iii

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Marian De Wane
2. Properties of Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Arden P. Zipp
3. Weak Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Valerie Ferguson
4. pH and the Properties of [H
+
] in Aqueous Solution . . . . . . . . . . . . . . . . . . . 29
Lew Acampora
5. Acid–Base Titrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Cheri Smith
6. Polyprotic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Lew Acampora
7. Salts and Buffers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Adele Mouakad
8. Acidic and Basic Reactions of Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Marian DeWane
9. Misconceptions in Chemistry Demonstrated on AP
®
Chemistry
Examinations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
George E. Miller
10. Acid–Base Chemistry Beyond AP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Arden P. Zipp
11. Acids–Bases Lesson Plans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Heather Hattori
12. About the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
13. About the Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
The Properties of Acids and Bases
Arden P. Zipp
SUNY Cortland
Cortland, New York
Acids and bases represent two of the most important classes of chemical compounds.
Some of the properties of acids (such as their sour taste) and bases (bitterness) have
been known to humans for hundreds of years even if their chemical explanations
have not. The reactions of these substances are signifcant in many atmospheric and
geological phenomena. In addition, acids and bases control many of the physiological
processes in the human body and can catalyze a variety of chemical reactions. This
chapter will address some of the fundamental aspects of acids and bases in order to
set the stage for subsequent discussions.
In addition to taste, which was mentioned above but is no longer used in the
chemistry lab, several other properties of acids and bases that can be observed readily
are given below. Table 1 shows that they have some properties in common, while they
do not share others.
Table 1
Properties of Acids and Bases
Acids Bases
1 conduct electricity in solution 1 conduct electricity in solution
2 react with product(s) formed 2 react with product(s) formed
many metals H
2
metal oxide and water H
2
carbonates CO
2
, H
2
O, a salt metal ions precipitates
bicarbonates CO
2
, H
2
O bicarbonates CO
3
2-
, H
2
O
a base H
2
O, a salt an acid H
2
O, a salt
dyes colors, often reddish dyes colors, often bluish
SPECIAL FOCuS: Acids and Bases
4
Teaching Tip
Students will appreciate these properties more if they are demonstrated by the
teacher, or better yet, investigated by students themselves. Inexpensive conductivity
meters can be purchased or constructed to investigate the frst property on the list
while the others can be studied using well plates and solutions dispensed from
dropper bottles.
Early History: Arrhenius Theory
Some of the properties in Table 1 were known to alchemists hundreds of years ago,
and classifcation schemes were developed by many noted scientists during the 1600s
and 1700s including Robert Boyle, Joseph Black, and Antoine Lavoisier.
However, the beginning of the modern understanding of acids is usually
attributed to Svante Arrhenius, who, in his 1884 Ph.D. thesis, explained the electrical
conductivity of aqueous solutions in terms of the presence of ions and attributed the
unique behavior of acids to H
+
ions. According to Arrhenius, an acid is a substance
that, when added to H
2
O, increases the [H
+
], while a base is a substance that
increases the [OH
-
].
Many of the reactions in Table 1 can be explained with the Arrhenius acid–base
theory by the presence of H
+
or OH
-
ions as shown in the equations below:
Acids Bases
2H
+
+ M (e.g. Mg) → H
2
+ M
2+
2OH
-
+ M
2
O
3
(e.g. Al) + 2H
2
O→ H
2
+ 2M(OH)
4


xOH
-
+ M
x+
→ M(OH)
x
(s)
2H
+
+ CO
3
2
- → H
2
O + CO
2
OH
-
+ HCO3
-
→H
2
O + CO
3
2-
H
+
+ HCO
3
- → H
2
O + CO
2
H
+
+ OH
-
→ H
2
O H
+
+ OH
-
→ H
2
O
State of H
+
in H
2
O.
In the above equations the acid is represented as H
+
, a bare proton. However, it is
generally agreed that the charge density of a proton is too large for it to exist in that
form in aqueous solutions. Many texts represent protons as hydronium ions, H
3
O
+
,
as if each proton is bonded to a single H
2
O molecule. Current evidence suggests,
however, that the actual species has three additional H
2
O molecules attached via
hydrogen bonds to form H
9
O
4
+
. H
+
will be used in this volume but it should be
recognized that the actual species is more complex. Interestingly, the same texts that
make a point of using H
3
O
+
usually show the hydroxide ion as OH
-
even though it also
appears to be hydrated, existing in H
2
O as H
7
O
4
-
.
The Properties of Acids and Bases
5
Strong and Weak Acids
Arrhenius related the degree of electrical conductivity to the strength of acids, thereby
introducing the concept of strong and weak acids. Strong acids are those that ionize
completely (or nearly so) in solution, while weak acids ionize only partially, i.e., have
solutions that contain signifcant amounts of the parent acid and lower concentrations
of H
+
. In terms of equations, the reaction of a strong acid goes completely to the
right, so is written with a simple arrow while that for a weak acid is reversible and is
depicted with a double-headed arrow.
Strong acid: HA(aq) → H
+
(aq) + A
-
(aq)
Weak acid: HA(aq) ↔ H
+
(aq) + A
-
(aq)
Among the standard acids commonly encountered in aqueous solutions, six are strong.
HCl hydrochloric acid HNO
3
nitric acid
HBr hydrobromic acid HClO
4
perchloric acid
HI hydroiodic acid H
2
SO
4
sulfuric acid
All other acids behave as weak acids in water. Although strong and weak acids
produce the same types of reactions, the rates at which these reactions occur
vary depending on the concentration of free H
+
ions in solution. It should be noted
that in the above table, only the frst proton from H
2
SO
4
can really be described as
“completely ionized,” the second proton has a measurable equilibrium constant.
Teaching Tip
The difference between strong and weak acids can be made more concrete for
students by demonstrations (or experiments) in which they compare the behavior of
1.0 M solutions of strong (e.g., HCl) and weak (HC
2
H
3
O
2
) acids. Properties of interest
include electrical conductivity and the rate of reaction with Mg metal (using a balloon
attached to the mouth of a conical fask to capture the evolved H
2
). Equal volumes of
the weak and strong acids will produce the same volume of H
2
but the rates at which
they do so will differ substantially. Reactions with calcium carbonate, capturing
the CO
2
, work similarly. Students can measure how much time it takes for a short
measured length of Mg ribbon or a measured scoop of calcium carbonate to dissolve
completely.
SPECIAL FOCuS: Acids and Bases
6
Strong and Weak Bases
There are also six common strong bases that ionize completely in H
2
O, though some
have limited solubility, which should not be confused with amount of ionization.
LiOH lithium hydroxide Ca(OH)
2
calcium hydroxide
NaOH sodium hydroxide Sr(OH)
2
strontium hydroxide
KOH potassium hydroxide Ba(OH)
2
barium hydroxide
A solution of a strong base in H
2
O may be obtained by dissolving the appropriate
solid hydroxide but may also be formed by reacting a solid metallic oxide with H
2
O.
For example, sodium oxide dissolves in H
2
O according to the following equation:
Na
2
O + H
2
O → 2 Na
+
+ 2 OH
-

Similar reactions to produce strongly basic solutions occur with several other
anions but these will not be considered here. There are a variety of compounds
that behave as weak bases, although few of these contain OH
-
ions. These will be
discussed further below.
Concentrations
Water itself is a weak acid, existing in equilibrium with its ions, H
+
and OH
-,
as
shown in the reversible equation:
H
2
O ↔ H
+
+ OH
-
for which K =
[H
+
][OH

]
=1.8 x 10
-16
[H
2
O]
where the square brackets, [], represent concentrations in moles per liter. When the
above value of K is multiplied by [H
2
O], (55.5 M), the expression is K
w
= [H
+
][OH
-
] with
a value of K
w
= 1.0 x 10
-14
at 25 ˚C. Using the K
w
expression it is possible to calculate
[H
+
] for any [OH
-
] and vice versa. In a 1.0 M solution of a strong acid, [H
+
] =1.0, while
in a 1.0 M solution of a strong base, [OH
-
] = 1.0 and [H
+
] = 1.0 x 10
-14
. Because of this
extremely wide range of [H
+
], an alternative method of comparing [H
+
] concentrations,
called the pH scale, has been devised, where pH is defned as -log [H
+
]. Thus, a
solution with [H
+
] = 1.0 has a pH = 0.00 and one with [H
+
] = 1.0 x 10
-14
has a pH =
14.00.
In pure H
2
O, [H
+
] = [OH
-
] = 1.0 x 10
-7
and pH = pOH = 7.00. Acid solutions
are those in which [H
+
] > 1.0 x 10
-7
or pH < 7.00 while basic (alkaline) solutions have
[OH
-
] > 1.0 x 10
-7
, [H
+
] < 1.0 x 10
-7
or pH > 7.00. A more extensive discussion of pH and
further calculations are provided in a later chapter.
The Properties of Acids and Bases
7
Teaching Tip
Students typically enjoy determining the pH values of common household materials
(with indicator paper or drops of universal indicator). This activity can be useful for
AP students if it is coupled with pH calculations and practice in pH ↔ [H
+
] or pOH ↔
[OH-] conversions.
Formation of Acidic or Basic Solutions
It is easy to see how adding a strong acid like hydrochloric acid, HCl, or even a weak
acid such as ethanoic (acetic) acid, HC
2
H
3
O
2
, to water will increase the concentration
of [H
+
] above 1.0 x 10
-7
as these species ionize completely (HCl, a strong acid) or
partially (HC
2
H
3
O
2
, a weak acid) to release H
+
ions. Similarly, the release of OH
-
ions
can be envisioned from the addition of one of the strong bases to H
2
O. However, the
production of acidic solutions by substances that contain no H
+
(or basic ones by
substances that do not possess OH
-
) is less apparent. Clearly, an acid–base theory
other than that proposed by Arrhenius is required.
Brønsted-Lowry Acid–Base Theory
As outlined above, Arrhenius defned acids as substances that produce H
+
ions
in H
2
O and bases as species that produce OH
-
ions. In 1923 Johannes Brønsted
and Thomas Lowry independently described acids as proton donors and bases as
proton acceptors, thereby broadening the concept of acids and bases signifcantly.
In addition, they introduced the notion that acids and bases exist in pairs (called
conjugate pairs) that differ by the presence (acid) or absence (base) of a proton.
Further, they suggested that when acid–base reactions occur, stronger acids and
bases react to form weaker acids and bases as in the equation below, where HA and
A
-
are a conjugate pair, and B and HB
+
are a conjugate pair:
HA + B ↔ HB
+
+ A
-
Such reactions are reversible and the relative amounts of the various substances
depend on the strengths of the acids (bases) involved. Where HA is a stronger acid
than HB
+
and B is a stronger base than A
-
, the equilibrium constant will be >1. The
strengths of Brønsted-Lowry acids and their conjugate bases are inversely related.
This is because stronger acids donate protons more readily and, hence, their conjugate
bases have lower attractions for protons (i.e., are weaker).
The Brønsted-Lowry theory includes as acids all the substances identifed by
Arrhenius as acids because they donate H
+
ions to water and would also classify the
SPECIAL FOCuS: Acids and Bases
8
OH
-
ion as a base because it is a proton acceptor. For example, HCl acts as an acid
according to both defnitions in the equation:
HCl + H
2
O → H
3
O
+
+ Cl
-

because it releases an H
+
ion (Arrhenius) or donates a proton (Brønsted-Lowry). In
this reaction, H
2
O behaves as the base. However, the Brønsted-Lowry theory can also
account for the acidic behavior of metal ions and nonmetallic oxides, neither of which
contain H
+
ions. In addition, it can explain the basic behavior of weak bases such as
ammonia.
Acidities of Metal Ions and Nonmetallic Oxides
Just as protons are hydrated (described above), most metal ions are also hydrated,
usually with six H
2
O molecules. In both instances lone pairs of electrons in H
2
O
molecules are attracted to the positive charge of the ion. For metal ions with large
charge densities (due to high charges and/or small radii), the attraction for the oxygen
of the H
2
O may be strong enough to polarize the O-H bond and cause an H
+
ion to be
released. This process is depicted in the equation:
M(H
2
O)
6
x+
+ H
2
O ↔ M(HO)
5
OH
(x-1)+
+ H
3
O
+

The effect of charge and radius on the acidic behavior of selected metal ions is
shown in the Table 2 below.
Table 2
Li
+
Be
2+
slightly acidic weakly acidic
Na
+
Mg
2+
Al
3+
neutral weakly acidic acidic
K
+
Ca
2+
Sc
3+
Ti
4+
neutral slightly acidic acidic very acidic
Teaching Tip
The relative acidities of these (and other) metal ions can be shown by adding a few
drops of universal indicator to solutions containing these ions and comparing the
solution colors with those of pH standards.
The Properties of Acids and Bases
9
The acidic behavior of nonmetallic oxides can be explained on the basis of their
reaction with water to form oxyacids as represented in the equation for SO
2
:
SO
2
+ H
2
O → H
2
SO
3
Such oxyacids ionize to release H
+
ions as:
H
2
SO
3
+ H
2
O ↔ H
3
O
+
+ HSO
3
-
Thus, the Brønsted-Lowry theory offers an explanation for the acidic behavior
of both metal ions and nonmetallic oxides, neither of which contain H
+
. A more
extensive discussion of oxides (both nonmetallic and metallic) is undertaken in a later
section as is the relative acidities of oxyacids.
Behavior of Weak Bases
As mentioned above, there are six strong bases, each of which contains hydroxide
ions. In contrast to the small number of strong bases, there are many substances
that behave as weak bases. These substances produce an excess of OH
-
ions in
water even though they do not contain OH
-
ions themselves. Most of these materials
contain a nitrogen atom that can act as a Brønsted-Lowry base by accepting a proton,
although some contain other atoms that can behave in this same manner. When a
proton is abstracted from a water molecule, an excess of OH
-
ions remains in the
solution as shown in the equation:
H
2
O + B ↔ BH
+
+ OH
-
The [OH
-
] produced in such a reaction depends on the position of the above
equilibrium, which is a function of the strength of B as a Brønsted-Lowry base. (H
2
O
is acting as the acid in this reaction.)
For ammonia, NH
3
, the most common weak base, [OH
-
] = 4.2 x 10
-3
M in a 1.0 M
NH
3
solution. Weak acids and bases will be treated in more detail in another section
of this book.
Lewis Acid–Base Theory
By emphasizing the transfer of protons, the Brønsted-Lowry theory is able to account
for several acid–base reactions that can not be treated by the Arrhenius theory. The
same year that Brønsted and Lowry proposed their theory, G.N. Lewis noted that
the reaction of a proton with a base involved the donation of a pair of electrons from
the base to form a bond with the proton. He defned bases as electron pair donors,
and acids as electron pair acceptors. Hence, Lewis acid–base reactions encompass
SPECIAL FOCuS: Acids and Bases
10
all Brønsted-Lowry reactions but also cover many processes that do not involve
proton transfer. Examples of these include all cases in which a pair of electrons is
donated, such as the hydration of metal ions and the reaction of ammonia with boron
compounds:
M
x+
+ 6H
2
O → M(H
2
O)
6
x+

NH
3
+ BCl
3
→ H
3
N-BCl
3
This brief discussion of various aspects of acids and bases is intended to
introduce the more extensive treatments in later chapters. Because of the importance
of acids and bases in modern chemistry, this material has been tested frequently on
the AP Chemistry Exam, both Part I and Part II.
Sample Part I
Released Exam 2002 Questions
An analysis of this released exam revealed a total of 9 questions (out of 75)
related to acids and bases. Of these, the ones below are based solely on the above
material.
21. In the laboratory, H
2
(g) can be produced by adding which of the following to
1.0 M HCl(aq)?
I. 1 M NH
3
(aq)
II. Zn(s)
III. NaHCO
3
(s)
(A) I only
*
(B) II only
(C) III only
(D) I and II only
(E) I, II, and III
22. In liquid ammonia, the reaction represented below occurs.
2NH
3
↔ NH
4
+
+ NH
2
-
In the reaction, NH
4
+
acts as
(A) a catalyst
(B) both an acid and a base
*
(C) the conjugate acid of NH
3
The Properties of Acids and Bases
11
(D) the reducing agent
(E) the oxidizing agent
30. At 25˚C, aqueous solutions with a pH of 8 have hydroxide concentration,
[OH
-
], of
(A) 1 x 10
-14
M
(B) 1 x 10
-8
M
*
(C) 1 x 10
-6
M
(D) 1.0 M
(E) 8.0 M
Sample Part II
Released Exam 2004 Questions
Question 4
(c) A 0.1 M nitrous acid solution is added to the same volume of a 0.1 M
sodium hydroxide solution
HNO
2
+ OH
-
→ NO
2
-
+ H
2
O
(d) Hydrogen iodide gas is bubbled into a solution of lithium carbonate:
2 HI + CO
3
2-
→ 2 I
-
+ H
2
O + CO
2
(h) Concentrated hydrochloric acid is added to a solution of sodium sulfde:
2 H
+
+ S
2-
→ H
2
S
Released Exam 2005 Questions
Question 4
(d) Solid calcium carbonate is added to a solution of ethanoic (acetic) acid:
Na
2
CO
3
+ 2 HC
2
H
3
O
2
→ 2 C
2
H
3
O
2
-
+ H
2
O + CO
2
+ 2 Na
+
(f) Boron trifuoride gas is added to ammonia gas:
BF
3
+ NH
3
→ F
3
B-NH
3
(g) Sulfur trioxide gas is bubbled into a solution of sodium hydroxide:
SO
3
+ OH
-
→ HSO
4
-
SPECIAL FOCuS: Acids and Bases
12
Released Exam 2006 Questions
Question 4
(c) A solution of ethanoic (acetic) acid is added to a solution of barium
hydroxide:
HC
2
H
3
O
2
+ OH
-
→ H
2
O + C
2
H
3
O
2

-

(d) Ammonia gas is bubbled into a solution of hydrofuoric acid:
NH
3
+ HF → NH
4
+
+ F
-
(f) Hydrogen phosphide (phosphine) gas is added to boron trichloride gas:
PH
3
+ BCl
3
→ H
3
P-BCl
3
Released Exam 2007 Questions
Question 4
(b) (i) Excess nitric acid is added to solid calcium carbonate.
2 H
+
+ CaCO
3
→ Ca
2+
+ H
2
O + CO
2
(ii) Briefy explain why statues made of marble (calcium carbonate)
displayed outdoors in urban areas are deteriorating.
The H
+
ions in acid rain react with the marble statues and the soluble
compounds of calcium that are formed are washed away.
Bibliography
Brown, T. L., H. E. LeMay Jr., and B. E. Bursten. Chemistry: The Central Science, 5th
ed. Englewood Cliffs, NJ: Prentice Hall, 1991.
Huheey, J. E., E. A. Keiter, and R. L. Keiter. Inorganic Chemistry, 4th ed. New York:
Harper Collins, 1993.
Rayner-Canham, G., and T. Overton. Descriptive Inorganic Chemistry, 4th ed. New
York: W.H. Freeman, 2006.
Salzberg, H. W. From Caveman to Chemist. Washington, DC: American Chemistry
Society, 1991.
Weak Acids and Bases
Valerie Ferguson
Moore High School
Moore, Oklahoma
Many substances dissolve in water to cause a change in the pH of pure water. Some
of the substances ionize completely and others only partially ionize.
Strong acids and bases are strong electrolytes in water solutions, and are almost
totally ionized. The reaction depicted below of a strong acid in water occurs with all of
the HCl molecules in water. Since all of the HCl molecules are converted to H
3
O
+
and
Cl
-
, the concentration of the hydronium ion is equal to the initial concentration of HCl
in the solution. Strong acids and bases are not thought of as establishing equilibria
since the reaction essentially goes to completion. However, equilibria never “turn
off.” The equilibrium autodissociation of water is always present and operative in any
aqueous solution even though the conjugate ion concentration (OH
-
in acid, H
3
O
+
in
base) is extremely small.
Weak acid and base solutions are partially ionized. The Brønsted-Lowry
defnition describes many acid and base interactions as a proton transfer from one
particle to another. The particle that donates a proton is the acid and the particle
accepting the proton is the base. The products of these reactions are called conjugate
acids and conjugate bases. The acid and its product, the conjugate base, are a
conjugate acid–base pair.
SPECIAL FOCuS: Acids and Bases
14
Conjugate acid–base pairs are two substances whose formulas differ by a proton.
The example below illustrates a Brønsted-Lowry reaction with acetic acid in water.
Examples from Prior AP Chemistry Examinations
(2005 Form B)
K
a
= [H
3
O
+
][OCl
-
]/[HOCl] = 3.2 x 10
-8
1. Hypochlorous acid, HOCl, is a weak acid in water.
The K
a
expression for HOCl is shown above.
(a) Write a chemical equation showing how HOCl behaves as an acid in water.
HOCl(aq) + H
2
O(l) ↔ OCl
-
(aq) + H
3
O
+
(aq)
Teaching Tips
Students need to practice writing equations for the reactions of weak acids and
bases in water. Opportunities for such practice occur several times during the course.
Questions on the AP Chemistry Exam commonly ask students to demonstrate their
knowledge of writing these equations.
The illustration below shows the Brønsted-Lowry reaction of a weak base,
ammonia, in water. Brønsted-Lowry bases are proton acceptors.
Weak Acids and Bases
15
(2002)
2 NH
3
↔ NH
4
+
+ NH
2
-
22. In liquid ammonia, the reaction represented above occurs. In the reaction, NH
4
+

acts as
(A) a catalyst
(B) both an acid and a base
*
(C) the conjugate acid of NH
3
(D) the reducing agent
(E) the oxidizing agent
(1994)
HSO
4
-
+ H
2
O ↔ H
3
O
+
+ SO
4
2-
22. In the equilibrium represented above, the species that act as bases include
which of the following?
I. HSO
4
-
II. H
2
O
III. SO
4
2
-
(A) II only
(B) III only
(C) I and II
(D) I and III
*
(E) II and III
SPECIAL FOCuS: Acids and Bases
16
(1989)
34. All of the following species can function as Brønsted-Lowry bases in
solution EXCEPT
(A) H
2
O
(B) NH
3
(C) S
2-
*
(D) NH
4
+
(E) HCO
3
-
* Proton acceptors must have a lone pair of electrons.
Brønsted-Lowry reactions are reversible and will establish a chemical
equilibrium between the forward and reverse reactions. The position of the
equilibrium depends on the strength of the acid and/or base, in aqueous solutions,
in comparison to water. The relative strengths of the various weak acids can be
described in different ways: the value of the acid dissociation, K
a
, the [H
+
] compared
to the initial [HA], strength of the conjugate base compared to water, or the position of
the dissociation.
The weaker acids have stronger conjugate bases. Stronger acids and bases
tend to react with each other to produce their weaker conjugates. Since the stronger
species are more likely to react, the conjugates are less likely to react and are thus
weaker. The strong acids and bases are essentially totally ionized. The conjugates are
very weak and less likely to react with water. Since the weaker species is less likely
to react, it is in higher concentrations in the solution. The weaker species will be in
greater concentration when equilibrium is established.
(1999)
HC
2
H
3
O
2
(aq) + CN
-
(aq) ↔ HCN(aq) + C
2
H
3
O
2
-
(aq)
62 . The reaction represented above has an equilibrium constant equal to
3.7 x 10
4
. Which of the following can be concluded from this information?
*
(A) CN
-
(aq) is a stronger base than C
2
H
3
O
2
-
(aq).
(B) HCN(aq) is a stronger acid than HC
2
H
3
O
2
(aq).
(C) The conjugate base of CN
-
(aq) is C
2
H
3
O
2
-
(aq).
(D) The equilibrium constant will increase with an increase in temperature.
(E) The pH of a solution equimolar amounts of CN
-
(aq) and HC
2
H
3
O
2
(aq) is 7.0.
Weak Acids and Bases
17
(1989)
H
2
PO
4
-
+ HBO
3
2-
↔ HPO
4
2-
+ H
2
BO
3
-
55. The equilibrium constant for the reaction represented by the equation
above is greater than 1.0. Which of the following gives the correct relative
strengths of the acids and bases in the reaction?
Acids Bases
*
(A) H
2
PO
4
-
> H
2
BO
3
-
and HBO
3
2
-
> HPO
4
2-

(B) H
2
BO
3
-
> H
2
PO
4
-
and HBO
3
2
-
> HPO
4
2-

(C) H
2
PO
4
-
> H
2
BO
3
-
and HPO
4
2
-
> HBO
3
2-

(D) H
2
BO
3
-
> H
2
PO
4
-
and HPO
4
2
-
> HBO
3
2-

(E) H
2
PO
4
-
= H
2
BO
3
-
and HPO
4
2
-
= HBO
3
2-
(1984)
49. Each of the following can act as both a Brønsted acid and a Brønsted
base EXCEPT
(A) HCO
3
-
(B) H
2
PO
4
-
*
(C) NH
4
+
(D) H
2
O
(E) HS
-

Periodic trends are observed in the relative strength of acids. Binary hydro-
acids—those that contain only hydrogen and a nonmetal—tend to increase in
strength from left to right across the periodic table within the same period. The
strength of a binary acid increases from top to bottom within the same group. The
graphic below represents the reaction of a binary acid in water.
SPECIAL FOCuS: Acids and Bases
18
Electronegativity of E increases 2.5 < 2.8 < 3.0
HOI HOBr HOC
Acid strength increases K
a
=2.3 × 10
-11
< 2.5 × 10
-9
< 2.9 × 10
-8
Acids composed of hydrogen, oxygen, and some other element are called
oxoacids or oxyacids. Oxoacids are composed of a central atom with one or more O-H
groups attached to it. The strength of an oxoacid depends upon the ease with which
the hydrogen ion is released from the O-H group. The other atoms in the molecule
affect the polarity of the O-H bond. As the electronegativity of the central atom
increases, the electrons are pulled to the central atom and away from the O-H bond.
The probability that H
+
will be released is increased. The more readily the hydrogen
ion is released, the stronger the acid. When the number of oxygens is held constant,
the strength of the oxoacid increases from top to bottom within a group and from left
to right across a period.
For the same central atom, the stronger
acids contain more oxygen atoms.
Weak Acids and Bases
19
(2002)
1(e). HOBr is a weaker acid than HBrO
3
. Account for this fact in terms of molecular
structure.
The H-O bond is weakened or increasingly polarized
by the additional oxygen atoms bonded to the central
bromine atom in HBrO
3
.
1 point earned
for a correct
explanation.
Teaching Tips
Students need to demonstrate an understanding of the strength of the O-H bond as
related to the strength of the acid. The greater the number of electronegative atoms in
the molecule, the weaker the O-H bond as the electrons are pulled away from the O-H
bond. Many students found it helpful to draw a structural formula to help answer this
question.
An important group of oxoacids is the carboxylic acids. These organic
compounds are characterized by containing a chain of carbon atoms with one or
more carboxyl groups, -COOH, attached. These compounds are weak acids called
carboxylic acids. Acetic acid is an example of a simple carboxylic acid. Its reaction
with water is shown on page 1. Most carboxylic acids react in a similar fashion. Only
the O-H bond is polar enough so the hydrogen is readily donated as a hydrogen ion.
Acetic acid
SPECIAL FOCuS: Acids and Bases
20
(2007 Form B)
5. Answer the following questions about laboratory solutions involving acids, bases
and buffer solutions.
(a) Lactic acid, HC
3
H
5
O
3
, reacts with water to produce an acidic solution. Show
below are the complete Lewis structures of the reactants.
In the space provided above, complete the equation by drawing the complete Lewis
structures of the reaction products.
(2001)
4(d). Write the net ionic equation for the following reaction: Solutions of
potassium hydroxide and propanoic acid are mixed.
C
2
H
5
COOH + OH
-
→ C
2
H
5
COO
-
+ H
2
O
(2005 Form B)
4(d). Write the net ionic equation for the following reaction: Ethanoic acid (acetic acid)
is added to a solution of barium hydroxide.
OH
-
+ HC
2
H
3
O
2
→ C
2
H
5
O
2
-
+ H
2
O
The strength of the carboxylic acids is affected by the substitution of one or more
hydrogen atoms with electronegative atoms. More electronegative atoms pull the
electron density away from the O-H bond and cause an increase in acid strength. The
closer the electronegative atoms are to the O-H bond, the greater the effect on acid
strength by weakening the O-H bond.
Weak Acids and Bases
21
I—CH
2
CH
2
COOH Cl—CH
2
CH
2
COOH CH
3
CHCLOOH CH
3
CCL
2
COOH
3-ledopropanoic acid 3-Chloropropanoic acid 2-Chloropropanoic acid 2,2-Dichloropropanoic acid
K
a
= 8.3 x 10
-5
< K
a
= 1.0 x 10
-4
< K
a
= 1.4 x 10
-3
< K
a
= 8.7 x 10
-3
Increasing acid strength
Amines are organic compounds that act as weak bases. The structure is an
ammonia molecule, NH
3
, with one hydrogen substituted by a hydrocarbon group.
Amines react as bases similar to reactions of NH
3
. The amines act as Brønsted-Lowry
bases and are proton acceptors. The proton attaches to the nitrogen in the amine group.
NH
3
(aq) + H
2
O(aq) ↔ NH
4
+
(aq) + OH
-
(aq)
H
3
CNH
2
(aq) + H
2
O(l) ↔ H
3
CNH
3
+
(aq) + OH
-
(aq)
Teaching Tips
The equation for the reaction of ammonia with water is compared to the equation for
the reaction of methylamine with water. In each reaction the water acts as a Brønsted-
Lowry acid and ammonia or methylamine as a Brønsted-Lowry base.
Examples of other amines.
(1999)
4(f). Write the net ionic equation for the following reaction: Methylamine gas is
bubbled into distilled water.
CH
3
NH
2
+ H
2
O → CH
3
NH
3
+
+ OH
-
(2003)
C
6
H
4
NH
2
(aq) + H
2
O(l) ↔ C
6
H
5
NH
3
+
(aq) + OH
-
(aq)
1. Aniline, a weak base, reacts with water according to the reaction represented above.
SPECIAL FOCuS: Acids and Bases
22
Teaching Tips
The examples above demonstrate the inclusion of amines on past AP Exams.
Students need to have a background of the behavior of amines as weak bases. In
question 1 from 2003, students were asked to demonstrate an understanding of the
characteristics of an amine equilibrium. Students should be encouraged to develop
an understanding of the similarity of amine reactions to those of ammonia. The
discussion of weak acids and bases is a good time to include some organic chemistry.
Lewis acids can be described as electron-pair acceptors and Lewis bases as
electron-pair donors. Sometimes the Lewis acid has fewer than eight electrons, as in
compounds such as BF
3
.
(2005)
4(f). Write the net ionic equation for the following reaction: Boron trifuoride gas is
added to ammonia gas.
BF
3
+ NH
3
→ BF
3
NH
3
(2006)
4(f). Write the net ionic equation for the following reaction: Hydrogen phosphide
(phosphine) gas is added to boron trichloride gas.
PH
3
+ BCl
3
→ H
3
PBCl
3
CO
2
(g) + OH
-
(aq) → HC0
3
-
(aq)
Lewis acid-base theory represents the movement of electrons in this reaction as
follows.
Weak Acids and Bases
23
(1999)
4(g). Write the net ionic equation for the following reaction: carbon dioxide gas is
passed over hot, solid sodium oxide.
CO
2
+ Na
2
O → Na
2
CO
3
(2001)
4(a). Write the net ionic equation for the following reaction: Sulfur dioxide gas is
bubbled into distilled water.
SO
2
+ H
2
O → H
2
SO
3
Hydrated metal ions can act as acids in water. The smaller metal ions with
greater charge have a greater charge density and produce more acidic solutions.
SPECIAL FOCuS: Acids and Bases
24
(2004 Form B)
4(g). Write the net ionic equation for the following reaction: Excess saturated sodium
fuoride solution is added to a solution of aluminum sulfate.
F

+ Al
3
+
→ [AlF
6
]
3-
(2003 Form B)
4(g). Write the net ionic equation for the following reaction: Excess concentrated
potassium hydroxide solution is added to a solution of nickel(II) chloride.
OH

