution Basics

In this section, we will assess the acidity of salt solutions⏤that is, a
solution containing a soluble ionic compound dissolved in water. Salt
solutions produce, by definition, a cation and an anion that could have acid-
base properties; you must understand that NOTHING will change in our
analysis from the previous sections. We will apply the same weak acid-base
tools to cations and anions as we did for neutral species!
Before we look at some examples, recall that
(40) Ka ⋅ Kb = Kw
Equation 40 reminds us that the stronger the acid, the weaker the conjugate base
(and vice-versa); in fact, the strong acids are so strong that they render their
conjugates as ineffective bases. We summarize the relationships in Table 14.8.
TABLE 14.8 Conjugate Strength Relationships
Acid Strength Base Strength

Strong (HCl, HNO3, H2SO4, Ineffective (Cl−, NO3−, HSO4−,
HClO4, HI, HBr) ClO4−, I−, Br−)
Weak (HF, CH3COOH, NH4+, etc) Weak (F−, CH3COO−, NH3)
Ineffective (H2, etc) Strong (H−, etc)
HSO4− is acidic but ineffective as a base. Stronger bases than OH− exist as
noted in the chart. You are not responsible for this information.
728
We will use these results from Table 14.8 as well as the following guidelines
as we consider the acid-base reactions of salt solutions. Cations and anions
will often function as acids and bases, respectively, with the exceptions being
Group 1 and 2 metal ions and the conjugate bases of the strong acids. Note
that these are basic rules that are not universal⏤we will see that they are more
nuanced later in the section.
Depending on the acid–base properties of its component ions, a salt can
FIGURE 14.2 Salt Solution Guidelines
dissolve in water to produce a neutral solution, a basic solution, or an acidic

solution. Let’s look at each case.
Neutral Solution
When analyzing what a salt will do in water, we first separate the
component ions and then consider their acid-base behavior. For example,
aqueous sodium chloride exists in solution as separate Na+ and Cl− ions. We
generally think of cations as acids and anions as bases; however, we recognize
Na+ as a Group 1 cation and Cl− as the conjugate base of a strong acid. It
follows that both are ineffective and the solution must be neutral. What
equilibrium would determine the pH? The autoionization of water, which
means we have a pH of 7, or neutral conditions!
(41) H2O (l) ⇌ H+ (aq) + OH− (aq)
Basic Solution
729
Now let's compare the behavior of an aqueous solution of potassium
cyanide, KCN. In solution, this creates the cation K+ and the anion CN−. The
potassium ion is an ineffective acid as it is a Group 1 cation while CN− can act
as a base (as the conjugate base of a weak acid). It follows that the CN− will act
as a weak base and the solution will be basic (pH > 7). We can write this
equation using the Bronsted-Lowry framework which we have already learned!
(42) CN− (aq) + H2O (l) ⇌ HCN (aq) + OH− (aq)
While Kb for CN− is listed in Table 14.4, we remind you that it could be
calculated using the Ka for HCN:
Kw 10−14 −5
(43) Kb = = = 2.0 ⋅ 10
Ka(HCN ) 4.9 ⋅ 10−10
Note that the autoionization of water (with a Kw = 10−14) is insignificant

compared to the ionization of CN− (Kb >>> Kw).
Acidic Solution
Now let's compare the behavior of an aqueous solution of ammonium nitrate,
NH4NO3. In solution, this creates the cation NH4+ (conjugate acid of a weak
base) and the anion NO3− (conjugate base of a strong acid). Ammonium will
act as a weak acid while nitrate will be ineffective as a base. Hence, the most
relevant ionization equation will be:
(44) NH4+ (aq) ⇌ NH3 (aq) + H+ (aq)
The solution will be acidic and Ka for NH4+ could also be determined using
the Kb for ammonia:
Kw 10−14 −10
(45) Ka = = = 5.6 ⋅ 10
Kb(NH3) 1.8 ⋅ 10−5
Acidic and Basic Ions Together in a Salt Solution
730
What will happen if the salt contains both an acidic and basic ion? Let’s take a
look at the behavior of an aqueous solution of ammonium cyanide, NH4CN. In
solution, this creates the cation NH4+ and the anion CN− (two ions that we have
already investigated above). We have established that ammonium is acidic and
cyanide is basic through the following hydrolysis reactions:
(46) NH4+ (aq) ⇌ NH3 (aq) + H+ (aq)
(47) CN− (aq) + H2O (l) ⇌ HCN (aq) + OH− (aq)
Since the NH4+ makes H+ and the CN− makes OH−, we have to compare the
equilibrium constants to determine whether we are going to produce more H+
or OH−. Looking up the Ka for NH4+ and the Kb for CN−, we will see which
goes more towards products at equilibrium.
Ka(NH4+) = 5.6×10−10
Kb(CN−) = 2.0×10−5
Since Kb > Ka, the basic reaction of CN− hydrolysis will proceed more
towards products than the acidic reaction of NH4+. The solution will therefore
be basic after the addition of this salt to water.
EXAMPLE 14.13
Write out any hydrolysis reaction that occurs and determine whether the pH
of the resulting solution is acidic, basic, or neutral.
a) KNO3
b) CH3NH3Br
c) (NH4)2SO4
SOLUTION
731
For each of these we will need to consider the ions we have and whether
hydrolysis will occur in each case.
a) KNO3 dissolves in water to give K+ and NO3−. Looking at the potential

hydrolysis reactions, we can see that K+ is an ineffective acid (Group 1
metal ion) and NO3− is an ineffective base (conjugate base of a strong
acid). Mo reactions will occur and this solution will be neutral.
b) CH3NH3Br dissolves in water to give CH3NH3+ and Br−. We can see that
CH3NH3+ is the conjugate acid of a weak base and Br− is the conjugate
of a strong acid so only the CH3NH3+ will react and this solution will be
acidic.
CH3NH3+ (aq) ⇌ CH3NH2(aq) + H+ (aq)
c) (NH4)2SO4 dissolves in water to give NH4+ and SO42−. Ammonium is a

cation and will act as an acid; sulfate is an anion and CAN act as a base.
It is the conjugate base of HSO4− which is not a strong acid! Both will
react and we will have to look up the Ka and Kb.
NH4+ (aq) ⇌ NH3(aq) + H+ (aq)
SO42− (aq) + H2O (l) ⇌ HSO4− (aq) + OH− (aq)
Ka (NH4+) = 5.6×10−10
Kb (SO42−) = 9.8×10−13
Ka>Kb so this solution will be acidic.

Write out any hydrolysis reaction that occurs and determine whether the pH
of the resulting solution is acidic, basic, or neutral.
732
a) KI
b) NH4ClO4
c) NH4CH3COO
Answer: a) no hydrolysis; neutral b) NH4+(aq) ⇌ NH3(aq)+H+ (aq); acidic c) NH4+(aq)
⇌ NH3(aq)+H+; CH3COO−(aq)+H2O(l)⇌CH3COOH(aq)+OH−(aq); Ka ≈ Kb so
effectively neutral
Finding the pH of a Salt Solution

Now we have the background to determine whether a salt will undergo
hydrolysis and determine whether it will act as an acid, base, or just be a
spectator ion. We can therefore extend this one more step to find the pH of a
solution with a salt. We won’t ask you to figure out the pH of a solution with
two salts that hydrolyze or with an amphoteric ion (see later in the chapter),
but we can expect that much like the problems in the weak acid and weak base
section you can use an initial concentration and equilibrium constant to find
the pH. Let’s look at an example problem.
EXAMPLE 14.14
What is the pH of a solution made by adding 1.5 grams of potassium acetate
to 400 mL of water?
SOLUTION
Our first step is to take a look at the salt and consider the hydrolysis so we
know what we are dealing with for a reaction. Potassium acetate is
KCH3COO and in solution it will dissolve in water to form the ions K+ and
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CH3COO−. K+ is an alkali metal and therefore will not react, but CH3COO− is
and anion and the conjugate of a weak acid, so it will act as a weak base as
follows:
CH3COO− (aq) + H2O (l) ⇌ CH3COOH (aq) + OH− (aq)
From here, it is a normal weak base equilibrium problem, we need to make a

RICE chart, find the relevant Ka and solve for the [H+] and ultimately the pH.
First, let’s write the equilibrium expression and look up the Kb for acetate on
Table 14.5 (remember you could also find it by using the Ka of acetic acid and
converting with Kw):
[CH3COOH][OH ]
−
Kb = = 5.8 × 10−10
[CH3COO −]
( 98.15 g )( 400 mL )( 1 L )

1 mol 1 1000 mL
initial [CH3COO −] = 1.5 g = 3.8 × 10−2 M
R CH3COO− (aq) ⇌ CH3COOH (aq) OH− (aq)

I 0.038 M 0 0
C −x +x +x
E 0.038−x x x
Using the approximation method gives us the following:
[x][x]
Kb = = 5.8 × 10−10
[0.038−x]
x = 4.7 × 10−6 M = [OH −]
pOH = − log[OH −] = − log[4.7 × 10−6] = 5.33
pH = 14 − pOH = 8.67
734
Write any hydrolysis reaction and calculate the pH of a 0.24 M sodium
formate (NaHCOO) solution
Answer: HCOO−(aq)+H2O(l)⇌HCOOH(aq)+OH−(aq); 8.58
Special Case: Salts with Amphoteric Ions

Hydrolysis problems sometimes involve amphoteric ions — species that
can act as both an acid and a base. If we had an aqueous solution of sodium
bicarbonate, NaHCO3, for instance, we would know that it would contain Na+
and HCO3−. We have already established that the Na+ won’t react, but
something interesting happens with the HCO3−. As an anion that is the
conjugate of a weak acid, bicarbonate can act as a weak base:
(48) HCO3− (aq) + H2O (l) ⇌ H2CO3 (aq) + OH− (aq)
However, Table 14.6 indicates that carbonic acid (the conjugate acid of
bicarbonate) is diprotic; as a result, HCO3− can also act as a weak acid:
(49) HCO3− (aq) ⇌ CO32− (aq) + H+ (aq)
As we did before when we had two hydrolysis reactions, we have to

compare the Ka and Kb to figure out which goes more towards products at
equilibrium. By definition, the Ka for bicarbonate is Ka2 of carbonic acid:
(50) K a(HCO3−) = K a2(H2CO3) = 5.6 × 10-11
The Kb can be calculated by using Ka1 of H2CO3 and our familiar relationship:
Kw
(51) Kb(HCO3−) = = 2.3 × 10-8
K a1(H2CO3)
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Note that it is Ka1 (and not Ka2) in Equation 51 since the conjugate acid of
bicarbonate is H2CO3. Since Kb > Ka, the basic reaction of HCO3− hydrolysis
will proceed more towards products than the acidic reaction of HCO3−. The
solution will therefore be basic after the addition of this salt to water.
How can you determine which ions will be amphoteric? Look for the
conjugate bases of diprotic or triprotic acids as these species must have both
acidic and basic character. Figures 14.8 and 9 summarize these points, although
you should keep in mind that there are many more amphoteric species than
the ones listed. You should be able to identify them from a more expansive Ka
table. HSO4− is a slightly more complicated case and is covered below.
FIGURE 14.3 Identifying Amphoteric Species
Diprotic and triprotic acids will have amphoteric conjugate bases.

