bases.

• The equilibrium constant of the autoionization of water is the ion-product constant,

Kw. In acidic solutions, [H3O]+ > [OH]− while in basic solutions [OH]− > [H3O]+.

Review of Concepts & Facts

15.2.1 If the H+ ion concentration in an aqueous solution is 0.0010 M, why is it not
possible for the OH− ion concentration to be 1.0 × 10−10 M?
15.2.2 Determine [H+] in a solution where [OH−] = 2.3 × 10−5 M.

15.3 pH—A Measure of Acidity

Learning Objectives
• Utilize the pH scale to classify a solution as being acidic, basic, or neutral.
• Use pH, pOH, the concentration of protons, or the concentration of hydroxide ions to
conduct calculations asking for one of these terms.

Because the concentrations of H+ and OH− ions in aqueous solutions are frequently Page 677
very small numbers and therefore inconvenient to work with, Soren Sorensen † in
1909 proposed a more practical measure called pH. The pH of a solution is defined as the
negative logarithm of the hydrogen ion concentration (in mol/L):
(15.4)
Keep in mind that Equation (15.4) is simply a definition designed to give us convenient
numbers to work with. The negative logarithm gives us a positive number for pH, which
otherwise would be negative due to the small value of [H+]. The pH of concentrated acid
solutions can be negative; for example, the pH of 2.0 M HCl is −0.30. Furthermore, the term
[H+] in Equation (15.4) pertains only to the numerical part of the expression for hydrogen ion
concentration, for we cannot take the logarithm of units. Thus, like the equilibrium constant,
the pH of a solution is a dimensionless quantity.
Because pH is simply a way to express hydrogen ion concentration, acidic and basic
solutions at 25°C can be distinguished by their pH values, as follows:
Acidic solutions: [H+] > 1.0 × 10−7 M, pH < 7.00
Basic solutions: [H+] < 1.0 × 10−7 M, pH > 7.00

Neutral solutions: [H+] = 1.0 × 10−7 M, pH = 7.00

Notice that pH increases as [H+] decreases.
Sometimes we may be given the pH value of a solution and asked to calculate the H+ ion
concentration. In that case, we need to take the antilog of Equation (15.4) as follows:
 (15.5)

Be aware that the definition of pH just shown, and indeed all the calculations involving
solution concentrations (expressed either as molarity or molality) discussed in previous
chapters, are subject to error because we have implicitly assumed ideal behavior. In reality,
ion-pair formation and other types of intermolecular interactions may affect the actual
concentrations of species in solution. The situation is analogous to the relationships between
ideal gas behavior and the behavior of real gases discussed in Chapter 5. Depending on
temperature, volume, and amount and type of gas present, the measured gas pressure may
differ from that calculated using the ideal gas equation. Similarly, the actual or “effective”
concentration of a solute may not be what we think it is, knowing the amount of substance
originally dissolved in solution. Just as we have the van der Waals and other equations to
reconcile discrepancies between the ideal gas and nonideal gas behavior, we can account for
nonideal behavior in solution.
One way is to replace the concentration term with activity, which is the effective
concentration. Strictly speaking, then, the pH of solution should be defined as
(15.6)

where aH+ is the activity of the H+ ion. As mentioned in Chapter 14 (Section 14.2), for an
ideal solution activity is numerically equal to concentration. For real solutions, activity
usually differs from concentration, sometimes appreciably. Knowing the solute concentration,
there are reliable ways based on thermodynamics for estimating its activity, but the details are
beyond the scope of this text. Keep in mind, therefore, that, except for dilute Page 678
solutions, the measured pH is usually not the same as that calculated from Equation
(15.4) because the concentration of the H+ ion in molarity is not numerically equal to its
activity value. Although we will continue to use concentration in our discussion, it is
important to know that this approach will give us only an approximation of the chemical
processes that actually take place in the solution phase.
In the laboratory, the pH of a solution is measured with a pH meter (Figure 15.2). Table
15.1 lists the pH of a number of common fluids. As you can see, the pH of body fluids varies
greatly, depending on location and function. The low pH (high acidity) of gastric juices
facilitates digestion whereas a higher pH of blood is necessary for the transport of oxygen.
These pH-dependent actions will be illustrated in Chemistry in Action essays in this chapter
and Chapter 16.