+ Ni
2+
→ [Ni(OH)
4
]
2-
(some other products were accepted)
(2003)
4(e). Write the net ionic equation for the following reaction: Excess concentrated
aqueous ammonia is added to solid silver chloride.
AgCl + NH
3
→ Ag(NH
3
)
2
+
+ Cl
-
(1984)
48. Which of the following ions is the strongest Lewis acid?
(A) Na
+
(B) Cl
-
(C) CH
3
COO
-
(D) Mg
2+
*
(E) Al
3+

I highly suggest using the following Web sites with simulations of weak acid and
weak base behavior:
• The frst is the work of Thomas Greenbowe of Iowa State University,
located at: www.chem.iastate.edu/group/Greenbowe/sections/projectfolder/
animationsindex.htm.
• The second is part of a collaboration of John I. Gelder, Michael Abraham,
and Kirk Haines, which can be found at: genchem1.chem.okstate.edu/CCLI/
Startup.html
Weak Acids and Bases
25
Bibliography
Brady, James E., and Fred Senese. Chemistry: Matter and Its Changes, 4th ed.
Hoboken, NJ: Wiley, 2003.
Brown, Theodore E., Eugene H . LeMay, and Bruce E. Bursten. Chemistry: The Central
Science, 10th ed. Upper Saddle River, NJ: Pearson/Prentice-Hall, 2006.
Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry. General
Chemistry, 4th ed. Upper Saddle River, NJ: Pearson/Prentice-Hall, 2005.
Silberberg, Martin S. Chemistry: The Molecular Nature of Matter and Change, 2nd ed.
New York: McGraw-Hill Higher Education, 2000.
Whitten, Kenneth W., Raymond E. Davis, Larry M. Peck, and George G. Stanley.
Chemistry, 8th ed. Belmont, CA: Thomson/Brooks/Cole, 2007.
Zumdahl, Steven S., and Susan A. Zumdahl. Chemistry, 7th ed. Boston: Houghton
Miffin, 2007.
SPECIAL FOCuS: Acids and Bases
26
Graphics Index
(Picture 1) Brady, James E., and Fred Senese. Chemistry: Matter and Its Changes, 4th
ed., 738. Hoboken, NJ: Wiley, 2003.
(Picture 2) Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry.
General Chemistry, 4th ed., 617. Upper Saddle River, NJ: Pearson/Prentice-Hall,
2005.
(Picture 3) Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry.
General Chemistry, 4th ed., 617. Upper Saddle River, NJ: Pearson/Prentice-Hall,
2005.
(Picture 4) Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry.
General Chemistry, 4th ed., 621. Upper Saddle River, NJ: Pearson/Prentice-Hall,
2005.
(Picture 5) Brown, Theodore E., Eugene H. LeMay, and Bruce E. Bursten. Chemistry:
The Central Science, 10th ed., 703. Upper Saddle River, NJ: Pearson/Prentice-
Hall, 2006.
(Picture 6) Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry.
General Chemistry, 4th ed., 622. Upper Saddle River, NJ: Pearson/Prentice-Hall,
2005.
(Picture 7) Brady, James E., and Fred Senese. Chemistry: Matter and Its Changes, 4th
ed., 748. Hoboken, NJ: Wiley, 2003.
(Picture 8) Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry.
General Chemistry, 4th ed., 622. Upper Saddle River, NJ: Pearson/Prentice-Hall,
2005.
(Picture 9) Brown, Theodore E., Eugene H. LeMay, and Bruce E. Bursten. Chemistry:
The Central Science, 10th ed., 705. Upper Saddle River, NJ: Pearson/Prentice-
Hall, 2006.
(Picture 10) Brown, Theodore E., Eugene H. LeMay, and Bruce E. Bursten. Chemistry:
The Central Science, 10th ed., 706. Upper Saddle River, NJ: Pearson/Prentice-
Hall, 2006.
Weak Acids and Bases
27
(Picture 11) Hill, John W., Ralph H. Petrucci, Terry W. McCreary, and Scott S. Perry.
General Chemistry, 4th ed., 623. Upper Saddle River, NJ: Pearson/Prentice-Hall,
2005.
(Picture 12) Silberberg, Martin S. Chemistry: The Molecular Nature of Matter and
Change, 2nd ed., 780. New York: McGraw-Hill Higher Education, 2000.
(Picture 13) Brady, James E., and Fred Senese. Chemistry: Matter and Its Changes, 4th
ed., 751. Hoboken, NJ: Wiley, 2003.
(Picture 14) Brady, James E., and Fred Senese. Chemistry: Matter and Its Changes, 4th
ed., 752. Hoboken, NJ: Wiley, 2003.
(Picture 15) Silberberg, Martin S. Chemistry: The Molecular Nature of Matter and
Change, 2nd ed., 792. New York: McGraw-Hill Higher Education, 2000.
(Picture 16) Silberberg, Martin S. Chemistry: The Molecular Nature of Matter and
Change, 2nd ed., 786. New York: McGraw-Hill Higher Education, 2000.
pH and the Properties of [H
+
] in Aqueous
Solution
Lew Acampora
St. Francis School
Louisville, Kentucky
The neutralization of a strong acid with a strong base occurs according to the net
ionic equation
1
:
Equation 1: H
+
+ OH
-
→ H
2
O

; ΔHº = -55.6
kJ

mol
; ΔGº
298K
= -79.8
kJ

mol

The negative sign of ΔGº
298K
, and experience tell us that the reaction proceeds
spontaneously from standard initial concentrations of 1.0 M H
+
and 1.0 M OH
-
.
Rather than proceeding to completion, where the concentration of one or both of the
reactants is completely exhausted, the reaction does attain a state of equilibrium in
which small but measurable concentrations of both H
+
and OH
-
are present. The state
of equilibrium is quantitatively described by the equilibrium constant expression.
Because the concentration of the pure water is unaffected by the progress of the
reaction, it is omitted from the equilibrium constant expression, K
eq
:
K
eq
1
H OH
=
[ ] ⋅
+ −
The value of K
eq
can be readily calculated as:
K e e
eq
nG
RT
o
= =
-
- -
kJ
mol
0.00
79.8
8831
kJ
mol K
298 K


= = × e 1.0
32.2
10
14
1. The symbol “H
+
(aq)” is a shorthand representation of the hydrated proton. In aqueous solutions, the acidic proton is
undoubtedly coordinated to several water molecules through and is often written as the hydronium ion, “H
3
O
+
(aq).”
Because the number of water molecules coordinated to a single proton varies with time, it is probably most accurately
represented as “H
2n+1
O
n
+
(aq),” where “n” represents the number of water molecules. In terms of calculations, when used
correctly, the symbol H
+
(aq)” is a convenient and suitable representation.
SPECIAL FOCuS: Acids and Bases
30
While the magnitude of the value of K
eq
refects the observation that the
equilibrium state of this reaction lies far to the right, the equilibrium mixture will
maintain small but measurable concentrations of both hydrogen ion and hydroxide ion.
Commonly, the reverse reaction of Equation 1, which represents the auto-
ionization of water, is used to determine the [H
+
] and [OH
-
] in aqueous solutions. In
this case:
Equation 2:
H
2
O

H
+
+ OH
-
; ΔGº
298K
= +79.8
kJ

mol
; K
w
= [ H+ ] ∙ [ OH

] = 1.0 × 10
-14
The implication of this calculation is that even in the purest sample of water at
25
o
C, there are small but measurable concentrations of H
+
and OH
-
ion. In pure water
2
:
[ H
+
] = [ 0Hˉ ]
Η
+
= = × = × OH 1.0 10 1.0 10
- -14 -7
M
While the [H
+
] = [OH
-
] in pure water, many solutes (acids or bases) will change
the relative concentrations of these ions. In any case, the equilibrium relation, [H
+
]
[OH
-
] = 1.0 x 10
-14
, will remain applicable in any aqueous solution at 25
o
C. Therefore,
any substance that increases the [H
+
] must also decrease the [OH
-
] in order to satisfy
the equilibrium relation. Solutes that have this effect on the relative concentrations of
H
+
and OH
-
are called acids. Conversely, bases are substances that will increase the
[OH
-
] and will decrease the [H
+
].
In determining the [H
+
] and the [OH
-
] in an acid, base, or buffer solution
containing solutes of reasonable concentration, the contribution from the auto-
ionization of water can be neglected. In a solution of an acid, the [H
+
] can be
determined directly from the concentration and strength of the acid, and the [OH
-
]
is subsequently calculated using Equation 2. For example, the [H
+
] ion in a 0.020 M
solution of the strong acid hydrochloric acid is readily determined as follows:
Equation 3: HCl(g) → H
+
(aq) + Cl
-
(aq)
[ ]
o
0.020 ~0 0
Δ[ ] -0.020 +0.020 +0.020
[ ]
f
0 0.020 0.020
The [H
+
] = 0.020 M. The [OH
-
] ion determined from Equation 2:

H OH 1.0 10
OH
1.0
-14 + −

⋅ = ×
=
××
=
×
= ×
+
10
H
1.0 10
2.0 1
-14 -14
0 020 .
00 M
-13
2. The symbol K
w
represents the specifc equilibrium constant that refers to the auto-ionization of water. Like all equilibrium
constants, its value is a function of the temperature. In terms of calculations expected on the AP Chemistry Examination,
the value of K
w
at 25
o
C is commonly used.
pH and the Properties of [H+] in Aqueous Solution
31
For an aqueous solution of a base, the [OH-] is directly calculated, and
subsequently the [H+] can be determined. For example, the concentrations of each ion
in a 0.050 M solution of barium hydroxide are determined as:
Equation 4: Ba(OH)
2
(s) → Ba
2+
(aq) + 2 OH
-
(aq)
[ ]
o
0.050 0 ~0
Δ[ ] -0.050 +0.050 +0.10
[ ]
f
0 0.050 0.10
The [OH-] = 0.10 M. The [H+] ion determined from Equation 2:

H OH 1.0 10
H
1.0
-14 + −
+
⋅ = ×
=
× 10
OH
1.0 10
1.0 10
-14 -14

=
×
= ×
0 10 .
--13
M
The preceding examples illustrate that both the [H
+
] and the [OH
-
] in aqueous
solutions vary over a range that is greater than 14 orders of magnitude. The pH scale
is commonly used as an alternative expression to the [H
+
], where pH is defned as
pH = -log
10
[H
+
]. Algebraically, this is equivalent to [H
+
] = 10
-pH
, and shows that the pH
value is the negative of the exponent of 10 when the concentration is expressed as a
power of 10. The range of values for [H
+
] in aqueous solutions, approximately 1.0 x 10
-14

M < [H
+
] < 1.0 M , translates to a pH range from 14.00 to 0.00. Referring to the previous
examples, the pH of the 0.020 M HCl(aq) solution is pH = -log
10
0.020 = 1.70, the pH of
the 0.050 M Ba(OH)
2
(aq) solution is pH = -log
10
1.0 x 10
-13
= 13.00, and the pH of pure,
neutral water is then pH = -log
10
1.0 x 10
-7
=7.00. Analogously, the pOH of an aqueous
solution is defned as pOH = -log
10
[OH

], and [OH

] = 10
-pOH
.
The logarithmic pH scale conveniently represents the [H
+
] over the 14 orders of
magnitude, but no additional information is conveyed by the pH of the solution that
is not already indicated by the [H
+
]. In fact, the above relationships among [H
+
], [OH
-
],
pH, and pOH imply that the value of any one of these will fx the values of the others.
3

Calculation of these values for aqueous solutions will depend on the type of solute, and
fve types of calculations can be identifed:
• Solutions of strong acids only.
• Solutions of strong bases only.
• Solutions of weak acids only.
• Solutions of weak bases only.
3. The value of K
w
, like all equilibrium constants, is temperature dependent. While the relation: K
w
= [H
+
] [OH
-
]

is generally
true, the value of K
w
= 1.0 x 10
-14
at standard temperature of 25
o
C.
SPECIAL FOCuS: Acids and Bases
32
• Buffer solutions (containing appreciable concentrations of a weak acid and
its conjugate base).
Examples of these calculations are described elsewhere in this manual.
The laboratory determination of the [H
+
] of an aqueous solution, or equivalently,
its pH, can be done in two ways. The use of indicators, either in solution or adsorbed
onto pH paper, affords a crude determination of the pH of a sample. An indicator is
itself a weak acid whose color is different from that of its conjugate base. The indicator
is intensely colored, so that a negligible concentration of the indicator is added to the
solution – suffciently dilute so that it does not have an appreciable effect on the [H
+
] of
the solution. The indicator will then ionize according to the equation:
H-In


H
+
+ In
-
The acid dissociation constant of the indicator is written as
K
a,In
=

− [ ]
+ −
H In
H In
.
This equation can be rearranged as
In
H In H

+
− [ ]
=
K
a,In
, showing that the ratio of the
concentration of the conjugate base form to the acid form depends on the value of K
a
,
of the indicator, and the [H
+
] in the solution. For K
a, In
>> [H
+
], [In
-
] >> [H-In], and the
solution will have the color of the base form of the indicator. Conversely, for K
a, In
<<
[H
+
], [In
-
] << [H-In] and the solution will have the color of the acid form of the indicator.
In practice, the pK
a
of the indicator, defned as –log
10
K
a, In
, is compared to the pH of
the solution, and the color of the solution changes from that of the acid form to the
color of the base form as the pH of the solution changes from (pK
a
– 1) to (pK
a
+ 1).
Indicators with different pK
a
’s can be used to measure different ranges of pH values.
A chart of commonly used indicators and their transition point (pK
a
’s) can be found in
most textbooks.
More precise pH measurements are made with a pH meter. Though the technical
details vary by instrument, the fundamental operation of a pH meter is to measure
the electrochemical potential difference between a glass membrane electrode, whose
electrochemical potential is sensitive to the [H
+
] in the solution being measured, and
an internal reference electrode.
4
The measured potential depends on the [H
+
] in the
external solution, and the pH meter is simply a high impedance voltmeter that is
calibrated to refect the pH of the solution. With careful calibration using standard
buffer solutions, laboratory pH meters are routinely capable of making accurate pH
measurements to ±0.01 pH unit.
4. In practice, the test electrode and the reference electrode are combined into the same body, referred to as a combination
electrode.
pH and the Properties of [H+] in Aqueous Solution
33
In closing, the equilibrium that exists between H
+
ions and OH
-
ions in any
aqueous solution determines much of the chemistry of the solutions. Because
chemical properties of the solution are sensitive to variations in the concentrations
of these ions, the concentrations of these ions in such solutions are often critically
important. Though these equilibrium concepts are sometimes diffcult for students to
master, the role of pH as a measure of the concentration of not only the H
+
ion but also
the OH
-
ion is an important step that will allow students to go further in their mastery
of the material.
Exercises
Complete the following table:
Solute and Concentration [H
+
] [OH-] pH pOH
? M HCl 0.050 M
0.10 M CH
3
COOH
[K
a
= 1.8 x 10
-5
]
0.10 M CH
3
COOH
[K
a
= 1.8 x 10
-5
] & ? M CH
3
COO
-
5.12
Pure Water
0.10 M NH
3
[K
b
= 1.8 x 10
-5
]
& 0.20 M NH4
+
? M NH
3
[K
b
= 1.8 x 10
-5
] 1.0 x 10
-3
M
? M Ba(OH)
2
13.70
Answer:
Solute and Concentration [H
+
] [OH
-
] pH pOH
0.050 M HCl 0.050 M 2.0 x 10
-13
M 1.30 13.70
0.10 M CH
3
COOH
[K
a
= 1.8 x 10
-5
]
1.3 x 10
-3
M 7.5 x 10
-12
M 2.87 11.13
0.10 M CH
3
COOH
[K
a
= 1.8 x 10
-5
] & 0.24 M CH
3
COO
-
1.2 x 10
-5
M 8.8 x 10
-8
M 5.12 8.88
Pure Water 1.0 x 10
-7
M 1.0 x 10
-7
M 7.00 7.00
0.10 M NH
3
[K
b
= 1.8 x 10
-5
] & 0.20
M NH
4
+
1.1 x 10
-9
M 9.0 x 10
- 6
M 8.95 5.05
0.056 M NH3 [Kb = 1.8 x 10
-5
] 1.0 x 10
-11
M 1.0 x 10
-3
M 11.00 3.00
0.25 M Ba(OH)
2
2.0 x 10
-14
M 0.50 M 13.70 0.30
SPECIAL FOCuS: Acids and Bases
34
AP Exam Questions – Past Exams
(1984)
2. The pH of 0.1-molar ammonia is approximately
(A) 1
(B) 4
(C) 7
* (D) 11
(E) 14
Students should recognize that ammonia is a weak base and that a solution of
a weak base will have a pH > 7. Because a 0.1-molar solution of a strong base would
have a [OH
-
] = 0.1 M, a [H
+
] ion = 1 x 10
-13
M and pH = 13, the same concentration of
a weak base would have to have a lower pH value. Choice (D) is the only choice that
matches these constraints.
3. Find the pH of each of the following:
a. 0.10 M HCl.
b. A solution prepared by mixing 10.0 mL of a solution of 0.10 M HCl with
990.0 mL of distilled water.
c. A solution prepared by mixing 45.0 mL of 0.10 M HCl with 55.0 mL of
0.10 M NaOH.
d. A solution prepared by mixing 50.0 mL of a buffer of pH 4.00 with 50.0
mL of distilled water.
3. Answers:
a. 0.10 M HCl is a solution of a strong acid:

H HCl 0.10M
pH log 0.10 1.00
f
o
10
+
=[ ] =
= − =
b. Solution of a strong acid:

H 0.10 M
10 mL
990 mL 10 mL
f
+
= ×
+
=
= − =
0.0010 M
pH log 0.0010 3.00
10
c. The strong acid and strong base will neutralize, and there will be excess
base remaining:
pH and the Properties of [H+] in Aqueous Solution
35
Rxn: H
+
+ OH
-
→ H
2
O
mol
o
0.0045 0.0055 0
∆mol -0.0045 -0.0045 +0.0045
mol
f
0 0.0010 0.0045

OH
0.0010 M
0.10 L
0.010 M
pOH log
f
1

= =
= −
00
0.010 2.00
pH 14.00 - 2.00 12.00
=
= =
d. Because solution (d) is a buffer solution, the ratio
A
HA

[ ]
will not be
affected by dilution and the pH will remain unchanged. pH = 4.00
(assuming that after dilution, [A
-
], [HA] >> [H
+
], [OH
-
].
(2006B, Q1ai, Q1aii)
C
6
H
5
COOH(s)


C
6
H
5
COO
-
(aq) + H
+
(aq) K
a
= 6.46
x
10
-5
2. Benzoic acid, C
6
H
5
COOH, dissociates in water as shown in the equation above.
A 25.0 mL sample of an aqueous solution of pure benzoic acid is titrated using
standardized 0.150 M NaOH.
(a) After addition of 15.0 mL of the 0.150 M NaOH, the pH of the resulting
solution is 4.47. Calculate each of the following.
(i) [H
+
] in the solution
(ii) [OH
-
] in the solution
2. Answers:
Students should be able to convert among [H
+
], [OH
-
], pH, and pOH easily.
(a)(i)
H 0 10 3.4 10 M
-pH -4.47 -5 +
= = = × 1
(a)(ii)
OH
H
1.0 10
10
-14
-5

+
= =
×
×
=
K
w
3 4 .
3.0 10 M
-10
×
or

pOH p - pH 14.00 - 4.47 9.53
OH
= = =

K
w
== = = × 0 10 3.0 10 M
-pOH -9.53 -10
1
SPECIAL FOCuS: Acids and Bases
36
(2007, Q1c - e)
HF(aq) + H
2
O(l)


H
3
O
+
(aq) + F

(aq) K
a
= 7.2
x
10
-4
Hydrofuoric acid, HF(aq), dissociates in water as represented by the
equation above.
HF(aq) reacts with NaOH(aq) according to the reaction represented
below.
HF(aq) + OH-(aq)


H2O(l) + F

(aq)
2. A volume of 15.0 mL of 0.40 M NaOH(aq) is added to 25.0 mL of 0.40 M HF(aq)
solution. Assume that volumes are additive.
(c) Calculate the number of moles of HF(aq) remaining in the solution.
(d) Calculate the molar concentration of F

(aq) in the solution.
(e) Calculate the pH of the solution.
2. Answers:
(c) mol HF(aq) = initial mol HF(aq) − mol OH

(aq) added
= (0.025 L)(0.40 mol L
−1
) − (0.015 L)(0.40mol L
−1
)
= 0.010 mol − 0.0060 mol = 0.004 mol
(d) [HF]
.004 mol HF
.040L
0.10MHF = =
(e)
K
a
K
a
=
+ −
+

[ ]
=
[ ]×
H O F
HF
H O
HF
F
3
3
=
× × ( )
= ×
0.10 M 7.2 10
0.15 M
4.8
-4
110 M
pH -log 4.8 10 3.32
-4
10
-4
= × ( ) =
OR

pH pK
a
F
HF
M
M
= +

= + =
[ ]
log . log
.
.
. 3 14
15
10
3 32
pH and the Properties of [H+] in Aqueous Solution
37
Teaching Strategies
Introduce the auto-ionization of pure water as the reverse of the neutralization reaction
of a strong acid and a strong base. Emphasize that both H
+
and OH
-
are present
in any aqueous solution, and that the concentration of either particle will fx the
concentration of the other.
Emphasize the mathematical relationships among [H
+
], [OH
-
], pH, and pOH for
aqueous solutions and that, given the value of any one of these data, values for the
remaining are fxed and can easily be determined. Remind students that the relevant
equations are provided on the insert for the free-response section of the AP Chemistry
Examination, but they are not available for the multiple-choice questions.
In determining the [H
+
] in an aqueous solution, be sure that students can identify
the type of solution that they are dealing with:
• strong acid, only
• strong base, only
• weak acid, only
• weak base, only
• buffer solution containing both a weak acid and its conjugate base
Students should understand which principles/equations are applicable to each of
these instances.
Acid–Base Titrations
Cheri Smith
Yale Secondary School
Abbotsford, British Columbia
Titration is an important type of volumetric analysis usually used to determine the
number of moles of solute in a certain amount of aqueous solution. Once the amount
is known, other quantities may be discerned, such as the concentration of the solution
or the molar mass of the solute. The titration procedure generally involves the addition
of carefully measured portions of a “standard” solution of known concentration to a
measured mass or volume of an unknown. In many acid–base titrations, a chemical
indicator is added to signal the point at which the two reactants have been combined
in just the right ratio to give a complete reaction. This is sometimes called the
stoichiometric point or, more commonly, the equivalence point. Alternatively, the
equivalence point may be determined using a pH meter to follow the progress of
the reaction.
Approaching Titration Problems with an AP
®
Chemistry
Class
AP students may or may not be already familiar with introductory titration problems
such as those involving the determination of an unknown solution’s concentration or
fnding the volume of a solution required to react with a standard solution, from their
frst course in chemistry. In any event, the AP Chemistry teacher would be wise to
briefy review some simple problems before using a more sophisticated lecture and
laboratory approach. Simple problems should involve the idea of “matching” equivalent
amounts of strong acids and strong bases in solutions, for example, how many mL of
0.25 M sodium hydroxide will it take to be equivalent to 20 mL of 0.50 M hydrochloric
acid. For students who have done little lab, a good introduction may be to titrate
HCl with NaOH by drop counting in a well tray using phenolphthalein indicator. (For
SPECIAL FOCuS: Acids and Bases
40
example, how many drops of 0.1M NaOH are equivalent to 10 drops of 0.2 M HCl?)
Examples of more sophisticated lecture topics and labs that should be done in AP
Chemistry include:
• Determination of the molar mass of a unknown monoprotic acid. (KHP,
KHSO
4
, and NaHSO
3
are good unknowns to use in lab as their masses vary
signifcantly from one another.)
• Determination of the K
a
value for an unknown monoprotic acid.
(Approximately 0.1 mol/L acetic acid, formic acid and propanoic acids
are good unknowns for lab use as their K
a
values differ by a full order of
magnitude.)
• Back titrations to determine the strength of antacid products.
Once the teacher has reviewed and reinforced the students’ basic understanding
of titration, he or she can move on to the determination of pH experimentally and
mathematically at different points during a titration. Included should be titrations of a
strong acid with a strong base and, more important for AP Chemistry, a strong acid or
base with a weak acid or base. The teacher may elect to include diprotic titrations and
should certainly consider the selection of appropriate acid–base indicators, as well as
the use of pH meters or probeware.
Calculating the pH at various points during a theoretical titration is an extremely
valuable exercise for AP Chemistry students, as it requires the application of virtually
every type of pH problem encountered in the acid–base unit. An AP Chemistry
teacher would fnd it benefcial to begin with strong–strong titration curves, thus
reviewing the determination of the pH of strong acids and bases alone and in
combination with one or the other in excess, including the applications of K
w
and/
or pK
w
. Weak–strong curves are the source of a wealth of review, including weak
acid and base pH problems (ICE table calculations), buffer calculations, hydrolysis
problems, and strong acids or bases in excess. These should be reinforced by either
student run pH mater/probe use, or at least teacher demonstration of actual variation
of pH during titrations, buffer use, and hydrolysis reactions.
Calculation of pH in a Theoretical Titration Curve—
Use of the ICF Table
Most AP Chemistry students are able to handle the calculation of pH in a solution
containing only one dissolved species. When two solutions are combined, however,
they fnd the problem considerably more diffcult. One of the biggest issues is the
Acid–Base Titrations
41
organization of the increased amount of information given in such problems. The ICF
table is a valuable tool for AP Chemistry teachers and students facing problems that
involve chemical reactions such as neutralization with limiting and excess reactants.
It is similar to the ICE chart used for equilibrium problems in that the “I” represents
“initial” concentrations or numbers of moles and the “C” is the “change” in the initial
quantities during the reaction. The traditional “E,” for “equilibrium” in an ICE chart,
is replaced by an “F” that stands for “fnal” quantities following a reaction that goes to
completion in one direction. Such a reaction in a titration curve calculation will involve
neutralization by a strong acid or base. Because one (or both) of the reacting species
is strong, the reaction goes virtually to completion, hence “F” replaces “E.” Such a
reaction is said to be quantitative and is useful for analytic calculations.
Strong Acid–Strong Base Titrations
Though the pH at various points during the titration of a strong acid with a strong
base (or vice versa) is relatively easy to determine, pre-AP and AP Chemistry
teachers alike would be wise to apply the ICF technique early as it will build student
confdence for its application to more diffcult problems later. Consider the curve that
describes the titration of 25.0 mL of 0.100 mol/L HCl with NaOH.
FIGuRE 1
pH
Providing such a curve for the titration of 25 mL of 0.100 mol/L HCl, with no
further information, the AP Chemistry teacher might ask the class members to take
several minutes, working alone or collaboratively, to list any information they can
SPECIAL FOCuS: Acids and Bases
42
determine about the titration from the pH profle. Sample student responses might
include:
• Base is being added to acid.
• The reaction is represented by: HCl + NaOH → NaCl + H
2
O
• The initial pH = 1.0
• The initial [HCl] = [H
+
] = 10
-pH
= 10
-1.0
= 0.1 mol/L
• The acid is strong as the initial [H
+
] = the initial [HCl] indicates 100%
ionization.
• The pH at equivalence = 7.0
• The volume of base required to reach equivalence = 23.5 mL.
• The moles NaOH = moles OH
-
= 25.0 mL x 0.100 mol HCl x 1 mol NaOH =
1000 mL 1 mol HCl
0.00250 mol NaOH are required to reach equivalence.
• The [NaOH] = 0.00250 mol x 1000 mL = 0.106 mol/L
23.5 mL 1 L
AP Chemistry teachers should reinforce the importance of beginning titration
calculations with a balanced chemical equation, ideally in molecular form. This leads
to a proper mole ratio that is most likely to be correct when units include the formula
of the species they refer to. Any AP Chemistry text will contain a sample curve
to which teachers can refer; however, the teacher might prefer to produce a curve
using probeware (such as that available from Vernier or Pasco) or to use a variety
of simulations available commercially or on the Internet (see suggestions in the
laboratory section at the end of this chapter). Production of the curve could be done
after, during, or even before the calculations.
Once students have examined a pH profle, or a titration curve for a strong
monoprotic acid being titrated with a strong base, the AP Chemistry teacher can
discuss the calculation of pH at various points throughout the curve.
Example 1
Calculate the pH of the 25.0 mL sample of 0.100 mol/L solution of HCl being titrated in
the profle above.
Acid–Base Titrations
43
Strategy:
The student should recognize that pH = - log [H
+
] and that the concentration of a
solution is independent of its volume. Hence, 25.0 mL is irrelevant to the problem at
this point. Strong acids such as HCl, ionize completely, hence, [H
+
] = [HCl].
(AP Chemistry students must be aware of the “BIG 6” strong acids: HCl, HBr,
HI, HClO
4
, HNO
3
, and H
2
SO
4
(HClO
3
is included in some texts, although it ionizes less
than 100%); H
2
SO
4
is only nearly completely ionized for its frst ionization) as there is no
table of acid ionization constants included with the AP Chemistry Exam.)
Solution:
pH = - log [H
+
] = - log [HCl] = - log (0.100 mol/L) = 1.000
Example 2
Calculate the pH of the 25.0 mL sample of HCl following the addition of 10.0 mL of
0.106 mol/L NaOH. Note that a “rounder” concentration of base might be used for
introduction; however, this is what we’ve determined for our example.
Strategy:
The ICF table is very useful for helping students keep track of everything necessary to
solve this problem. If concentrations are to be used (which may be preferable because
pH depends upon concentration rather than moles), students must recognize that the
concentration of a solution is affected by the addition of water or another solution as
both of these cause dilution.
Step one is to dilute. The dilution factors are 25/35ths and 10/35ths,respectively.
Step two is to neutralize by applying the ICF table. Step three is to examine the
bottom line of the ICF table to determine what affects the pH.
Solution:
[HCl]
in
= 0.100 mol/L (25.0 mL) [NaOH]
in
= 0.106 mol/L (10.0 mL)
(35.0 mL) (35.0 mL)

= 0.0714 mol/L = 0.0303 mol/L
Neutralization in ICF shows: HCl(aq) + NaOH(aq) → NaCl(aq) + H
2
O(l)
I: 0.0714 M 0.0303 M 0 M
C: -0.0303 -0.0303 +0.0303
F: 0.0411 0 0.0303
SPECIAL FOCuS: Acids and Bases
44
The bottom line indicates a [HCl] = [H
+
] = 0.0411 mol/L, hence, pH
= - log [H
+
] = - log (0.0411) = 1.386
(Note that moles might have been used by multiplying the molarity of each
reactant by its volume and using the moles in the “I” line. The changes
would then have been 0.00106 moles. The fnal moles of acid divided
by a total volume of 0.0350 L would give the same concentration and
consequently, the same pH as shown.)
One fnal note that should be mentioned is that the ICF table indicates that the
[NaOH]
fnal
= 0 mol/L, following the neutralization. This is, of course, impossible, as
[H
+
][OH
-
] must always = 10
-14
= K
w
(at 25
o
C). Hence, [OH
-
] = [NaOH] at equivalence is
negligible and approaches 0, though it can never actually equal 0. If [H
+
] = [OH
-
], then
each = √ 10
-14
= 10
-7
, which is very small compared to the molarity numbers on the
problem, and so ≈ 0.
Example 3
Calculate the pH of the 25.0 mL sample of HCl following the addition of 23.5 mL of
0.106 mol/L NaOH.
Strategy:
As in example 2, dilute and neutralize, then examine the bottom line of the ICF table.
Solution:
[HCl]
in
= 0.100 mol/L (25.0 mL) [NaOH]
in
= 0.10638 mol/L (23.5 mL)
(48.5 mL) (48.5 mL)
= 0.0515 mol/L = 0.0515 mol/L
Neutralization in ICF shows: HCl(aq) + NaOH(aq) → NaCl(aq) + H
2
O(l)
I: 0.0515 M 0.0515 M 0 M-
C: -0.0515 -0.0515 +0.0515
F: 0 0 0.0515
This process shows that the pH of 7 at the equivalence point is due to the
formation of 48.5 mL of a 0.0515 mol/L solution of NaCl, which dissociates to form
the neutral cation, Na
+
and an anion, Cl
-
. As the conjugate base of the strong acid,
HCl, Cl
-
is too weak to accept any appreciable quantity of protons from the water it is
dissolved in and hence, it too is neutral. Determination of the pH at some point beyond
Acid–Base Titrations
45
equivalence in the same fashion is helpful as it involves the application of Kw and/or
pKw along with the ICF table.
Example 4
Calculate the pH of the 25.0 mL sample of HCl following the addition of 30.0 mL of
0.106 mol/L NaOH solution.
Strategy:
As in example 2, dilute and neutralize, then examine the bottom line of the ICF table.
The application of K
w
and/or pK
w
will be required to convert the [OH
-
].
Solution:
[HCl]in = 0.100 mol/L (25.0 mL) [NaOH]in = 0.10638 mol/L (30.0 mL)
(55.0 mL) (55.0 mL)
= 0.0455 mol/L = 0.0580 mol/L
Neutralization in ICF shows: HCl(aq) + NaOH(aq) → NaCl(aq) + H
2
O(l)
I: 0.0455 M 0.0580 M 0 M-
C: -0.0455 -0.0455 +0.0455
F:

0 0.0125 0.0455
As explained in example 3, the salt, NaCl, is completely neutral and does not
affect the pH at all. However, the [NaOH]
excess
is very signifcant. From this number,
it becomes evident that the pOH = - log [OH
-
] = -log[NaOH] = - log (0.0125) = 1.90.
Consequently, as pK
w
= pH + pOH = 14.00 at 25
o
C, the pH = 14.00 – 1.90 = 12.10. The
alternative approach would be to recognize that [H
+
] = K
w
/[OH
-
] = 10
-14
/0.0125 = 8.0 x
10
-13
M. Hence, pH = - log (8.0 x 10
-13
) = 12.10.
Weak–Strong Titrations
A classic weak–strong titration involves the titration of a weak carboxylic acid, such
as ethanoic (acetic) acid or methanoic (formic) acid, with a strong base. Once students
have examined a pH profle, or titration curve for a weak monoprotic acid being
titrated with a strong base, the AP Chemistry teacher can compare the calculation of
pH at various points throughout the curve with that of a strong–strong titration.
SPECIAL FOCuS: Acids and Bases
46
FIGuRE 2
ml NaOH added
pH
Providing such a curve, for the titration of 25 mL of 0.100 mol/L acetic acid, with no
further information, the AP Chemistry teacher might ask the class to take several
minutes, working collaboratively with a partner, to list any information they can
determine about the titration from the pH profle, with emphasis on any obvious
differences they notice between this curve and the earlier strong–strong one. Sample
student responses might include:
• Base is being added to acid.
• The reaction is represented by: CH
3
COOH + NaOH→ NaCl + H
2
O.
• The net ionic reaction is CH
3
COOH + OH
-
→ H
2
O + CH
3
COO
-
.
• The initial pH approximates 2.9 (higher than the strong acid).
• The initial [H
+
] = 10
-pH
= 10
-2.9
= 0.0013 mol/L.
• The acid is not as strong as the initial [H
+
] << the initial [CH
3
COOH]
indicates less than 100% ionization.
• The % ionization = 0.0013 x 100% = 1.3%. This is typical of a weak acid.
0.100
• The pH rises more quickly during a weak–strong titration.
• The pH at equivalence is between 8 and 9 (above the neutral value of 7).
• The volume of base required to reach equivalence = 23.5 mL (same value).
• This is a particularly signifcant point for students to recognize and it should
be emphasized that the strength of an acid has no bearing on the volume
Acid–Base Titrations
47
of base required to neutralize it. One mole of monoprotic acid requires one
mole of base to neutralize it completely whether the acid is strong or weak.
• The moles NaOH = 25.0 mL x 0.100 mol HA x 1 mol NaOH = 0.00250 mol
1000 mL 1 mol HA
required to reach equivalence.
• The [NaOH] = 0.00250 mol x 1000 mL = 0.106 mol/L.
23.5 mL 1 L
The same sources suggested for strong–strong curves may be relied upon for
weak–strong curves. Once students have examined a pH profle, or titration curve
for a weak monoprotic acid being titrated with a strong base, the AP Chemistry
teacher can discuss the calculation of pH at various points throughout the curve. The
ICF table is particularly useful for students attempting to deal with the additional
complexity of these problems. AP Chemistry teachers should stress the review of
weak acid, weak base, buffer, and hydrolysis calculations as they arise. It is important
for students to consider the chemical composition of the solution being titrated as well
as the process for calculating its pH at any particular point.
Example 5
Calculate the pH of the 25.0 mL sample of a 0.100 mol/L solution of CH
3
COOH being
titrated in the profle above. (Given the K
a
of acetic acid = 1.8 x 10
-5
.)
Strategy:
The student should recognize that acetic acid is a weak acid, hence an ICE table type
of calculation is required to determine the [H
3
O
+
].
Solution:
According to the Brønsted-Lowry defnition, an acid will donate a proton to the base
it is dissolved in. Because this acid is weak, only a small percentage of the molecules
will donate protons, resulting in the following equilibrium:
CH
3
COOH + H
2
O ↔ H
3
O
+
+ CH
3
COO
-

I: 0.100 M - 0 M 0 M
C: - x + x + x [H
+
] formed is defned as x
E: ~ 0.100 x x For weak acids that ionize less than 5%,
x may be considered negligible compared with the initial concentration.
SPECIAL FOCuS: Acids and Bases
48
K
a
= [H
3
O
+
] [CH
3
COO
-
] = x
2
= 1.8 x 10
-5

[CH
3
COOH] 0.100
Simple algebra reveals x = [H
3
O
+
] = 1.3 x 10
-3
mol/L and pH = - log [H
3
O
+
]
= - log (1.3 x 10
-3
) = 2.87.
Example 6
Calculate the pH of the 25.0 mL sample of CH
3
COOH following the addition of 10.0 mL
of 0.106 mol/L NaOH.
Strategy:
The ICF table may be used in an identical series of steps to those used for example 2
for the strong–strong titration shown previously.
Solution:
[CH
3
COOH]
in
= 0.100 M (25.0 mL) [NaOH]
in
= 0.106 M (10.0 mL)
(35.0 mL) (35.0 mL)
= 0.0714 mol/L = 0.0303 mol/L
Neutralization in ICF shows:
CH
3
COOH(aq) + NaOH(aq) → NaCH
3
COO(aq) + H
2
O(l)
I: 0.0714 M 0.0303 M 0 M -
C: -0.0303 -0.0303 +0.0303
F: 0.0411 0 0.0303
The bottom line indicates a [CH
3
COOH] = 0.0411 M and a [CH
3
COO
-
] =
[CH
3
COO
-
] = 0.0303 M. The student should recognize the presence of a weak
conjugate pair with signifcant quantities of both the conjugate acid and base present.
The AP Chemistry teacher should point out that such a solution constitutes a buffer.
The pH of this solution may be calculated as a weak acid with conjugate base present
as a common ion:
K
a
= [H
3
O
+
] [CH
3
COO
-
] = [H
3
O
+
] (0.0303) = 1.8 x 10
-5

[CH
3
COOH] 0.0411
Since [H
3
O
+
] = 2.4 x 10
-5
mol/L, pH = - log (2.4 x 10
-5
) = 4.61.
The pH of a buffer may also be calculated using the Henderson-Hasselbalch
equation:
Acid–Base Titrations
49
pH = pK
a
+ log [CH
3
COO
-
] = 4.74 + log (0.0303) = 4.61
[CH
3
COOH] (0.0411)
This portion of the curve is referred to as the “buffer zone.” It is particularly
instructive for the AP Chemistry teacher to point out that exactly half way to
equivalence, the quantity of excess weak acid exactly equals the quantity of
conjugate base formed by the neutralization. Substitution into each of the equations
above, in turn, shows:
K
a
= [H
3
O
+
] [CH
3
COO
-
] = [H
3
O
+
] and pH = pK
a
+ log [CH
3
COO
-
] = pK
a
+ log(1) = pK
a
[CH
3
COOH] [CH
3
COOH]
The teacher should encourage AP Chemistry students to use either or both of
these equations to recognize and to verify the changes that occur during the buffer
zone portion of a weak–strong titration curve:
• halfway to equivalence, [H
+
] = K
a
and pH = pK
a
.
• prior to halfway, [H
+
] exceeds K
a
and so pH < pK
a
.
• past halfway and before equivalence, [H
+
] < K
a
and so pH exceeds pK
a
.
Example 7
Calculate the pH of the 25.0 mL sample of CH
3
COOH following the addition of 23.5 mL
of 0.106 mol/L NaOH.
Strategy:
As in example 6, dilute and neutralize, then examine the bottom line of the ICF table.
Solution:
[CH
3
COOH]
in
= 0.100 M (25.0 mL) [NaOH]
in
= 0.10638 M (23.5 mL)
(48.5 mL) (48.5 mL)
=0.0515 mol/L =0.0515 mol/L
Neutralization in ICF shows:
CH
3
COOH(aq) + NaOH(aq) → NaCH
3
COO(aq) + H
2
O(l)
I: 0.0515 M 0.0515 M 0 M -
C: -0.0515 -0.0515 +0.0515
F: 0 0 0.0515
The bottom line shows that the basic pH at the equivalence point is due to
the formation of 48.5 mL of a 0.0515 mol/L solution of the salt, NaCH
3
COO,
SPECIAL FOCuS: Acids and Bases
50
which dissociates to form the neutral cation, Na
+
and the weakly basic
anion, CH
3
COO
-
. As the conjugate base of the weak acid, CH
3
COOH,
CH
3
COO
-
is strong enough to accept an appreciable quantity of protons from
the water it is dissolved in and hence, it forms hydroxide ions by hydrolysis.
CH
3
COO
-
(aq) + H
2
O(l) → CH
3
COOH(aq) + OH
-
(aq)
I: 0.0515 M - 0 M 0 M
C: -x + x + x [OH
-
] formed is
E: ~ 0.0515 x x defned as x
K
b
= [CH
3
COOH][OH
-
] = K
w
= 10
-14
= 5.6 x 10
-10
= x
2
hence,
[CH
3
COO
-
] K
a
1.8 x 10
-5
0.0515
x = [OH
-
] = 5.3 x 10
-6
mol/L and pOH = - log(5.3 x 10
-6
) = 5.27,
and pH = 14 – 5.27 = 8.73
Example 8
Calculate the pH of the 25.0 mL sample of CH
3
COOH following the addition of 30.0 mL
of 0.106 mol/L NaOH solution.
Strategy:
As in example 7, dilute and neutralize, then examine the bottom line of the ICF table.
As in the strong–strong example 4 shown previously, the application of K
w
and/or
pKw will be required to convert the [OH
-
].
Solution:
[CH
3
COOH]
in
= 0.100 M (25.0 mL) [NaOH]
in
= 0.10638 M (30.0 mL)
(55.0 mL) (55.0 mL)
= 0.0455 mol/L = 0.0580 mol/L
Neutralization in ICF shows:
CH
3
COOH(aq) + NaOH(aq) ↔ NaCH
3
COO(aq) + H
2
O(l)
I: 0.0455 M 0.0580 M 0 M -
C: -0.0455 -0.0455 +0.0455
F: 0 0.0125 0.0455
As explained in example 7, the salt, NaCH
3
COO, is weakly basic due to
hydrolysis. However, the [NaOH]
excess
is much more signifcant. In fact, the hydroxide
Acid–Base Titrations
51
ion from the NaOH forces the hydrolysis reaction so far left that its contribution to the
[OH
-
] may be completely ignored. The [OH
-
] = [NaOH]
excess
for all intents and purposes.
Consequently, the pOH = - log [OH
-
] = - log (0.0125) = 1.90. Hence, as pK
w
= pH + pOH
= 14.00 at 25
o
C, the pH = 14.00 – 1.90 = 12.10. The alternative approach would be to
recognize that [H
3
O
+
] = K
w
/[OH
-
] = 10
-14
/0.0125 = 8.0 x 10
-13
M. Hence, pH = - log (8.0 x
10
-13
) = 12.10.
The alternative to titrating a weak acid with a strong base is, of course, the
titration of a weak base with a strong acid. A classic example might be the titration of
ammonia with hydrochloric acid.
FIGuRE 3
Such a titration would include the calculation of pH by:
• The use of the ionization constant of a weak base, K
b
. Initially one is
determining the pH of a solution of ammonia.
• The use of a K
b
expression or Henderson-Hasselbalch during the buffer zone.
In this portion of the curve the solution contains the weak conjugate pair
ammonia and ammonium ion, therefore it is a basic buffer.
SPECIAL FOCuS: Acids and Bases
52
• The use of the acid ionization constant of a weak acid, K
a
at equivalence due
to the formation of an acidic salt, in this case, ammonium chloride, which
undergoes cationic hydrolysis.
• The application of the standard defnition of pH applied to the excess [H
3
O
+
]
present in a solution of ammonium chloride once excess strong acid has
been added and the titration proceeds beyond equivalence.
Selection of an Appropriate Acid-Base Indicator
An acid–base indicator is a chemical species that has an acid and a base form with
one or both forms being visibly colored. Many indicators were originally isolated
from organic plants or foods. Some have been used as dyes. The general form for the
equation that represents the equilibrium for an indicator is:
HIn(aq) + H
2
O(l)

↔ H
3
O
+
(aq) + In
-
(aq)
acid form base form
(color one) (color two)
If the indicator is placed in a stronger acid, the acid will donate protons to the
indicator, producing the HIn form (and color). A stronger base will pull protons from
the indicator, producing the In
-
form (and color). When indicators are in the middle
of their color change, the [HIn] = [In
-
] and the color shown will be a combination of
the acid and base form colors. This is called the endpoint or transition point for the
indicator.
Since indicators are actually weak acids, they do have K
a
and consequently pK
a

values. Substitution into familiar equations shows:
K
a
= [H
3
O
+
] [In
-
] = [H
3
O
+
] and pH = pK
a
+ log [ In
-
] = pK
a
+ log(1) = pK
a
[HIn] [HIn]
Hence, an indicator will reach its endpoint and change color when the [H
3
O
+
]
in the system equals the indicator’s K
a
. Similarly, during the color change (at the
indicator’s endpoint), the pH of the system will equal the indicator’s pK
a
.
Ideally, endpoints should occur exactly at equivalence. Thus, different types of
titrations will require different indicators. Phenolphthalein changes color between
pH 8.2 and 10.0. It has a pK
a
of approximately 9.1, hence it would be quite appropriate
for the acetic acid titration because example 7’s calculated equivalence point was
pH 8.73. On the other hand, it would be absolutely wrong for use in the titration of
ammonia with hydrochloric acid because the pH at equivalence for that titration
Acid–Base Titrations
53
would be around 5.4, as shown in the third curve (Figure 3). One signifcant point
demonstrated by each of the curves we’ve studied is the rapid change in pH that
suddenly occurs at equivalence. AP Chemistry teachers can demonstrate this
dramatically through the use of a pH meter or probe ware (such as that available
from Vernier or Pasco) or a variety of simulations available commercially or on the
Internet (see suggestions in the laboratory section at the end of this chapter). Because
of this rapid change, an indicator’s pK
a
need not exactly match the pH expected at
equivalence. Rather, the indicator must simply complete its entire color change during
the vertical part of the titration curve. This means that phenolphthalein might be
selected ahead of an indicator having a pK
a
closer to the pH at equivalence simply
because its change from colorless to pink is so clearly visible and easy to detect.
The titration curve below shows that phenolphthalein or methyl red along with
many other indicators would be appropriate for determining the equivalence point for
a strong–strong titration.
FIGuRE 4
Sample Questions from Previous AP Chemistry Exams
The topic of titration appears on virtually every AP Chemistry exam. It is often a
signifcant topic in the free-response portion of the examination. Problem number
SPECIAL FOCuS: Acids and Bases
54
one of the three required problems is always an equilibrium problem. This problem
centers on an acid–base equilibrium nearly every other year. Such problems require
student confdence with acid–base calculations of the sort discussed in this chapter.
2002 Operational Exam
HOBr(aq) ↔ H
+
(aq) + OBr

(aq) K
a
= 2.3 x 10
-9
1. Hypobromous acid, HOBr, is a weak acid that dissoci ates in water, as represented
by the equation above.
(a) Calculate the value of [H
+
] in an HOBr solution that has a pH of 4.95.
(b) Write the equilibrium constant expression for the ionization of HOBr in
water, then calculate the concentration of HOBr(aq) in an HOBr solution that
has [H
+
] equal to 1.8 x 10
-5
M.
(c) A solution of Ba(OH)
2
is titrated into a solution of HOBr.
(i) Calculate the volume of 0.115 M Ba(OH)
2
(aq) needed to reach the
equivalence point when titrated into a 65.0 mL sample of 0.146 M
HOBr(aq).
(ii) Indicate whether the pH at the equivalence point is less than 7, equal to
7, or greater than 7. Explain.
(d) Calculate the number of moles of NaOBr(s) that would have to be added to
125 mL of 0.160 M HOBr to produce a buffer solution with [H
+
] = 5.00 ´ 10
–9

M.
Assume that volume change is negligible.
(e) HOBr is a weaker acid than HBrO
3
. Account for this fact in terms of
molecular structure.
Solution:
(a) pH = –log[H
+
] ; [H
+
] = 10
-4.95
= 1.1 x 10
-5
mol/L
(b) K
a
= [H+][OBr] = 2.3 x 10
-9
[HOBr]
[H
+
] = [OBr

] = 1.8 x 10
-5
M
(1.8 x 10
-5
)
2

= 2.3 x 10
-9

X
x = [HOBr] = 0.14 M
Acid–Base Titrations
55
(c) (i) 65.0 mL x
0.146 mol HOBr
x
1 mol H+ x 1 mol OHˉ x 1 mol Ba(OH)
2
1000 mL 1 mol HOBr 1mol H+ 2 mol OHˉ

x
1000 mL
= 41.3 mL
0.115 mol Ba(OH)
2
(ii) pH > 7; salt of a weak acid is a weak base (hydrolysis of OBr
-
)
(d) pH = pK
a
+ log [A

]
or [A

] =
[HA]K
a
[HA] [H+]
[OBr

] = (0.160)(2.3 ′ 10
9
)
= 0.0736 M
5.00 ′ 109
125 mL x 0.736 mol OBr


x
1 mol NaOBr
= 0.00920 mol NaOBr
1000 mL 1 mol OBr

(e) very electronegative oxygen is able to draw elec trons away from the bromine
and weaken the O–H bond, making it easier for the hydrogen ion to be
donated.
O
Br — O – H

O
2003 Operational Exam
C
6
H
5
NH
2
(aq) + H
2
O(l) ↔ C
6
H
5
NH
3
+
(aq) + OH

(aq)
1. Aniline, a weak base, reacts with water according to the reaction represented
above.
(a) Write the equilibrium constant expression, K
b
, for the reaction represented
above.
(b) A sample of aniline is dissolved in water to produce 25.0 mL of 0.10 M
solution. The pH of the solution is 8.82. Calculate the equilibrium constant,
K
b
, for this reaction.
(c) The solution prepared in part (b) is titrated with 0.10 M HCl. Calculate the
pH of the solution when 5.0 mL of the acid has been titrated.
(d) Calculate the pH at the equivalence point of the titration in part (c).
(e) The pK
a
values for several indicators are given below. Which of the
indicators listed is most suitable for this titration? Justify your answer.
SPECIAL FOCuS: Acids and Bases
56
Indicator pK
a
Erythrosine 3
Litmus 7
Thymolphthalein 10
Solution
(a) K
b
=
C H NH OH
C H NH
6 5 3
6 5 2
+ −
[ ]
(b) pOH = 14 – pH = 14 – 8.82 = 5.18
–log[OH

] = 5.18; [OH

] = 6.61×10
–6
M
[OH
-
] = [C
6
H
5
NH
3
+
]
K
b
=
6 61 10
0 10 6 61 10
6
2
6
.
. – .
× ( )
×


= 4.4×10
–10
(c) 25 mL x
0 1
1
. mol
L

= 2.5 mmol C
6
H
5
NH
2
5 mL ×
0 1
1
. mol
L
= 0.5 mmol H
+
added
2.0 mmol base remains in 30.0 mL solution (may determine from ICF)
4 4 10
0 50
30 0
20 0
3
10
.
.
.
.
×
[ ] +







X X
mmol
ml
mmol
00 0 . mL






X = 1.80×10
–9
= [OH

]
[H
+
] =
1 10
1 8 10
14
9
×
×


.
= 5.6×10
–6
; pH = 5.26
(d) When neutralized, there are 2.5 mmol of C
6
H
5
NH
3
+
in 50.0 mL of solution,
giving a [C
6
H
5
NH
3
+
] = 0.050 M (may determine from ICF.)
This cation will partially ionize according to the following equilibrium:
C
6
H
5
NH
3
+
(aq) ↔ C
6
H
5
NH
2
(aq) + H
+
(aq)
at equilibrium, [C
6
H
5
NH
2
] = [H
+
] = X
[C
6
H
5
NH
3
+
] = (0.050–X)

X
X
2
0 050 ( . ) −
= K
a
= 2.3×10
–5
X = 1.06×10
–3
= [H
+
]
pH = –log[H
+
] = 2.98
Acid–Base Titrations
57
(e) Erythrosine; the indicator will change color when the pH is near its pK
a
,
since the equivalence point is near pH 3, the indicator must have a pK
a
near
this value.
The lab-based essay question has focused on acid-base titrations. Occasionally,
the core concepts of titrimetry will be tested in an essay question that is not lab
based. The following is an example of a lab-based acid–base essay question:
1998 Operational Exam
Lab-Based Question
An approximately 0.1–molar solution of NaOH is to be standardized by titration.
Assume that the following materials are available.
• Clean, dry 50 mL buret
• 250 mL Erlenmeyer fask
• Wash bottle flled with distilled water
• Analytical balance
• Phenolphthalein indicator solution
• Potassium hydrogen phthalate, KHP, a pure solid monoprotic acid (to be
used as the primary standard)
(a) Briefy describe the steps you would take, using the materials listed above,
to standardize the NaOH solution.
(b) Describe (i.e., set up) the calculations necessary to determine the
concentration of the NaOH solution.
(c) After the NaOH solution has been standardized, it is used to titrate a weak
monoprotic acid, HX. The equivalence point is reached when 25.0 mL of
NaOH solution has been added. In the space provided at the right, sketch
the titration curve, showing the pH changes that occur as the volume
of NaOH solution added increases from 0 to 35.0 mL. Clearly label the
equivalence point on the curve.
SPECIAL FOCuS: Acids and Bases
58
FIGuRE 5
pH
Volume of NaOH Solution Added (mL)
(d) Describe how the value of the acid–dissociation constant, K
a
, for the weak
acid HX could be determined from the titration curve in part (c).
(e) The graph below shows the results obtained by titrating a different weak
acid, H
2
Y, with the standardized NaOH solution. Identify the negative ion
that is present in the highest concentration at the point in the titration
represented by the letter A on the curve.
FIGuRE 6
Volume of NaOH Solution Added
pH
Acid–Base Titrations
59
Solution:
(a) • Exactly mass a sample of KHP in the Erlenmeyer fask and add distilled
water to dissolve the solid.
• Add a few drops of phenolphthalein to the fask.
• Rinse the buret with the NaOH solution and fll.
• Record starting volume of base in buret.
• With mixing, titrate the KHP with the NaOH solution until it just turns
slightly pink.
• Record end volume of buret.
• Repeat to check your results.
(b)
mass of KHP
= moles of KHP;
molar mass KHP
since KHP is monoprotic, this is the number of moles of NaOH.

moles of NaOH
= molarity of NaOH

L of titrant
FIGuRE 7
equivalence point
pH
Volume of NaOH Solution Added (mL)
(d) From the titration curve, at the 12.5 mL volume point, the acid is half-
neutralized and the pH = pK
a
. K
a
= 10
-pKa
(e) Y
2–

SPECIAL FOCuS: Acids and Bases
60
Recommended Laboratory Exercises Related to
Acid–Base Titration
Wet Labs
Of the 22 recommended laboratory experiments for AP Chemistry, three involve
acid–base titrimetry. As suggested earlier, the frst experiment should involve
the preparation of a primary standard that could be used to standardize a base
that might be used to determine a molar mass, a K
a
value, the moles of water of
hydration, the effciency of an antacid or the concentration of a diprotic acid, to list a
few possibilities. An even simpler experiment (titration by drops) may be useful for
students who have not encountered any form of titration in a previous class. Such
an experiment will help bridge students’ pre-AP or general chemistry skills to those
required for AP Chemistry.
The second experiment should involve the development of experimental titration
curves to be graphed and interpreted by the students. The classic two curves are,
of course, the titration of frst, HCl and second, CH
3
COOH with NaOH as examples
of strong acid–strong base and weak acid–strong base curves. Other possibilities
include the titration of a weak base such as NH
3
with HCl or a polyprotic acid, such as
H
3
PO
4
with NaOH. A potentiometric titration, based on conductivity of, for example,
Ba(OH)
2
with H
2
SO
4
is another possibility.
The third experiment involves the determination of appropriate indicators for
different acid–base titrations.
There are a number of excellent resources for laboratories such as these. Essential
Experiments in Chemistry by Morrison and Scodellaro, SMG Lab Books, 2005,
includes all three of these labs (14A, 14G and 14 H). Laboratory Investigations: AP
Chemistry by Hostage and Fossett, Peoples Publishing Group, 2005, contains two of
them (#8 and #10). Additionally Chemistry and Computers by Holmquist and Volz,
2003, contains fve of these labs (#23–#27) each with specifc direction for use of probe
ware.
Virtual Labs
There are a number of laboratory exercises that may be done virtually. Some of them
are commercially available on DVD or CD. One of the more popular is the Virtual
Chemlab disc provided with the text, Chemistry, the Central Science, 10th edition,
by Brown, LeMay and Bursten (Prentice Hall, 2006). This disc includes several lab
exercises that students may perform virtually, on the computer, including a titration
Acid–Base Titrations
61
lab that allows them to select various reagents to use in a variety of titrations. The
data they collect may be presented in tabular and/or graphic form.
Bridging to the Lab by Jones and Tasker, W.H. Freeman and Company, 2002,
includes 11 different virtual lab exercises, one of which uses an acid-base titration to
determine the pK
a
of a food preservative. Students produce a titration curve and use it to
determine the pK
a
of a weak acid as well as its concentration and fnally its molar mass.
In addition to the commercial lab exercises, there are some Web sites whose
authors have graciously provided their lab exercises free of charge. A fantastic source
of Flash-based chemistry simulations has been prepared by Tom Greenbowe from
Iowa State. Start at www.chem.iastate.edu/group/Greenbowe/sections/projectfolder/
fashfles/to select a titration simulation that is very easy to use. Students may select
from several weak or strong acids, one of two possible indicators, and four different
bases that may be placed in the buret.
Another great Web site for curves was prepared by Yue-Wing Long from Wake
Forest University. Visit www.wfu.edu/~ylwong/chem/titrationsimulator/index.html to
actually plot a titration curve that may be used to determine the concentration and/or
the pK
a
of a variety of weak acids. This site is particularly useful as it allows students
to alter the strength of the acid they use by selecting various K
a
or concentration
values for the acids they titrate.
Polyprotic Acids
Lew Acampora
St. Francis School
Louisville, Kentucky
According to Brønsted-Lowry formalism, an acid is defned as a proton donor.
5
The
common and unique reactivity of the proton, also represented as the H
+
ion, imbues
acids with their familiar properties. Though all Brønsted-Lowry acids contain
hydrogen, the converse statement—that all hydrogen-containing compounds act
as acids—is not generally true. The extent to which a species donates a proton is a
measure of the acidity of the species and is ultimately determined by the electronic
structure of the particle. For example, because gaseous hydrogen chloride dissolves
and ionizes completely in aqueous solutions, it is classifed as a strong acid:
HCl(aq) + H
2
O(l) → H
3
O
+
(aq) + Cl
-
(aq)
or
HCl(aq) → H
+
(aq) + Cl
-
(aq)
Hydrogen fuoride, however, dissolves into water and reaches a state of
dynamic equilibrium in which a fraction of the HF molecules will be ionized at any
instant. This state of equilibrium is indicated by the double arrows and leads to the
classifcation of hydrofuoric acid as a weak acid:
HF(aq) + H
2
O(l)  H
3
O
+
(aq) + F
-
(aq)
or
HF(aq)  H
+
(aq) + F
-
(aq)
The difference in the behavior of HCl and HF can be traced to such factors as the
relative strength of the H-X bond, the strength of the intermolecular forces between
the HX molecule and the water molecules, and the energy of hydration of the X
-
ion.
5. The more general defnition of acids, attributed to G. N. Lewis, defnes acids and bases in terms of their capacity to
accept or donate pairs of electron. A Lewis acid is an electron-pair acceptor. Though this defnition is more general, most
quantitative problems in AP Chemistry can be approached using the Brønsted-Lowry formalism.
SPECIAL FOCuS: Acids and Bases
64
Hydrochloric acid and hydrofuoric acid are examples of monoprotic acids
because each molecule contains only one ionizable hydrogen. Acetic Acid, CH
3
COOH,
is another example of a monoprotic acid because, though each molecule contains four
hydrogen atoms, it is only the carboxylic hydrogen that is ionized in aqueous solution:
CH
3
COOH(aq)  H
+
(aq) + CH
3
COO
-
(aq)
Because of the covalent character of the C – H bond, the hydrogen atoms that are
directly bonded to carbon are not ionized in aqueous solution.
Many substances contain more than one ionizable hydrogen atom, and such
substances are generally referred to as polyprotic acids, with subsets including
diprotic, triprotic, etc. In these substances, each acidic hydrogen can be donated. For
example, one of the most common diprotic acids is sulfuric acid, H
2
SO
4
. A structural
diagram for sulfuric acid shows that both hydrogen atoms are directly bonded to
oxygen atoms, and the character of these O-H bonds leads to the acidity of both
hydrogen atoms. Thus, the sulfuric acid molecule can lose both protons sequentially
to become, frst, the hydrogen sulfate ion, HSO
4
-
, and fnally the sulfate ion, SO
4
2-
.
FIGuRE 1
The underlying principles of reactivity that govern the behavior of monoprotic acids
are generally true for polyprotic acids; however, there are two additional factors or
considerations that should be noted. The presence of more than one acidic hydrogen
per molecule will affect the stoichiometry of reactions of those polyprotic acids.
Additionally, the tendency to donate each proton will be different, and will have
ramifcations in terms of the acid strength.
The Brønsted-Lowry formalism considers an acid–base reaction as simply a
proton transfer reaction between a proton donor (the acid) and a proton acceptor (the
base). A general schema for such a reaction with a monoprotic acid is:
HA + B →A
-
+ HB
+
Polyprotic Acids
65
The stoichiometry of the reaction shows that acid and base are consumed in
equimolar quantities. If the reactant is a diprotic acid, then each mole of acid will
contribute two moles of protons. In order to neutralize a given quantity of base, then,
only half as many moles of the diprotic acid are required:
H
2
A + 2 B → A
2-
+ 2 HB
+
or
½ H
2
A + B →½ A
2-
+ HB
+
While 1 mole of hydrochloric acid will completely neutralize 1 mole of sodium
hydroxide, the same neutralization would require only ½ mole of sulfuric acid.
6
The tendency of a particular species to donate a proton—the acid strength—is
ultimately traced to the electronic structure of the acid and its conjugate base. For this
reason, successive ionizations of a polyprotic acid are generally weaker. As protons
are removed from the substance, any remaining ionizable protons are more strongly
bonded because a positively charged proton will be more strongly attracted to the
more negatively charged particle. The resulting species is a weaker acid than the
original particle. This is refected in the values of the acid dissociation constants,
7
K
an
,
for polyprotic acids, which decrease in value for successive ionizations. Consider, for
example, the triprotic weak phosphoric acid, H
3
PO
4
. Steps in the complete ionization
of phosphoric acid and the values of the acid dissociation constants are shown here:
Reaction Equation Equilibrium Constant Expression Equilibrium Constant Value
H
3
PO
4