We will often calculate Kb from the Ka of the conjugate acid; the
presence of multiple ionization constants confirms that the ion is
amphoteric.
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FIGURE 14.4 Complete Guidelines for Hydrolysis Problems
EXAMPLE 14.15
Write out all hydrolysis reactions that occur and determine whether the pH
of the resulting solution is acidic, basic, or neutral. Include all relevant
ionization constants.
a) NaC5H7O6
b) KHSO4
SOLUTION
a) We begin by noting that this salt ionizes into Na+ and C5H7O6−. The
cation is ineffective as an acid and the anion we recognize first as a
weak base:
C5H7O6− (aq) + H2O (l) ⇌ HC5H7O6 (aq) + OH− (aq)
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Kb can be calculated through a Ka chart and we immediately notice that
HC5H7O6 is diprotic!
Kw
Kb(C5H7O6−) = = 1.3 × 10-10
K a1(HC5H7O6)
Accordingly, it follows that the anion is also capable of acting as an

acid, with an ionization constant equal to Ka2 of HC5H7O6:
C5H7O6− (aq) ⇌ C5H6O62− (aq) + H+ (aq)
K a(C5H7O6−) = K a2(HC5H7O6) = 1.6 × 10-12
Kb > Ka for the anion and the solution is basic.
b) KHSO4 ionizes to K+ and HSO4−. As always, Group 1 metal cations do

not function as acids or bases in solution. We might at first glance
think that a solution of HSO4− is basic. Remember that it is the
conjugate base of a strong acid (sulfuric) and is therefore ineffective as
a base! Sulfuric acid, on the other hand, is diprotic, indicating that
HSO4− can lose another proton to form sulfate:
HSO4− (aq) ⇌ SO42− (aq) + H+ (aq)
K a(HSO4−) = K a2(H2SO4) = 1.0 × 10-2
The solution is acidic and you should also recognize that HSO4− can
only function as an acid. It is not amphoteric!
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14.7
Lewis Structures and Acid Strength
LEARNING OBJECTIVES
• To be able to use Lewis structures to predict the relative strength of
acids
We have seen that the strengths of acids and bases vary over many orders
of magnitude. In this section, we explore some of the structural and electronic
factors that control the acidity of a molecule.
Bond Strength
In general, the stronger the A–H bond is in an acid, the less likely the bond is
to break to form H+ ions and thus the less acidic the substance will be (lower
Ka). Therefore, anything that shifts the electrons away from the bond to the
hydrogen will weaken the bond and make it is much easier to break and lose
the H+.
Stability of the Conjugate Base

Recall the weak acid equilibrium equation:
(52) HA (aq) ⇌ H+ (aq) + A− (aq)
When we write this reaction, the conjugate base (A−) contains one more lone
pair of electrons than the parent acid (HA). Any factor that stabilizes that lone
pair on the conjugate base favors dissociation of H+ and makes the parent acid
a stronger acid. For example, the observed acidity of CH4 is millions of times
less than HF. That is because the conjugate base of CH4 is CH3−, and the
conjugate base of HF is F−. Because fluorine is much more electronegative than
carbon, fluorine can better stabilize the negative charge in the F− ion than
carbon can stabilize the negative charge in the CH3− ion. Consequently, HF has
739
a greater tendency to dissociate to form H+ and F− than does methane to form
H+ and CH3−, making HF a much stronger acid than CH4.
FIGURE 14.5 An
Application to Oxyacids oxyacid
Oxyacids are acids with O-H bonds that are able to

lose the hydrogen to act as an acid. We would draw them
The strength of an
in the general form H-O-X, where X is a non-metal
oxyacid depends
group. A more electronegative X group will cause the on the X group.
oxygen to have relatively less electrons in the bond and
make the oxygen-hydrogen bond a weaker bond, thus increasing the ability to
lose an H+. Commonly this is seen with the addition of more terminal oxygens
—oxygens bonded only to the central atom—which will make the X group more
electronegative and add resonance possibilities for the conjugate. Thus, HNO2
is a weak acid while HNO3 is a strong acid and dissociates completely.
Evaluating Oxyacid Strength

1. Attaching more terminal oxygens to the electronegative X group will
increase the strength of the acid
2. Oxyacids of the structure H-O-X will be stronger acids as X contains
more electronegative elements.
Note that if your X group has very low electronegativity—such as a metal—

the relative bond strength is flipped and the X—O bond is weaker than the
O—H bond so the X group will break off and leave you with a base (OH− is
made)
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Application to Carboxylic acids
Carboxylic acids are another common type of acid with the general
formula R-COOH (R represents any carbon containing fragment). Remember
that the bond strength and stability of the conjugate base are the two main
factors that play a role in the strength of an acid. In the case of carboxylic
acids, that means we need to look at the electronegativity of the attached group
and the resonance of the conjugate base to help explain why they are acidic,
especially compared to molecules with an alcohol group.
Just like in the oxyacids, having more electronegative atoms as part of the
R group will make a carboxylic acid a stronger acid as well. Looking at acetic
acid versus trifluoroacetic acid, we can see that the R group in trifluoroacetice
acid clearly has much more electronegativity and therefore the O-H bond will
be weaker as the oxygen holds the electrons tighter.
FIGURE 14.6 Acetic vs. Fluoracetic acid
The fluorines in fluoroacetic acid are very electronegative and weaken the bond between the
O and the H
When ionized in their conjugate base form, carboxylic acids can share the
negative charge between two oxygens by resonance. This helps the acid
strength by stabilizing the conjugate base. By comparison, while alcohols have
an electronegative oxygen to hold the charge, they are fairly weak acids by
comparison because they don’t have resonance to share the charge. Figures 14.4
and 14.5 demonstrate the difference between the resonance in the conjugates.
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FIGURE 14.7 The Acetate Ion FIGURE 14.8 The Methoxide Ion
The acetate ion (conjugate of acetic acid) shows The methoxide ion (conjugate of
resonance to share the negative charge methanol) can’t share the charge
You might also note that the acetic acid also had a more electronegative
group since it had another oxygen attached in the carboxylic acid group,
whereas an alcohol like methanol would only have the one oxygen. This
electronegative oxygen is also part of the reason why carboxylic acids good
acids compared to alcohols.
Evaluating Carboxylic Acid Strength

1. A more electronegative R group attached to the carboxyl (-COOH)
group will increase the strength of the acid
An important note: One might think that ammonia would be an acid since
the N-H bond has a large electronegativity difference and as we have pointed
out that make the bond to hydrogen weaker.
However, the lone pair overrides that tendency and FIGURE 14.9 Ammonia
makes it act as a base by accepting a proton and
forming NH4+.
The lone pair on ammonia

makes it a proton acceptor
742
• The more electronegative the group attached to an O-H bond, the
stronger the acid.
• The more stable a conjugate base is — because of electronegativity or
resonance — the stronger the acid.
EXAMPLE 14.16
Draw the Lewis structures of the following acids and explain the following
observations:
a) H2SO4 is a stronger acid than H2SeO4
b) HOF is a stronger acid than HOCl
SOLUTION
For both of these, the first step is to draw the lewis structures of each to be
able to see where things are bonded. See Chapter 7 if you need to review the
rules for forming lewis structures. After we have the structure we will
evaluate the acid.
a)
It’s okay for the purposes of this course if you didn’t draw this with the
double bond between sulfur and oxygen as we don’t know formal charge, but
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the actual Lewis structure would be the one above. Note that S and Se can
both hold more than an octet.
Looking at the structures we see that the only difference between the two is
that the central atom is sulfur vs. selenium. Since everything else is the same,
we don’t have to worry about the conjugate base making a difference or a
different number of oxygens, so it just comes down to electronegativity of the
central atoms. In this case, sulfur is higher on the table than selenium and
therefore has more electronegativity. Thus, we would expect that the sulfuric
acid would be more acidic as it is.
b)
These two are oxyacids that are very similar except for the fluorine vs
chlorine as the X group. Once more, we will choose the one with the more
electronegative X group, which is the fluorine and say that it is the stronger
acid.

Draw the lewis structures of the following acids and explain the following
observations:
a) H2SeO3 is a weaker acid than H2SeO4
b) HOBr is a stronger acid than HOI
Answer: a) H2SeO3 has fewer terminal oxygens than H2SeO4 so it is a weaker acid. b) Br is
more electronegative than I so HOBr is a stronger acid.
744
745
14.8
The Chemistry of Acid Rain
LEARNING OBJECTIVES
• To understand the chemical reactions involved in acid rain.
Acid–base reactions can have a strong environmental impact. For

example, a dramatic increase in the acidity of rain and snow over the past 150
years is dissolving marble and limestone surfaces, accelerating the corrosion of
metal objects, and decreasing the pH of natural waters. This environmental
problem is called acid rain and has significant consequences for all living
organisms. The term acid rain is actually somewhat misleading because even
pure rainwater collected in areas remote from civilization is slightly acidic (pH
≈ 5.6) due to dissolved carbon dioxide, which reacts with water to give
carbonic acid, a weak acid:
(53) CO2(g) + H2O(l) ⇌ H2CO3 (aq) ⇌ H+ (aq) + HCO3− (aq)
The English chemist Robert Angus Smith is generally credited with

coining the phrase acid rain in 1872 to describe the increased acidity of the rain
in British industrial centers (such as Manchester), which was apparently
caused by the unbridled excesses of the early Industrial Revolution, although
the connection was not yet understood. At that time, there was no good way to
measure hydrogen ion concentrations, so it is difficult to know the actual pH of
the rain observed by Smith. Typical pH values for rain in the continental
United States now range from 4 to 4.5, with values as low as 2.0 reported for
areas such as Los Angeles.
What is the source of the increased acidity in rain and snow? Chemical
analysis shows the presence of large quantities of sulfate (SO42−) and nitrate
(NO3−) ions, and a wide variety of evidence indicates that a significant fraction
746
of these species come from nitrogen and sulfur oxides produced during the
combustion of fossil fuels.
The general form of these reactions is as follows:
(54) nonmetal oxide + water → oxoacid
We already saw this with the carbon dioxide in Equation 53. Let’s look at
some other common reactions nonmetal oxide reactions.
(55) SO2 (g) + H2O (l) → H2SO3 (aq)
Note that this is an acid-base reaction and not a redox reaction. We can
prove this by looking at the oxidation numbers on the left and right. S is +4 in
SO2 and also +4 in H2SO3, all of the H’s are +1 and the O’s are −2. Since there
is no change in these oxidation numbers, there is no redox reaction taking
place.
(56) SO3 (g) + H2O (l) → H2SO4 (aq)
(57) N2O5 (g) + H2O (l) → 2HNO3 (aq) **
**There are numerous and complicated nitrogen reactions in the