Table 15.1 The pH of Some Common Fluids

Figure 15.2 A pH meter is commonly used in the laboratory to determine the pH of a solution.
Although many pH meters have scales marked with values from 1 to 14, pH values can, in
fact, be less than 1 and greater than 14.
Photongpix/iStock/Getty Images

A pOH scale analogous to the pH scale can be devised using the negative logarithm of the
hydroxide ion concentration of a solution. Thus, we define pOH as
(15.7)

If we are given the pOH value of a solution and asked to calculate the OH− ion concentration,
we can take the antilog of Equation (15.7) as follows
(15.8)
Now consider again the ion-product constant for water at 25°C:
[H+][OH−] = Kw = 1.0 × 10−14

Taking the negative logarithm of both sides, we obtain

−(log [H+] + log [OH−]) = −log (1.0 × 10−14)
−log [H+] − log [OH−] = 14.00
From the definitions of pH and pOH we obtain
(15.9)

Equation (15.9) provides us with another way to express the relationship between the H+ ion
concentration and the OH− ion concentration.
Examples 15.3, 15.4, and 15.5 illustrate calculations involving pH.
Page 679
Example 15.3
The concentration of H+ ions in a bottle of table wine was 3.2 × 10−4 M right after the cork
was removed. Only half of the wine was consumed. The other half, after it had been
standing open to the air for a month, was found to have a hydrogen ion concentration equal
to 1.0 × 10−3 M. Calculate the pH of the wine on these two occasions.
Strategy We are given the H+ ion concentration and asked to calculate the pH of the
solution. What is the definition of pH?
Solution According to Equation (15.4), pH = −log [H+]. When the bottle was first opened,
[H+] = 3.2 × 10−4 M, which we substitute in Equation (15.4)

On the second occasion, [H+] = 1.0 × 10−3 M, so that

Comment In each case, the pH has only two significant figures. The two digits to the right
of the decimal in 3.49 tell us that there are two significant figures in the original number.
The increase in hydrogen ion concentration (or decrease in pH) is largely the result of the
conversion of some of the alcohol (ethanol) to acetic acid, a reaction that takes place in the
presence of molecular oxygen.
Practice Exercise Nitric acid (HNO3) is used in the production of fertilizer, dyes, drugs,
and explosives. Calculate the pH of a HNO3 solution having a hydrogen ion concentration
of 0.76 M.
Similar problems: 15.17, 15.18.

Example 15.4
 The pH of rainwater collected in a certain region of the northeastern United States on a
particular day was 4.82. Calculate the H+ ion concentration of the rainwater.
Strategy Here we are given the pH of a solution and asked to calculate [H+]. Because pH is
defined as pH = −log [H+], we can solve for [H+] by taking the antilog of the pH; that is,
[H+] = 10−pH, as shown in Equation (15.5).
Solution From Equation (15.4)

pH = −log [H+] = 4.82

Therefore,

log [H+] = −4.82

To calculate [H+], we need to take the antilog of −4.82:

Check Because the pH is between 4 and 5, we can expect [H+] to be between 1 × 10−4 M
and 1 × 10−5 M. Therefore, the answer is reasonable.
Practice Exercise The pH of a certain orange juice is 3.33. Calculate the [H+] ion
concentration.
Similar problem: 15.19.

Page 680

CHEMISTRY in Action
Antacids and the pH Balance in Your Stomach
An average adult produces between 2 and 3 L of gastric juice daily. Gastric juice is a thin,
acidic digestive fluid secreted by glands in the mucous membrane that lines the stomach. It
contains, among other substances, hydrochloric acid. The pH of gastric juice is about 1.5,
which corresponds to a hydrochloric acid concentration of 0.03 M—a concentration strong
enough to dissolve zinc metal! What is the purpose of this highly acidic medium? Where do
the H+ ions come from? What happens when there is an excess of H+ ions present in the
stomach?
A simplified diagram of the stomach is shown here. The inside lining is made up of parietal
cells, which are fused together to form tight junctions. The interiors of the cells are protected
from the surroundings by cell membranes. These membranes allow water and neutral
molecules to pass in and out of the stomach, but they usually block the movement of ions
such as H+, Na+, K+, and Cl−. The H+ ions come from carbonic acid (H2CO3) formed as a
result of the hydration of CO2, an end product of metabolism:
These reactions take place in the blood plasma bathing the cells in the mucosa. By a process
known as active transport, H+ ions move across the membrane into the stomach interior.
(Active transport processes are aided by enzymes.) To maintain electrical balance, an equal
number of Cl− ions also move from the blood plasma into the stomach. Once in the stomach,
most of these ions are prevented from diffusing back into the blood plasma by cell
membranes.
The purpose of the highly acidic medium within the stomach is to digest food and to activate
certain digestive enzymes. Eating stimulates H+ ion secretion. A small fraction of these ions
normally are reabsorbed by the mucosa, causing many tiny hemorrhages. About half a million
cells are shed by the lining every minute, and a healthy stomach is completely relined every
three days or so. However, if the acid content is excessively high, the constant influx of H+
ions through the membrane back to the blood plasma can cause muscle contraction, pain,
swelling, inflammation, and bleeding.

A simplified diagram of the human stomach.