H
+
+ H
2
PO
4
-
K
H H PO
H PO
a1
2 4
3 4
=




⋅ 



[ ]
+ −
7.3 x 10
-3
H
2
PO
4
-


H
+
+ HPO
4
2-
K
H HPO
H PO
a2
4
2
2 4
=




⋅ 







+ −

6.2 x 10
-8
HPO
4
2-
 H
+
+ PO
4
3-
K
H PO
HPO
a3
4
3
4
2
=




⋅ 







+ −

4.8 x 10
-13
6. The concept of “normality” has fallen somewhat out of favor and can be omitted from the AP Chemistry course, but it still
may be useful in describing the stoichiometry of acid–base reactions. Normality in this context is defned as “moles of
ionizable protons per liter of solution.” For a diprotic acid, the normality is simply twice the molarity. Thus, a 0.10 M H
2
SO
4

solution would be considered 0.20 N, or 0.20 normal. Similarly, a 0.10 M solution of the triprotic phosphoric acid, H
3
PO
4
,
would be 0.30 N.
7. The acid dissociation constants for polyprotic acids are generally denoted as K
an
, where the “n” refers to the nth proton
donated by the molecular species. A diprotic acid would have different values of K
a1
and K
a2
, a triprotic acid would have K
a1
,
K
a2
, and K
a3
.
SPECIAL FOCuS: Acids and Bases
66
The phosphoric acid molecule H
3
PO
4
is the strongest acid among the substances
listed. Its conjugate base, the dihydrogen phosphate ion H
2
PO
4
-
, still contains two
ionizable protons and is itself an acid.
8
Because of its overall negative charge and the
bond electron density, the H-O bonds in H
2
PO
4
-
are stronger than those in H
3
PO
4
, and
H
2
PO
4
-
is a weaker acid.
The observation that successive protons are increasingly diffcult to remove from
polyprotic acids implies that these polyprotic acids ionize stepwise when reacting
with strong bases. For phosphoric acids, the following net ionic equations apply:
Reaction Description Net Ionic Equation
Equal volumes of 0.10 M phosphoric acid and 0.10 M sodium
hydroxide are mixed.
H
3
PO
4
+ OH
-
→ H
2
PO
4
-
+ H
2
O
Equal volumes of 0.10 M phosphoric acid and 0.20 M sodium
hydroxide are mixed.
H
3
PO
4
+ 2 OH
-
→ HPO
4
2-
+ 2 H
2
O
Equal volumes of 0.10 M phosphoric acid and 0.30 M sodium
hydroxide are mixed.
H
3
PO
4
+ 3 OH
-
→ PO
4
3-
+ 3 H
2
O
Equal volumes of 0.10 M sodium dihydrogen phosphate and 0.20 M
sodium hydroxide are mixed.
H
2
PO
4
-
+ 2 OH
-
→ PO
4
3-
+ 2 H
2
O
Since phosphoric acid, dihydrogen phosphate ion, and monohydrogen phosphate ion
can each act as acids, their respective conjugate bases are dihydrogen phosphate,
monohydrogen phosphate, and phosphate ion. These bases are listed in order of
increasing base strength, and the values of the respective base dissociation constants
refect this:
Reaction Equation Equilibrium Constant Expression Equilibrium Constant Value
PO
4
3-
+ H
2
O 

HPO
4
2-
+ OH
-
K
HPO OH
PO
b3
4
2
4
3
=




⋅ 







− −

2.1 x 10
-2
HPO
4
2-
+ H
2
O  H
2
PO
4
-
+ OH
-
K
H PO OH
HPO
b2
2 4
4
2
=




⋅ 







− −

1.6 x 10
-7
H
2
PO
4
-
+ H
2
O  H
3
PO
4
+ OH
-
K
H PO OH
H PO
b1
3 4
2 4
=
[ ]
⋅ 









1.3 x 10
-12
Again, since the bases will accept protons stepwise, the following net ionic equations
can be written:
8. A species such as H
2
PO
4
-
, which can either donate a proton, acting as an acid, or accept a proton, acting as a base, is
termed amphiprotic or amphoteric. Though these terms are not strictly synonymous, for the purposes of the AP Chemistry
curriculum, they can be considered interchangeable. Other examples of such species include the monohydrogen
phosphate ion, HPO
4
2-
, and the hydrogen carbonate or bicarbonate ion, HCO
3
-
.
Polyprotic Acids
67
Reaction Description Net Ionic Equation
Equal volumes of 0.10 M hydrochloric acid and 0.10 M sodium
phosphate are mixed.
PO
4
3-
+ H
+
→ HPO
4
2-
Equal volumes of 0.20 M hydrochloric acid and 0.10 M
sodium phosphate are mixed.
PO
4
3-
+ 2 H
+
→ H
2
PO
4
-
Equal volumes of 0.30 M hydrochloric acid and 0.10 M
sodium phosphate are mixed.
PO
4
3-
+ 3 H
+
→ H
3
PO
4
Equal volumes of 0.10 M hydrochloric acid and 0.10 M sodium
monohydrogen phosphate are mixed.
HPO
4
2-
+ H
+
→ H
2
PO
4
-
Because a solution of a polyprotic acid or its conjugate base(s) may contain several
species related by different equilibrium reactions and constants, calculations to
determine the concentration of each species may seem intractable. Fortunately, the
values of the relevant acid dissociation constants are suffciently diverse that the
solution chemistry is usually dominated by one ionization, and the concentrations
of each species can be determined from straightforward calculation. Consider, for
example, a solution of 0.10 M phosphoric acid. In principle, the solution contains
the species H
3
PO
4
, H
2
PO
4
-
, HPO
4
2-
, and PO
4
3-
, in addition to the H
+
and OH
-
ions. In
practice, the chemistry of the solution is dominated by the ionization reaction of the
frst proton:
H
3
PO
4
 H
+
+ H
2
PO
4
-
Ionization of subsequent protons:
H
2
PO
4
-
 H
+
+ HPO
4
2-
and
HPO
4
2

-
 H
+
+ PO
4
3-
will have a negligible effect on the [H
+
] in the solution. The [H
+
] of the
resulting solution can be determined from the ionization of the frst proton:
H
3
PO
4
 H
+
+ H
2
PO
4
-
[ ]
o
0.10 M ~0 0
∆[ ] -x +x +x
[ ]
eq
0.10 – x x x
K
a1
=
[H
+
] ∙ [H
2
PO
4

]
[H
3
PO
4
]
7.5 × 10
–3
=
x ∙ x
0.10 – x
[H
+
] = [H
2
PO
4

] = x = 0.024 M
SPECIAL FOCuS: Acids and Bases
68
The resulting [H
+
] and [H
2
PO
4
-
] can be used to determine the [HPO
4
2-
]:
K
a2
2
2
=

× =
+ −


H HPO
H PO
6 10
0.0
4
2 4
8
.
224 M x
0.024 M
HPO x 6 10 M
4
8
( )⋅
( )
= = ×
− − 2
2 .
x
x
As expected, the relatively small [HPO
4
2-
] implies that the second ionization
occurs to a negligible extent and has no measurable effect on the [H
+
] or the [H
2
PO
4
-
].
Similarly, the [PO
4
3-
] can be determined using previously calculated concentrations:
K
a3
3
2
3
4 8
=

× =
+ −


H PO
HPO
10
0.0
4
4
1
.
224 M x
6 10 M
PO x 1 10
8
4
8
( )⋅
× ( )
= = ×

− −
.
.
2
2
3 1
MM
x
x
Not surprisingly, the calculated [PO
4
3-
] is extremely small.
FIGuRE 2
The behavior of polyprotic acids in acid–base titrations refects the same
considerations. Each of the ionizable protons is lost from the acid sequentially with
increasing pK
a
values. The graph of pH vs. volume base added, above, illustrates
Polyprotic Acids
69
what happens when a solution of a weak, monoprotic acid is titrated with a strong
base. Important points on the graph are the equivalence point, where the moles of
added OH
-
are equal to the moles of HA initially present, and the half-equivalence
point. At the half-equivalence point, half of the initial moles of weak acid remain, and
half have been converted to the conjugate base. At this point in the titration, [HA] =
[A
-
], and K
a
=

[ ]
=
+ −
+
H A
HA
H , so p pH
1
2
Eq. Pt.
K
a
= and K
a
K
a
10
-p
= .
FIGuRE 3
The graph of pH vs. volume base shows two buffering regions corresponding to
the sequential ionization of each proton from the acid when a solution of a weak
diprotic acid is titrated with a strong base. As in the case of the monoprotic acid, the
equilibrium constants for each ionization may be determined from the pH values at
each half-equivalence point. At the frst half-equivalence point in the titration curve,
[H
2
A] = [HA
-
] and:
K
a1
=

[ ]
=
+ −
+
H HA
H A
H
2
, so p pH
1
2
Eq. Pt. 1
K
a1
= , and K
a
K
a
1
1
10
-p
= .
At the half-equivalence point corresponding to the second ionization, [HA
-
] = [A
2-
] and
K
a2
=

=
+
+
H A
HA
H
2-
-
, so p pH
1
2
Eq. Pt. 2
K
a2
= , and K
a
K
a
2
2
10
-p
= .
The fundamental principles of acid–base chemistry remain valid for acids
that have many ionizable protons, and a solid understanding of the chemistry of
monoprotic acids and bases is essential for students before they can grasp the details
of the chemistry of polyprotic species.
SPECIAL FOCuS: Acids and Bases
70
Examples from Prior AP Chemistry Examinations
(1994)
H
2
C
2
O
4
+ 2 H
2
O  2 H
3
O
+
+ C
2
O
4
2-
31. Oxalic acid, H
2
C
2
O
4
, is a diprotic acid with K
1
= 5.36 x 10
-2
and K
2
= 5.3 x 10
-5
. For
the reaction above, what is the equilibrium constant?
(A) 5.36 x 10
-2
(B) 5.3 x 10
-5
(C) 2.8 x 10
-6
(D) 1.9 x 10
-10
(E) 1.9 x 10
-13
31. Answer: (C) From Hess’s Law
H
2
C
2
O
4
+ H
2
O  H
3
O
+
+ HC
2
O
4
-
K
1
= 5.36 x 10
-2
HC
2
O
4
-
+ H
2
O  H
3
O
+
+ C
2
O
4
2-
K
2
= 5.3 x 10
-5
H
2
C
2
O
4
+ 2 H
2
O  2 H
3
O
+
+ C
2
O
4
2-
K = K
1
x K
2
= 2.8 x 10
-6
(1998)
5(e). The graph below shows the results obtained by titrating a different weak acid,
H
2
Y, with the standardized NaOH solution. Identify the negative ion that is
present in the highest concentration at the point in the titration represented by
the letter “A” on the curve.
FIGuRE 4
5(e). Answer: A
2-
Polyprotic Acids
71
(1997)
1. The overall dissociation of oxalic acid, H
2
C
2
O
4,
is represented below. The overall
dissociation constant is also indicated.
H
2
C
2
O
4
 2 H
+
+ C
2
O
4
2-
K = 3.78
x
10
-6
(a) What volume of 0.400-molar NaOH is required to neutralize completely a
5.00 x 10
-3
-mole sample of pure oxalic acid?
(b) Give the equations representing the frst and second dissociations of oxalic
acid. Calculate the value of the frst dissociation constant, K
1
, for oxalic acid
if the value of the second dissociation constant, K
2
, is 6.40 x 10
-5
.
(c) To a 0.015-molar solution of oxalic acid, a strong acid is added until the pH
is 0.5. Calculate the [C
2
O
4
2-
] in the resulting solution. (Assume the change in
volume is negligible.)
(d) Calculate the value of the equilibrium constant, K
b
, for the reaction that
occurs when solid Na
2
C
2
O
4
is dissolved in water.
Answers:
(a)
5.00 10 mol H C O 2 5.00 10 mol H 1.
3
2 2 4
3
× = × × ( ) =
− − +
000 10 mol H 1.00 10 mol OH
1.00 10 mol
2 2
2
× = ×
×
− + − −

OH
0.400M
0.0250 L 25.0 mL

= =
(b) There are two successive dissociations:
H
2
C
2
O
4
 H
+
+ HC
2
O
4
-
(equilibrium constant = K
1
)
HC
2
O
4
-
 H
+
+ C
2
O
4
2-
(equilibrium constant = K
2
)

K K K
K
K
K
= ×
= =
×
×
1 2
1
2
3.78 10
6.40 10
-4
-5
5.91 10
-2
= ×
(c) pH 0.5 H 10 0.32 M
-0.5
= = =
+
Because K << 1, [H
2
C
2
O
4
]
eq
≈ 0.015 M

K
H C O
H C O
C O
2 4
2
2 2 4
2 4
2
=

[ ]
+ −

2
=
⋅[ ]
=
× ( ) ×
+
H C O
H
3.78 10
2 2 4
-6
K
2
0.015
0.32
6.0 10 M
-7
( )
( )
= ×
2
(d) C
2
O
4
2-
+ H
2
O  HC
2
O
4
-
+ OH
-
K
K
K
b
w
a
= =
×
×
=
2
1.00 10
6.40 10
1.56
-14
-5
10
-10
×
SPECIAL FOCuS: Acids and Bases
72
(1994)
7. A chemical reaction occurs when 100. milliliters of 0.2000-molar HCl is added
dropwise to 100. milliliters of 0.100-molar Na3PO4 solution.
(a) Write the two net ionic equations for the formation of the major species.
(b) Identify the species that acts as both a Brønsted acid and as a Brønsted
base in the equations in (a). Draw the Lewis electron-dot diagram for this
species.
(c) Sketch a graph using the axis provided, showing the shape of the titration
curve that results when 100. milliliters of the HCl solution is added slowly
from a buret to the Na
3
PO
4
solution. Account for the shape of the curve.
(d) Write the equation for the reaction that occurs if a few additional milliliters
of HCl solution are added to the solution resulting from the titration in (c).
7. Answers:
(a) H
+
+ PO
4
3-
 HPO
4
2-
H
+
+ HPO
4
2-
 H
2
PO
4
-
(b) HPO
4
2-
Polyprotic Acids
73
(c)
(d) H
+
+ H
2
PO
4
-
 H
3
PO
4
Salts and Buffers
Adele Mouakad
St. John’s School
San Juan, Puerto Rico
Acid–Base Properties of Salt Solutions
A salt is an ionic compound that can be considered to be the product of the reaction
between an acid and a base. The salt that is produced is sometimes neutral, but in
many instances it dissolves in water to form a solution that is acidic or basic. This can
be clearly explained from the Brønsted-Lowry theory, which shows that some ions can
act as acids or bases. These ions can act as acids or bases because they react with
water. This reaction with water is called hydrolysis. Hydrolysis is the reaction of an ion
with water to produce the conjugate acid and hydroxide ion or the conjugate base and
hydronium ion.
Notable examples are:
(i) The reaction of the acetate ion with water.
CH
3
COO
-
+ H
2
O → CH
3
COOH + OH
-
This resulting solution would be basic due to the presence of the
hydroxide ion. Since this solution has the form of a base ionization, you can
write an expression for K
b
. K
b
= [OH
-
][CH
3
COOH]
[CH
3
COO
-
]
(ii) The reaction of the ammonium ion with water.
NH
4
+
+ H
2
O → NH
3
+ H
3
O
+
This resulting solution would be acidic due to the presence of the
hydronium ion. Since the resulting solution has the form of an acid
ionization, the expression for K
a
is: K
a
= [H
3
O
+
][NH
3
]
[NH
4
+
]
SPECIAL FOCuS: Acids and Bases
76
How can you predict whether a salt will be acidic, basic or neutral?
When the acetate ion hydrolyzes, it produces acetic acid, which is a weak acid.
This means that the acetate ion holds fairly strongly to the proton (i.e., it does not
ionize readily). So we can say that the acetate ion acts as a base. In general, we can
say that anions of weak acids will be basic. On the other hand, the anions of strong
acids (e.g., Cl
-
from HCl) have very little basic character. In other words, these anions
do not hydrolyze.
Let us examine the cation conjugate to a weak base, such as the ammonium
(NH
4
+
) ion, which we used in our example above. It is clearly seen that it behaves
like an acid. So we can generalize that the cations of weak bases are acidic. On the
other hand, the cations of strong bases (alkali metal cations and alkaline earth metal
cations) have hardly any acidic character.
Aqueous metal ions, that are not those of the alkali or alkaline earth metals,
usually hydrolyze by acting as acids. Many of these ions form hydrated metal ions.
For example, copper (II) ion forms the Cu(H
2
O)
4
2+
ion. The Cu
2+

ion acts as a Lewis
acid, forming bonds with a lone pair of electrons in the O atoms of H
2
O. Because the
electrons are drawn away from the oxygen atoms by the Cu atom, the O atoms, in
turn, tend to draw electrons from the O – H bonds, making them increasingly polar
and weaker. As a result, the H
2
O molecules in Cu(H
2
O)
4
2+
are acidic. Copper (II) salts
tend to have a pH around 3.5.
Cu(H
2
O)
4
2+
hydrolyzes by donating a proton to a free water molecule. One of the
water molecules loses a proton, reducing the charge of the ion by 1, and the water
molecule becomes a hydroxide as shown in the reaction below.
Cu(H
2
O)
4
2+

(aq)
+ H
2
O
(l)
↔ Cu(H
2
O)
3
(OH)
+
(aq)
+ H
3
O
+
(aq)
We can summarize this in the following tables:
IONS OF NEuTRAL SALTS
Cations
Na
+
, K
+
, Rb
+
, Cs
+

Mg
2+
, Ca
2+
, Sr
2+
, Ba
2+

Anions Cl
-
, Br
-
, I
-
, ClO
4
-
, BrO
4
-
, ClO
3
-
, NO
3
-
Some Common Basic Ions
F
-
CH
3
COO
-
NO
2
-
CN
-
HCO
3
-
CO3
2-
S
2-
HS
-
SO
4
2-
HPO
4
2-
PO
4
3-
ClO
-
ClO
2
-
Salts and Buffers
77
Some Common Acidic Ions
NH
4
+
CH
3
NH
3
+
Al
3+
Pb
2+
Transition metal ions (e.g., Cu
2+
)
HSO
4
-
H
2
PO
4
-
To predict whether the salt solution is acidic, basic, or neutral you need to know
whether the ions comprising the salt are acidic or basic or do not hydrolyze. In other
words, you have to determine the acidity or basicity of the ions comprising the
salt. Consider sodium cyanide, NaCN. This salt is composed of the potassium ion,
Na
+
and the cyanide ion, CN
-
. Sodium is an alkali metal, so Na
+
does not hydrolyze.
However, the CN
-
is the conjugate base of a weak acid, hydrocyanic acid, a weak acid.
Therefore, the cyanide ion, CN
-
, is basic. A salt of sodium cyanide is expected to be
basic. Conclusions regarding acid or basic hydrolysis can be made by examining the
K
a
or K
b
values in the literature for the species involved.
Let us examine the following exercise from the 1981 AP Exam.
Exercise 1
Al(NO
3
)
3
K
2
CO
3
NaHSO
4
NH
4
Cl
(a) Predict whether a 0.10 molar solution of each of the salts above is acidic,
neutral, or basic.
(b) For each of the solutions that is not neutral, write a bal anced chemical
equation for a reaction oc curring with wa ter that supports your prediction.
Solution:
(a) Al(NO
3
)
3
= acidic K
2
CO
3
= basic
NaHSO
4
= acidic NH
4
Cl = acidic
(b) Al(NO
3
)
3
:
Al(H
2
O)
6
3+
+ H
2
O ↔ H
3
O
+
+ Al(H
2
O)
5
(OH)
2+

NO
3
--
+ H
2
O →No reaction (conjugate base of a strong acid; it does not
hydrolyze)

K
2
CO
3
:
K
+
+ H
2
O → No reaction.

CO
3
2-
+ H
2
O ↔ HCO
3
-
+ OH
-

NaHSO
4
:
SPECIAL FOCuS: Acids and Bases
78
Na
+
+ H
2
O → No reaction
HSO
4
-
+ H
2
O ↔ H
3
O
+
+

SO
4
2-
NH
4
Cl:
Cl
-
+ H
2
O → No reaction (conjugate base of strong acid; it does not
hydrolyze)

NH
4
+
+ H
2
O ↔ NH
3
+ H
3
O
+
One of the things to note from the above exercise is that students need to be aware
that the transition metal ions and other metallic ions mentioned above do form
complex ions with water. Students need to know the coordination number for the
more common ions, such as Al
3+
, Cu
2+
, Zn
2+
, etc.
A few basic rules would be:
1. A salt of a strong acid and a strong base. (e.g. NaCl). The salt does not have
any ions that will hydrolyze, so it will be neutral.
2. A salt of a strong base and a weak acid. The anion is the conjugate base of a
weak acid, so it hydrolyzes giving a basic solution.
3. A salt of a weak acid and a strong base. The cation of this salt is the
conjugate of a weak base, so it hydrolyzes producing an acidic solution.
4. A salt of a weak acid and weak base. In this case both ions hydrolyze, the
acidity or basicity depends on the K
a
and K
b
of the conjugate acids and
bases respectively. If the K
a
> K
b
, the solution will be acidic. If the K
b
> K
a
,
the solution will be basic.
Buffers
Defnition: A buffer solution is one that resists changes in pH when small quantities
of an acid or a base are added to it. If 0.01 mol of HCl is added to 1.0 L of sodium
chloride solution, the pH changes from 7.0 to 2.0. On the other hand, if this same
amount of hydrochloric acid is added to 1.0 L of ocean or sea water, the pH changes by
only 0.1 unit. Obviously, sea water has other substances present that maintain the pH
of sea water at a fairly constant level. The pH of sea water ranges from 7.5 to 8.4. This
is very important because many aquatic organisms are very sensitive to changes in
pH. The pH of mammalian blood is also maintained at a pH of close to 7.38.
Composition: A buffer contains a weak acid and its conjugate base or a weak base
and its conjugate acid. Thus a buffer solution contains both an acid species and a
Salts and Buffers
79
base species. The buffer in sea water is mostly due to the presence of carbonic acid,
H
2
CO
3,
and its conjugate base, the bicarbonate ion HCO
3
-
. In blood, both the carbonate
and phosphate buffers are present.
Adding an acid to the buffer: The buffer solution must remove most of the new
hydrogen ions otherwise the pH would drop markedly. The hydrogen ions will
combine with the bicarbonate ion to make carbonic acid:
HCO
3
-
(aq)
+ H
+
(aq)
↔ H
2
CO
3(aq)
Even though the reaction is reversible, most of the new hydrogen ions have been
removed, so the pH won’t change very much. But because the reaction is reversible,
the pH will decrease a very small amount.
Adding a base to the buffer solution: Bases contain hydroxide ions or react to
form them, so the buffer solution must remove most of these ions. There are two
ways in which the carbonic/bicarbonate buffer can remove the hydroxide ion. Either
carbonic acid or bicarbonate ion reacts:
H
2
CO
3(aq)
+ OH
-
(aq)
↔ HCO
3
-
(aq)
+ H
2
O
(l)
HCO
3
-
(aq)
+ OH
-
(aq)
↔ CO
3
2-
(aq)
+ H
2
O
(l)
Since most of the hydroxide has been removed, the pH of the buffer changes very little.
The pH of a buffer: The pH of buffers can vary from being in the acid range of
the pH scale all the way to the basic range. The pH of a buffer is determined by the
relative amounts of acid and conjugate base that are present in the solution and the K
a

of the acid. Let us examine a buffer made of acetic acid and sodium acetate. This is
similar to one of citric acid and sodium citrate that is often found in commercial fruit
juices, to maintain the pH of the juice.
Let us compare the pH of two different buffer solutions.
1.(a) A buffer made of 50.0 mL of a 0.10 M solution of acetic acid, CH
3
COOH, and
50.0 mL of a 0.10 M sodium acetate, CH
3
COONa.
• The K
a
of acetic acid is 1.7 x 10
-5
.
• The equilibrium reaction is CH
3
COOH
(aq)
+ H
2
O
(l)
↔ CH
3
COO
-
(aq)
+
H
3
O
+
(aq)
.
• The total volume of the buffer is 100.0 mL.
• The concentration of acetic acid is 0.0050 moles of acid/0.100L = 0.050 M.
• The concentration of the acetate ion is 0.0050 moles of acetate ion/0.100
L = 0.050 M.
SPECIAL FOCuS: Acids and Bases
80
Filling in the ICE concentration table:
CH
3
COOH H
2
O CH
3
COO
-
H
3
O
+
Initial 0.050 M 0.050 M 0
Change -X +X +X
Equilibrium 0.050 M – X 0.050 M + X X
In this solution
K
a
= [H
3
O
+
] [CH
3
COO
-
] / [CH
3
COOH].
We substitute the equilibrium concentrations in the above equation. In
doing so we can assume that X is small compared with 0.050 M.
So the net equation is:
1.7 x 10
-5
= [X] [0.050 M]/ [0.050 M]
After rearranging, we get
[H
3
O
+
] = (1.7 x 10
-5
) (0.050 M)/ (0.050 M)
[H
3
O
+
] = 1.7 x 10
-5
M
pH = - log [1.7 x 10
-5
M] = 4.76 which is in the acid range
Now in this example the concentrations of the acid and the conjugate base
are equal and the concentration of the hydronium ion is equal to K
a
. The pH
of this buffer can be altered by adjusting the relative concentrations of the
acid and the conjugate base.
(b) For example, if the equilibrium concentration of the acetate ion is 0.070
M and the equilibrium concentration of the acetic acid is 0.025 M, the
concentration of hydronium ion is
[H
3
O
+
] = K
a
[HA]/ [A
-
].
Substituting in the above equation we can see that the ratio [HA]/[A
-
] =
0.025/0.070, is less than 1, and the resulting [H
3
O
+
] = 5.67 x 10
-5
has a pH of
5.25. It is slightly more basic than the previous solution, but still well within
the acid range.
A conclusion from the above problem:
If the ratio [HA]/[A
-
] = 1 then the pH of the resulting solution will be equal to
pK
a
If the ratio [HA]/[A
-
] > 1 then the resulting solution will be more acidic than
pK
a
.
If the ratio [HA]/[A
-
] < 1 then the resulting solution will be more basic than
pK
a
.
Salts and Buffers
81
2. A buffer solution is made up of 50.0 mL of 0.10 M NH
4
+
and 50.0 mL of 0.10 M
NH
3
. The K
a
of ammonium ion is K
w
/ K
b

K
a
= 1 x 10
-14
/ 1.8 x 10
-5

K
a
= 5.56 x 10
-10
The equilibrium reaction is NH
4
+
(aq)
+ H
2
O
(l)
↔ NH
3(aq)
+ H
3
O
+
.
The fnal volume is 100 mL, so the fnal concentration of [NH
4
+
] = 0.050 M.
The fnal concentration of [NH
3
] = 0.050 M .
Filling in the ICE concentration table:
NH
4
+
H
2
O NH
3
H
3
O
+
Initial 0.050 M 0.050 M 0
Change -X +X +X
Equilibrium 0.050 M – X 0.050 M + X X
Now K
a
= [H
3
O
+
] [NH
3
]/ [NH
4
+
].
We can assume that X is small compared to 0.050 M.
Substituting we get:
• 5.56 x 10
-10

= (X) (0.050 M) / (0.050 M)
• We can see that X = [H
3
O
+
] = 5.56 x 10
-10
M
• pH = -log [5.56 x 10
-10
]
This gives a pH of 9.3, which is in the basic range.
3. From studying the two different buffers, we can clearly see that the pH of
the buffer will be determined mainly by the value of K
a
.
a. For a buffer with pH 3, we choose an acid/conjugate base combination
that has a pK
a
close to 3.
b. For a buffer with a pH of 9, we choose an acid/conjugate base
combination that has a pK
a
close to 9.
4. The addition of water affects a buffer solution (dilutes of a buffer). When
water is added to a buffer solution, the pH remains unchanged. Let us
examine this.
HA ↔ H
+
+ A
-
K
a
= [H
+
] [A
-
] / [HA]
SPECIAL FOCuS: Acids and Bases
82
Rearranging this, we can see that:
[H
+
] = K
a
[HA] / [A
-
].
The addition of more water to the buffer does not change the ratio [HA]/[A
-
],
since the same amount of water is being added to both. If this ratio remains
unchanged, the pH stays the same. This analysis does not consider new
effects that appear if the solution becomes extremely dilute.
5. A buffer resists change to pH when small amounts of acid or base are
added. We are now going to examine this quantitatively.
Suppose we have a buffer consisting of 0.10 M nitrous acid and 0.20 M
sodium nitrite. The K
a
of nitrous acid is 4.5 x 10
-4
. To 95.0 mL of this buffer
solution we add 5.0 mL of 0.10 M hydrochloric acid. This type of problem
becomes a two-part problem.
This frst part is a stoichiometric calculation where we assume that all the
H
3
O
+
from the strong acid reacts with the nitrite ion forming nitrous acid.
The second part is an equilibrium problem where the concentrations from
the frst part are used.
Solution
Part 1—Stoichiometric Calculation
When a hydronium ion is added to the buffer it reacts with the nitrite ion:
H
3
O
+
(aq)
+ NO
2
-

(aq)
→ HNO
2

(aq)
+ H
2
O
(l)
Because the nitrous acid is a weak acid, we assume that the reaction goes to
completion.
First, we must calculate amounts of hydrogen ions, nitrous acid and nitrite ions
in the solution before the reaction. Because HCl is a strong acid, the hydrogen ion
concentration is equal to the molarity of the acid.
• HCl is 0.10 M, therefore the concentration of H
3
O
+
is 0.10 M.
• The moles of H
3
O
+
= (0.10 moles/L) (0.005L) = 0.00050 moles.
• The moles of HNO
2
= (0.10 moles/L) (0.095L) = 0.0095 moles.
• The moles of NO
2
-
= (0.20 moles/L) (0.095L ) = 0.019 moles.
We assume that all the H
3
O
+
added reacts with the nitrite ion. Therefore, 0.00050
moles of acid is produced and 0.00050 moles of nitrite ion is used up.
• Moles of nitrite ion remaining = (0.019 – 0.00050) mol = 0.0185 mol.
Salts and Buffers
83
• Moles of nitrous acid after reaction = (0.0095 + 0.00050) mol = 0.010 mol.
• [HNO
2
] = 0.010 mol/0.10 L = 0.10 M.
• [NO
2
-
] = 0.0185 moles/ 0.10L = 0.185M .
Part 2—Equilibrium Problem
Using the concentration found in Part 1, you construct the following ICE table:
HNO
2
(mol/L) H
3
O
+
(mol/L) NO
2
-
(mol/L)
Initial 0.10 M 0 0.185 M
Change - X + X + X
Equilibrium 0.10 – X X 0.185 + X
The equilibrium constant equation is:
K
a
= [H
3
O
+
] [NO
2
-
] / [HNO
2
]
Substituting, you get:
4.5 x 10
-4
= [ X ] [0.185 + X] / [0.10 – X]
Assuming that X is small enough that 0.1855 + x ≈ 0.185 and 0.10 – X ≈ 0.10,
x 10
-4
= (X) (0.185) /0.10
[H
3
O
+
] = X = 2.43 x 10
-4
The pH of the original buffer was 3.65, the pH after the addition of the 5.0 mL of
0.10 M HCl
(aq)
is 3.61. So the pH changed by only 0.04 units The buffer pH changed
much less than 0.5 units, which is considered the maximum change that a buffer
should have and continue to be effective at pH control.
Examples from Prior AP Chemistry Examinations
(1983)
2(a). Specify the properties of a buffer solution. De scribe the components and the
composition of ef fective buffer solu tions.
2(b). An employer is interviewing four applicants for a job as a laboratory
technician and asks each how to pre pare a buffer solution with a pH close
to 9.
Archie A. says he would mix acetic acid and sodium acetate solutions.
Beula B. says she would mix NH
4
Cl and HCl so lutions.
Carla C. says she would mix NH
4
Cl and NH
3
so lutions.
Dexter D. says he would mix NH
3
and NaOH so lutions.
SPECIAL FOCuS: Acids and Bases
84
Which of these applicants has given an appropri ate pro ce dure? Explain your
answer, referring to your dis cussion in part (a). Explain what is wrong with the
er roneous proce dures.
(No calculations are necessary, but the following acid ity constants may be
helpful: acetic acid, K
a
= 1.8 x10
–5
; NH
4
+
, K
a
= 5.6 x 10
–10
)
Answer:
2(a). A buffer solution resists changes in pH when small amounts of an acid or a
base are added. Preparation of a buffer: Mix a weak acid with the conjugate
base of the acid.
2(b). Archie has a buffer solution: he has a weak acid and its conjugate base, but it
does not have the correct pH since the pK
a
is close to 5. So he does not have
the correct buffer.
• Beula does not have a buffer, since she has a weak acid (NH
4
+
) and a strong
acid (HCl).
• Carla has the correct buffer. She has a weak acid, (NH
4
+
) and its conjugate
base (NH
3
). She also has the correct pH, since the pK
a
is close to 9.
• Dexter does not have a buffer since he has mixed a weak base and a strong
base.
(1977A)
3. The value of the ionization constant, K
a
, for hypochlor ous acid, HOCl, is 3.1 X 10
–8
.
(a) Calculate the hydronium ion concentration of a 0.050 molar solution of HOCl.
(b) Calculate the concentration of hydronium ion in a so lu tion prepared
by mixing equal volumes of 0.050 molar HOCl and 0.020 molar sodium
hypochlorite, NaOCl.
Answer:
(a) HOCl + H
2
O ↔ H
3
O
+
+ OCl
-
X << 0.050
X = [H
3
O
+
] = 4.0 x 10
–5
M
(b) HOCl + H
2
O ↔ H
3
O
+
+ OCl
-
X ‹‹ 0.010
X = [H
3
O
+
] = 8.0 x 10
–8
M
Salts and Buffers
85
(2005A)
HC
3
H
5
O
2
(aq) ↔ C
3
H
5
O
2