atmosphere, we will use this as an example of one nitrogen oxide reaction
Concerns about the harmful effects of acid rain have led to strong pressure
on industry to minimize the release of SOx and NOx compounds. For example,
coal-burning power plants now use SO2 “scrubbers,” which trap SO2 by its
reaction with lime (CaO).
The damage that acid rain does to limestone and marble buildings and
sculptures is due to a classic acid–base reaction. Marble and limestone both
consist of calcium carbonate (CaCO3), a salt derived from the weak acid H2CO3.
The reaction of a strong acid with a salt of a weak acid goes to completion.
Thus we can write the reaction of limestone or marble with dilute sulfuric acid
as follows:
(58) CaCO3 (s) + H2SO4 (aq) → CaSO4 (s) + H2O (l) + CO2 (g)
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Because CaSO4 is sparingly soluble in water, the net result of this reaction is
to dissolve the marble or limestone.
EXAMPLE 14.17
Write out the reaction of selenium dioxide with water.
SOLUTION
Selenium dioxide is SeO2, which is a nonmetal oxide. We will show the
reaction with water and should form an oxyacid H2SeO3.
SeO2 (g) + H2O (l) → H2SeO3 (aq)
748
14.9
Chapter 14 Homework Problems
Identifying acids and bases
14.1 Classify each compound as a strong acid, a weak acid, a strong base, or
a weak base in aqueous solution.
a) NH3
b) H2CO3
c) CH3COOH
d) NaOH
e) H2SO4
f) NH4+
g) HNO3
h) CH3CH2NH2
14.2 Classify each compound as a strong acid, a weak acid, a strong base, or
a weak base in aqueous solution.
a) magnesium hydroxide
b) ammonia
c) acetate ion
d) nitric acid
e) hydrofluoric acid
14.3 List the conjugate base of the following acids
a) CH3COOH
749
b) HCN
c) HNO3
d) H2PO4−
e) HCO3−
14.4 List the conjugate acid of the following bases
a) NH3
b) F−
c) SO42−
d) S2−
e) CH3CH2NH2
pH of solutions and strong acids and bases
14.5 What is the pH of the following solutions?
a) [H+] = 1.5 × 10−3 M
b) [H+] = 8.7 × 10−12 M
c) [OH−] = 2.7 × 10−9 M
d) [OH−] = 9.1 × 10−3 M
14.6 Fill in the blanks on the following chart
[H+] [OH−] pH pOH

9.1 × 10−3 M
10.25
4.57× 10−13 M
8.34
750
14.7 What is the pH of each solution?
a) 2.2 × 10−2 M HNO3
b) 1.05 M HI
c) 0.011 mol of HClO4 in 1500 mL of water
d) 20.8 grams of HBr in 5.00 L of water
e) 15 grams of sodium hydroxide in 750

ml of water TUTORIAL 14.8
f) 0.52 M KOH
g) 1.2 M Sr(OH)2
14.8 What is the pH of a solution prepared

by diluting 25.00 mL of 0.879 M HCl to a
volume of 555 mL?
https://youtu.be/NwHFL5ZhXnc
pH of Weak Acids
14.9 Given the following three acids
acid A: Ka = 3.0 × 10−2
acid B: Ka = 1.2 × 10−7
acid C: Ka = 1.4 × 10−4

TUTORIAL 14.10
a) Arrange these acids in order of
increasing strength.
b) Given solutions with the same initial

concentration of each acid, which
would have the highest percent
ionization?
https://youtu.be/XN76FkNHiZM
14.10 Calculate the pH of a 0.10 M solution
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of HCN.
14.11 Calculate the percent ionization and pH of a 1.5 M solution of the

ammonium ion.
14.12 Calculate the percent ionization and pH of a solution of acetic acid if

3.2 g are added to 700 mL of water.
14.13 Which of the following solutions has the lower pH? A 0.10 M solution
of formic acid (HCOOH) or a 3.0 M solution of hypochlorous acid (HOCl)?
14.14 Vinegar is primarily an aqueous solution of acetic acid. A sample of

commercial vinegar contains 5.0 g of acetic acid in 95.0 ml of solution. What
is the concentration (in molarity) of commercial vinegar? If the percent
ionization is only 3.1% for this acetic acid, what is the pH of the solution?
Ka of Weak Acids
TUTORIAL 14.15
14.15 Find the Ka of a 0.10M solution of

HCN if the pH is 5.15.
14.16 The pH of a 1.0 M solution of acetic

acid is 2.38. What is the Ka for acetic acid?
14.17 Salicylic acid (molar mass=138 g/mol) https://youtu.be/yWMr_tvCZtk

is used in the synthesis of acetylsalicylic acid,
or aspirin. 1.0 grams dissolve in 460 mL of water to create a saturated
solution with a pH of 2.40. What is the Ka of salicylic acid?
14.18 A 1.00 M solution of fluoroacetic acid (FCH2COOH) has a 5% percent

ionization in water. What is the equilibrium constant expression and Ka for
the dissociation reaction?
752
Polyprotic acids
TUTORIAL 14.19
14.19 Calculate the concentrations of all
species at equilibrium and the pH for a 0.10
M solution of carbonic acid.
14.20 Calculate the concentrations of all

species at equilibrium and the pH for a 0.50
M solution of sulfurous acid, H2SO3. (note
https://youtu.be/jDHVkB81i50
that the approximation does not work for the
first reaction here!)
14.21 Calculate the concentrations of all species at equilibrium and the pH

for a 1.10 M solution of phosphoric acid.
pH of Weak bases
14.22 What is the pH of a 0.20 M ammonia TUTORIAL 14.22
solution?
14.23 What is the percent ionization and pH

of a 0.15 M solution of the cyanide ion, CN-?
14.24 What is the percent ionization and pH

of a 1.4 M solution of the formate ion, https://youtu.be/Zz1yrOnqSyY
HCOO-?
14.25 Aromatic amines, in which the nitrogen atom is bonded directly to a

phenyl ring (−C6H5) tend to be much weaker bases than simpler amines. For
example, aniline (C6H5NH2) has a Kb of 7.4×10−10 at 25°C. What is the pH of
a 0.050 M solution of aniline?
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14.26 The Ka for a weak acid HA is 1.9×10−6. What is the pH of a 0.34 M
solution made from its conjugate base A-?
14.27 Using the Ka1 and Ka2 for carbonic TUTORIAL 14.27
acid from Table 14.3, calculate the pH and all

species present in a solution of 1.0 M
carbonate (CO32−)? Hint: carbonate is
dibasic.
Kb of Weak bases
https://youtu.be/3w5yo-V5isw
14.28 A 1.0 M aqueous solution of
ammonia has a pH of 11.63 at 25°C.
Calculate the Kb for ammonia.
14.29 The pH of a solution of 0.63 M pyridine is 9.51, what is the Kb of

pyridine? What is the Ka of its conjugate acid?
14.30 The pH of a 0.15 M solution of aniline C6H5NH3+ is 2.70. What is the

Kb of the conjugate base, aniline (C6H5NH2)?
Lewis Structures and Acid Strength
14.31 Identify which is the stronger acid in each case
a) H2SO3 or H2SeO3
b) HNO2 or HNO3
c) H3PO4 or H3AsO4
14.32 Draw Lewis structures and explain the following observations
a) H2SO4 is a stronger acid than H2SeO4
b) HNO3 is a stronger acid than HNO2
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c) CCl3COOH is a stronger acid than CH3COOH
14.33 Draw Lewis structures and explain why formic acid (HCOOH) is a
moderately strong acid, while methanol (CH3OH) is an extremely weak acid.
14.34 Draw Lewis structures and explain why benzoic acid (C6H5COOH) is a
stronger acid than phenol (C6H5OH) (hint: the carbons are in a ring)
Salt Hydrolysis
14.35 Write out any relevant hydrolysis reactions and determine whether
solutions of the following salts are acidic, basic, or neutral.
a) KBr
b) NaClO
c) NH4CN
14.36 Determine whether solutions of the following salts are acidic, basic, or
neutral.
a) NH4NO3
b) NaC7H5COO
c) CH3NH3I
d) LiF TUTORIAL 14.37
e) KClO4
f) Ba(OCl)2
14.37 Is a salt solution of NaHSO3 acidic,

basic, or neutral? Write out the relevant
hydrolysis reactions and equilibrium https://youtu.be/y2ZmTtrPipU
constants to support your answer.
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14.38 Are the following salt solutions acidic, basic, or neutral? Write out the
relevant hydrolysis reactions and calculate equilibrium constants to support
your answer.
a) KHC3H2O4
b) KH3P2O7
c) NaH4IO6
14.39 Calculate the pH of solutions of the following salts.
a) 1.0 M NH4NO3
b) 0.80 M KNO2
c) 0.10 M CH3NH3I
d) 0.90 M NaClO4
14.40 A 0.030 M solution of NH4I has a pH of 5.39. What is the Ka for

ammonium? (Do not use the chart for this)
14.41 A 0.50M solution of KCH3COO has a pH of 9.23. What is the Ka for

acetic acid? (Do not use the chart for this)
Acid-Base Reactions in the Atmosphere
14.42 Write out the reaction of sulfur trioxide with water. Use oxidation
numbers to show this is not a redox reaction.
14.43 The pH of distilled water that is left sitting out on a counter is in the 5
range. Write out the reaction of carbon dioxide with water and explain why
this is the case.
CLICK FOR ANSWERS
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14.10
Chapter 14 Review Test
Review Test
1. Classify each compound as a strong acid, a weak acid, a strong base, or a
weak base in aqueous solution.
a. CH3NH2
b. LiOH
c. HOF
d. Nitric acid
e. Ammonia
2. Identify the acid and base below and write out the conjugates that are
formed to complete the reaction:
HCN (aq) + NH3 (aq) → ?? + ??
3. Calculate the pH of the following solutions.
a. A 0.024 M solution of nitric acid
b. A 3.0×10-3 M solution of calcium hydroxide.
4. A 0.020 M weak acid HA, has a pH of 3.21. What is the Ka of the acid?
5. Calculate the pH and percent ionization of a 1.2 M solution of ethylamine