One way to temporarily reduce the H+ ion concentration in the stomach is to take an antacid.
The major function of antacids is to neutralize excess HCl in gastric juice. The table “Some
Common Commercial Antacid Preparations” lists the active ingredients of some popular
antacids. The reactions by which these antacids neutralize stomach acid are as follows:

NaHCO3(aq) + HCl(aq) → NaCl(aq) + H2O(l) + CO2(g)

CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)

MgCO3(s) + 2HCl(aq) → MgCl2(aq) + H2O(l) + CO2(g)

Mg(OH)2(s) + 2HCl(aq) → MgCl2(aq) + 2H2O(l)

Al(OH)2NaCO3(s) + 4HCl(aq) → AlCl3(aq) + NaCl(aq) + 3H2O(l) + CO2(g)

Page 681
When an Alka-Seltzer tablet dissolves in water, the bicarbonate ions in it react with the acid
component in the tablet to produce carbon dioxide gas.
Ken Karp/McGraw-Hill

Some Common Commercial Antacid Preparations

Commercial
Active Ingredients
Name
Alka-2 Calcium carbonate
Alka-Seltzer Aspirin, sodium bicarbonate, citric acid
Bufferin Aspirin, magnesium carbonate, aluminum glycinate
Buffered aspirin Aspirin, magnesium carbonate, aluminum hydroxide-
glycine
Milk of magnesia Magnesium hydroxide
Rolaids Dihydroxy aluminum sodium carbonate
Tums Calcium carbonate
The CO2 released by most of these reactions increases gas pressure in the stomach, causing
the person to belch. The fizzing that takes place when an Alka-Seltzer tablet dissolves in water
is caused by carbon dioxide, which is released by the reaction between citric acid and sodium
bicarbonate:

This action helps to disperse the ingredients and even enhances the taste of the solution.
The mucosa of the stomach is also damaged by the action of aspirin, the chemical name of
which is acetylsalicylic acid. Aspirin is itself a moderately weak acid:
 In the presence of the high concentration of H+ ions in the stomach, this acid remains
largely nonionized. A relatively nonpolar molecule, acetylsalicylic acid has the ability to
penetrate membrane barriers that are also made up of nonpolar molecules. However, inside
the membrane are many small water pockets, and when an acetylsalicylic acid molecule
enters such a pocket, it ionizes into H+ and acetylsalicylate ions. These ionic species become
trapped in the interior regions of the membrane. The continued buildup of ions in this fashion
weakens the structure of the membrane and eventually causes bleeding. Approximately 2 mL
of blood are usually lost for every aspirin tablet taken, an amount not generally considered
harmful. However, the action of aspirin can result in severe bleeding in some individuals. It is
interesting to note that the presence of alcohol makes acetylsalicylic acid even more soluble
in the membrane, and so further promotes the bleeding.
Page 682
Example 15.5
In a NaOH solution [OH−] is 2.9 × 10−4 M. Calculate the pH of the solution.
Strategy Solving this problem takes two steps. First, we need to calculate pOH using
Equation (15.7). Next, we use Equation (15.9) to calculate the pH of the solution.
Solution We use Equation (15.7):

pOH = −log [OH−]

= −log (2.9 × 10−4)

= 3.54

Now we use Equation (15.9):

Alternatively, we can use the ion-product constant of water, Kw = [H+][OH−], to calculate

[H+], and then we can calculate the pH from the [H+]. Try it.
Check The answer shows that the solution is basic (pH > 7), which is consistent with a
NaOH solution.
Practice Exercise The OH− ion concentration of a blood sample is 2.5 × 10−7 M. What is
the pH of the blood?
Similar problem: 15.18.

Summary of Concepts & Facts

• The acidity of an aqueous solution is expressed as its pH, which is defined as the
negative logarithm of the hydrogen ion concentration (in mol/L).
 • At 25°C, an acidic solution has pH < 7, a basic solution has pH > 7, and a neutral
solution has pH = 7.

Review of Concepts & Facts

15.3.1 What is the pH of a solution in which [H+] = 5.8 × 10−7 M? What is the pOH of
this solution?
15.3.2 Determine [H+] in a solution in which pOH = 10.93.
15.3.3 What is the pOH of a solution in which [H+] = 9.1 × 10−11 M?
15.3.4 Which is more acidic: a solution where [H+] = 2.5 × 10−3 M or a solution where
pOH = 11.6?

15.4 Strength of Acids and Bases

Learning Objectives
• Calculate the pH of a strong acid or strong base solution.
• Appraise the value of the equilibrium constant in an acid-base reaction using relative
acid strengths.

Video
The Dissociation of Strong and Weak Acids
Strong acids are strong electrolytes that, for practical purposes, are assumed to ionize Page 683
completely in water (Figure 15.3). Most of the strong acids are inorganic acids:
hydrochloric acid (HCl), nitric acid (HNO3), perchloric acid (HClO4), and sulfuric acid
(H2SO4):