(aq) + H
+
(aq) K
a
= 1.34 × 10
–5
Propanoic acid, HC
3
H
5
O
2
, ionizes in water ac cording to the equation above.
(a) Write the equilibrium constant expression for the reaction.
(b) Calculate the pH of a 0.265 M solution of propanoic acid.
(c) A 0.496 g sample of sodium propanoate, NaC
3
H
5
O
2
, is added to a 50.0 mL
sample of a 0.265 M solution of propanoic acid. Assuming that no change in
the volume of the solution occurs, calculate each of the following.
(i) The concentration of the propanoate ion, C
3
H
5
O
2

(aq) in the solution
(ii) The concentration of the H
+
(aq) ion in the so lution
Answer:
(a) [C
3
H
5
O
2-
][H
+
]
= K
a
[HC
3
H
5
O
2
]
(b) let X be the amount of acid that ionizes, then
X = [C
3
H
5
O
2

] = [H
+
]
0.265 – X = [HC
3
H
5
O
2
]
X
2


= K
a
= 1.34 x10
–5
0.265 – X
X = 0.00188 M = [H
+
]
[you can assume that 0.265 – X ≈ 0.265 in order to simplify your calculations]
pH = –log[H
+
] = 2.73
(c) (i)
0 496
0 50
.
.
g
1mol
96.0g
L
×
= 0.103 M
since each sodium propanoate dissociates com pletely when dissolved,
producing 1 propanoate ion for every sodium propanoate, and this is
more than thousands of times larger than the propanoate ions from the
acid, then [C
3
H
5
O
2

] = 0.103 M
(ii) let X be the amount that ionizes, then:
X = [H
+
]
X + 0.103 = [C
3
H
5
O
2

]
0.265 – X = [HC
3
H
5
O
2
]
SPECIAL FOCuS: Acids and Bases
86
(X) (0.103 + X)
= K
a
= 1.34 x 10
–5
0.265 – X
X = 3.43 x 10
–5
M = [H
+
]
[We can assume that 0.265 – X ≈ 0.265 and X + 0.103 ≈ 0.103, in order to
simplify calculations.]
Buffer capacity is the amount of acid or base that can be added to a buffer
solution before a major pH change (more than +- 0.5 units) occurs. All buffers have
a buffer capacity. They will resist change to pH when only small amounts of acid or
base added. If large amounts of acid or base are added, then the buffer’s capacity is
exceeded and a major pH change will occur. The buffer’s capacity is determined by
the amount of acid and conjugate base. A buffer with a large capacity has a large
concentration of HA and of A
-
, so that it can absorb a relatively large amount of H
3
O
+

or OH
-
. The pH of a buffered solution is determined by the ratio [HA]/[A
-
]. The capacity
of a buffer is determined by the magnitude of [HA] and [A
-
].
A good laboratory activity to do with the students is to study the buffering
capacity of seawater as compared to that of a 0.50 M NaCl solution. (This
concentration ≈ the concentration of NaCl in seawater.) The students can see the
importance of a natural buffer such as is present in seawater and also study the
buffering capacity of seawater.
Bibliography
Cyberspace Chemistry. “Hydrolysis of Metal Salts.” University of Waterloo. http://www.
science.uwaterloo.ca/~cchieh/cact/c123/salts.html (accessed January 2008).
Mitchell, Philip, and Norris Rakestraw. “The Buffer Capacity of Sea Water”, The
Biological Bulletin 65 (December 1933): 437–451.
Ebbing, Darrell, and Steve Gammon. General Chemistry, 8th ed. Boston: Houghton
Miffin Company, 2005.
Acidic and Basic Reactions of Oxides
Marian DeWane
Centennial High School
Boise, Idaho
The oxides of the elements form an interesting group of acidic and basic compounds.
The combination of element X with the highly electronegative oxygen results in a
polarized bond (in every instance except two oxygen atoms bonding to form O
2
),
which then can be a reaction site when the oxide is added to water to form an
aqueous solution, or when the oxide is reacted directly with an acid or a base.
Two types of reactions can result:
(1) M – O
-
+ H
2
O → M—O—H + OH
-

Here the oxide is a proton acceptor from water leaving an excess of hydroxide
ion in solution, hence forming a basic solution. In this case the oxides are classifed
as basic oxides. Oxides behaving in this way include those of lithium, sodium,
potassium, cesium, calcium, strontium, and barium. These are among the least
electronegative elements or metals group.
(2) X = O + H
2
O →
-
O—X—O
-
+ 2H
+

Here the oxide is an oxygen acceptor from water, which releases hydrogen ions
into the solution, hence forming an acidic solution and in effect acting as a proton
donor. Such oxides are classifed as acidic oxides. Oxides behaving in this way
include those of carbon, nitrogen, sulfur, phosphorous, and the halogens. These are
among the most electronegative elements or nonmetals group.
These reactions are obviously oversimplifed, and can be studied more closely as
follows:
(1) An alternative view of the basic oxides is that these are mostly ionic
compounds (with a high degree of ionic character) and can be thought of as
SPECIAL FOCuS: Acids and Bases
88
containing ions in the solid state. When added to water, it is these ions that
act as proton acceptors as follows:
O
2-
+ H
2
O → 2 OH
-
, each O
2-
ion reacting to form two hydroxide ions, hence
the highly basic nature of the resulting solution.
Thus it is the ionic structure of the metal oxides that best explains their
reaction in aqueous solution. The combination of the highly electronegative
oxygen atom with the low electronegativity atom of a typical metal produces
the ionic bond in metal oxides. The electronegative oxygen is easily able to
attract the most weakly bonded electron away from a metal atom to form the
ionic bond. Two electrons can be taken from an alkaline earth element such
as magnesium to form Mg
2+
O
2-
. Typical oxides are Na
2
O, K
2
O, MgO, CaO, etc.
(2) In the acidic oxides, the nonmetal atom readily forms covalent bonding
with the oxygen, as in common examples such as CO
2
, SO
3
, NO
2
, Cl
2
O, for
example. While this uses some electron density of the central atom, the
more electronegative atoms in the nonmetals still have suffcient remaining
electron density to form additional bonding with oxygen atoms in water
molecules. This weakens the O-H bond in water, releasing H
+
ion. The
complete reaction may take place in two steps to release two H
+
ions.
For example:
SO
3
+ H
2
O → HSO
4

-
+ H
+

HSO
4

-
→ SO
4

2-
+ H
+
Direct reactions of oxides can occur without water being an obvious
reagent. So, for example, sodium oxide can react with hydrochloric acid to
form sodium chloride and water in a typical acid–base reaction forming a
salt and water:
Na
2
O + 2HCl → 2 NaCl + H
2
O
However, when an acidic oxide reacts with some bases water must be
present to provide the oxygen transferred to the central atom. For example,
sulfur trioxide can react with ammonia to form ammonium sulfate. Water
has to be included as a reagent to provide the oxygen transferred.
SO
3
+ 2NH
3
+ H
2
O → (NH
4
)
2
SO
4

Acidic and Basic Reactions of Oxides
89
Amphoteric Oxides
As in all other areas of chemistry, there are chemical behaviors that fall in between
two extremes, and oxides are no exception. Amphoteric oxides can act as acids
or bases, depending on the circumstances. With hydrogen as an exception (water
is clearly an example of an amphoteric oxide), metals in the center of periods and
semimetals tend to form such oxides. For example aluminum oxide, Al
2
O
3
, can act as
an acid or a base, as can SiO
2.
Aluminum oxide is a compact strong structure relatively insoluble in water, but
it can be dissolved by reacting in strong HCl. Here the aluminum oxide is acting as a
base, neutralizing the hydrochloric acid, as represented in the reaction below:
Al
2
O
3
+ 6HCl → Al
2
Cl
6
+ 3H
2
O
However, aluminum oxide also dissolves in strong sodium hydroxide solution
acting as an acid neutralizing the sodium hydroxide. This reaction can be represented
by the equation:
Al
2
O
3
+ 2NaOH + 3H
2
O → 2Al(OH)
4
-
+ 2Na
+

AP Exam Examples of Free-Response Questions:
Free-response questions about oxides are usually in the equations section, question
4. The question now requires students to provide a balanced net equation and answer
a question about the reaction. The year these questions were given, no additional
questions were asked.
Metal oxide plus water examples:
2004 Form B Question 4 (f): Powdered barium oxide is mixed with water.
BaO + H
2
O → Ba
2+
+ 2OH
-
2002 Question 4 (c): Solid cesium oxide is added to water.
Cs
2
O + H
2
O → 2Cs
+
+2OH
-
2000 Question 4 (g): Powdered strontium oxide is added to distilled water.
SrO + H
2
O → Sr
2+
+2OH
-
1999 Question 4 (a) Calcium oxide powder is added to distilled water.
CaO + H
2
O → Ca
2+
+2OH
-
Nonmetal oxide plus water examples:
2003 Question 4 (h): Solid dinitrogen pentoxide is added to water.
N
2
O
5
+ H
2
O → 2H
+
+ 2NO
3
-
2003 Form B Question 4 (f): Sulfur trioxide gas is bubbled into water.
SO
3
+ H
2
O → H
+
+ HSO
4
-
2002 Form B Question 4 (e): Sulfur dioxide gas is bubbled into a beaker of water.
SO
2
+ H
2
O → H
+
+ HSO
3
-
SO
2
+ H
2
O → H
2
SO
3
was also accepted.
2001 Question 4 (a): Sulfur dioxide gas is bubbled into distilled water.
SO
2
+ H
2
O → H
+
+ HSO
3
-
SO
2
+ H
2
O → H
2
SO
3
was also accepted.
Bibliography
Brady, J., and F. Senese. Chemistry: Matter and Its Changes, 4th ed. New York: John
Wiley and Sons, 2004.
Cotton, F. A., G. Wilkinson, Carlos Murillo, and M. Bochmann. Advanced Inorganic
Chemistry, 6th ed. New York: John Wiley and Sons, 1999.
Oxtoby, D. W., and N. H. Nachtrieb. Principles of Modern Chemistry, 2nd ed. New York:
Saunders, 1990.
Rayner-Canham, G. Descriptive Inorganic Chemistry, 2nd ed. New York: Freeman,
1998.
Misconceptions in Chemistry
Demonstrated on AP Chemistry
Examinations
George E. Miller
University of California, Irvine
Irvine, California
Misconceptions and misunderstandings are often demonstrated by students on
both multiple-choice and free-response portions of the AP Chemistry Examination.
Many may refect prior thinking brought to the AP class. These are often termed
“preconceptions.” Others refect misunderstanding of material presented within the
AP class or read from the textbook. Frequently, misunderstandings arise from a lack of
depth and/or accuracy of thinking about a topic or question.
On multiple-choice questions, frequent misconceptions are often included by
the item writers as possible wrong answers, or distracters. Students who select these
answers are showing they have that misconception. Teachers should always ask
students to explain why they selected a particular distracter. The teacher can then
proceed to help the student correct the misconception in their thinking, which will
help the student make the correct selection.
In free-response questions, perhaps the most common misconception
demonstrated is a lack of understanding of the words “explain,” or “justify.” This
persists even when the examination question tries to provide guidance as to what
is expected. Use of familiar examples is helpful. If a sportswriter or commentator
explained why team X won the game against team Y by stating, “It was because
team X scored more points,” they would not survive long in their jobs. Yet that is the
format a considerable number of students exhibit when providing an explanation on
the AP Chemistry Exam. Restating the question also does not answer the question.
SPECIAL FOCuS: Acids and Bases
92
For example, the following question and answer might have appeared in AP:
Using the information given in the following table, explain the difference in K
a
values
for HClO and HBrO.
Acid K
a
Electronegativity of halogen
HClO 3.0 x 10
-8
3.0
HBrO 2.8 x 10
-9
2.8
Incorrect response (1):
The table shows there is a difference between the K
a
values of HClO and
HBrO.
Incorrect response (2):
HBrO has a larger K
a
because 2.8 x 10
-9
is larger than 3 x 10
-8
.
Mathematical errors even creep in as a result of carelessness or real
misunderstandings of conceptual algebra, or exponential notation (as seen above).
For example, students may transcribe K = [H][A] / [HA] ≅ [H]2 /[HA] incorrectly
as [H] = √ K/[HA]. Refective conceptual thinking would always look for responses
where numerator and denominator values moved in the same direction. To foster
correct thinking, teachers should encourage students to always answer the question
qualitatively before plugging in any numbers.
The remaining document addresses selected topics where frequent
misunderstandings are demonstrated, together with some hints for instructors.
Misconceptions Regarding Acids, Bases, and
Aqueous Equilibria
There is confusion on a number of issues relating to acids and bases, as noted below.
Student and teacher dialogue (almost more than demonstrations, which also can
easily be misconstrued) is key. The answer is to start with basic principles, arguing
somewhat as follows:
1. Reactions of acids and bases occur in water. (No nonaqueous systems are
dealt with in AP Chemistry.) Lewis acids are barely mentioned, so master
Brønsted-Lowry or proton transfer systems before even thinking about
anything else.
2. The largest numbers of molecules present in solutions are therefore water
molecules.
Misconceptions in Chemistry Demonstrated on AP Chemistry Examinations
93
3. The obvious species for anything to react with is, therefore, water. If you
jump into a crowded swimming pool, the chances are that you will hit water
molecules frst!
4. Thus, frst-cut reactions are water reactions.
5. Water is amphiprotic and amphoteric, so its reactions are to accept a proton
or donate a proton. Free protons do not exist in water solutions—they must
be attached to something. Most will be attached to water molecules in the
form of H(H
2
O)
n
+
where n is 1-4. In most texts, this is abbreviated to H
+
.
6. Thus, acid–base chemistry is almost exclusively (>99%!) the study of proton
transfer reactions all of which are equilibrium reactions and each of which
has a well-defned equilibrium constant that only varies with temperature.
7. So we simply must list all possible reactions of any given system in water
and ask: “Is the system at equilibrium?” If not, then consider reactions that
happen as they go to equilibrium; if it is at equilibrium, then what do we
know about all the possible equilibrium constants?
8. In one system at equilibrium, all possible equilibria and the corresponding
equilibrium constant expressions must be simultaneously satisfed. One
cannot have some OK, and some not OK.
9. Correspondingly, there can only be ONE value of a species concentration
(e.g., one value of [H
+
] or [OH
-
]. The solution cannot track what H
+
came from
what source to create separate values.
So what are the misconceptions, and why do they exist? The following examples are
given mostly for an acid, but the corresponding idea for a base also exists.
1. Acid–base “strength” is related to acid–base concentration.
This is a semantic problem caused by the unfortunate choice of terms by chemists. To
the lay public, putting a lot of any chemical in water makes it “strong.” Strong coffee or
strong lemonade has a high concentration of those chemicals.
However, acids and bases are defned as strong or weak solely on the basis of
their equilibrium constants in reaction with water. An acid with a high K value (K
value > 10
-1
) for the reaction HA + H
2
O ↔ A
-
+ H
3
O
+
is a strong acid. This is often
stated in terminology regarding the “degree of ionization.” Conversely, strong bases
have a high K value for the reaction B + H
2
O ↔ B
+
+ OH
-
.
Some texts still may use the term “dissociation” based on the idea that HA
becomes H
+
and A
-
by simple dissociation. Generally, it is now recognized that proton
SPECIAL FOCuS: Acids and Bases
94
transfer reactions to water are what actually takes place. It is the K value for the
transfer to water that determines whether an acid is classifed as strong or weak.
The “concentration” of a solution of an acid in water strictly refers to the formal
concentration which is the same as [HA] + [A
-
] , or the corresponding values for a
base. This concentration expression is the same for either a strong or a weak acid.
Thus, one can have a high concentration of a weak acid, or a small concentration
of a strong acid, and vice versa. Weaker students fnd this quite diffcult.
A class of one strong student is a strong class, but a class of 40 weak students is
still a weak class.
2. “Reaction to completion can only occur as the K value will allow.”
So a weak acid cannot react to neutralize a strong base. For example: 5 mL of 0.1
M NaOH is added to 10 mL of 0.1 M acetic acid. What is the end result? Beginning
students who have learned to correctly write an equilibrium constant for the weak
acid in water as HAc + H
2
O ↔ H
+
+ Ac
-
with K
a
= 1.8 x 10
-5
frequently will argue that
since [H
+
] = [Ac
-
], now 1.8 x 10
-5
= [H
+
]2 / (0.1) and the concentration of hydrogen ion is
now only √ (1.8 x 10
-6
) or 1.3 x 10
-3
M.
Thus the reaction can only consume 1.3 x 10
-3
moles of OH-, leaving the
remainder in solution, so the result is strongly basic.
When the solution is mixed, it is not at equilibrium. All reactions must be
allowed to proceed to equilibrium before the equilibrium mixture is analyzed. With
this in mind, the ICE tabulation method can be used to obtain a result.
3. “Acids are the only source of protons in water.”
In many problems with high or medium concentrations of acids, this is approximately
true, so often neglecting water as a source works. The full treatment of this, which
leads to a third order equation for [H+], is usually given in college analytical chemistry
courses. However, there are circumstances where the contribution of the “auto-
ionization” or “autoprotolysis” of water according to H
2
O + H
2
O ↔ H(H
2
O)
+
+ OH
-

cannot be ignored. The classic catch question is:
What is the [H+] of a 1 x 10
-10
M solution of HCl in water? Since HCl is a strong
acid, we assume complete transfer, so [H+] from HCl is 1 x 10
-10
M. (pH = 10). A good
student will recognize this as nonsense since this is a basic solution. The water is
contribution 1 x 10
-7
, so the true value is close to 1 x 10
-7
+ 1 x 10
-10
or 1 x 10
-7
M, a
“neutral” solution of pH = 7.
Misconceptions in Chemistry Demonstrated on AP Chemistry Examinations
95
Usually the examination committee for AP has tried to set problems on the free-
response section where the water contribution can be ignored and approximations are
simple.
4. [H
+
] and [OH
-
] values are independent of each other.
A small but signifcant number of students fail to apply the water equilibrium in
acid–base solutions. Thus they are comfortable to report a pH of 4 and a pOH of 4 (or
the equivalent concentrations values) in the same solution. Perhaps a focus during
discussions on the need to satisfy the water equilibrium, or at least a frequent
repetition of the mantra pH + pOH ALWAYS = 14 (at normal room temperature) could
help.
5. Acids are compounds containing H atoms, bases are
compounds containing OH.
Unfortunately, this defnes NH
3
as an acid. Acids and bases are defned according to
their ability to donate or accept protons, almost exclusively (for AP) in reaction with
water. Accepting a proton from water creates a basic solution (larger [OH
-
] than [H
+
]).
This enables reactions such as NH
3
+ H
2
O ↔ NH
4
+
+ OH
-
to be written to
correctly identify ammonia as a (weak) base. Much practice in writing reaction
equations with water as reagent and seeking the K values for the reactions in tables
will help students learn how to classify more correctly. Of course there are nonaqueous
systems, but these are rarely dealt with in any signifcant way in AP or frst-year
college chemistry courses.
Acid–Base Chemistry Beyond AP
®
Arden P. Zipp
SUNY Cortland
Cortland, New York
Most of the acid–base behavior discussed in AP Chemistry occurs in water. However,
the use of water as a solvent limits the species that can act as acids or bases and
restricts the range of reactions that can be legitimately considered as acid–base
reactions. This article will address acid–base chemistry beyond water and, thus,
beyond the usual considerations of AP. A further extension is provided by acidity and
basicity measurements in the gas phase, where the relative tendency of a molecule
to donate or accept a proton can be measured. Trends in acidity as a function of
molecular structure in the gas phase can often be more easily understood, as many
trends in solution depend on solvation energy considerations, which are absent in the
gas phase (Barntmess, Scott, McIver 1979).
Leveling Effect of Water
It is well known that H
2
O ionizes into H
+
(or H
3
O
+
) and OH
-
. Acids that are
stronger than H
3
O
+
will donate protons to H
2
O to form H
3
O
+
ions, while bases
that are stronger than OH
-
will abstract protons from H
2
O to leave OH
-
ions. As a
consequence, all stronger acids (or bases) are made to appear as if they are of equal
strength. This is the situation with HCl, HBr, HI, HNO
3
, HClO
4
, and H
2
SO
4
(frst
proton), which appear equally strong in water. Although the K
a
of these substances
actually varies from 10
1
to 10
11
, these differences are not apparent in water because
H
2
O molecules attract the H
+
from the various anions so strongly that all the acid
is converted into H
3
O
+
and the corresponding anion. This occurs because H
2
O
molecules are stronger bases toward H
+
than any of the anions in these acids, so the
differences in anion attraction for the H
+
are not apparent. (Recall from the discussion
of Brønsted-Lowry acids and bases that reactions with H
+
ions involve competitions
SPECIAL FOCuS: Acids and Bases
98
between two bases.) The same “leveling” phenomenon occurs with bases that are
stronger than OH
-
(e.g., H
-
, C
2
H
5
O
-
or S
2-
) because they react with an H
+
from water
to form H
2
, C
2
H
5
OH, or HS
-
, respectively, leaving OH
-
as the predominant anion in
solution.
The opposite effect occurs for very weak acids (or bases), which are not strong
enough to exhibit their acid or base properties in water. As an example of this
behavior, alcohols (ROH) contain hydroxyl (-OH) groups but exhibit neither acidic nor
basic properties in H
2
O. The K
a
for a typical alcohol is about 10
-18
(pK
a
= 18).
Note: Saying that alcohols are very weak acids is equivalent to stating that their
conjugate bases (RO
-
) are very strong, which would lead to them being leveled in
water as discussed above. (There is virtually no tendency for an alcohol to behave as a
base by either gaining an H
+
or losing an OH
-
in water.)
Nominally, acids with K
a
values that range from 10
0
to 10
-14
(pK
a
s from 0 to
14) can be studied in water and substances with values outside this range must be
investigated in other solvents. One way to compare the useful ranges of different
solvents is to graph their effective pK
a
ranges relative to H
2
O as depicted below
(Atkins, Overton, Rourke, Weller, and Armstrong 2006, 117).
pK
a
Ranges of pure Solvents Relative to Water
H
2
SO
4
HF
HCOOH
H
2
O
(CH
3
)
2
SO
Effective pK
a
in water
NH
3
-20 -10 0 10 20 30 40
In order to discriminate among the acidities of the six strong acids mentioned above,
a less basic solvent than water (one with a more negative pK
a
value) can be used.
Two examples of such solvents are liquid methanoic (formic) acid, HCOOH, and liquid
HF. Because these solvent molecules have less attraction for H
+
than does H
2
O, the
acids do not ionize completely. Thus, it is possible to measure the relative amounts of
the ionized and un-ionized acids, to calculate their ionization constants, and to relate
these values to aqueous solutions. In this way, the K
a
values of HNO
3
, H
2
SO
4
, HCl,
HBr, HClO
4
and HI have been found to be 10
1
, 10
2
, 10
7
, 10
9
, 10
10
,

and 10
11
, respectively.
99
Acid–Base Chemistry Beyond AP
On the other hand, bases stronger than OH
-
can be distinguished by using solvents
such as liquid dimethyl sulfoxide, (CH
3
)
2
SO, or liquid NH
3
, which have pK
a
values
greater than 14.
The opposite strategy applies to the task of distinguishing among very weak
acids (or bases). In the case of very weak bases a more acidic solvent than H
2
O is
needed in order to protonate the basic site more effectively and for very weak acids
a more basic solvent must be employed to help remove H
+
. For a series of alcohols
their relative strengths could potentially be determined by studying them in either
dimethylsulfoxide or ammonia.
Once the constraints of an aqueous solution have been eliminated, a variety
of other acid–base reactions can be observed. Chemists have developed “super
acids,” i.e., acids that are stronger than 100% sulfuric acid, which can even protonate
hydrocarbons! At the other extreme are super bases, such as butyllithium—LiC
4
H
9
,
which can remove H
+
ions from virtually anything including many hydrocarbons,
which do not show acidic properties under other circumstances.
Relative Acid Strengths
Although it is common to classify acids as either strong or weak, there is a great deal
of variation among the species in each category. These variations can be accounted
for on the basis of the structures of the molecules involved. Although the specifc
structural factors depend on the acid category (hydroacids vs. oxoacids), the fact
that acid strengths can be correlated with structures for a given category of acids
provides a very powerful organizational tool. Consideration of acid strength from gas
phase species, which can be done both theoretically and experimentally, can lead to
interestingly different results as solvation effects are removed (Bartmess and Hinde
2005).
Hydroacids
These acids can be represented by the general formula H
x
Y and include species in
which an atom of a nonmetal is attached directly to one or more hydrogen atoms.
Such substances ionize according to the equation:
H
x
Y <=> H
+
+ H
(x-1)
Y
-
,
with the extent of this reaction dependent on the ease with which the bond between
H
+
and H
(x-1)
Y
-
can be broken. The K
a
values for the compounds in groups 14 to 17,
SPECIAL FOCuS: Acids and Bases
100
most of which had to be measured in solvents other than water, cover a range of 10
60

(from 10
-49
to 10
11
) as refected in the pK
a
s given in the table below (Bowser 1993, 314).
pKa for Hydroacids
CH
4
49 NH
3
39 H
2
O 15.74 HF 3.45
SiH
4
35 PH
3
27 H
2
S 7.05 HCl -7
GeH
4
25 AsH
3
23 H
2
Se 3.8 HBr -9
H
2
Te 2.6 HI -11
The pK
a
values of these substances decrease down the periodic table and from left
to right, refecting an increase in K
a
values and, therefore, acid strength in the same
directions.
There are two factors that infuence the ease with which the H-Y bond can be
broken. These are the electronegativity (EN) and the size of the atom Y. The increase
in acidity going across the periodic table can be accounted for by the change in EN.
As the EN of Y increases across the period, the electron pair in the H-Y bond will be
drawn closer to Y, increasing the polarity of the bond. Because the atomic size does
not vary appreciably across a period, the change in EN is the major factor affecting
the acidity.
The increase in the acidity down the table cannot be explained in terms of the
EN, however, because the EN changes in the wrong direction, decreasing down the
table. However, there is a large increase in atomic size descending in any group. As
the size of an anion increases, its electrostatic attraction for H
+
decreases, which
would increase the acidity.
Oxoacids
This group of acids is more extensive and diverse than the hydroacids discussed
above, with changes in both the central atom and the number of oxygen and/or
hydrogen atoms as shown in the list of several of the more common oxoacids: HClO,
HClO
2
, HClO
3
, HClO
4
, HNO
2
, HNO
3
, H
2
CO
3
, H
2
SO
3
, H
2
SO
4
, and H
3
PO
4
. Despite
this variability in formula, all of the acids in this group can be represented by the
general formula (HO)
m
YO
n
, which emphasizes the fact that the ionizable protons are
bonded to oxygen atoms, which, in turn, are bonded to the central atom Y. Thus, the
structure of HClO is actually HOCl, while that of HClO
2
is HOClO and that of H
2
SO
4

is (HO)
2
SO
2
. When these species are compared in this manner, their strengths
as represented by their K
a
(or pK
a
) values are found to fall into different categories
depending on the number of unprotonated oxygen atoms, regardless of the number of
ionizable H’s in the molecule. This is shown in the table below (Bowser 1993, 314).
101
pK
a
Table for Oxoacids
(HO)mY
Very weak pK
a
> 7
(H0)mYO
Weak pK
a
2 – 5
(H0)mYO
2

Strong pK
a
< 1
(H0)mYO
3

Very Strong pK
a
< 5
HOCl 7.54 HOClO 1.94 HOClO
2
-2.0 HOClO
3
-7.3
HOBr 8.49 HONO 3.20 HONO
2
-1.44
(HO)
3
As 9.18 (HO)
2
CO 3.60 (HO)
2
SO
2
-3
(HO)
4
Si 9.77 (HO)
2
SO

1.89 (HO)
2
SeO
2
1.66
(HO)
2
SeO 2.62
(HO)
3
PO

2.15
(HO)
3
AsO 2.21
Several points are notable about the data in this table. First, the acid strength
increases with the number of unprotonated oxygen atoms in the molecule. An
increase in the number of such electron-attracting oxygen atoms will withdraw
electrons more effectively from the H in the O-H bond. This increases the polarity
of the bond and makes the H atom more H
+
-like. Second, the acid strength changes
little with variations in atomic size or electronegativity in contrast to the behavior
observed for the hydroacids discussed above. This can be accounted for by the fact
that the ionizable H
+
is always attached to an oxygen atom whose size doesn’t change
and, further, any change in the size of the central atom has little effect on the size of
the anion as a whole. Similarly, changes in the electronegativity of the central atom
represent a small effect on the attraction for the H
+
compared to the infuence of the
greater EN effects of one or more (more electronegative) oxygen atoms.
Acidity of Metal Ions
Metal ions behave as Lewis acids, accepting a share of a pair of electrons from
appropriate donors.
One of the most common electron pair donors is the H
2
O molecule, especially in
aqueous solutions, where most metal ions exist as octahedral species as shown by the
equation:
M
x+
+ 6H
2
O --> M(H
2
O)
6
x+

The interaction of some metal ions (most notably alkali metal ions and larger
alkaline earth metal ions such as Ca
2+
, Sr
2+
and Ba
2+
) with H
2
O goes no further.
However, many metal ions attract the electron pairs of the coordinated H
2
O molecules
so strongly that one or more molecules may actually be torn apart, releasing H
+
and
making the solution acidic as represented in the equation:
M(H
2
O)
6
x+
--> M(H
2
O)
5
OH
x-1
+ H
+