(CH3CH2NH2), which is used in the synthesis of some dyes and medicines.
The Kb of ethylamine is 6.5×10−4.
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6. Find the pH and concentrations of all compounds in a 0.50 M solution of
the diprotic acid ascorbic acid (HC5H7O6)
7. Draw Lewis structures for CCl3COOH and CF3COOH. Which should be the
stronger acid and why?
8. Determine whether a solution of the following salts will be acidic, basic, or

neutral?
a. CH3NH3Br
b. NaNO3
c. CaF2
9. A 0.10 M solution of KOCl has a pH of 10.20. What is the Ka for

hypochlorous acid? (Do not use the chart for this)
10.A 0.1268 g sample of a monoprotic weak acid was dissolved in 25 mL of

water and titrated with 0.0625 M NaOH. If 17.9 mL of base was required
to reach the equivalence point, calculate the molar mass of the acid to the
correct number of significant figures.
CLICK FOR ANSWERS
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APPENDIX A
Answers to Homework Problems and Chapter Review Tests
The answers are provided for your benefit and to check your work.
Remember that you will not grow as a student if you simply record the answers
on your homework; chemistry is a discipline that must be practiced!
Problem 2
Chapter 1 Answers: a) 5.04 x 104 mg
b) 3 x 10−5 yrs
Homework Problems
Problem 3
1. a) 6.378 x 102 b) 4.79 x 10−2 c) 7.86 or 88 mL or 88 cm3
7.86 x 100 d) 1.2378 x 104 e) 3.2 x 10−4 f)
6.106700 x 10 or 6.106700 x 101 g) Problem 4
2.002080 x 103 h) 1.020 x 10−2 629 g
2. a) 0.37 kg b) 5.92 x 10−4 km c) 2.7 x 10−4
m3 Problem 5
3. a) 14 yds b) 1.1 x 104 cm c) 5.38 x 105 mL a. (12.38*5.5)/10.26 = 6.6
d) 0.427 kg b. (0.010/0.0821)*100 = 12
4. a) 3 b) 3 c) 1 d) 4
5. The 100mL graduated cylinder; 2 significant Problem 6
figures. a. 2.00 g/mL
6. a) 2.5 x 10−3 km b) 2 x 109 ms c) 1.9 x 102 b. see graph
kg d) 1.332 gal
7. a) 12.00−10.8 = 1.2 b) 1.5/12.4 = 0.12 c)
101/1.3 = 78 d) 12.4−3.2 = 9.2
8. a) 1.2 m b) 0.085 m3 c) 43 km/hr
9. 4.404 x 103 cm3
10. 52 g

c) The average density will be the slope of the
Problem 1 line of best fit. This is easily determined
a) 4 using Excel; however, on a test you can
b) 3 calculate the slope by hand. Although we
c) 5 will use the first and second data point for
convenience, you should feel free to use any
dccclxxv
of the points. Remember that this is an 11. a) 9.9 x 1023 molecules, 3.0 x 1024 H atoms
estimate. We were asked to provide the b) 8.6157 x 1019 O atoms
answer to 2 significant figures — note that c) 2.0 x 1021 C atoms
we are not following proper s.f. rules here. 12. a) 36.20% b) 57.14%
5g − 1g g
13. a) C3H4O3 b) C6H8O6
! d= = 1.3 14. a) C6H10S2O b) C6H10S2O
5m L − 2m L mL
15. a) C7H14O2 b) C7H14O2
d) While there are a number of correct c) 4.62 x 1010 molecules
answers, the best option would be to expand 16. a) PbCrO4 b) CrKS2O8
the sample size to reduce systematic error. 17. C16H19O5N3S
18. a) 51.16% b) 6.998 c) MgSO4·7H2O
Chapter 2 Answers:
Homework Problems
Problem 1
Notes: a) Hg(CH3COO)2
b) Ba3(PO4)2
• Formula units are not drawn in the answer c) ZnCl2
key for clarity. d) Co3N4
• Answers may be slightly different depending e) Al(OH)3
on number of significant figures carried in
molar mass calculations Problem 2
a) ammonia
1. a) Cl− b) P3− c) K+ d) Mg2+ e) O2− b) sulfuric acid
2. a) Li3P b)(NH4)2S c) Ag2CO3 d) Na2SO4 c) ammonium carbonate
e) FeF3 f) Al(NO3)3 g) Cu(OH)2 d) glucose
h) Ca3(PO4)2 i) Zn(HCO3)2 e) vanadium(II) oxide
j) NH4CH3COO
3. a) lead(II) iodide b) silver carbonate Problem 3
c) barium nitride d) rhodium(II) hydroxide C
e) tin(IV) sulfate f) tin(II) sulfate
4. a) iron(III) oxide b) sodium carbonate Problem 4
c) MgSO4 d) Cu3N C
5. 2.56 x 1022 atoms
6. 5.4 kg Problem 5
7. a) 2.59 x 1023 atoms b) 2.99 x 103 mg 105 kg
8. 0.087 mg
9. a) 0.0750 kg b) 7.307 x 1022 molecules Problem 6
c) 1.295 x 10−6 L d) 610. g 2.6 x 1026 H atoms
10. 10.9 L
Problem 7
a) Na2SO3
dccclxxvi
b) Na2SO3 6. a) PbS + 4 H2O2 → PbSO4 + 4 H2O
b) 1.9 g
7. 1.3 x 104 g of solution
Problem 8 8. a) 95.1% b) depends on the identity of the
56.1% impurities and if they are toxic!
9. a) LR = HBr b) TY = 132.7 g MnBr2
Problem 9 c) xs = MnO2, 96.3 g remaining
a) mhydrate = 13.88 g, msalt = 8.93g, mwater = 10.a) H2 + Cl2 → 2HCl, LR = Cl2
4.95g b) 205.7 g HCl c) xs = H2, 4.3 g remaining
b) 35.7% 11.C3H8 + 5 O2 → 3 CO2 + 4 H2O, 62.0 g CO2
c) x = 2.03 12. 2 HCl + Zn → ZnCl2 + H2, 2.46 g H2
d) LiCH3COO·2H2O 13. a)LR = Ba(OH)2 b) 4.21 g H2O
c) xs = HCl, 6.0 g remaining
14. 70.9%
15. a) 4.22 mg b) 81%
16. a) C6H5Cl b) 9.51 g c) 50.3%
Chapter 3 Answers: 17. a) 10.8 g b) C6H5COOH c) 73%
18. 81%
19. a) chlorobenzene b) ammonia c) 8.74 g d)
Homework Problems
55% e) 24.4 g chlorobenzene at 92% purity
1. a) 2 KI +Br2 → 2 KBr + I2 20. a) CO + 2 H2 ⟶ CH3OH b) .90 g H2
b) MnO2 + 4 HCl → MnCl2 + Cl2 + 2 H2O 21. 11.4 g
c) Na2O + H2O → 2 NaOH
d) Cu + 2 AgNO3 → Cu(NO3)2 + 2 Ag
e) SO2 + H2O → H2SO3 Chapter 3 Review Test
f) 6 S2Cl2 + 16 NH3 → S4N4 + S8 + 12
NH4Cl Problem 1:
g) 2 N2O5 → 4 NO2 + O2 a) MgCO3 + 2 HBr → MgBr2 + H2O + CO2
h) 2 NaNO3 → 2 NaNO2 + O2 b) LR = MgCO3
i) 2 Al + 3 NH4NO3 → 3 N2 + 6 c) 1.11 x 1023 molecules CO2
H2O+ Al2O3 d) xs = HBr, 13.6 g remaining
j) 4 C3H5N3O9 → 12 CO2 + 6 N2 + 10
H2O+ O2 Problem 2
k) CO2 + Na2O → Na2CO3 2 NH3 + 2 O2 → N2O + 3 H2O
l) 2 C4H10 + 13 O2 → 8 CO2 + 10 H2O
m)2 NaNO3+ H2SO4 → Na2SO4 + 2 HNO3 Problem 3
2. a) 2 C8H18 + 25 O2 → 16 CO2 + 18 H2O a) CO + 2 H2 ⟶ CH3OH
b) 7.02 g b) 58.3%
3. a) 2 NH3 + H2SO4 → (NH4)2SO4
b) 1.14 x 1025 molecules Problem 4
4. a) C6H12O6 → 2 CO2 + 2 C2H5OH a) Mn2+: Mn + FeSO4 → MnSO4 + Fe
b) 0.327 L Mn4+: Mn + 2 FeSO4 → Mn(SO4)2 + 2 Fe
5. a) 4 HCl + O2 → 2 Cl2 + 2 H2O b) 6.4 kg b) Mn + 2 FeSO4 → Mn(SO4)2 + 2 Fe
dccclxxvii
c) No change. Stoichiometry predicts that you 24. a) CH3 b) C2H6
would yield double the mass of Fe. Hence, 25. a) C4H10O b) M=74.0 g/mol, C4H10O
the ratio is still the same! 26. P(CH4)=395 mmHg
27. a) P(CH4)=1.54 atm, P(CO2)=0.851 atm,
Problem 5 PT=2.39 atm b) P(CO)=0.0918 atm,
a) 10.8 g (note that benzoic acid is LR!) P(NO2)=0.0264 atm, PT=0.1182 atm c)
b) 7.9 g P(CH3Cl)=34.5 atm, P(SO2)=14 atm,
PT=49 atm
28.P(SO2)=0.0935 atm, P(O2)=0.187 atm,
PT=0.281 atm
Chapter 4 Answers: 29.P(Ar) = 382 mmHg, P(Ne) = 221, PT=603
mmHg
30. a) 2KClO3(s) → 2KCl(s) + 3O2(g) b) 2.20 g
Homework Problems
KClO3 c) 0.863 g O2 d) 604 mL O2
1. Harder on mars because not as much 31. a) 2.28g CO b) 1.82 L CO c) 3.02g Fe
atmospheric pressure to push water up the 32. 34.5 g NaN3
straw. Could only raise it a few inches. 33. 894L
2. 1.40atm=1.06x103 mmHg=1.06x103 torr; 34. a) 2C2H6 + 7O2 → 4CO2 + 6H2O b)
723mmHg=723torr=.951atm; P(C2H6)=.402atm c) P(CO2)=1.29atm
324 torr=324mmHg=.426atm 35. a) 2SO2 + O2 → 2SO3; 108 L b) 2C2H6 +
3. 724 mmHg 7O2 → 4CO2 + 6H2O; 605 L c) H2 + Cl2 →
4. a) 0.557atm, b) 0.741atm, c) 0.329atm 2HCl; 25 L
5. a) 1.06atm, b) .867atm c) 1.17atm 36. a) 3.82L b) 7.64L c) CO2=4.95L,
6. a) 1.5 L b) 4.87 mL c) 650 mL NH3=9.89L
7. 0.52 L 37. 0.170 g NaClO3
8. a) 7270°C b) 55.9 K 38. a) Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
9. 6.55 atm b) P(H2)=.954 atm c) 1.56x10−3mol d)
10. 5.1 atm .102g
11. 23.4 atm 39. 5.9 g oxalic acid, 7.8 L
12. 4.8 atm 40. 278 L
13. a) 7.05×10−2 mol b) 3.78×10−2 mol c) 41. 33% Mg, 67% Fe
0.2138 mol 42. a) increase b) increase c) increase d)
14. a) 0.21 g HI b) 840 g H2S c) 0.988 g CH4 increase e) increase
15. a) 0.449 L Kr b) 1510 L C3H8 c)
3.13×10−4 L (CH3)2O
16. 281 mmHg
Problem 1
17. 1.23 x 103 mol H2
0.26 atm
18. 2.70 x 104 L
19. 4.07×103 bulbs
Problem 2
20. a) 1.0 g/L b) 1.1 g/L c) 4.6 g/L
9.1 L
21. 32.0 g/mol
22. Br2 (molar mass of 159.8g/mol)
Problem 3
23. 30.1g/mol so NO(g)
0.79 atm
dccclxxviii
2. a)Fe, 26p, 29n b)As, 33p, 41n c)Mg, 12p,
Problem 4 12n d)I, 53p, 74n
20 g 3. a) 35 − 63
17Cl b) 29Cu
2+
c) 16
8 O
2−
d) 27
13 Al
3+
4. a)43p,54n,43e b)28p,35n,26e c)49p,64n,49e

Problem 5 d)26p,29n,23e e)82p,125n,82e
P(SO2)=1.1 atm, P(CH4)=.83 atm, PTotal=1.9 5. 63.55amu
atm 6. 28.09amu
7. 22.09amu
Problem 6 8. a)N b)Sc c)Sb d)B e)Ni f)Te g)Ba
a. C3H6O 9. a) 1s22s22p63s23p64s23d104p5
b. M=116 g/mol, C6H12O2 b) 1s22s22p63s23p64s23d104p65s24d105p2
c) 1s22s22p63s23p64s23d10
Problem 7 d) 1s22s22p63s23p64s23d7
a. 5.8 g oxalic acid e) 1s22s22p63s23p64s23d104p65s24d105p66s2
b. 1.43 L 4f145d106p3
10. a)[Xe]4f145d106s26p2 b)[Kr]4d105s25p3
Problem 8 c)[Ne]3s23p1 d)[He]2s22p5
a+b) e)[Kr]4d105s25p1 f)[Ar]3d104s24p2
11. a)[Ar] b)[Ne]3s23p6 c)[Kr]
d)[Kr] 4d105s25p6 e)[Ar]3d10 f)[Ar]3d10
12.
c) the average speed is higher as more of the

molecules are going faster than before with
the increase in temperature
d) the pressure will increase because of the 13.
increased speed of the molecules resulting in
more impacts on the walls of the container
per unit time. 4, para
1, para
Chapter 5 Answers:
0, diamagnetic
Homework Problems
2, para
1. a) 19 4 159 197 93
9 F b) 2 He c) 65 T b d) 79 Au e) 41 Nb 2, para
dccclxxix
a)
2, para
b)
5, para
2, para
Chapter 6 Answers:

Homework Problems
Problem 1
1. a) Ga b)S c)Br d)Si e)Na
a) 31 127 55
15 P b) 53 I c) 25 Mn
2. F<N<B<Ba<Cs
3. Pt>Au>Ag>Si>C
Problem 2
4. a) C4−<N3−<F1−<Mg2+
a) Eu, 63p, 89n b)Ar 18p, 22n
b)Mg2+<F1−<N3−<C4−
5. a)P3− b) Cl1− c)Rb+ d) F− e) Br1−
Problem 3
6. Ti4+<Sr2+<Rb+<Kr<Br1−<Se2−
a)8p,10n,10e b)19p,21n,18e c)18p,22n,18e
7. O2−>F1−>Ne>Na+>Mg2+>Al3+
8. a)Al b)C c)N d)Kr e)Na+ f)Mg2+
Problem 4
9. Smaller; all successive I get larger and I4
32.06 amu
would remove from an inner core shell. I of
Ca should be less because fewer protons and
Problem 5
held less tightly
a) 1s22s22p63s23p64s1
10. a)Pb<Bi<Te b)Rb<K<Na c)Ge<P<N
b) 1s22s22p63s23p64s23d2
11.Al [Ne]3s23p1 (so 4th electron comes from
c) 1s22s22p63s23p64s23d104p4
an inner core)
12. K; breaking into an inner shell
Problem 6
13. a)Cl b)Ca c)Al d)Li
a) [Kr]5s24d1 or [Kr]4d15s2
14. a)Ar<O<F b)Cs<Rb<Na
b) [Kr]4d105s25p5
15. a)False; decrease b)true; held less tight so
c) [Xe]4f145d106s26p1
easier to remove c)true; easier to add =
harder to remove d)true; held less tight so
Problem 7
easier to remove e)false; increases because
a) [Ne]
held tighter
b) [Kr]4d105s1
Problem 8
a) 0
b) 2
Problem 1
c) 3
a)Na
b) Br−
Problem 9
dccclxxx
c) Si
d) Ge
Chapter 7 Answers:
Problem 2
Sr2+<Rb+<Kr<Br1−<Se2−
Homework Problems
Problem 3 1. Fe < Se < S < O < F
a) Ar 2. a) nonpolar or polar covalent (right on
b) N threshold) b) polar covalent c) ionic d)
c) Ar nonpolar covalent e) nonpolar covalent f)
d) F polar covalent g) polar covalent h) nonpolar
e) Ra covalent i) ionic
f) Ne
3. E
Problem 4
Te<Se<Br<Cl
Problem 5
Ar<Ne<Br<Cl
Problem 6
a) increasing with each successive ionization b/
c same protons but less shielding each time.
Therefore, held stronger and harder to
remove.
b) Si
c) smaller
Problem 7
e
Problem 8
b
Problem 9
e
Problem 10
a
Problem 11
c
dccclxxxi
4.
8. a)
b) 1.5 c) CO2 (double bond or bond order of 2)
9. a) phosphorus pentachloride b) cobalt(II)
chloride c) oxygen difluoride d) dinitrogen
pentoxide e) ammonium sulfate f) glucose
g) sulfur hexafluoride h) bromine triiodide

Problem 1
A
Problem 2
A
5. Problem 3
C
Problem 4
B
6.
Problem 5
7.a)
b)
c) SO3: 1.33, SO2: 1.5 d) SO3

Problem 6
dccclxxxii
Problem 7
SF4 and OF4 have the same number of valence electrons and require a lone pair to be placed on the
center atom. Sulfur can accommodate an expanded octet;
oxygen cannot.
Problem 8
a) sulfur trioxide b) diphosphorus pentoxide c) nickel(II) sulfide d) acetic acid e) ammonia f)
nitrogen dioxide
Chapter 8 Answers:
Homework Problems
1.
2.
dccclxxxiii
3.
4.
dccclxxxiv
Problem 1
C
Problem 2
C
Problem 3
dccclxxxv
19. 229mL
20. 4mL stock and 96mL of H2O
Chapter 9 Answers: 21. 5.2x104 g
22. 18.1g
23. H2SO4 limits b)3.43gCO2 c)0.33g
Homework Problems
24. a)HBr limits b)2.72gH2O c)12.7g
1. b, f, g are insoluble 25. a)Pb(NO3)2(aq)+ 2HI(aq)→ PbI2(s)
2. a, c, f are insoluble +2HNO3(aq)
3. a) 2Ag+(aq)+CO32−(aq)→ Ag2CO3(s) b) 0.0470M
26. [NO3-] = 0.10 M; [Na+] = 0.33 M; [Ba2+]
b) Ag+(aq)+Cl−(aq)→ AgCl(s)
= 0 M; [SO42-] = 0.11 M
c) 3Ca2+(aq)+2PO43−(aq)→ Ca3(PO4)2(s)
27. 66.7 mL
d) no reaction
28. a)34mL b)106mL
e) Pb2+(aq)+SO42−(aq)→ PbSO4(s)
29. a) 2HNO3(aq)+Ba(OH)2(aq) → 2H2O(l)
f) Pb2+(aq)+Cr2O72−(aq)→ PbCr2O7(s)
+Ba(NO3)2(aq)
g) no reaction
b) 0.113M
h) Ca2+(aq)+CO32−(aq)→ CaCO3(s)
i) Ba2+(aq)+SO42−(aq)→ BaSO4(s)
4. a) HCl(aq)+KOH(aq) → H2O(l)+KCl(aq)
b) HI(aq)+LiOH(aq) → H2O(l)+LiI(aq) Problem 1
c) H2SO4(aq)+2NaOH(aq) → 2H2O(l) a) soluble
+Na2SO4(aq) b) insoluble
d) 2HBr(aq)+Ba(OH)2(aq) → 2H2O(l) c) soluble
+BaBr2(aq) d) insoluble
5. a)HCl(aq)+NaOH(aq) → H2O(l)+NaCl(aq)
b) H2SO4(aq)+Sr(OH)2(aq) → 2H2O(l) Problem 2
+SrSO4(aq) Fe3+(aq)+3OH−(aq)→ Fe(OH)3(s)
c) CH3COOH(aq)+NaOH(aq) → H2O(l)
+NaCH3COO(aq) Problem 3
6. 1.50M Mg2+(aq)+CO32−(aq)→ MgCO3(s)
7. a) 0.17M b) 0.30M
8. a) 0.048M b) 0.25M Problem 4
9. a) 161g b) 29.7g c) 73.9g 2HNO3(aq)+Ba(OH)2(aq) → 2H2O(l)
10. a) 0.334M b) 0.134M +Ba(NO3)2(aq)
11. 24.8g
12. a) 1.7M Na+ and 0.85M CO32− Problem 5
b) 2.30M K+ and 1.15M SO42− 22.6 g
c) 1.59M NH4+ and 0.53M PO43−
13. a) 1,000 mL b) 520 mL Problem 6
14. 14.7mL or .0147L 0.121 M
15. 60ml HCl and 140ml H2O
16. 0.278M Problem 7
17. 3.00M 351 mL
18. 1.46M
dccclxxxvi
regardless of how the reactants are
Problem 8 converted to products.
1.21 M Pb2+ and 2.42 M NO3− 10. −198 kJ/mol
11. −868 kJ/mol
Problem 9 12. −184 kJ/mol
5.90g 13. −851.1 kJ/mol
14. −83 (rounded from −82.7 due to sf) kJ/
Problem 10 mol
0.181M 15. The “naught” indicates that the enthalpy
change is calculated under standard
Problem 11 conditions
a) HCl(aq)+NaOH(aq) → H2O(l)+NaCl(aq) 16. a) 3 Cgraphite (s) + 4 H2 (g) + 1/2 O2 (g) ⟶
b)0.0965M C3H7OH (l) b) Al (s) + 3/2 Br2 (l) ⟶ AlBr3
(s) c) 1/2 I2 (s) + 5/2 F2 (g) ⟶ IF5 (g)
17. a) −902.0 kJ/mol b) −802.0 kJ/mol
Chapter 10 Answers:
18. a) −114.9 kJ/mol b) −2802.5 kJ/mol c)
combustion of glucose −− releases more
Homework Problems energy! d) build up of lactic acid (although
this is probably not the cause of Delayed
1. −14.4 kJ Onset Muscle Soreness −− DOMS).
2. a) exothermic b) −82.2 kJ 19. −3/2 ∆Ho1 + ∆Ho2 + 1/2 ∆Ho3
3. a) −24.5 kJ b) 60.6 g 20. a) −1203.2 kJ/mol b) −483.9 kJ/mol c)
4. a) ethanol b) combustion c) C2H5OH + 3 O2 −77.6 kJ/mol
⟶ 2 CO2 + 3 H2O d) 60.0 g 21. a) (NH4)2SO4 + Ca(OH)2 ⟶ CaSO4 + 2
5. a) endothermic b) 0.00438 mol c) 0.113 L NH3 + 2 H2O; 68.2 kJ/mol b) Pb + PbO2 +
6. a) exothermic b) exothermic c) endothermic 2 H2SO4 ⟶ 2 PbSO4 + 2 H2O; −315.0 kJ/
d) exothermic e) endothermic mol
7. exothermic 22. Cu: 58 J; Al: 1.3 x 102 J; the copper will cool
8. A state function is a thermodynamic down faster since it has a lower specific
property that depends only on the current heat. In fact, SAl ≈ 2 x SCu , indicating that
state of the system. It does not depend on temperature of Cu will go down twice as
the path taken to reach the present state. much as that of Al per 1 J of heat loss.
Hess’s Law exploits this fact to calculate 23. The iron since it possesses a larger specific
enthalpy changes of reactions using other heat (see answer to 22 as well).
known heats of reactions. 24. 715 kJ
9. We can calculate the heat of reaction for any 25. −2.6 x 102 J
process as long as we have a series of other 26. 0.24 J/goC
reactions (with known enthalpy changes) 27. 0.23 J/goC
that add up to the desired transformation. It 28. 23.9 oC
does not matter that the reaction may not 29. 32.6 oC
occur as written −− state functions are 30. NH4NO3 (s) ⟶ NH4+ (aq) + NO3− (aq);
independent of the path taken! In other 26.6 kJ/mol
words, the enthalpy change will be the same
dccclxxxvii
31. NaOH (s) ⟶ Na+ (aq) + OH− (aq); −44.4
kJ/mol Problem 7
32. LiCl (s) ⟶ Li+ (aq) + Cl− (aq); −38 kJ/ −0.9 kJ/mol
mol
33.∆H=−57.2 kJ/mol Problem 8
34.∆H=−56.0 kJ/mol −28 kJ/mol
35.KOH (aq) + HCl (aq) ⟶ H2O (l) + KCl
(aq); −57 kJ/mol Problem 9
36. a) 3 KOH + H3PO4 ⟶ 3 H2O + K3PO4 b) a) Na3PO4
b) −94 kJ/mol
KOH c) exothermic, T increases d) −24 kJ/
c) 3 Ba2+ (aq) + 2 PO43− (aq) ⟶ Ba3(PO4)2
mol
37. 29.3˚C (s)
38. 29.0˚C
39. 28.7˚C Problem 10
40. 17.8g a) No − 2 mol of product is formed
41. 11.1g b) −78 kJ/mol
42. a) −210 kJ/mol b) −345 kJ/mol c) −4446
kJ/mol d) 114 kJ/mol Problem 11
43. −1255 kJ/mol a) Ag +(aq) + Cl −(aq) → AgCl(s)
44. −2112 kJ/mol b) 32.2˚C
Chapter 10 Review Test Chapter 11 Answers:

Problem 1
41 g
Homework Problems
Problem 2 1. a) spon b) spon c) nonspon d) nonspon
B 2. a) N2 at 350 K b) CH3CH2OH c) Na (l) d)
O2 in 6L
Problem 3 3. a) −9.1 J/mol⋅K b) 114.5 J/mol⋅K c) 87.6 J/
−1224.4 kJ/mol mol⋅K
Problem 4 4. > 0
1/2 N2 (g) + 2 H2 (g) + 1/2 Br2 (l) ⟶ NH4Br 5. < 0
(s) 6. a) > 0 b) < 0 c) ≈ 0 d) < 0 e) ≈ 0 f) > 0
7. a) −72.6 kJ/mol b) 33.8 kJ/mol
Problem 5 8. a) −241.9 kJ/mol; spon b) 8.0 kJ/mol;
50.9 oC nonspon c) 141.9 kJ/mol; nonspon
9. Use the ethylenediamine (en). Enthalpic
Problem 6 terms for both methylamine and en are
a) 0.54 J/goC nearly identical; however, the en reaction
b) Use a calorimeter that better approximates has a much more favorable entropic term.
an isolated system. A thermos would be an We want the reaction to occur to remove the
easy and cheap suggestion. Cd2+ and the most negative ∆G possible.
dccclxxxviii
10. ∆So > 0 −− a fact that is supported by the 1. System 2 − both 1+3 have reached
equation (more moles of gas on product equilibrium by t3 while 2 is still changing
side)
[CO2] (PCO2)
11.a) T > 1040 oC (1.0 ⋅ 103 according to s.f.) 2. a) Kc = 1
; Kp = 1
[CO][O2] (PCO)(PO2)
2 2
b) T < 697 oC (7.0 ⋅ 102 according to s.f.)
(PCO) (PO2)
c) T > 688 oC; only (b) is spon at 25 oC 2
[CO] [O2]
2
12. a) nonspon at all T b) T > 7175 oC (7.2 ⋅ b) Kc = ; Kp =
(PCO2)
[CO2]
2 2
103 according to s.f.) c) T < 191 oC; only (c)
is spon at 25 oC 1
(PN2)(PO2)
1 2
[N2][O2]
2
13. −19.1 kJ/mol; rxn is spon at all T
c) Kc = ; Kp =
(PN2O)
14. B [N2O]
(PCO2) (PH2O)
16 18
[CO2] [H2O]
16 18
Chapter 11 Review Test d) Kc = ; Kp =
(PC8 H18) (PO2)
[C8 H18] [O2]
2 25 2 25
Problem 1
(PHI)
2
−361.1 J/mol⋅K [HI ]2
e) Kc = ; Kp =
(PH2)(PI2)
[ 2][ 2]
H I
Problem 2 1 1
Spon at T < 764 oC. So spon at 25 but not 800 3. a) Kc = ; Kp =
o
C.
[O2] (PO2)
[CH4] (PCH4)
b) Kc = ; Kp =
Problem 3
(PH2)
[H2]
2 2
T > 646 oC.