Acid–Base Chemistry Beyond AP
SPECIAL FOCuS: Acids and Bases
102
The tendency of metal ions to behave in this manner depends primarily on two
factors: charge and size, as shown in the table below where the pK
a
values for several
metal ions participating in this reaction are given along with their radii (Wulfsberg
1991, 25).
pKa values and Radii of Common Metal Ions
Ion Na
+
Ca
2+
Pu
3+
Mg
2+
Ca
2+
Ba
2+
pK 14.2 12.8 7.0 11.4 12.8 13.5
Radius (nm) 0.116 0.114 0.114 0.086 0.114 0.149
The radius and charge can be combined into a single quantity called the charge
density. (It is not necessary to consider the details of calculating this quantity but
only to deal with it qualitatively, where it increases with an increase in charge and/or
a decrease in ionic radius.) As a frst approximation, solutions containing metal ions
become more acidic as the charge density of the metal ion increases.
As the charge density of metal ions increases, this reaction may proceed further,
to the precipitation of metal hydroxides:
M(H
2
O)
6
x+
--> M(OH)
x
+ xH
+
+ (6-x) H
2
O
The pH at which this reaction is initiated decreases as the charge density of
the metal ion increases, as shown by the pH values for the formation of the following
hydroxides, which are characterized by a decrease in size and/or an increase in the
charge of the cation (Masterton and Hurley 2006, 427).
Ca(OH)
2
pH 12.3 Fe(OH)
2
pH 8.67 Fe(OH)
3
pH 4.49
For species with extremely high charge densities, the potential cations may exist
as oxoanions. This is illustrated by the ions VO
4
3-
, CrO
4
2-
and MnO
4
-
, in which the
charges on the nonexistent cations would be +5, +6, and +7, respectively.
Hard and Soft Acids and Bases (HSAB)
This concept represents one of the most signifcant developments in acid–base theory
in recent years. It represents an extension of the Lewis theory and was developed to
account for the results obtained when a variety of electron-pair acceptors were reacted
with several electron pair donors.
Specifcally, it was found that a cation such as Ag
+
reacts with halide ions in the
order I
-
> Br
-
> Cl
-
> F
-
, whereas (as was pointed out above) H
+
reacts with this same
series of ions in the opposite order: F
-
> Cl
-
> Br
-
> I
-
.
103
To account for this difference in behavior, the electron-pair acceptors (Lewis
acids) H
+
and Ag
+
were labeled as hard and soft, respectively, while the halide ions F
-
,
Cl
-
, Br
-
,

and I
-
were assumed to progress from hard to soft. Hard acids and bases are
species that interact in an electrostatic manner, whereas soft acids and bases exhibit
covalent interactions. A fundamental principle of this theory is that hard acids interact
preferentially with hard bases. Thus, hard H
+
reacts more strongly with hard F
-
(to
form the weak acid HF) than with the soft I
-
(since HI is a strong acid) and the soft
Ag
+
interacts more strongly with soft I
-
(to form the less soluble AgI) than with harder
F
-
(AgF is more soluble).
The HSAB theory has provided the basis to account for a wide range of chemical
phenomena. For example, it offers explanations for the strengths of the hydrohalic
acids and the solubilities of the silver halides as described above. Further, however,
it provides the basis to understand the distribution of metal ions in nature between
sulfdes (soft species such as Ag
+
, Hg
2+
, Pt
2+
) and oxides (hard species Fe
2+/3+
, Cu
2+
).
Activities
(1) Determine the pK
a
value of an acid with a K
a
= 1.2 x 10
2
.
(2) Give the formula for the acidic and basic species in CH
3
COOH.
(3) Organic amines behave as weak bases in aqueous solutions when an H
+
ion
reacts with the lone pair of electrons on the N atom.
a. Predict the relative strength of an organic amide (RCONH
2
) behaving as
a weak base.
b. Give the formula of an appropriate solvent in which an amide would
behave this way.
(4) Give an approximate pK for the hydroacid stibine (SbH
3
).
(5) The oxoacid pyrosulfuric acid (H
2
S
2
O
7
) is produced when SO
3
is bubbled
into H
2
SO
4
. Write the formula in the (HO)
m
EO
n
style, determine the number
of free O atoms per S atom and predict its strength relative to that of H
2
SO
4
.
(6) Use the charge density to
a. Account for the fact that the reaction of alkali metal ions and H
2
O goes
only to M(H
2
O)
6
+
.
b. Identify the alkali metal ion that would be most likely to go beyond this
stage.
Acid–Base Chemistry Beyond AP
SPECIAL FOCuS: Acids and Bases
104
(7) Copper can form the ions Cu
+
and Cu
2+
. State and explain which of these is
more likely to react with the hard base F
-
.
Conclusion
This essay has attempted to present several aspects of acid–base theory beyond those
discussed in earlier selections (or in the average AP Chemistry course). The topics
covered here were chosen in the hope that they would further the understanding and
appreciation of the topics usually found in AP courses.
Bibliography
Atkins, P. W., T.L. Overton, J.P. Rourke, M.T. Weller, and F.A. Armstrong. Inorganic
Chemistry, 4th ed., Oxford, UK: Oxford University Press, 2006, 117.
Bartmess, J. E., J. A. Scott, and R. T. McIver Jr. “Scale Of Acidities in the Gas Phase
from Methanol to Phenol.” Journal of American Chemistry Society 101 (1979):
6046–56.
Bartmess, J. E., and Robert J. Hinde. “The Gas-Phase Acidities of the Elemental
Hydrides are Functions of Electronegativity and Bond Length.” Canadian
Journal of Chemistry 83(11) (2005): 2005–12.
Bowser, J. R. Inorganic Chemistry. Pacifc Grove, CA: Brooks/Cole Publishing, 1993,
312–14.
Masterton, W. L., and C. N. Hurley. Chemistry: Principles and Reactions, 5th ed. Pacifc
Grove, CA: Brooks/Cole Publishing, 2006, 427.
Wulfsberg, G. Principles of Descriptive Inorganic Chemistry. Mill Valley, CA: University
Science Books, 1991, 25.
Acid–Base Lesson Plans
Heather Hattori
John H. Guyer High School
Denton, Texas
This is one of my favorite units of the year. It brings back familiar concepts and
calculations to second-year students, as well as a wealth of laboratory activities
to keep them engaged. I teach on an A/B day 90-minute block schedule so some
activities are done during class while others are done outside (either after school or on
Saturdays). Tenth-, eleventh-, and twelfth-grade students enroll in AP Chemistry with
an Algebra II minimum math co-requisite, since we teach the frst year of chemistry
to freshmen. The text provided to students is Zumdahl’s Chemistry, 5th edition, from
the Houghton Miffin Company.
You may fnd my problem selections in the study guide odd, but that would be
dependent on when I teach acids and bases. This past year, we as a district moved
equilibrium into the frst semester with the acid–base unit following directly after
it. This may be disconcerting to some who would prefer to follow the textbook in the
order it is presented. It works for us, but may not work for you. Be that as it may, here
is a basic outline of what I would cover in my acid–base unit in years where I did not
teach the pre-AP class and was unsure of the students’ background.
General Outline
Day 1:
• Review characteristics and examples of acids and bases
• Review acid/base theories (Arrhenius, Brønsted-Lowry, and Lewis) and
associated concepts
• Review strong/weak acids and bases as well as additional classifcations of
acids (monoprotic, diprotic, polyprotic, ternary, oxy acids, etc.)
SPECIAL FOCuS: Acids and Bases
106
• Review concentration terms (concentrated, dilute) and calculations (molarity)
• Review acid–base reactions including acid–base formation from acid–base
anhydrides
• Review pH scale, logarithms, and associated strong acid–base calculations
([H
3
O
+
], [OH
-
], pH, and pOH)
• Pre-lab: Determining the pH of a Substance

(fts AP suggested lab topic:
Determination of Appropriate Indicators for Various Acid–Base Titrations;
pH Determination)
• Assign Study Guides for Chapters 14 and 15.
Day 2:
• Determining the pH of a substance lab
• Discussion of titration curves
• Pre-lab: Titration Curves of Weak and Strong Acids and Bases
Day 3:
• 7ittotiot Cutvcs ot !co| oto Sttotj Acios oto Boscs Lab
• Review titration problems
• Pre-lab: % Acetic Acid in Vinegar (fts AP suggested lab topic:
Determination of Concentration by Acid–Base Titration, Including a Weak
Acid or Weak Base)
Day 4: (this lab has been done outside the school day)
• ° Acctic Acio it \itcjot Lab
Day 5:
• Weak acid–base equilibria—revisiting K
• Calculating the pH of a weak acid or base
• Use past AP free-response questions for practice
Day 6:
• Common-ion Effect
• Buffers
Acid–Base Lesson Plans
107
• Pre-lab: Preparation of a Buffer Solution at a Given pH or A Resistance to
Change (fts AP suggested lab topic: Preparation and Properties of Buffer
Solutions)
Day 7: (this lab has been done outside the school day)
• Ptcµototiot ot o Buttct So|utiot ot o Givct µH Lab
Day 8: (If time permits. If not, then skip to Day 9)
• Complex Ion Equilibria
Day 9:
• Unit Assessment
Additional Attachments:
• Study Guides to Accompany Zumdahl’s Chemistry, 5th edition. Hattori,
Heather R. 2001.
• Acids and Bases Introduction-Review Notes
• Titration Notes
• Calculating the pH of a Weak Acid or Base Notes
• Common Ion Effect and Buffers Notes
• Dctcttititj tlc µH ot o Su|stotcc. Hattori, Heather R. 1995.
• AcioBoscs, Pcoctiots, oto 7ittotiot Co|cu|otiot Pcvicu !ot|slcct. Hattori,
Heather R. 2007.
• Dissociotiot oto µH Ptocticc Hattori, Heather R. 2005.
Bibliography
Holmquist Dan D., Jack Randall, and Don Volz. In Chemistry with Calculators,
Beaverton, OR: Vernier Software & Technology, 2000.
Hostage, David, and Martin Fossett. “Finding the Mass Percent of Acetic Acid in
Vinegar,” in Laboratory Investigations: AP Chemistry, Saddle Brook, NJ: The
Peoples Publishing Group, Inc., 2006.
SPECIAL FOCuS: Acids and Bases
108
Hostage, David, and Martin Fossett. Laboratory Investigations: AP Chemistry, Saddle
Brook, NJ: The Peoples Publishing Group, 2006.
Moore, John T., and Richard Langley. 5 Steps to a 5 AP Chemistry, McGraw-Hill, 2004.
Pasco Scientifc. “A Resistance to Change,” in PasPort Explorations in Chemistry.
Roseville, CA: PASCO Scientifc, 2003.
Zumdahl, Steven S., and Zumdahl. Chemistry, 5th ed. Houghton Miffin Company,
2000.
Appendix A
Review Notes on Acids and
Bases Introduction
Common Acids and Bases
Where do I fnd acids?
• Fruits (lemons, oranges, etc.) contain citric acid.
• Vinegar contains acetic acid.
• Rain water contains sulfuric acid.
• Soft drinks contain carbonic and phosphoric acids.
Where do I fnd bases?
• Cleaners contain ammonia.
• Milk of magnesia contains magnesium hydroxide.
• Drano contains sodium hydroxide.
Characteristics of Acids and Bases
• Acids
• Taste sour
• Turn blue litmus paper red
• Have a pH < 7.0
• Are corrosive
• Bases
• Taste bitter
• Turn red litmus paper blue
• Have a pH > 7.0
• Are caustic
SPECIAL FOCuS: Acids and Bases
110
Three Acid–Base Theories
The following theories are where we get our defnitions of what acids and bases are:
• Arrhenius Concept
• Brønsted-Lowry Model
• Lewis Theory
Arrhenius Concept
Acids produce H
+
(hydrogen ions) in solution.
HCl(aq)

→ H
1+
(aq) + Cl
1-
(aq)
H
3
PO
4
(aq)



3 H
1+
(aq) + PO
4
3-
(aq)
Bases produce OH
-
(hydroxide ions) in solution.
NaOH (aq)



Na
1+
(aq) + OH
1-
(aq)
Ca(OH)
2
(aq)



Ca
2+
(aq) + 2OH
1-
(aq)
Brønsted-Lowry Model
Acids are proton donors. In other words, acids donate H
+
(hydrogen ions) in solution.
HCl(aq) + H
2
O (l)



H
3
O
1+
(aq) + Cl
1-
(aq)
H
3
PO
4
(aq) + 3H
2
O (l)



3 H
3
O
1+
(aq) + PO
4
3-
(aq)
Bases are proton acceptors. In other words, bases accept H
+
(hydrogen ions) in
solution.
NH
3
(aq) + H
2
O (l)



NH
4
1+
(aq) + OH
1-
(aq)
CaO (s) + H
2
O (l)



Ca(OH)
2
(aq)
The frst equation sets up two interesting relationships. Not only does
the ammonia accept a hydrogen ion to become the ammonium ion, the
hydroxide ion could accept a hydrogen ion from the ammonium and become
water. These two relationships make the ammonia/ammonium ion and the
water/hydroxide ion conjugate acid/base pairs.
Lewis Theory
Acids are electron-pair acceptors in solution.
Bases are electron-pair donors in solution.
BF
3
(aq) + :NH
3
(aq)



F
3
B:NH
3
Appendix A
111
The pH Concept
pH represents the relative acidity of a solution based on hydrogen ion or hydronium ion
concentration and can be found using either of the following equations:
pH = -log[H
+
] or pH = -log[H
3
O
+
]
.
Since concentrations can be large or small, such as 12

M or 4.2 X 10
-13
M,
sometimes it is hard to compare the [H
3
O
1+
]. The pH scale was developed to make it
easier to recognize if a substance was acidic or basic.
The amphoteric nature of pure water contributes to its neutral nature. This
means that water can act as an acid or a base due to the concept known as auto-
ionization shown in the following two examples.
Remember that:
H
2
O (l) ↔ H
+1
(aq) + OH
-1
(aq) (Arrhenius concept)
According to the Arrhenius concept water (in the equation above) is acting as an
acid by producing hydrogen ions as well as a base by producing hydroxide ions.
2H
2
O (l) ↔ H
3
O
+1
(aq) + OH
-1
(aq) (Brønsted-Lowry model)
According to the Brønsted-Lowry model one water molecule (in the equation
above) is acting as an acid by donating a hydrogen ion to the other molecule of water
forming a hydronium ion. The water molecule that is accepting the hydrogen ion is
acting as the base.
If we write the equilibrium expression for this we get:
K
w
= [H
3
O
1+
][OH
1-
] = 1.0 X 10
-14
always at 25°C
We can solve for the [H
3
O
1+
] or [OH
1-
] based on the above equation.
For every H
3
O
1+
produced, one OH
1-
is made, so:
[H
3
O
1+
][OH
1-
] = 1.0 X 10
-14
becomes
[x][x] = 1.0 X 10
-14
x
2
= 1.0 X 10
-14
x = 1.0 X 10
-7
∴ [H
3
O
1+
] = 1.0 X 10
-7
M = [OH
1-
]
In solutions when the:
[H
1+
] > [OH
1-
], then the solution is acidic
[H
1+
] < [OH
1-
], then the solution is basic
[H
1+
] = [OH
1-
], then the solution is neutral
SPECIAL FOCuS: Acids and Bases
112
Based on this and the fact that [H
1+
] and [OH
1-
] can be calculated if you know one
or the other, it’s time to solve some problems.
Examples
1. Given the [OH
1-
] = 1.0 X 10
-5
M, solve for the [H
3
O
1+
] and determine the solution’s
nature (acidic, basic, or neutral).
2. Given the [H
3
O
1+
] = 1.0 X 10
-2
M, solve for the [OH
1-
] and determine the solution’s
nature (acidic, basic, or neutral).
Substances other than water can also be amphoteric. Let’s look at a
hydrated aluminum hydroxide ion as an example.
[Al(H
2
O)
4
(OH)
2
]
1+
+ NaOH ↔ Al(H
2
O)
3
(OH)
3
+ OH
1-
When a water of hydration from [Al(H
2
O)
4
(OH)
2
]
1+
donates the hydrogen ion
to becomes the third hydroxide ion, it is acting as a Brønsted-Lowry acid.
[Al(H
2
O)
4
(OH)
2
]
1+
+ HCl ↔ [Al(H
2
O)
5
OH]
2+
+ Cl
1-
When a hydroxide from [Al(H
2
O)
4
(OH)
2
]
1+
accepts the hydrogen ion to create
the ffth water of hydration, it is acting as a Brønsted-Lowry base.
pH scale
Based on logarithms, the pH scale was developed.
0 7 14
Acidic Neutral Basic
pH = -log[H
+
] or pH = -log [H
3
O
+
]
3. What is the pH of a solution with a [H
+
] = 1.0 X 10
-9
M?
A similar formula can be used to calculate the pOH (relative basicity) if you know the
[OH
1-
].
pOH = -log [OH
1-
]
4. What is the pOH of a solution with a [OH
1-
] = 2.4 X 10
-7
M?
By combining all three of the previous formulas:
K
w
= [H
3
O
1+
][OH
1-
] = 1.0 X 10
-14

pH = -log [H
3
O
1+
]
Appendix A
113
pOH = -log [OH
1-
],
we can derive the formula:
pH + pOH = 14.
5. What is the pOH of a solution that has a pH of 10.0?
Vinegar has a pH of 2.8. What are the pOH, [H
3
O
1+
], and [OH
1-
] of a vinegar solution?
Relative Strengths of Acids and Bases
Acids and bases can be concentrated or dilute, weak or strong. Do not confuse the
frst two, which describe the solution concentration, with the last two, which describe
the amount of dissociation. A strong acid or base is one that completely dissociates in
water or has 100% ionization. A weak acid or base is one in which only a small portion
of the particles dissociate or one that only partially ionizes.
• Strong acids include: HCl, HBr, HI, HNO
3
, H
2
SO
4
, and HClO
4
. All others
are considered weak.
• Strong bases include: LiOH, NaOH, KOH, Mg(OH)
2
, Ca(OH)
2
, Sr(OH)
2,
and
Ba(OH)
2
. All others are considered weak.
Appendix B
Review Notes on Acids and Bases—
Teacher’s Edition
Common Acids and Bases
Where do I fnd acids?
• Fruits (lemons, oranges, etc.) contain citric acid.
• Vinegar contains acetic acid.
• Rain water contains sulfuric acid.
• Soft drinks contain carbonic and phosphoric acids.
Where do I fnd bases?
• Cleaners contain ammonia.
• Milk of magnesia contains magnesium hydroxide.
• Drano contains sodium hydroxide.
Characteristics of Acids and Bases
Acids:
• taste sour
• turn blue litmus paper red
• have a pH < 7.0
• are corrosive
Bases:
• taste bitter
• turn red litmus paper blue
• have a pH > 7.0
• are caustic
SPECIAL FOCuS: Acids and Bases
116
Three Acid–Base Theories
The following theories are where we get our defnitions of what acids and bases are:
• Arrhenius Concept
• Brønsted-Lowry Model
• Lewis Theory
Arrhenius Concept
Acids produce H
+
(hydrogen ions) in solution.
HCl(aq)

→ H
+
(aq) + Cl
-
(aq)
H
3
PO
4
(aq)



H
+
(aq) + H
2
PO
4
-
(aq)
Bases produce OH
-
(hydroxide ions) in solution.
NaOH (aq)



Na
+
(aq) + OH
-
(aq)
Ca(OH)
2
(aq)



Ca
2+
(aq) + 2OH
-
(aq)
Brønsted-Lowry Model
Acids are proton donors. In other words, acids donate H
+
(hydrogen ions) in solution,
usually to water. These are hydrated to form H(H
2
O)
n
+
, where n may be 1–6. For
convenience, this species is usually abbreviated to H+ except when a balanced
equation is desired, as shown in some of the examples below.
HCl(aq) + H
2
O (l) → H
3
O
+
(aq) + Cl
-
(aq)
H
3
PO
4
(aq) + H
2
O (l) →

H
3
O
+
(aq) + H
2
PO
4
-
(aq)
H
2
PO
4
-
(aq) + H
2
O (l) →

H
3
O
+
(aq) + HPO
4
2-
(aq)
HPO
4
2-
(aq) + H
2
O (l)



H
3
O
+
(aq) + PO
4
3-
(aq)
Bases are proton acceptors. In other words, bases accept H
+
(hydrogen ions) in
solution.
NH
3
(g) + H
2
O (l)

→ NH
4
+
(aq) + OH
-
(aq)
CaO (s) + H
2
O (l)



Ca(OH)
2
(aq)
The frst equation sets up two interesting relationships. Not only does
the ammonia accept a hydrogen ion to become the ammonium ion, the
hydroxide ion could accept a hydrogen ion from the ammonium ion and
become water. These two relationships make the ammonia/ammonium ion
and the water/hydroxide ion conjugate acid–base pairs. The reaction
goes both ways and so reaches equilibrium.
Appendix B
117
Lewis Theory
Acids are electron pair acceptors in solution.Bases are electron pair donors in solution.
BF
3
(aq) + :NH
3
(aq)



F
3
B:NH
3
The pH Concept
Conventionally, the symbol [H
+
] is used to represent the concentration of H
+
ions in
moles per liter. Since concentrations can be large or small, such as 12

M or 4.2 X 10
-13
M, sometimes it is hard to compare the [H
+
]. The pH scale was developed to make it
easier to recognize if a substance was acidic or basic.
pH represents the relative acidity of a solution based on hydrogen ion or
hydronium ion concentration and can be found using either of the following equations:
pH = -log[H
+
] or pH + -log[H
+
] .
The amphoteric nature of pure water contributes to its neutral nature. This
means that water can act as an acid or a base by accepting or donating protons.
Water also undergoes a process called auto-ionization, which is shown in the following
two examples.
Remember that:
H
2
O (l) ↔ H
+
(aq) + OH
-
(aq) (Arrhenius concept)
According to the Arrhenius concept, water, in the equation above, is acting as
an acid by producing hydrogen ions as well as a base by producing hydroxide ions.
H
2
O (l) + H
2
O (l) ↔

H
3
O
+
(aq) + OH
-
(aq) (Brønsted-Lowry model)
According to the Brønsted-Lowry model, one water molecule in the equation
above is acting as an acid by donating a hydrogen ion to the other molecule of water
forming a hydronium ion. The water molecule that is accepting the hydrogen ion is
acting as the base.
If we write the equilibrium expression for this we get:
K
w
= [H
3
O
+
][OH
-
] = 1.0 X 10
-14
at 25°C
We can solve for the [H
3
O
+
] or [OH
-
] based on the above equation.
In pure water, with no other substances present, for every H
3
O
+
produced, one
OH
-
is made so [H
3
O
+
] = [OH
-
] = x
[H
3
O
1+
][OH
1-
] = 1.0 X 10
-14
becomes
[x][x] = 1.0 X 10
-14
SPECIAL FOCuS: Acids and Bases
118
x
2
= 1.0 X 10
-14
x = 1.0 X 10
-7
∴ [H
3
O
+
] = 1.0 X 10
-7
M = [OH
-
]
In solutions when the:
[H
+
] > [OH
-
], then the solution is acidic.
[H
+
] < [OH
-
], then the solution is basic.
[H
+
] = [OH
-
], then the solution is neutral.
Based on this and the fact that [H
+
] and [OH
-
] can be calculated using K
w
if you
know one or the other, it’s time to solve some problems.
Examples
1. Given the [OH
-
] = 1.0 X 10
-5
M, solve for the [H
3
O
+
] and determine the solution’s
nature (acidic, basic, or neutral).
K
w
= [H
3
O
+
][OH
-
] = 1.0 X 10
-14
[H
3
O
+
] [1.0X 10
-5
] = 1.0 X 10
-14
[H
3
O
+
] = 1.0 X 10
-14
M
2
= 1.0 X 10
-9
M which is less than the [OH
-
] so the
1.0X 10
-5
M solution is basic.
2. Given the [H
3
O
+
] = 1.0 X 10
-2
M, solve for the [OH
-
] and determine the solution’s
nature (acidic, basic, or neutral).
K
w
= [H
3
O
+
][OH
-
] = 1.0 X 10
-14
[1.0X 10
-2
M][OH
-
] = 1.0 X 10
-14
[OH
-
] = 1.0 X 10
-14

M
2
= 1.0 X 10
-12
M which is less than the [H
3
O
+
] so
1.0X 10
-2
M the solution is basic.
Substances other than water can also be amphoteric. Let’s look at a hydrated
aluminum hydroxide ion as an example.
[Al(H
2
O)
4
(OH)
2
]
+
+ NaOH ↔ Al(H
2
O)
3
(OH)
3
+ OH
-
When a water of hydration from [Al(H
2
O)
4
(OH)
2
]
+
donates the hydrogen ion to
becomes the third hydroxide ion it is acting as a Brønsted-Lowry acid.
[Al(H
2
O)
4
(OH)
2
]
+
+ HCl ↔ [Al(H
2
O)
5
OH]
2+
+ Cl
-
When a hydroxide from [Al(H
2
O)
4
(OH)
2
]
+
accepts the hydrogen ion to create the
ffth water of hydration, it is acting as a Brønsted-Lowry base.
Appendix B
119
pH scale
Based on logarithms, the pH scale was developed.
0 7 14
Acidic Neutral Basic
pH = -log[H
+
] or pH = -log [H
3
O
+
]
3. What is the pH of a solution with a [H
+
] = 1.0 X 10
-9
M?
pH = -log[H
+
] pH = -log(1.0X10
-9
M) pH = 9.00
A similar formula can be used to calculate the pOH (relative basicity) if you know the
[OH
-
].
pOH = -log [OH
-
]
What is the pOH of a solution with a [OH
-
] = 2.4 X 10
-7
M?
pOH = -log [OH
-
] pOH = -log(2.4 X 10
-7
M) pOH = 6.62
By combining all three of the previous formulas:
K
w
= [H
+
][OH
-
] = 1.0 X 10
-14

pH = -log [H
+
]
pOH = -log [OH
-
],
we can derive the formula:
pH + pOH = 14
4. What is the pOH of a solution that has a pH of 10.0?
pH + pOH = 14 10.0 + pOH = 14 pOH = 4.0
Vinegar has a pH = 2.8. What are the pOH, [H
+
], and [OH
-
] of a vinegar solution?
pH + pOH = 14 2.8 + pOH = 14 pOH = 11.2
pH = -log[H
+
] 2.8 = -log[H
+
] [H
+
] = 2 X 10
-3
M
pOH = -log[OH
-
] 11.2 = -log[OH
-
] [H
+
] = 6 X 10
-12
M
SPECIAL FOCuS: Acids and Bases
120
Relative Strengths of Acids and Bases
Acids and bases can be concentrated or dilute, weak or strong. Do not confuse the
frst two, which describe the solution concentration, with the last two, which describe
the amount of dissociation. A strong acid or base is one that completely dissociates in
water or has 100% ionization. A weak acid or base is one in which only a small portion
of the particles dissociate, or one that only partially ionizes.
Strong acids include:
HCl, HBr, HI, HNO
3
, H
2
SO
4
, H
3
PO
4 ,
and HClO
4
.
All others are considered weak.
Strong bases include:
LiOH, NaOH, KOH, Mg(OH)
2
, Ca(OH)
2
, Sr(OH)
2,
and Ba(OH)
2
.
All others are considered weak.
Appendix C
Titration Notes
A titration is the experimental procedure used to determine the concentration of an
unknown acid or base. The necessary chemical components of a titration include a
standard solution, and solution of unknown concentration, and an indicator.
Titration curves are a way to visually represent the change in pH during a
titration.
Titrations and titration curves tell you many things about a reaction. During a
titration, the indicator experiences a color change at the endpoint of the titration.
If the best indicator is chosen, the endpoint and the equivalence point (when
there are equal amounts of acid and base) occur at nearly the same time. Common
indicators used in acid–base titrations include phenolphthalein (clear to pink pH =
8-10) and bromothymol blue (yellow to blue pH = 6-8). The equivalence point can be
visually determined from the titration curve. It is the area in which the slope of the
line approaches infnity (or is nearly vertical).
Acid–Base Reactions
When an acid reacts with a base a neutralization reaction occurs. The same thing
happens when a base reacts with an acid.
An acid–base reaction is a double displacement reaction.
AB + CD → AD + CB
The products of an acid–base reaction are a salt (metal/nonmetal compound)
and water.
Examples
HCl + NaOH → NaCl + HOH
H
2
SO
4
+ KOH →
SPECIAL FOCuS: Acids and Bases
122
H
3
PO
4
+ LiOH →
Hydrobromic acid + calcium hydroxide
HBr + Ca(OH)
2
→ CaBr
2
+ 2H
2
O
Hydrofuoric acid + aluminum hydroxide
HF + Al(OH)
3
→ AlF
3
+ 3H
2
O
Titration Problems
Often, the goal of a titration is to calculate the concentration of one of the reactants.
This can be done using a balanced equation and stoichiometry.
1. A 25.0 mL sample of HCl was titrated to the endpoint with 15.0 mL of 2.0 M
NaOH. What was the molarity of the acid?
2. A 10.0 mL sample of H
2
SO
4
was neutralized by 13.5 mL of 1.0 M KOH. What
was the molarity of the acid?
3. What volume of 1.50 M NaOH is necessary to neutralize 20.0 mL of 2.5M
H
3
PO
4
?
4. How much 0.5M HNO
3
is necessary to titrate 25.0 mL of 0.05M Ca(OH)
2

solution to the endpoint?
Appendix D
Titration Notes – Teacher’s Edition
A titration is the experimental procedure used to determine the concentration of
an unknown acid or base. The necessary chemical components of a titration include
a standard solution, a solution of unknown concentration, and may include a colored
indicator.
Titration curves are a way to visually represent the change in pH during a
titration.
Titrations and titration curves tell you many things about a reaction. During a
titration, the indicator experiences a color change at the endpoint of the titration. If
the best indicator is chosen, the endpoint and the equivalence point (when equivalent
amounts of acid and base have been added) occur at nearly the same time. Common
indicators used in acid–base titrations include phenolphthalein (clear to pink pH =
8–10) and bromothymol blue (yellow to blue pH = 6–8). The equivalence point can be
visually determined from the titration curve. It is the area where the slope of the line
approaches infnity (or is nearly vertical). Titration curves and the progress of titrations
can also be followed by using a pH meter or probe.
Acid–Base Reactions
When an acid reacts with a base, a neutralization reaction occurs. The same thing
happens when a base reacts with an acid.
An acid–base reaction is a double displacement reaction.
AB + CD → AD + CB
The overall products of an acid–base reaction are a salt (metal/nonmetal
compound) and water.
SPECIAL FOCuS: Acids and Bases
124
Examples
HCl + NaOH → NaCl + HOH (which also can be written H
2
O)
H
2
SO
4
+ 2KOH → K
2
SO
4
+ 2H
2
O
H
3
PO
4
+ 3LiOH → Li
3
PO
4
+ 3H
2
O
Hydrobromic acid + calcium hydroxide
HBr + Ca(OH)
2
→ CaBr
2
+ 2H
2
O
Hydrofuoric acid + aluminum hydroxide
HF + Al(OH)
3
→ AlF
3
+ 3H
2
O
Titration Problems
Often, the goal of a titration is to calculate the concentration of one of the reactants.
This can be done using a balanced equation and stoichiometry.
1. A 25.0 mL sample of HCl was titrated to the equivalence point with 15.0 mL
of 2.0 M NaOH. What was the molarity of the acid?
HCl + NaOH → NaCl + H
2
O
15.0 mL NaOH × 1 L NaOH × 2.0 mol NaOH × 1 mol HCl × 1 × 1000 mL
= 1.2 M HCl
1000mL NaOH 1 L NaOH 1 mol NaOH 25.0 mL HCl 1 L HCl
2. A 10.0 mL sample of H
2
SO
4
was completely reacted by 13.5 mL of 1.0 M
KOH. What was the molarity of the acid?
H
2
SO
4
+ 2KOH → K
2
SO
4
+ 2H
2
O
13.5 mL KOH × 1 L KOH × 1.0 mol KOH × 1 mol H
2
SO
4
× 1000 mL H
2
SO
4
× 1 = 0.68 M H
2
SO
4
1000mL 1L 2 mol KOH 1 L H
2
SO
4
10.0 mL H
2
SO
4
3. What volume of 1.50 M NaOH is necessary to completely react with 20.0 mL
of 2.5M H
3
PO
4
?
Note: M is molarity, which can be mol/L or millimoles/mL.
H
3
PO
4
+ 3NaOH → Na
3
PO
4
+ 3H
2
O
20.0 mL H
3
PO
4
× 2.5 mmol H
3
PO
4
× 3 mmol NaOH × 1mL NaOH
= 1.00 × 10
2
mL NaOH
1.0 mL H
3
PO
4
1 mmol H
3
PO
4
1.50mmol NaOH
Appendix D
125
4. How much 0.5M HNO
3
is necessary to titrate 25.0 mL of 0.05M Ca(OH)
2

solution to the equivalence point?
2HNO
3
+ Ca(OH)
2
→ Ca(NO
3
)
2
+ 2H
2
O
25.0 mL Ca(OH)
2
× 0.05 mmol Ca(OH)
2
× 2 mmol HNO
3
× 1mL HNO
3
= 5.00 mL HNO
3
1 mL Ca(OH)
2
1 mmol Ca(OH)
2
0.5 mmol HNO
3
Appendix E
Calculating the pH of a Weak Acid or Base
When working with weak acids, weak bases, or buffer systems, one must take into
account the fact that many species exist in the reaction vessel. Take, for example, the
case of calculating the pH of a 0.100 M acetic acid solution whose K
a
= 1.8 X 10
-5
.
The reaction: HC
2
H
3
O
2
(aq) + H
2
O (l) ↔ H
3
O
1+
(aq) + C
2
H
3
O
2
1-
(aq).
Acetic acid is a weak acid and thus, only a small percentage of it dissociates.
This becomes an equilibrium problem instead of a simple stoichiometry problem (like
it would if it were a strong acid).
We begin by writing the equilibrium expression:
Ka Ka
[H O ][ C H O ]
[ HC H O ]
3
1
2 3 2
1-
2 3 2
=
+
Next we need to look at the conditions during the reaction:
HC
2
H
3
O
2
H
3
O
1+
C
2
H
3
O
2
1-
Initial 0.100M 0 0
Change -x +x +x
Equilibrium 0.100M - x x x
Substituting into the equilibrium expression we get:
Ka =
[x][x]
= 1.8 X 10
-5
[ 0.100M -x ]
Assuming the effect of x on 0.100M is negligible because of the large difference
(power difference > 10
-3
units) in concentration and K
a
, solving for x we get:
x
2
x
2
= = =
− − +
1 8 10 1 34 10
6 3
3
1
. . [ ] X x X H O
SPECIAL FOCuS: Acids and Bases
128
Now we can solve for pH using the equation: pH = -log[H
3
O
1+
] and fnd the pH to
be 2.87.
Example 1
Calculate the pH of a 2.00M ammonia solution with a K
a
= 5.71 X 10
-10
@ 25°C.
A. -0.30
B. 2.22
C. 8.94
D. 11.78
Solution:
The correct answer is D. The reaction is NH3(aq) + H2O(l) ↔ NH41+(aq) + OH1-(aq)
Since K
w
= K
a
K
b
= 1.0 X 10
-14
so K
b
=
K
K
w
a
substituting in values we get:
K
b
=
1 0 10
5 71 10
1 8 10
14
10
5
.
.
.
X
X
X M