1 1
c) Kc = ; Kp =
(PO2)
Problem 4 [O2]
[Ag ][Cl ]
+ −
a) spon at high T b) nonspon at all T
d) Kc = ; Kp = not applicable
1
( SO2)
2
[SO2]
Problem 5 2 P
∆S < 0 so ∆H must also be <0. In addition, e) Kc = ; Kp =
( O2)
[ 2]
3 3
O P
the temperature must be low.
(PNH3) (PCO2)
2
[NH3] [CO2]
2
Problem 6 f) Kc = ; Kp =
1 1
a) −106.9 kJ/mol b) −2471.6 kJ/mol
4. b − has K>>1
5. 0.892 is approximately equal products and
reactants; 3.25×108 favors products,
Problem 7
5.26×10−11 favors reactants
C
6. Kc = 2.12×10−13
7. Kc = 12
8. a)Kp = 3.0×10−5 b)Kp = 2.9×10−1
c)Kp = 1.3 d) Kp = 12.3
Chapter 12 Answers:
9. Kc = 4.2×102
10.Kc=97.8
Homework Problems 11.Kc=1.09×10−4
dccclxxxix
12.Kp=63.1 37. a) K increases b) K decreases
13.Kc=4.85×10−4 38. endothermic; increasing heat causes
14.Kp=0.135 increase in K
15.a)PH2=49.5atm, PCO=43.2atm, 39. a)1.21×1066; equilibrium lies far to the
PCH3OH=594atm b) Kp=5.61×10−3 right. b)5.29×10−7; equilibrium lies to the
16.Qc=2.9×104; proceed towards products left. c) 8.25 × 1015; equilibrium lies far to
17.Qc=1.40×105; proceed towards reactants the right.
18.a)PSO3=.109atm, PSO2=0.0438atm, 40. +129.5 kJ/mol
PO2=5.47×10−4atm b) Qp=1.13×104
c)proceed towards reactants Chapter 12 Review Test
19. a)PN2=0.0182atm, PH2=0.0126atm,
PNH3=8.98×10−4atm b) Qp=22.1 c)proceed Problem 1
(PNO2)
2
towards reactants
[NO2]
2
20.[SO2]=2.7×10−3 M; [O2]=2.9×10−3 M; a) Kc = ; Kp =
(PN2O4)
[N2O4]
[SO3]=4.1×10−2 M
[Ca ][OCl ] [CO2]
2+ − 2
21.[H2] = 0.422M; [CO2]=0.484M;
b) Kc = ; Kp not applicable
[H2O]=0.148M; [CO]=0.148M
[HOCl]
2
22.[HI]=0.0882 M; [H2]=0.156 M;
[I2]=9.2×10−4 M Problem 2
23.PSO3=0.103atm, PSO2=0.0498atm, Kc=1.5×10−7
PO2=3.56×10−3atm
24.[C2H6] = 0.300M; [C2H4]=1.77×10−5 M; Problem 3
[H2]=1.77×10−5 M a) favors products
25.Kp = 1.86 × 10−3 b) 3.7×10−9
26.[CO]=0.0463M; [H2]=0.0159M;
[CH4]=8.80×10−4M; [H2O]=2.00×10−5M Problem 4
27. 4.8 × 10−31 atm Qc=4.53; proceed towards products
28.PNO2 = 3.2 at m; PN2O4 = 58.4 at m
29.Kc=53.6 Problem 5
30. a)[CO2] = 2.5 × 10−3 M; b)0.62g c)1.9g Kp = 2.0 × 10−31 at 25°C.
31. a)0.121atm b)0.363atm c)Kp=7.09×10−3
d)4.41g Problem 6
32. a) PCO = 1.77at m; PCO2 = 0.113at m b)0.392g [H2]=3.51×10−3M; [Cl2]=1.70×10−2M;
33. a)[H2O]=.311M; [H2]=4.65×10−3 M [HCl]=1.54 M
b).726g Co remain
34.a) [H2] increases; b) [H2] decreases; c) no Problem 7
effect; none of the stresses alter K PN2 = 0.0186 at m; PH2 = 0.127 at m;
35.a) the amount of Cu increases b) [CO] PNH3 = 3.40 × 10−5 at m
increases. c) no effect d) no effect; none of
the stresses alter K Problem 8
36.a)reactants b)reactants c)no change d)no a) amount of CaO(s) decreases
change e)products f) no change; only (e), K b) amount of CaCO3(s) decreases
increases c) no effect on Ca(s)
dcccxc
d) amount of CaCO3(s) decreases
e) no effect on [CO2]
f) [CO2] increases
Problem 9
Kc = 2.66 × 10−5
Problem 10
Kp = 4.5 × 105
Chapter 13 Answers:
Homework Problems
1. a) S, −2; N, −3; H, +1 b) P, +5; O, −2 c) F, −1; Al, +3 d) S, −2; Cu, +2 e) H, +1; O, −2; C, +4
f) H, +1; N, −3 g) H, +1; O, −2; S, +6 h) Br, 0
2. a) Cl, +4; O, −2 b) H, +1; O, −1 c) Na, +1; H, +1; C, +4; O, −2 d) Mn, +4; O, −2 e) P, +5; Cl,
−1 f) N, +5; O, −2
3. a)+4 b)+2 c)+6
4. a) Na = oxidized and reducing agent; Cl2 = reduced and oxidizing agent b) Mg = oxidized and
reducing agent; SiCl4 = reduced and oxidizing agent c) H2O2 is both oxidizing and reducing
agent. One molecule is oxidized while the other is reduced!
5. a) H2 = oxidized and reducing agent; I2 = reduced and oxidizing agent b) Na = oxidized and
reducing agent; H2O = reduced and oxidizing agent c) NaOH (or OH−) = oxidized and reducing
agent; F2 = reduced and oxidizing agent
6. No. All oxidation states stay the same. This is an acid−base reaction!
7. b) HAsO4 c) H3AsO4 (aq)+4 Zn (s)+8 H+ (aq) → AsH3 (g)+4 Zn2+ (aq)+4 H2O (l)
8. b) H2C2O4 c) 2 MnO4−(aq)+5 H2C2O4(aq)+6 H+ (aq) → 2 Mn2+ (aq)+10 CO2 (g)+8 H2O (l)
9. a) BrO3− (aq)+2 MnO2 (s)+H2O (l) → Br−(aq)+2 MnO4− (aq)+2 H+(aq) b)14 H+(aq) +Cr2O72−
(aq)+3 C2O42− (aq) → 2 Cr3+ (aq) +7 H2O (l)+6 CO2 (g) c) 4 H+ (aq)+3 Fe2+ (aq)+NO3− (aq)
→ NO (g)+3 Fe3+ (aq)+2 H2O (l)
10.C (Al)
11. C (Sn2+)
12. A (Cl2)
13. D (Fe2+)
14. a) Pb2+ b) Ag+ c) I2
15. a) Fe2+ b) H2 c) I−
16. We know that ΔG°=−nFE°. It follows that a positive voltage will yield a negative (and
spontaneous) value for ΔG°.
17. Au has a very negative voltage of oxidation (−1.50 V): Au → Au3++3e−. It will therefore be
unreactive and resistant to corrosion.
18. No. Potentials are intensive (not extensive) properties and does not depend on the amount of
reactant.
dcccxci
19. a) n = 2, Eocell = 0.48 V, ΔG° = −93 kJ/mol b) n = 6, Eocell = 1.26 V, ΔG° = −731 kJ/mol c) n =
2, Eocell = −1.59 V, ΔG° = 3.1 x 102 kJ/mol
20. a, b, c = spon; d, e, f = nonspon
21. b) ΔG° = −77 kJ/mol c) ΔH° = −241.8 kJ/mol d) 32%
22. a) NO REACTION b) NO3−+4 H++3 Ag → NO+2 H2O+3 Ag+; Eocell = 0.16 V, ΔG° = −46 kJ/
mol c) NO REACTION d) 2 Br−+Cl2 → 2 Cl−+Br2; Eocell = 0.27 V, ΔG° = −52 kJ/mol e) 2 Ag++
Sn2+ → 2 Ag + Sn4+; Eocell = 0.65 V, ΔG° = −1.3 x 102 kJ/mol f) Mg+ Cu2+→ Cu+Mg2+; Eocell =
2.71 V, ΔG° = −523 kJ/mol
23. a) Fe+2 H+→ H2 + Fe2+ b) 5 Fe2++8 H++MnO4−→ 5 Fe3++Mn2++ 4 H2O c) 0.1426 mol Fe2+
d) 7.965 g Fe e) 15.83% Fe
24. 3 Ni2+(aq)+2 Ga(s) → 2 Ga3+(aq)+3 Ni(s); Eocell = 0.29 V, ΔG° = −1.70 x 102 kJ/mol
25. 2 Au3+(aq)+3 Cd(s) → 3 Cd2+(aq)+2 Au(s); Eocell = 1.90 V, ΔG° = −1.10 x 103 kJ/mol
dcccxcii
26. 3 Ag+(aq)+ Al(s) → Al3+(aq)+3 Ag(s); Eocell = 2.66 V, ΔG° = −7.10 x 102 kJ/mol
27. The salt bridge would become ineffective and lead to an unequal distribution of charge within
the galvanic cell. It would cease to operate after a short period of time.
28. a) 0 V (reaction stops) b) 0.46 V (no change). Voltage does not depend on amounts!
29. a) anode: 2 I−(l) → I2 (l or g)+2 e− cathode: K+(l)+e− → K(l) b) 2K+(l)+2 I−(l) →2 K(l)+I2(l or
g); >3.47 V
dcccxciii
30. a) anode: 2 Cl−(l) → Cl2(g)+2 e− cathode: Mg2+(l)+2 e− → Mg(l) b) Mg2+(l)+2 Cl−(l) →Mg(l)
+Cl2(g); >3.73 V
31. a) anode: 2 F−(l) → F2(g)+2 e− cathode: Li+(l)+e− → Li(l) b) 2 Li+(l)+2 F−(l) →2 Li(l)+F2(g);
>5.91 V
32. a) anode: 2 Cl−(l) → Cl2(g)+2 e− cathode: Fe3+(l)+e− → Fe2+(l) b) 2 Fe3+(l)+2 Cl−(l) →2 Fe2+
(l)+Cl2(g); >0.59 V
dcccxciv
33. 67 g Li
34. 25.6 g Cu
35. 80.1 days
36. 0.679 L

Problem 1
a) H2O + CO → CO2 + H2; reduced/oxidizing agent = H2O; oxidized/reducing agent = CO
b) Al2O3 + 3 C + 3 Cl2 → 2 AlCl3 + 3 CO; reduced/oxidizing agent = Cl2; oxidized/reducing agent
=C
c) 2 HgO → 2 Hg + O2; reduced/oxidizing agent = HgO; oxidized/reducing agent = HgO
Problem 2
a) Cr2O72−: Cr = +6, O = −2; H3PO2: H = +1, P = +1, O = −2; Cr3+ : Cr = +3; H3PO4: H = +1,
P = +5, O = −2
b) reduced: Cr2O72−
c) OA: Cr2O72−
d) 2 Cr2O72− + 16 H+ + 3 H3PO2 → 3 H3PO4 + 4 Cr3+ + 8 H2O
Problem 3
a) anode: 2 I−(l) → I2(g)+2 e−
b) cathode: Ba2+(l)+2 e− → Ba (l)
c) >3.45 V
dcccxcv
Problem 4
a) 3 Ag (s) + NO3− (aq) + 4 H+ (aq) → NO (aq) + 2 H2O (l) + 3 Ag+ (aq); Eocell = 0.16 V, ΔG° =
−46 kJ/mol
b) NO REACTION
Problem 5
a)
b)
Problem 6
B
Problem 7
B
Problem 8
We are creating a galvanic cell. The ions in the potato function as the salt bridge, thereby
completing the circuit.
dcccxcvi
Problem 9
a) 3 Pb2+ (aq) + 2 Cr (s) → 2 Cr3+ (aq) + 3 Pb (s); Eocell = 0.61 V
b)
c) Cr = corroded, Pb = grows
Problem 10
a) 6.27 amps
dcccxcvii
21. [H3PO4]=1.0M;
[H2PO4−]=[H+]=9.1×10−2; [HPO42−]=
Chapter 14 Answers: 6.2×10−8;[PO43−]=3.0×10−13; pH=1.04
22. 11.28
23. 1.2%; pH=11.24
Homework Problems
24. 6.3×10−4%; pH=8.95
1. a) weak base b) weak acid c) weak acid d) 25. pH=8.78
strong base e) strong acid f) weak acid 26. pH=9.63
g)strong acid h) weak base 27. pH=12.11; [CO32−]=0.99M;
2. a) weak base b) weak base c) weak base [HCO3−]=[OH−]=1.3×10−2M;
d)strong acid e) weak acid [H2CO3]=2.3×10−8;
3. a) CH3COO− b) CN− c) NO3− d) HPO42− 28. Kb= 1.8×10−5
e)CO32− 29. Kb= 1.7×10−9; Ka=5.9×10−6
4. a) NH4+ b)HF c)HSO4− d)HS− 30. Kb= 3.7×10−10
e)CH3CH2NH3+ 31. a)H2SO3 b)HNO3 c)H3PO4
5. a)2.82 b)11.06 c)5.43 d)11.96 32. a)H2SO4 because S is more electronegative
6. 9.1×10−3M; 1.1×10−12M; 2.04; 11.96 than Se.
5.6×10−11M; 1.8×10−4M; 10.25; 3.75
2.19×10−2M; 4.57×10−13M; 1.660; 12.340
2.2×10−6M; 4.6×10−9M; 5.66; 8.34
7. a)1.65 b) −.021 c) 2.13 d) 1.29 e) 13.70
f) 13.72 g) 14.38
8. 1.40 b)HNO3 because more terminal O’s (so more
9. a) acid B< acid C< acid A eneg and more resonance for anion)
b) highest percent ionization is acid A
10. 5.15
11. 1.9×10−3 %; pH=4.54
12. 1.4 %; pH=2.96
13. 0.10M formic acid
14. 0.88M; pH=1.57 c)CCl3COOH is more electronegative
15. 5.0×10−10
16. 1.7×10−5
17. 1.3×10−3
18.FCH2COOH(aq) ⇌ H+(aq) + FCH2COO−(aq)
Ka= 2.6×10−3
19. [H2CO3]=0.10M; 33. Carboxylic acid group in formic acid so
[HCO3−]=[H+]=2.1×10−4M; more resonance and more electronegative
[CO32−]=5.6×10−11M because of extra oxygen.
20.[H2SO3]=0.42M;
[HSO3−]=[H+] =7.9×10−2M;
[SO32−]=1.0×10−7M;
pH=1.10
dcccxcviii
34.Benzoic acid on the left is better because it Chapter 14 Review Test
Problem 1
a)weak base
b)strong base
c)weak acid
d)strong acid
e)weak base
is a carboxylic acid so more terminal O’s
(more electronegativity and resonance) Problem 2
35. a)neutral b) basic; ClO−(aq)+H2O(l)⇌ HCN(aq) + NH3(aq) → NH4+(aq) + CN− (aq)
HCN= acid; NH3=base; NH4+conj. acid;
HClO(aq)+OH−(aq) c) basic; CN−(aq)
CN−=conj base
+H2O(l)⇌ HCN(aq)+OH−(aq) / NH4+
(aq)⇌NH3+H+/ Kb>Ka so basic Problem 3
36. a)acidic b)basic c)acidic d)basic e)neutral a) pH=1.62
f)basic b) pH=11.78 (note Ca(OH)2)
37. HSO3−(aq)⇌ H2SO3(aq)+H+ (aq)
Problem 4
HSO3−(aq)+H2O(l)⇌ H2SO3(aq)+OH− Ka=1.9×10−5
Ka>Kb so acidic
38. a) HC3H2O4−(aq) ⇌ H+(aq) + C3H2O42−; Problem 5
2.3%; pH=12.45
Ka = 2.0x10−6; HC3H2O4−(aq) + H2O(l) ⇌
OH−(aq) + H2C3H2O4; Kb = 6.6x10−12 b) Problem 6
H3P2O7−(aq) ⇌ H+(aq) + H2P2O72−(aq); Ka [HC5H7O6]=0.49 M
= 4.4x10−3; H3P2O7−(aq)+ H2O(l) ⇌ OH− [C5H7O6−]=6.3×10−3 M
[C5H6O62−]=1.6×10−12 M
(aq) + H4P2O7(aq); Kb = 3.0x10−13; acidic
[H+]=6.3×10−3 M
c) H4IO6−(aq) ⇌ H+(aq) + H3IO63−(aq); Ka
pH=2.20
= 5.3x10−4; H4IO6−(aq)+ H2O(l) ⇌ OH−
(aq) + H5IO6(aq); Kb = 3.6x10−13; acidic Problem 7
39. a)4.63 b)8.58 c)5.83 d)7 Both of these have very similar structures with
40. Ka=5.6×10−10 the carboxylic acid group so the difference we
41. Ka= 1.7×10−5 need to consider is the electronegativity of the
42. SO3(g)+H2O(l)⇌ H2SO4(aq); S=+6 in all, F vs Cl. Since F is more electronegative, we
would expect CF3COOH will be more acidic.
O=−2 in all, H=+1 in all.
43. CO2(g)+H2O(l)⇌H2CO3(aq); makes
carbonic acid which dissociates into H+ and
HCO3−
dcccxcix
Problem 8
a) acidic
b) neutral
c) basic
Problem 9
Ka=4.0×10−8
Problem 10
113 g/mol
Chapter 15 Answers:
Homework Problems
1. a, b, e, g
2. a, c
3. CHCl3 since it is asymmetrical and has a dipole while CCl4 has no dipole
4. bp is increasing with increasing molar mass because of higher London dispersion forces.
However HF has hydrogen bonds that make it much stronger.
5. H2 < Ne <N2<O2<Cl2
6. All have only dispersion forces so:
GeCl4(87°C)>SiCl4(57.6°C)>GeH4(−88.5°C) > SiH4(−111.8°C)>CH4(−161°C)
7. ethanol (1 H-bond) < ethylene glycol (2 H-bonds) < glycerin (3 H-bonds)
a. Boiling point of H2S should be lower than that of H2O. While H2S is slightly larger and
therefore a slight bit more polarizable, the hydrogen bonds of H2O are much stronger than the
dipole and slightly increased LDF in H2S.
8. propylamine is a lot longer molecule so while they all have hydrogen bonds, the propylamine has
stronger dispersion forces as well. The sum of these are enough to make it a liquid.
9. a) NH3; similar size but H-bond. b) CBr4; both nonpolar and CBr4 is more polarizable. c)n-
butanol b/c both have H-bonds, but n-butanol has significantly more London dispersion forces
10.Higher temp means faster movement and more kinetic energy in water molecules so more likely
to overcome forces and become a gas.
11.Ethanol; weaker forces with smaller London dispersion forces means more molecules leaving
liquid and forming gas at same temperature.
12.Both are similar size so London dispersion forces are similar. Formaldehyde has a dipole, but no
H-bond. Water has H-bonds so held together much stronger and less likely to overcome forces
and form vapor.
13.
14.Ionic solids are generally higher since they have a full +1/−1 or greater charge attraction
whereas molecular solids only have partial positive and negative charges to attract.
15.a) C b)CaO c)SiO2 d)I2 e)Al2O3 f)HF g)SO2
cm
16.a)K (metal) b) Cu (metal) c) C,graphite
17.Vial A=NaCl Vial B=SiO2 Vial C=zinc Vial D=sucrose
18.Breaking the intermolecular forces completely to make a gas takes much more energy than just
breaking the static state of those bonds and moving to a liquid where you break and form the
bonds continuously
19. a) endothermic b)exothermic c)endothermic d)exothermic e)exothermic
20. 486 kJ
21. 16.0 kJ
22. 3.08 kJ
23. 32.6 kJ
24. 5.04 kJ/mol
25. 57.5 g
26. 10.8 g

Problem 1
153 kJ
Chapter 16 Answers:
Homework Problems
1. Reaction rate generally increases with increasing reactant concentration, temperature and the
presence of a suitable catalyst. Solvent choice and ensuring that the mixture is homogeneous is
also very important.
2. Increasing the temperature increases the average kinetic energy of the molecules and ions,
causing them to collide more frequently and with greater energy. More of the molecules (see
Section 16.2) also exceed Ea. We would first want to dissolve the sugar in the hot tea since it
would dissolve more readily at higher temperature, then add the ice.
3. These catalysts would be homogenous -- in other words, they would be in solution along with the
reactant. A heterogenous catalyst can only react on the region where the two phases are in
contact; this decreases the number of collisions and the rate.
4. Any chemist needs to know how long a reaction takes. This is obviously of the utmost
importance in industrial settings!
5. This could be the case where there are two different products depending on temperature. The
cooler temperature in the winter leads to “Product 1” while the warmer temperature in the
summer leads to “Product 2.”
6. A catalyst speeds up a reaction by lowering the activation energy. It does not alter ∆H or ∆G.
7. a) −391.9 kJ/mol d) CFCs (a common one is CCl3F) decompose into free Cl atoms in the
atmosphere. We now know that Cl catalyzes the conversion of O3 to O2, depleting the ozone
layer.
cmi
8. D
9. D
10. C
11. B
12. a) 2 A → 2 D + F b) yes, B c) C, E
13. B
14. E
15. C
16. E
17. rate=k[NO2]2; k=0.54 M−1·s−1
18. second order in HO2; k = 1.4×109 M−1·s−1
19. rate = k[NO]2[O2]; k=1.16×103 M−2·s−1
20. rate = k[S2O82−][I−]; k= 20 M−1·s−1
21. 6.25×10−3 M·s−1
22. a) rate=k[N2O5] b) 4.82×10−4 s−1 c)t1/2=1.44×103 s d) 0.0190M
23. a) second order b) 0.0269 M−1·s−1 c)t1/2=18.6 s d) 1.58 M
24. a) rate=k[A] b) 5.02×10−4 s−1 c) 2,390 s
Chapter 17 Answers:
Homework Problems
1. a)0.355 m b)2.60 m c)0.0129 m d)0.0281 m
2. 0.053 m
3. 2.0×10−6 g
4. 6.65×10−5 mol sodium
5. 1.63×10−3 g
6. 2.35 M and 3.59 m toluene
7. a)−1.4°C b)101.2˚C c)−67.8°C
8. 100.10˚C
9. −8°C
10. 0.36 m NaCl, 2.6 g NaCl
11. 14 g NaBr
12. 12.5 KCl
13. 0.2 m CaCl2 (lowest freezing point)<0.3 m acetic acid <0.1 m NaCl = 0.2 m sucrose (highest
freezing point)
14. −12.5˚C
15. a) 260 g/mol b) S8
16. 847 g/mol; C70
17. a) 2.4˚C/m b) 171 g/mol
cmii
APPENDIX B
The Periodic Table
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Chapter 14

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CHAPTER 14

Acid and Base Equilibria

Many vital chemical and physical processes take place exclusively in

Previously we defined acids as substances that dissolve in water to

The Arrhenius Definition of Acids and Bases

(2) NaOH (aq) → Na+ (aq) + OH− (aq)

The Brønsted–Lowry Definition of Acids and Bases

According to Brønsted and Lowry, an acid is any substance that can

Let’s look at an example of a Brønsted–Lowry acid and base. The generic

(3) HA (aq) +H2O (l) → H3O+ (aq) + A− (aq)

(4) HA (aq) → H+ (aq) + A− (aq)

(5) B (aq) +H2O (l) → HB+ (aq) + OH− (aq)

(6) NH3 (aq) + CH3COOH (aq) → NH4+ (aq) + CH3COO- (aq)

NH3 is therefore Brønsted–Lowry base as it accepts a proton and

(7) NH3 (aq) + CH3COOH (aq) → NH4+ (aq) + CH3COO- (aq)

One of the biggest difficulties for a beginning chemistry student learning

(8) HA (aq) → H+ (aq) + A− (aq)

In contrast, only a fraction of the molecules of weak acids and

(9) HA (aq) ⇌ H+ (aq) + A− (aq)

Strong Acids Strong Bases

b) A CH3CH2OH is ethanol, an organic compound that contains the −OH

c) Sr(OH)2 is an ionic compound that contains one Sr2+ and two OH− ions

d) CH3CH2NH2 is an amine (ethylamine), an organic compound in which

e) HBrO is hypobromous acid. We can guess it is an acid as it has an H

PRACTICE PROBLEM 14.1

b. Write the conjugate acid for the base CH3NH2

b) A CH3NH2 is methylamine, a weak base. When it reacts therefore, it

LINK TO HOMEWORK PROBLEMS

The pH of a solution is the negative logarithm of the H+ ion concentration:

Because the hydrogen ion concentration is 1.0 × 10−7 M in pure water at

(12) pH = −log[1.0 × 10−7] = 7.00

FIGURE 14.1 The pH of Some Common Substances

Some common substances and their pH on the pH scale. (From: Slower -

(13) H2O (l) + H2O (l) ⇌ H3O+ (aq) + OH− (aq)

Sometimes this is just written as:

(14) H2O (l) ⇌ H+ (aq) + OH− (aq)

(15) Kw = [H+][OH−] = 1.0 × 10−14

Sometimes, we will have the [OH−] of a solution because of some amount

(18) pOH = − log[OH−]

pH = − log[H +] = − log(2.1 × 10−2) = 1.68

PRACTICE PROBLEM 14.4

Method 1: Find [H+] and convert to pH

[H ][OH ] = 1.0 × 10

Rearranging, gives us:

Now plug in and solve for pH:

pH = − log[H +] = − log(1.8 × 10−14) = 13.74

pOH = − log[OH −] = − log(0.55) = 0.26

As you can see, we get the same answer either way!

PRACTICE PROBLEM 14.5

Starting with the pH, we can solve for pOH:

14 − 9.65 = pOH = 4.35

Now we will be able to go from pOH to [OH−]:

PRACTICE PROBLEM 14.6

Answer: [OH−] = 1.1 × 10−6 M

LINK TO HOMEWORK PROBLEMS

The Magnitude of the Equilibrium Constant

(19) HA (aq) + H2O (l) ⇌ H3O+ (aq) + A− (aq)

Or to simplify further (recalling that H3O+ = H2O + H+):