= .
NH
3
NH
4
1+
OH
1-
Initial 2.00 M 0 0
Change - x +x +x
Equilibrium 2.00 - x x x
Substituting into the equilibrium expression we get:
K
b
=
[x][x]
= 1.8 X 10
-5
[ 2.00M -x ]
Assuming the effect of x on 2.00M is negligible because of the large difference
(power difference > 10
-3
units) in concentration and K
b
, solving for x we get:
x
2
x
2
= = =
− − −
3 6 10 6 0 10
6 3 1
. . [ ] X x X OH
Now we can solve for pOH using the equation: pOH = -log[OH
1-
] and fnd the pOH
to be 2.22.
Since pH + pOH = 14, pH = 14 – 2.22, and the pH = 11.78.
If you chose answer A, you only used the initial concentration of ammonia and
substituted it into the pH = -log[H
3
O
1+
] assuming that the concentration of ammonia
was equal to the hydronium ion concentration. If you chose answer B, you selected
the value that was equal to the pOH. If you chose answer C, you used 5.71 X 10
-10
for
your K
b
value instead of 1.8 X 10
-5
.
Appendix F
Applications of Aqueous Equilibria Notes
Different Constants (to hopefully clear confusion)
K
b
molal boiling point constant ∆t
b
= K
b
m
K
f
molal freezing point constant ∆t
f
= K
f
m
k rate constant Rate = k [reactants]
K
w
ionization constant for water K
w
= K
a
K
b
= 1.0 X 10
-14
@ 25°C
K
a
acid dissociation constant K
a
= [H
+
][A
-
]/[HA]
K
b
base dissociation constant K
b
= [X
+
][OH
-
]/[XOH]
K
c
equilibrium constant for concentrations
K
p
equilibrium constant based on pressures
K
sp
equilibrium constant for solubility product
K
d
equilibrium constant for decomposition reactions
K
f
equilibrium constant for formation reactions
The Effect of Common Ions
When a salt is added to an acid or base containing similar ions, the equilibrium shifts
to relieve the stress this is an application of .
If NaF is added to HF: If NH
4
Cl is added to NH
3
:
HF ↔ H
+
+ F
-
NH
3
+ H
2
O ↔ NH
4
+
+ OH
-
NaF ↔ Na
+
+ F
-
NH
4
Cl ↔ NH
4
+
+ Cl
-
More fuoride ions are added to
the solution.
More ammonium ions are added to
the solution.
The equilibrium shifts to the left. The equilibrium shifts to the left.
This shifting process is called the common ion effect. This complicates the
equilibrium by providing an additional source for ions.
SPECIAL FOCuS: Acids and Bases
130
Example 1
Calculate the pH of a mixture containing 0.100 M HC
3
H
5
O
2
and 0.100 M NaC
3
H
5
O
2
. K
a

= 1.3 x 10
-5
Buffers
Combinations of weak acids or weak bases with their salts form buffers. Buffers
are solutions that resist changes in pH when hydrogen or hydroxide ions are added.
When working with buffers, be sure to look at the stoichiometry before setting up the
equilibrium.
Example 2
What is the difference in pH of a solution containing 2.00 mol of ammonia and 3.00
mol of ammonium chloride in 1.00 L of solution versus the pH of the ammonia alone?
K
b
= 1.81 X 10
-5
The Henderson-Hasselbalch equation can also be used to solve for pH.
pH = pK
a
+ log ([A
-
]/[HA]) pOH = pK
b
+ log ([X
+
]/[WB])
Solution:
Titrations are laboratory procedures used to determine the concentration of acids
or bases. Along the way, the pH of the mixture can be calculated. Problems like this
have appeared in the past on the AP Exam.
A 100.0 mL sample of 0.150 M HNO
2
(pK
a
= 3.35) was titrated with 0.300 M
NaOH. Determine the pH after the following quantities of base have been added to
the acid solution and draw the resulting titration curve.
a. 0.00 mL
b. 25.00 mL
c. 49.50 mL
d. 50.00 mL
e. 55.00 mL
f. 75.00 mL
Indicators and Titrations
Common indicators used in acid base titrations are:
phenolphthalein (clear to pink pH =8-10)
bromothymol blue (yellow to blue pH = 6-8)
universal indicator (red to purple pH = 1-13)
Appendix F
131
To prepare a buffer with a specifc pH (part of pre-lab discussion):
pH = pKa + pH pK
A
HA
a
= +

log
[ ]
[ ]
6.0 = pKa + 6 pK
A
HA
a
. log
[ ]
[ ]
0 = +

Acids to choose from: Their K
a
values
H
2
SO
3
1.5 X 10
-2
1.0 X 10
-7
HOAc 1.8 X 10
-5
H
3
PO
4
7.3 X 10
-3
6.2 X 10
-8
4.8 X 10
-13
H
2
CO
3
4.3 X 10
-7
5.6 X 10
-11
HSO
4
1-
1.2 X 10
-2
H
2
SO
4
Large 1.2 X 10
-2
So if I am not mistaken, for a buffer with pH = 6, you would choose HOAc and
NaOAc since the pK
a
of HOAc is closest to 6.
6 p(1.8 X 10 )
A
HA
-5
. log
[ ]
[ ]
0 = +

6 0 4 74 . . log = +




[ ]

A
HA
1.26
A
HA
=

log
[ ]
[ ]
10
1 26 −

=
.
[ ] A
[HA]
0 055 .
[ ]
=

A
[HA]
If [HA] = 0.1 M, then [A
-
] = 0.0055M.
Solubility Equilibria
When solids dissolve to form aqueous solutions, the equilibrium involved is the
solubility equilibria. When a salt is added to water at frst, none is dissolved, then as
the water molecules collide with the salt and interact with the intermolecular forces,
the formula units of the salt begin to dissolve. Eventually the maximum amount of
SPECIAL FOCuS: Acids and Bases
132
solid that can dissolve at that particular temperature does dissolve and equilibrium is
reached.
BaCO
3
(s) ↔ Ba
2+
(aq) + CO
3
2-
(aq)
K
sp
= [Ba
2+
] [CO
3
2-
] = 1.6 X 10
-9

Why is the BaCO
3
not included in the K
sp
expression?
Notice that the K value is very small. We would expect this since barium carbonate
is not considered soluble in water based on what we have learned from solubility
rules. Do realize, however, that solubility and the solubility product are not the same.
Solubility is a position that changes with temperature and the concentration of
common ions present in the solution. The solubility product is a constant value for a
particular temperature (usually room temperature when you look it up in a chart).
K
sp
problems are much like K
a
and K
b
problems.
Calculating K
sp
from solubility
Calculating solubility from K
sp
PbSO
4
has a measured solubility of 1.14 X 10
-4
mol/L
Al(OH)
3
has a K
sp
of 2 X 10
-32
at 25°C.
At 25°C,what is the K
sp
of PbSO
4
?
What is its solubility of PbSO
4
at 25°C?
Relative Solubilities
If salts produce the same number of ions when they dissolve, then their K
sp
values can
be used to determine their solubilities relative to each other. The smaller the K
sp
, the
less soluble it is.
If the salts produce different numbers of ions when they dissolve, then you have
to calculate the solubilities from the K
sp
values, as in the previous example.
The Common Ion Effect on Solubility
A common ion affects the solubility of a solid, generally reducing the amount that
dissolves by providing an initial concentration of one of the ions. RICE diagrams are
very useful in demonstrating this affect.
Example 3
The K
sp
of silver sulfate is 1.2 X 10
-5
. Calculate the solubility of silver sulfate in a 0.20 M
solution of potassium sulfate.
Appendix G
Applications of Aqueous Equilibria Notes –
Teacher’s Edition
Different Constants (to hopefully clear confusion)
K
b
molal boiling point constant ∆t
b
= K
b
m
K
f
molal freezing point constant ∆t
f
= K
f
m
k rate constant Rate = k [reactants]
K
w
ionization constant for water K
w
= K
a
K
b
= 1.0 X 10
-14
@ 25°C
K
a
acid dissociation constant K
a
= [H
+
][A
-
]/[HA]
K
b
base dissociation constant K
b
= [X
+
][OH
-
]/[XOH]
K
c
equilibrium constant for concentrations
K
p
equilibrium constant based on pressures
K
sp
equilibrium constant for solubility product
K
d
equilibrium constant for decomposition reactions
K
f
equilibrium constant for formation reactions
The Effect of Common Ions
When a salt is added to an acid or base containing similar ions, the equilibrium shifts
to relieve the stress this is an application of LeChatlier’s Principle
If NaF is added to HF: If NH
4
Cl is added to NH
3
:
HF ↔ H
+
+ F
-
NH
3
+ H
2
O ↔ NH
4
+
+ OH
-
NaF ↔ Na
+
+ F
-
NH
4
Cl ↔ NH
4
+
+ Cl
-
More fuoride ions are added to the solution. More ammonium ions are added to the solution.
The equilibrium shifts to the left. The equilibrium shifts to the left.
This shifting process is called the common ion effect. This complicates the
equilibrium by providing an additional source for ions.
SPECIAL FOCuS: Acids and Bases
134
Example 1
Calculate the pH of a mixture containing 0.100 M HC
3
H
5
O
2
and 0.100 M NaC
3
H
5
O
2
. K
a

= 1.3 x 10
-5
HC
3
H
5
O
2
(aq)  H
+
(aq) + C
3
H
5
O
2
-
(aq)
HC
3
H
5
O
2
H
1+
C
3
H
5
O
2
1-
Initial 0.100M 0 0
Change -x +x x + 0.100 [The 0.100 comes from the NaC
3
H
5
O
2
.]
Equilibrium 0.100M - x x x + 0.100
K
a
=
[x][0.100 + x]
=1.3 X 10
-5
[0.100M -x]
If you consider x to be negligible, then this simplifes to :
K
a
K
[0.100x]
[ 0.100M]
a
= =

1 3 10
5
. X and x = 1.3 X 10
-5
M = [H
+
]
pH = -log[H
+
]
pH = -log(1.3X10
-5
)
pH = 4.89, which is consistent with a weak acid.
Buffers
Combinations of weak acids or weak bases with their salts form buffers. Buffers
are solutions that resist changes in pH when hydrogen or hydroxide ions are added.
When working with buffers, be sure to look at the stoichiometry before setting up the
equilibrium.
Example 2
What is the difference in pH of a solution containing 2.00 mol of ammonia and 3.00
mol of ammonium chloride in 1.00 L of solution versus the pH of the ammonia alone?
K
b
= 1.81 X 10
-5
2.00 mol NH
3
only 2.00 mole NH
3
+ 3.00 mol NH
4
Cl
NH
3
+ H
2
O(aq)  NH
4
+
(aq) + OH
-
(aq) NH
3
+ H
2
O(aq) ↔ NH
4
+
(aq) + OH
-
(aq)
NH
3
NH
4
1+
OH
1-
NH
3
NH
4
1+
OH
1-
Initial 2.00 M 0 0 2.00 M 0 0
Change -x +x +x -x 3.00 + x x
Equilibrium 2.00M - x x x 2.00M - x x x
Appendix G
135
K
a
=
[x][x]
= 1.81 X 10
-5
[2.00M -x]
K
a
=
[3.00M + x][x]
= 1.81 X 10
-5
[2.00M -x]
Considering x to be negligible: Considering x to be negligible:
x
2
= 2.00 M × (1.81 X 10
-5
) 3x = 2.00 M × 1.81 X 10
-5
x= 6.01 × 10
-3
M = [OH
-
] x = 1.21 × 10
-5
M = [OH
-
]
pOH = -log[OH
-
] pOH = -log[OH
-
]
pOH = 2.221 pOH = 4.917
pH + pOH = 14 pH + pOH = 14
pH + 2.221 = 14 pH + 4.917 = 14
pH = 11.779 pH = 9.083
The Henderson-Hasselbalch equation can also be used to solve for pH.
pH = pK
a
+ log ([A
-
]/[HA]) pOH = pK
b
+ log ([X
+
]/[WB])
Titrations are laboratory procedures used to determine the concentration of acids
or bases. Along the way, the pH of the mixture can be calculated. Problems like this
have appeared in the past on the AP Exam.
A 50.0 mL sample of 0.300 M HNO
2
(pK
a
= 3.35) was titrated with 0.450 M NaOH.
Determine the pH after the following quantities of base have been added to the acid
solution and draw the resulting titration curve:
a. 0.00 mL
b. 16.5 mL
c. 32.0 mL
d. 33.3 mL
e. 35.0 mL
f. 50.0 mL
a. HNO
2
(aq)  H
+
(aq) + NO
2
-
(aq) pKa = -log(K
a
) 3.35 = -log(K
a
)
K
a
= 4.5 × 10
-4

K
a
K
[H ][NO ]
[HNO ]
a
2
-
2
= =
+

4 5 10
4
. X =4.5 X 10
-4

SPECIAL FOCuS: Acids and Bases
136
[HNO
2
] [H
1+
] [NO
2
1-
]
Initial 0.300 M 0 0
Change -x +x +x
Equilibrium 0.300 M - x x x

K
a
=
[x][x]
=4.5 × 10
[0.300M -x]
x = 1.2 × 10
-2
M = [H
+
]
pH = -log[H
+
]
pH = 1.92
b. HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
50.0 mL HNO
2
× 1L/1000mL × 0.300 M = 0.0150 mol HNO
2
16.5 mL NaOH × 1L/1000mL × 0.450 M = 0.00743 mol NaOH
0.0150 mol – 0.007425 mol = 0.07575 mol HNO
2
left after reaction
50.0mL + 16.5mL = 66.5 mL or 0.0665 L
HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
[HNO
2
] [NaOH] [Na
1+
] [NO
2
1-
]
Initial 0.0150 mol 0.0743 mol 0 0
Change -0.0743mol -0.0743 mol + 0.0743 mol + 0.0743mol
Equilibrium 0.0757 mol 0 0.0743 mol 0.0743 mol
pH = pK
a
+ log ([A
-
]/[HA])
pH = 3.35 + log(0.0743 mol/0.0665 L ÷ 0.0757 mol/0.0665 L)
pH = 3.34
c. HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
50.0 mL HNO
2
× 1L/1000mL × 0.300 M = 0.0150 mol HNO
2
32.0 mL NaOH × 1L/1000mL × 0.450 M = 0.0144 mol NaOH
0.015 mol – 0.014 mol = 0.001 mol HNO
2
left after reaction
50.0mL + 32.0mL = 82.0 mL or 0.0820 L
HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
[HNO
2
] [NaOH] [Na
1+
] [NO
2
1-
]
Initial 0.0150 mol 0.0144 mol 0 0
Change -0.0144 mol -0.0144 mol + 0.0144 mol + 0.0144 mol
Equilibrium 0.0006 mol 0 0.0144 mol 0.0144 mol
Appendix G
137
pH = pK
a
+ log ([A
-
]/[HA])
pH = 3.35 + log(0.0144 mol/0.0820 L ÷ 0.0006 mol/0.0820 L)
pH = 4.73
d. HNO
2
(aq) + NaOH(aq) Na
+
(aq) + NO
2
-
(aq) + H
2
O
50.0 mL HNO
2
× 1L/1000mL × 0.300 M = 0.0150 mol HNO
2
33.3 mL NaOH × 1L/1000mL × 0.450 M = 0.0150 mol NaOH
0.0150 mol – 0.0150 mol = 0.00 mol HNO
2
left after reaction
50.0mL + 33.3mL = 83.3 mL or 0.0833 L
HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
[HNO
2
] [NaOH] [Na
1+
] [NO
2
1-
]
Initial 0.0150 mol 0.0150 mol 0 0
Change 0.0150 mol 0.0150 mol + 0.0150 mol + 0.0150 mol
Equilibrium 0 0 0.0150 mol 0.0150 mol
0.0150 mol NO
2
1-
= 0.180 M
0.0833 L
NO
2
-
is the conjugate base of a weak acid so
pK
a
+ pK
b
= 14.0 pK
b
= 14.0 – 3.35 = 10.65
NO
2
-
(aq) + H
2
O (l)  OH
-
(aq) + HNO
2
(aq)
[NO
2
-
] [H
2
O] [OH
-
] [HNO
2
]
Initial 0.180M 0 0
Change -x +x +x
Equilibrium 0.180M-x x x
pK
b
= -log(K
b
) K
b
= 2.24 × 10
-11

K
b
K
[OH ][HNO ]
[NO ]
b
2
2
-
= =


2 24 10
11
. X
x
2
= (0.180M) × 2.24 × 10
-11
x = 2.01 ×10
-6
= [OH
-
]
pOH = -log[OH
-
]
pOH = 5.697 14 - pOH = pH pH = 8.303
e. HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
50.0 mL HNO
2
× 1L/1000mL × 0.300 M = 0.0150 mol HNO
2
35.0 mL NaOH × 1L/1000mL × 0.450 M = 0.0158 mol NaOH
SPECIAL FOCuS: Acids and Bases
138
0.0158 mol – 0.0150 mol = 0.0008 mol NaOH left after reaction
50.0 mL + 35.0 mL = 85.0 mL or 0.0850 L
HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
[HNO
2
] [NaOH] [Na
1+
] [NO
2
1-
]
Initial 0.0150 mol 0.0158mol 0 0
Change 0.0150 mol 0.0150 mol + 0.0150 mol + 0.0150 mol
Equilibrium 0 0.0008 mol 0.0150 mol 0.0150 mol
Here the concentration of NaOH controls the pH since it is a strong base.
pOH = -log[OH
-
] pOH = -log(0.0008 M) pOH = 3
pH + pOH = 14 pH = 14 – pOH pH = 11
f. HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
50.0 mL HNO
2
× 1L/1000mL × 0.300 M = 0.0150 mol HNO
2
50.0 mL NaOH × 1L/1000mL × 0.450 M = 0.0225 mol NaOH
0.0225 mol – 0.0150 mol = 0.0075 mol NaOH left after reaction
50.0mL + 50.0mL = 100.0 mL or 0.1000 L
HNO
2
(aq) + NaOH(aq)  Na
+
(aq) + NO
2
-
(aq) + H
2
O
[HNO
2
] [NaOH] [Na
1+
] [NO
2
1-
]
Initial 0.0150 mol 0.0225 mol 0 0
Change 0.0150 mol 0.0150 mol + 0.0150 mol + 0.0150 mol
Equilibrium 0 0.0075 mol 0.0150 mol 0.0150 mol
Here the concentration of NaOH controls the pH since it is a strong base.
pOH = -log[OH
-
] pOH = -log(0.0075M) pOH = 2.125
pH + pOH = 14 pH = 14 – pOH pH = 11.875
Indicators and Titrations
Common indicators used in acid base titrations are:
• phenolphthalein (clear to pink pH = 8-10)
• bromothymol blue (yellow to blue pH = 6-8)
• universal indicator (red to purple pH = 1-13)
To prepare a buffer with a specifc pH (part of pre-lab discussion)
pH = pKa pH pK
A
HA
a
= +

log
[ ]
[ ]
Appendix G
139
6.0 = pKa 6 pK
A
HA
a
. log
[ ]
[ ]
0 = +

Acids to choose from: Their K
a
values
H
2
SO
3
1.5 X 10
-2
1.0 X 10
-7
HOAc 1.8 X 10
-5
H
3
PO
4
7.3 X 10
-3
6.2 X 10
-8
4.8 X 10
-13
H
2
CO
3
4.3 X 10
-7
5.6 X 10
-11
HSO
4
1-
1.2 X 10
-2
H
2
SO
4
Large 1.2 X 10
-2
So if I am not mistaken, for a buffer with a pH of 6, you would choose HOAc and
NaOAc since the pK
a
of HOAc is closest to 6.

6 p(1.8 X 10 )
A
HA
-5
. log
[ ]
[ ]
0 = +


6 4.74
A
HA
. log
[ ]
[ ]
0 = +


1.26
A
HA
=

log
[ ]
[ ]

10
1 26 −

=
.
[ ] A
[HA]

0 055 .
[ ]
=

A
[HA]
If [HA] = 0.1 M, then [A
-
] = 0.0055M.
Solubility Equilibria
When solids dissolve to form aqueous solutions, the equilibrium involved is the
solubility equilibria. When a salt is added to water at frst, none is dissolved, then as
the water molecules collide with the salt and the intermolecular forces interact with
the water, the formula units of the salt begin to dissolve. Eventually, the maximum
amount of solid that can dissolve at that particular temperature does dissolve and
equilibrium is reached.
BaCO
3
(s) ↔ Ba
2+
(aq) + CO
3
2-
(aq)
K
sp
= [Ba
2+
] [CO
3
2-
] = 1.6 X 10
-9

Why is the BaCO
3
not included in the K
sp
expression?
Barium carbonate is a solid and solids are not found in equilibrium expressions.
Notice that the K value is very small. We would expect this since barium
carbonate is not considered soluble in water, based on what we have learned from
solubility rules. Do realize, however, that solubility and the solubility product are not
the same. Solubility is a position that changes with temperature and the concentration
of common ions present in the solution. The solubility product is a constant value for a
particular temperature (usually room temperature when you look it up on a chart).
K
sp
problems are much like K
a
and K
b
problems.
Calculating K
sp
from solubility
PbSO
4
has a measured solubility of 1.14 X 10
-4
mol/L
What is the K
sp
of PbSO
4
?
PbSO
4
(s)  Pb
2+
(aq) + SO
4
2-
(aq)
K
sp
= [Pb
2+
][SO
4
2-
]
K
sp
= (x)(x)
K
sp
= (1.14 × 10
-4
)
2
K
sp
= 1.30 × 10
-8
Calculating solubility from K
sp
Al(OH)
3
has a K
sp
of 2 X 10
-32
at 25°C
Al(OH)
3
(s)  Al
3+
(aq) + 3OH
-
(aq)
K
sp
= [Al
3+
][OH
-
]
3
2 X 10
-32
= (x)(3x)
3
x = 5 × 10
-9
M
Relative Solubilities
If salts produce the same number of ions when they dissolve, then their K
sp
values can
be used to determine their solubilities relative to each other. The smaller the K
sp
, the
less soluble it is.
If the salts produce different numbers of ions when they dissolve, then you have
to calculate the solubilities from the K
sp
values, as in the previous example.
The Common Ion Effect on Solubility
A common ion affects the solubility of a solid, generally reducing the amount that
dissolves by providing an initial concentration of one of the ions. RICE diagrams are
very useful in demonstrating this effect.
Appendix G
141
Example 3
The K
sp
of silver sulfate is 1.2 × 10
-5
. Calculate the solubility of silver sulfate in a
0.20 M solution of potassium sulfate.
Ag
2
SO
4
(s)  2Ag
1+
(aq) + SO
4
2-
(aq)
K
sp
= [Ag
1+
]
2
[SO
4
2-
] The K
2
SO
4
solution contributes 0.20 M of SO
4
2-
[Ag
1+
] [SO
4
2-
]
Initial 0 0.20
Change +2x + x
Equilibrium 2x 0.20 + x
1.2 × 10
-5
= (2x)
2
(0.20 + x)
x = 3.9 × 10
-3
M
[Ag
1+
] = 2x = 7.7 × 10
-3
M
The rest of Chapter 15 discusses qualitative analysis, selective precipitation, and
complex ion equilibria—topics that generally receive very little attention on the AP
Exam. Read about it if you have time, otherwise, we will come back to it after all the
other AP material has been covered or after the AP Exam.
Appendix H
Study Guides and Worksheets
Chapter 14
Answer the following questions, in order, on notebook paper.
Due date:
1. Make a chart comparing the defnitions of an acid and a base according to
the Arrhenius concept, the Bronsted-Lowry model, and the Lewis acid–base
model.
2. What is a hydronium ion?
3. What is a conjugate acid–base pair? Give an example.
4. What is K
a
?
5. What is the difference between a strong and weak acid?
6. What is a diprotic acid? Give an example.
7. Organic acids are generally strong or weak? Why?
8. Water is amphoteric. What does that mean?
9. What is K
w
? What is its value at 25 °C?
10. When calculating pH from [H
+
], how do you determine the number of
signifcant digits in your answer?
11. How does calculating the pH of a strong acid differ from calculating the pH
of a weak acid?
12. How do you calculate percent dissociation?
13. How do you calculate the pH of a strong base?
14. Give examples of salts that produce acidic solutions, basic solutions, and
neutral solutions.
15. Hydrofuoric acid is the only weak acid consisting of a halogen. Why?
Read through the In-Class Discussion Questions. They may be used for warm-ups.
SPECIAL FOCuS: Acids and Bases
144
Complete the following problems, in order, from pages 712–717. (19, 21–23, 27, 29,
31–32, 37–38, 43–46, 49–54, 61, 63, 81, 89, 95–96, 103–04, 109–10, 115–118, 123, 129,
138, 142–143, and 153)
Chapter 15
Answer the following questions, in order, on notebook paper.
Due date:
1. What is a common ion?
2. How do common ions affect equilibrium?
3. What is a buffered solution? What does it do? What substance in our body is
considered a buffered solution?
4. When dealing with a strong acid or strong base being added to a buffer,
what do you do before setting up the ICE chart?
5. What is the Henderson-Hasselbalch equation? When can you use it?
6. What is buffer capacity and how is it calculated?
7. Draw the pH curves for a strong acid/strong base titration, a weak acid–
strong base titration, and a weak base–strong acid titration.
8. What is the solubility product?
9. What is the common ion effect?
10. How are pH and solubility related?
11. What is the ion product? How is it related to K
sp
and precipitation?
12. What is selective precipitation and what is it used for?
13. What is qualitative analysis?
14. What is a complex ion?
15. What is a ligand?
Read through the In-Class Discussion Questions. They may be used for
warm-ups.
Complete the following problems, in order, from pages 781–789. (13–14, 18–19,
23–24, 33 –36, 40, 51–53, 55, 57–60, 61, 64, 69, 71–72, 79–82, 84–85, 88, 92, 97–99, 106,
119–121, and 123)
Appendix H
145
Acid–Bases, Reactions, and Titration Calculation Review Worksheet
1. Complete the following table. Show all work on a separate sheet of paper.
[H
3
O
+
] [OH
-
] pH pOH
7.23 X 10
-2
M
8.89 X 10
-7
M
10.3
9.39
3.99 X 10
-5
M
1.19 X 10
-10
M
2. The approximate pH of oranges is 3.5. What are the pOH, the [OH
-
], and the
[H
3
O
+
]?
3. The approximate pOH of tomatoes is 9.8. What are the pH, the [H
3
O
+
], and the
[OH
-
]?
4. Write and balance the chemical equation for the reaction between:
a. barium hydroxide and sulfuric acid
b. aluminum hydroxide and nitric acid
c. phosphoric acid and potassium hydroxide
5. How many mL of 1.50M magnesium hydroxide are necessary to titrate 25.0 mL
of 2.50 M phosphoric acid?
6. What is the molarity of a lithium hydroxide solution if 15.0 mL is neutralized by
7.5 mL of a 0.020 M acetic acid solution?
7. A student reacted a 25.00 mL sample of vinegar (acetic acid solution) with
38.25 mL of 0.500 M sodium hydroxide.
a. Write and balance the chemical equation for the reaction.
b. Calculate the molarity of the vinegar solution.
c. How many grams of acetic acid would be in 1.00 L of the vinegar?
d. What is the percent by mass of acetic acid in the vinegar solution
(assume a density of 1.00 g/mL)?
SPECIAL FOCuS: Acids and Bases
146
Acid–Bases, Reactions, and Titration Calculation Review Worksheet—
Teacher’s Edition
1. Complete the following table. Show all work on a separate sheet of paper.
[H
+
] [OH
-
] pH pOH
7.23 X 10
-2
M 1.38 × 10
-13
M 1.141 12.859
1.12 × 10
-8
M 8.89 X 10
-7
M 7.949 6.051
1.38 × 10
-13
M 1.38 × 10
-13
M 10.3 3.7
1.38 × 10
-13
M 1.38 × 10
-13
M 4.61 9.39
2.51 × 10
-10
M 3.99 X 10
-5
M 9.601 4.399
1.19 X 10
-10
M 8.40 × 10
-5
M 9.924 4.076
2. The approximate pH of oranges is 3.5. What are the pOH, the [OH
-
], and the
[H
+
]?
a. pOH = 10.5
b. [OH
-
]=3 × 10
-11
M
c. [H
+
] =3 × 10
-4
M
3. The approximate pOH of tomatoes is 9.8. What are the pH, the [H
+
], and the
[OH
-
]?
a. pH = 4.2
b. [H
+
] = 6× 10
-5
M
c. [OH
-
] = 2 × 10
-10
M
4. Write and balance the chemical equation for the complete reaction between:
a. barium hydroxide and sulfuric acid Ba(OH)
2
+ H
2
SO
4
→ BaSO
4
+ 2H
2
O
b. aluminum hydroxide and nitric acid Al(OH)
3
+ 3HNO
3
→ Al(NO
3
)
3
+ 3H
2
O
c. phosphoric acid and potassium hydroxide H
3
PO
4
+ 3KOH → K
3
PO
4
+
3H
2
O
5. How many mL of 1.50M magnesium hydroxide are necessary to completely
titrate 25.0 mL of 2.50 M phosphoric acid?
3Mg(OH)
2
+ 2H
3
PO
4
→ Mg
3
(PO
4
)
2
+ 6H
2
O
25.0 mL H
3
PO
4
× 1 L H
3
PO
4
× 2.50 mol H
3
PO
4
× 3 mol Mg(OH)
2
× 1L Mg(OH)
2
× 1000mLMg(OH)
2

= 62.5mL Mg(OH)
2
1 1000mL H
3
PO
4
1L H
3
PO
4
2 mol H
3
PO
4
1.50 mol Mg(OH)
2
1L Mg(OH)
2
Appendix H
147
6. What is the molarity of a lithium hydroxide solution if 15.0 mL is completely
titrated by 7.5 mL of a 0.020 M acetic acid solution?
LiOH + HC
2
H
3
O
2
→ LiC
2
H
3
O
2
+ H
2
O
7.5 mL HC
2
H
3
O
2
× 0.020 mmol HC
2
H
3
O
2
× 1 mmol LiOH

× 1
= 0.010M LiOH
1 1mL HC
2
H
3
O
2
1mmol HC
2
H
3
O
2
15.0 mL LiOH
7. A student reacted a 25.00 mL sample of vinegar (acetic acid solution) with
38.25 mL of 0.500 M sodium hydroxide.
a. Write and balance the chemical equation for the reaction.
HC
2
H
3
O
2
(aq)+ NaOH(aq)→ NaC
2
H
3
O
2
(aq) + H
2
O
b. Calculate the molarity of the vinegar solution.
38.25 mL NaOH × 0.500 mmol NaOH × 1 mmol HC
2
H
3
O
2
× 1
= 0.765M HC
2
H
3
O
2
1mL NaOH 1mmol NaOH 25.00 mL HC
2
H
3
O
2
1
c. How many grams of acetic acid would be in 1.00 L of the vinegar?
1.00 L HC
2
H
3
O
2
× 0.765M HC
2
H
3
O
2

× 60.05 g HC
2
H
3
O
2

= 45.9 g HC
2
H
3
O
2
1 1L HC
2
H
3
O
2
1mol HC
2
H
3
O
2

d. What is the percent by mass of acetic acid in the vinegar solution
(assume a density of 1.00 g/mL)?
45.9 g HC
2
H
3
O
2
× 1L HC
2
H
3
O
2
× 1 mL HC
2
H
3
O
2
× 100 = 4.59% HC
2
H
3
O
2
1L HC
2
H
3
O
2
1000mL HC
2
H
3
O
2
1.00 g HC
2
H
3
O
2
Appendix I
Dissociation and pH Practice
Weak Acid or Weak Base Systems
The ionization constant (or equilibrium constant) is very important here. Only ions
contribute. Water, which is usually the solvent, does not participate in any major
way here.
The general form for a reaction containing an acid is: HA + 2H
2
O ↔ H
3
O
+
+ A
-
so:
K
a
=
HA is an acid because it begins with hydrogen or because it donates a proton to
form H
3
O
+
. The A
-
is the element or polyatomic ion portion of the acid with a negative
charge. Write the K
a
for the dissociation of chlorous acid, HClO
2
, and formic acid,
HCOOH.
K
a
= K
a
=
Weak polyprotic acids dissociate (break apart) stepwise. Each step is written as a
different reaction. Generally there is a different value for K
a
each time an acid loses a
hydrogen ion.
H
3
PO
4
+ H
2
O ↔H
3
O
+
+ H
2
PO
4
1-
K
a1
=
H
2
PO
4
1-
+ H
2
O ↔ H
3
O
+
+ HPO
4
2-
K
a2
=
HPO
4
2-
+ H
2
O ↔ H
3
O
+
+ PO
4
3-
K
a3
=
Examples:
Write the dissociation reactions for sulfuric acid and carbonic acid.
H
2
SO
4
H
2
CO
3
This also holds true for weak bases like ammonia.
SPECIAL FOCuS: Acids and Bases
150
Write the K
b
for NH
3
+ H
2
O ↔ NH
4
+
+ OH
-
K
b
=
Steps for calculating the pH of a weak acid or base:
1) Write and balance the equation if it is not already done for you.
2) Determine the equilibrium expression, K
a
or K
b
.
3) Develop the ICE table.
4) Substitute the fnal values into the equilibrium expression.
5) Solve for the concentrations.
6) Solve for pH or pOH based on the [H
+
] or [OH
-
].
Calculate the pH of a 1.00M acetic acid solution with a K
a
= 1.8 X 10
-5
1) HC
2
H
3
O
2
(aq) + H
2
O (l) ↔ H
3
O
1+
(aq) + C
2
H
3
O
2
1-
(aq)
2) K
a
=
3)
HC
2
H
3
O
2
H
3
O
1+
C
2
H
3
O
2
1-
Initial
Change
Equilibrium
4) K
a
=
5) pH = -log[H
3
O
1+
]
Try this one: Calculate the pH of a 0.500M ammonia solution with a K
b
= 1.75 X 10
-5
1) NH
3
(aq) + H
2
O (l) ↔ NH
4
1+
(aq) + OH
1-
(aq)
2) K
b
=
3)
NH
3
NH
4
1+
OH
1-
Initial
Change
Equilibrium
4) K
b
=
5) pOH = -log[OH
1-
] pH + pOH = 14
Appendix J
Dissociation and pH Practice—Teacher’s
Edition
Weak Acid or Weak Base Systems
The ionization constant (or equilibrium constant) is very important here. Only ions
contribute. Water, which is usually the solvent, does not participate in any major way
here.
The general form for a reaction containing an acid is: HA + 2H
2
O ↔ H
3
O
+
+ A
-
so:
K
a
= [H
3
O
+
][A
-
]
[HA]
HA is an acid because it begins with hydrogen or because it donates a proton to
form H
3
O
+
. The A
-
is the element or polyatomic ion portion of the acid with a negative
charge. Write the K
a
for the dissociation of chlorous acid, HClO
2
, and formic acid,
HCOOH.
K
a
= [H
+
][ClO
2
-
] K
a
= [H
+
][COOH
-
]
[HClO
2
] [HCOOH]
Polyprotic acids dissociate (break apart) stepwise. Each step is written as a
different reaction. Generally there is a different value for K
a
each time an acid loses a
hydrogen ion.
H
3
PO
4
+ H
2
O ↔ H
3
O
+
+ H
2
PO
4
-
K
a1
= [H
3
O
+
][ H
2
PO
4
-
]
[H
3
PO
4
]
H
2
PO
4
-
+ H
2
O ↔ H
3
O
+
+ HPO
4
2-
K
a2
= [H
3
O
+
][ HPO
4
2-
]
[H
2
PO
4
-
]
HPO
4
2-
+ H
2
O ↔ H
3
O
+
+ PO
4
3-
K
a3
= [H
3
O
+
][ PO
4
3-
]
[HPO
4
2-
]
SPECIAL FOCuS: Acids and Bases
152
Practice
Write the dissociation reactions for sulfuric acid and carbonic acid.
H
2
SO
4
H
2
CO
3
H
2
SO
4
+ H
2
O ↔ H
3
O
+
+ HSO
4
-
H
2
CO
3
+ H
2
O ↔ H
3
O
+
+ HCO
3
-
HSO
4
-
+ H
2
O ↔ H
3
O
+
+ SO
4
2-
HCO
3
-
+ H
2
O ↔ H
3
O
+
+ CO
3
2-
Equilibrium expressions also can be written for weak bases like ammonia.
Write the K
b
for NH
3
+ H
2
O ↔ NH
4
+
+ OH
-
K
b
= [NH
4
+
][OH
-
]
[NH
3
]
Steps for calculating the pH of a weak acid or base:
1) Write and balance the equation if it is not already done for you.
2) Determine the equilibrium expression, K
a
or K
b
.
3) Develop the ICE table.
4) Substitute the fnal values into the equilibrium expression.
5) Solve for the concentrations.
6) Solve for pH or pOH based on the [H
+
] or [OH
-
].
Examples:
Calculate the pH of a 1.00M acetic acid solution with a K
a
= 1.8 X 10
-5
1) HC
2
H
3
O
2

(aq)
+ H
2
O
(l)
↔ H
3
O
+

(aq)
+ C
2
H
3
O
2
-

(aq)
2) K
a
= [H
3
O
+
][C
2
H
3
O
2
-
]
[HC
2
H
3
O
2
]
3)
[HC
2
H
3
O
2
] [H
+
] [C
2
H
3
O
2
-
]
Initial 1.00 M 0 0
Change -x +x +x
Equilibrium 1.00 M - x x x
4) K
a
= [x][x] = 1.8×10
-5
[1.00-x]
5) x = 4.2×10
-3
M = [H
+
]
6) pH = -log[H
+
] = 2.87
Calculate the pH of a 0.500M ammonia solution with a K
b
= 1.75 X 10
-5
Appendix J
153
1.) NH
3

(aq)
+ H
2
O
(l)
↔ NH
4
+

(aq)
+ OH
-

(aq)
2) K
b
= [NH
4
+
][OH
-
]
[NH
3
]
3.)
[NH
3
] [NH
4
+
] [OH
-
]
Initial 0.500 M 0 0
Change -x +x +x
Equilibrium 0.500-x x x
4) K
b
= [x][x] = 1.75×10-5
[0.500-x]
5) x = 2.96×10
-3
M = [OH
-
]
6) pOH = -log[OH-] pH + pOH = 14
pOH = 2.529 pH = 14 – pOH
pH = 11.471
Appendix K
Lab: Determining the pH of a Substance
Introduction
Many classifcation systems for compounds exist. One way to classify substances is
based on the relative amount of acid present. An acid produces hydrogen ions in an
aqueous solution according to the Arrhenius concept. The pH scale was developed to
measure the amount of hydrogen ions present in a solution. The use of an indicator, a
weak organic acid that changes colors, is another way to measure the hydrogen ion
concentration. Different indicators work in different pH ranges.
Use the following table as a reference:
Indicators
Color at a bottom of
range
Color at top of
range
pH range
Methyl red Red Yellow 4.8-6.0
Litmus Red Blue 5.2-7.5
Bromothymol blue Yellow Blue 6.0-7.6
Phenolphthalein Clear Pink 8.0-10.0
Universal indicator: changes colors at different pH values as follows
3.0 red-orange 4.0 orange 5.0 yellow 6.0 green-yellow 7.0 green
8.0 blue-green 9.0 blue-gray 10.0 violet
Objectives
1. To observe typical reactions of several indicators when treated with acids
and bases.
2. To estimate the pH of some common household products using these
reactions.
SPECIAL FOCuS: Acids and Bases
156
Procedure
Part 1:
1. Obtain a set of standard solutions
and a set of indicators.
2. Add 1–3 drops of each standard
across a row in wells according to
data table 1.
3. Add 1 drop of indicator down the
wells according to data table 1.
4. Record the colors observed for
each reaction in the data table.
5. Estimate the pH of each solution.
Record in the data table.
6. Rinse out the spot plate with deionized water.
Part 2:
1. Obtain a set of household products.
2. Add 1–3 drops of each product across a row in wells according to data
table 2.
3. Add 1 drop of indicator down the wells according to data table 2.
4. Record the colors observed for each reaction in the data table.
5. Estimate the pH of each solution. Record in the data table.
6. Rinse out the spot plate with deionized water.
Part 3: (To be done after you estimate the pH of each household substance
based on the indicator colors.)
1. Go to a station set up for measuring the pH of the products.
2. Follow the directions for calibrating your pH probe.
3. Submerge the probe tip in a small amount of the frst solution to be
measured.
4. Record the pH value in the data table.
5. Rinse the probe thoroughly with deionized water.
6. Repeat steps 3–5 with each household product to be tested.
Appendix K
157
Data Table 1:
Standard
Solution
Methyl
Red
Litmus
Indicator
Bromthy-
mol Blue
Phenol-
phthalein
universal
Indicator
Estimated
pH
0.1 M HCl
0.1 M acetic acid
distilled water
0.1 M NH3
(ammonia)
0.1 M NaOH
Data Table 2:
Product
Methyl
Red
Litmus
Indicator
Bromthy-
mol Blue
Phenol-
phthalein
universal
Indicator
Estimated
pH
aspirin
bleach
detergent
eggs
lemon juice
milk
milk of magnesia
clear soft drink
tea
SPECIAL FOCuS: Acids and Bases
158
Analysis:
1. Based on your observations, how does the estimated pH of the hydrochloric
acid compare to the estimated pH of the acetic acid?
2. Based on your observations, how does the estimated pH of ammonia
compare to the estimated pH of sodium hydroxide?
3. Using your textbook, fnd the strengths of the listed acids and bases.
How does your estimated pH values compare to the rankings of these
substances?
4. Indicators also can come from objects found in nature, your home, or even in
an offce. Locate one such indicator through research and explain how you
could tell the difference between an acid and a base using this indicator.
Conclusions
Describe your results. Where they as you expected?
Does one indicator work better than another? If so, which one and in what cases?
Appendix K
159
Was it diffcult to determine the color of the indicator in any particular substance? If
so, which one(s)? Why do you think this might have been the case?
If you start with 15.0 mL of hydrochloric acid in a beaker, add a couple drops of methyl
red and a couple drops of phenolphthalein, what would you expect to happen as you
add 10.0 mL of sodium hydroxide? 15.0 mL of NaOH? 20.0 mL of NaOH?
161
About the Editor
Marian DeWane teaches AP Chemistry at Centennial High School in Boise, Idaho.
She has a long list of accomplishments including Teacher of the Year, National Board
Certifcation in Chemistry, and Presidential Scholar Teacher. She is currently a
Question Leader for the AP Chemistry Examination and has also served as a Reader
and Table Leader. She also serves on the ACS Exams Institute Advanced High School
Committee and National Chemistry Olympiad Task Force, and is a National Leader for
the College Board.
About the Authors
Lew Acampora currently teaches AP Chemistry at the St. Francis School in
Louisville, Kentucky. For the last 16 years he has taught AP Chemistry at independent
schools across the country. Since 1995, he has served as a Reader, Table Leader,
and Question Leader at the AP Chemistry Exam Reading. He is a consultant for
the College Board and serves on the ACS Exams Institute Advanced High School
Committee.
Valerie Ferguson teaches AP Chemistry at Moore High School in Moore, Oklahoma.
She has served as a Reader and Table Leader for the AP Chemistry Examination. She
also works as a consultant for the College Board and teaches Summer Institutes for
AP Chemistry teachers. She has served as chair of the Oklahoma ACS, president of
the Oklahoma Science Teachers Organization, and was co-organizer of the Teaching
AP Chemistry symposium at the 14th Biennial Conference on Chemistry Education.
Adele Mouakad is an award-winning teacher at St. John’s School in San Juan,
Puerto Rico. She has been teaching AP Chemistry since 1983. She has won the
Presidential Award for Excellence in Science Teaching, and has been a member of
the Woodrow Wilson Foundation Teacher Outreach Program and a Dreyfus Master
Teacher. She has also been a Reader for the AP Chemistry Examination and a
member of the National Chemistry Olympiad Task Force.
Cheri Smith is an award-winning teacher of AP Chemistry at Yale Secondary School
in Abbotsford, British Colombia in Canada. She has been a Reader and Table Leader
for the AP Chemistry Examination. She has also served as a consultant for the College
Board, conducting AP workshops worldwide. Smith has contributed to numerous
publications and served as a reviewer for the AP Vertical Teams
®
Guide for Science
and the Pre-AP
®
: Topics for Vertical Teams in Science workshop.
Arden Zipp is a distinguished faculty member at State University of New York
College at Cortland in Cortland, New York. He has served in every capacity for the
College Board in the development and scoring of the AP Examination: He has been a
Reader, Table Leader, Questions Leader, Chief Reader, and Development Committee
member and chair. He is also involved in the development and scoring of the IB
Chemistry Program, and is chair of the National Chemistry Olympiad Examination
Task Force.
Heather Hattori teaches AP Chemistry, AP Environmental Science, pre-AP
chemistry, and pre-AP physics at John H. Guyer High School in Denton, Texas. Hattori
received her bachelor’s degree in chemistry and English from Stephen F. Austin
State University in 1991 and is currently attending the University of North Texas
in pursuit of a Ph.D. in chemistry. She has been teaching AP Chemistry and/or AP
Environmental Science since 2000 and has been an AP Chemistry Reader since 2005.
Hattori was a College Board consultant in the mid-90s, but has been taking a break to
raise Arabian horses and most recently attend graduate school in her spare time.
George E. Miller is a senior lecturer emeritus in the Chemistry department at the
University of California Irvine, where he is also principal scientist and supervisor
of the nuclear reactor facility and responsible for K–12 science teacher professional
development. He has been on the chemistry faculty at UCI since 1965, and has taught
freshman chemistry, analytical chemistry, radiochemistry, and instrumental analysis.
He was member and chair of the AP Chemistry Development Committee and a
member of the College Board Subject Test in Chemistry Committee. He has been a
Reader, Table Leader, and Question Leader for AP Chemistry over a period of 20 years,
and has presented both day- and weeklong workshops for AP and general chemistry
teachers. He has more than 60 publications in analytical chemistry and in science
education.
F08CMSF131

The Properties of Acids and Bases
Arden P. Zipp SUNY Cortland Cortland, New York Acids and bases represent two of the most important classes of chemical compounds. Some of the properties of acids (such as their sour taste) and bases (bitterness) have been known to humans for hundreds of years even if their chemical explanations have not. The reactions of these substances are significant in many atmospheric and geological phenomena. In addition, acids and bases control many of the physiological processes in the human body and can catalyze a variety of chemical reactions. This chapter will address some of the fundamental aspects of acids and bases in order to set the stage for subsequent discussions. In addition to taste, which was mentioned above but is no longer used in the chemistry lab, several other properties of acids and bases that can be observed readily are given below. Table 1 shows that they have some properties in common, while they do not share others.

Table 1 Properties of Acids and Bases
Acids 1 2
conduct electricity in solution react with many metals carbonates bicarbonates a base dyes product(s) formed H2 CO2, H2O, a salt CO2, H2O H2O, a salt colors, often reddish

Bases 1 2
conduct electricity in solution react with metal oxide and water metal ions bicarbonates an acid dyes product(s) formed H2 precipitates CO32-, H2O H2O, a salt colors, often bluish

SPECIAL FOCuS:

Acids and Bases

Teaching Tip
Students will appreciate these properties more if they are demonstrated by the teacher, or better yet, investigated by students themselves. Inexpensive conductivity meters can be purchased or constructed to investigate the first property on the list while the others can be studied using well plates and solutions dispensed from dropper bottles.

Early History: Arrhenius Theory
Some of the properties in Table 1 were known to alchemists hundreds of years ago, and classification schemes were developed by many noted scientists during the 1600s and 1700s including Robert Boyle, Joseph Black, and Antoine Lavoisier. However, the beginning of the modern understanding of acids is usually attributed to Svante Arrhenius, who, in his 1884 Ph.D. thesis, explained the electrical conductivity of aqueous solutions in terms of the presence of ions and attributed the unique behavior of acids to H+ ions. According to Arrhenius, an acid is a substance that, when added to H2O, increases the [H+], while a base is a substance that increases the [OH-]. Many of the reactions in Table 1 can be explained with the Arrhenius acid–base theory by the presence of H+ or OH- ions as shown in the equations below:
Acids
2H + M (e.g. Mg) → H2 + M 2H+ + CO32- → H2O + CO2 H+ + HCO3 - → H2O + CO2 H+ + OH - → H O
2

Bases
2+

+

2OH - + M2O3 (e.g. Al) + 2H2O→ H2 + 2M(OH)4 – xOH - + Mx+→ M(OH) (s) OH - + HCO3 - →H2O + CO32 H+ + OH - → H2O
x

State of H+ in H2O.
In the above equations the acid is represented as H+, a bare proton. However, it is generally agreed that the charge density of a proton is too large for it to exist in that form in aqueous solutions. Many texts represent protons as hydronium ions, H3O+, as if each proton is bonded to a single H2O molecule. Current evidence suggests, however, that the actual species has three additional H2O molecules attached via hydrogen bonds to form H9O4+. H+ will be used in this volume but it should be recognized that the actual species is more complex. Interestingly, the same texts that make a point of using H3O+ usually show the hydroxide ion as OH- even though it also appears to be hydrated, existing in H2O as H7O4-.
4

. Properties of interest include electrical conductivity and the rate of reaction with Mg metal (using a balloon attached to the mouth of a conical flask to capture the evolved H2).. Teaching Tip The difference between strong and weak acids can be made more concrete for students by demonstrations (or experiments) in which they compare the behavior of 1. Strong acid: Weak acid: HA(aq) → H+(aq) + A-(aq) HA(aq) ↔ H+(aq) + A-(aq) Among the standard acids commonly encountered in aqueous solutions. Strong acids are those that ionize completely (or nearly so) in solution. only the first proton from H2SO4 can really be described as “completely ionized.” the second proton has a measurable equilibrium constant. so is written with a simple arrow while that for a weak acid is reversible and is depicted with a double-headed arrow. the reaction of a strong acid goes completely to the right. Equal volumes of the weak and strong acids will produce the same volume of H2 but the rates at which they do so will differ substantially. while weak acids ionize only partially. have solutions that contain significant amounts of the parent acid and lower concentrations of H+. It should be noted that in the above table. HCl) and weak (HC2H3O2) acids. Students can measure how much time it takes for a short measured length of Mg ribbon or a measured scoop of calcium carbonate to dissolve completely. HCl HBr HI hydrochloric acid hydrobromic acid hydroiodic acid HNO3 HClO4 H2SO4 nitric acid perchloric acid sulfuric acid All other acids behave as weak acids in water. i. six are strong. thereby introducing the concept of strong and weak acids. work similarly. 5 . In terms of equations. capturing the CO2.0 M solutions of strong (e.g. Although strong and weak acids produce the same types of reactions.e.The Properties of Acids and Bases Strong and Weak Acids Arrhenius related the degree of electrical conductivity to the strength of acids. Reactions with calcium carbonate. the rates at which these reactions occur vary depending on the concentration of free H+ ions in solution.

0 x 10-7 or pH > 7. sodium oxide dissolves in H2O according to the following equation: Na2O + H2O → 2 Na+ + 2 OHSimilar reactions to produce strongly basic solutions occur with several other anions but these will not be considered here.SPECIAL FOCuS: Acids and Bases Strong and Weak Bases There are also six common strong bases that ionize completely in H2O. [].ions. [H+] = [OH-] = 1. H+ and OH-.0. represent concentrations in moles per liter. though some have limited solubility. Because of this extremely wide range of [H+]. Acid solutions are those in which [H+] > 1. while in a 1. as shown in the reversible equation: [H+][OH–] =1. Thus.8 x 10-16 [H2O] where the square brackets. existing in equilibrium with its ions.0 x 10-7 and pH = pOH = 7.0 x 10-14 at 25 ˚C.00 while basic (alkaline) solutions have [OH-] > 1. an alternative method of comparing [H+] concentrations. In a 1. These will be discussed further below. [H+] =1. (55. A more extensive discussion of pH and further calculations are provided in a later chapter. [H+] < 1. Concentrations Water itself is a weak acid.00. When the above value of K is multiplied by [H2O].0 x 10-7. although few of these contain OH.0 M solution of a strong acid.00 and one with [H+] = 1. There are a variety of compounds that behave as weak bases. LiOH lithium hydroxide NaOH sodium hydroxide KOH potassium hydroxide Ca(OH)2 Sr(OH)2 Ba(OH)2 calcium hydroxide strontium hydroxide barium hydroxide A solution of a strong base in H2O may be obtained by dissolving the appropriate solid hydroxide but may also be formed by reacting a solid metallic oxide with H2O.0 has a pH = 0. In pure H2O.00. where pH is defined as -log [H+]. which should not be confused with amount of ionization. [OH-] = 1.00. called the pH scale. Using the Kw expression it is possible to calculate [H+] for any [OH-] and vice versa.0 M solution of a strong base. H2O ↔ H+ + OHfor which K = 6 .0 x 10-14. a solution with [H+] = 1.5 M).0 and [H+] = 1.0 x 10-7 or pH < 7. the expression is Kw = [H+][OH-] with a value of Kw = 1. has been devised. For example.0 x 10-14 has a pH = 14.

an acid–base theory other than that proposed by Arrhenius is required. are weaker). In 1923 Johannes Brønsted and Thomas Lowry independently described acids as proton donors and bases as proton acceptors. the equilibrium constant will be >1. Further. This is because stronger acids donate protons more readily and. where HA and A. hence. a weak acid) to release H+ ions. Formation of Acidic or Basic Solutions It is easy to see how adding a strong acid like hydrochloric acid. Similarly. The Brønsted-Lowry theory includes as acids all the substances identified by Arrhenius as acids because they donate H+ ions to water and would also classify the 7 . they suggested that when acid–base reactions occur. the production of acidic solutions by substances that contain no H+ (or basic ones by substances that do not possess OH-) is less apparent. thereby broadening the concept of acids and bases significantly. Brønsted-Lowry Acid–Base Theory As outlined above. This activity can be useful for AP students if it is coupled with pH calculations and practice in pH ↔ [H+] or pOH ↔ [OH-] conversions.ions.e. The strengths of Brønsted-Lowry acids and their conjugate bases are inversely related. and B and HB+ are a conjugate pair: HA + B ↔ HB+ + ASuch reactions are reversible and the relative amounts of the various substances depend on the strengths of the acids (bases) involved. to water will increase the concentration of [H+] above 1. they introduced the notion that acids and bases exist in pairs (called conjugate pairs) that differ by the presence (acid) or absence (base) of a proton. Arrhenius defined acids as substances that produce H+ ions in H2O and bases as species that produce OH. their conjugate bases have lower attractions for protons (i.ions can be envisioned from the addition of one of the strong bases to H2O. HC2H3O2.are a conjugate pair.0 x 10-7 as these species ionize completely (HCl. In addition.. Clearly. stronger acids and bases react to form weaker acids and bases as in the equation below. However. a strong acid) or partially (HC2H3O2. HCl. the release of OH. Where HA is a stronger acid than HB+ and B is a stronger base than A-.The Properties of Acids and Bases Teaching Tip Students typically enjoy determining the pH values of common household materials (with indicator paper or drops of universal indicator). or even a weak acid such as ethanoic (acetic) acid.

8 . H2O behaves as the base. the Brønsted-Lowry theory can also account for the acidic behavior of metal ions and nonmetallic oxides. In both instances lone pairs of electrons in H2O molecules are attracted to the positive charge of the ion. HCl acts as an acid according to both definitions in the equation: HCl + H2O → H3O+ + Clbecause it releases an H+ ion (Arrhenius) or donates a proton (Brønsted-Lowry).ion as a base because it is a proton acceptor. it can explain the basic behavior of weak bases such as ammonia. Acidities of Metal Ions and Nonmetallic Oxides Just as protons are hydrated (described above). This process is depicted in the equation: M(H2O)6x+ + H2O ↔ M(HO)5OH(x-1)+ + H3O+ The effect of charge and radius on the acidic behavior of selected metal ions is shown in the Table 2 below. For example. Table 2 Li+ slightly acidic Be2+ weakly acidic Na+ neutral Mg2+ weakly acidic Al3+ acidic K+ neutral Ca2+ slightly acidic Sc3+ acidic Ti4+ very acidic Teaching Tip The relative acidities of these (and other) metal ions can be shown by adding a few drops of universal indicator to solutions containing these ions and comparing the solution colors with those of pH standards. usually with six H2O molecules. For metal ions with large charge densities (due to high charges and/or small radii). In addition. neither of which contain H+ ions. most metal ions are also hydrated. However. the attraction for the oxygen of the H2O may be strong enough to polarize the O-H bond and cause an H+ ion to be released.SPECIAL FOCuS: Acids and Bases OH. In this reaction.

although some contain other atoms that can behave in this same manner. The same year that Brønsted and Lowry proposed their theory. When a proton is abstracted from a water molecule. the Brønsted-Lowry theory is able to account for several acid–base reactions that can not be treated by the Arrhenius theory. which is a function of the strength of B as a Brønsted-Lowry base. each of which contains hydroxide ions. He defined bases as electron pair donors. In contrast to the small number of strong bases. Hence. These substances produce an excess of OH. A more extensive discussion of oxides (both nonmetallic and metallic) is undertaken in a later section as is the relative acidities of oxyacids. Lewis acid–base reactions encompass 9 . Weak acids and bases will be treated in more detail in another section of this book. neither of which contain H+. there are many substances that behave as weak bases. [OH-] = 4. G.ions themselves. Lewis Acid–Base Theory By emphasizing the transfer of protons. Lewis noted that the reaction of a proton with a base involved the donation of a pair of electrons from the base to form a bond with the proton. an excess of OH. Most of these materials contain a nitrogen atom that can act as a Brønsted-Lowry base by accepting a proton.ions remains in the solution as shown in the equation: H2O + B ↔ BH+ + OHThe [OH-] produced in such a reaction depends on the position of the above equilibrium. (H2O is acting as the acid in this reaction.The Properties of Acids and Bases The acidic behavior of nonmetallic oxides can be explained on the basis of their reaction with water to form oxyacids as represented in the equation for SO2: SO2 + H2O → H2SO3 Such oxyacids ionize to release H+ ions as: H2SO3 + H2O ↔ H3O+ + HSO3Thus. the most common weak base.0 M NH3 solution.N. there are six strong bases. NH3.) For ammonia. and acids as electron pair acceptors. the Brønsted-Lowry theory offers an explanation for the acidic behavior of both metal ions and nonmetallic oxides.2 x 10-3 M in a 1.ions in water even though they do not contain OH. Behavior of Weak Bases As mentioned above.

the reaction represented below occurs. H2(g) can be produced by adding which of the following to 1. Because of the importance of acids and bases in modern chemistry. Examples of these include all cases in which a pair of electrons is donated. Sample Part I Released Exam 2002 Questions An analysis of this released exam revealed a total of 9 questions (out of 75) related to acids and bases.SPECIAL FOCuS: Acids and Bases all Brønsted-Lowry reactions but also cover many processes that do not involve proton transfer. 21. NH4+ acts as (A) a catalyst (B) both an acid and a base * (C) the conjugate acid of NH3 10 . II. 2NH3 ↔ NH4+ + NH2In the reaction. In liquid ammonia. and III 22. NaHCO3(s) (A) * (B) (C) (D) (E) I only II only III only I and II only I. Zn(s) III. In the laboratory.0 M HCl(aq)? I. such as the hydration of metal ions and the reaction of ammonia with boron compounds: Mx+ + 6H2O → M(H2O)6x+ NH3 + BCl3 → H3N-BCl3 This brief discussion of various aspects of acids and bases is intended to introduce the more extensive treatments in later chapters. this material has been tested frequently on the AP Chemistry Exam. 1 M NH3(aq) II. Of these. both Part I and Part II. the ones below are based solely on the above material.

aqueous solutions with a pH of 8 have hydroxide concentration.+ H2O (d) Hydrogen iodide gas is bubbled into a solution of lithium carbonate: 2 HI + CO32.1 M sodium hydroxide solution HNO2 + OH. of (A) (B) * (C) (D) (E) 1 x 10-14 M 1 x 10-8 M 1 x 10-6 M 1.→ 2 I.0 M Sample Part II Released Exam 2004 Questions Question 4 (c) A 0.→ NO2.+ H2O + CO2 (h) Concentrated hydrochloric acid is added to a solution of sodium sulfide: 2 H+ + S2.The Properties of Acids and Bases (D) the reducing agent (E) the oxidizing agent 30. At 25˚C.→ HSO4- 11 .→ H2S Released Exam 2005 Questions Question 4 (d) Solid calcium carbonate is added to a solution of ethanoic (acetic) acid: Na2CO3 + 2 HC2H3O2 → 2 C2H3O2.1 M nitrous acid solution is added to the same volume of a 0.0 M 8. [OH-].+ H2O + CO2 + 2 Na+ (f) Boron trifluoride gas is added to ammonia gas: BF3 + NH3 → F3B-NH3 (g) Sulfur trioxide gas is bubbled into a solution of sodium hydroxide: SO3 + OH.

The H+ ions in acid rain react with the marble statues and the soluble compounds of calcium that are formed are washed away. Huheey. LeMay Jr. Chemistry: The Central Science. Freeman. Englewood Cliffs.→ H2O + C2H3O2 (d) Ammonia gas is bubbled into a solution of hydrofluoric acid: NH3 + HF → NH4+ + F(f) Hydrogen phosphide (phosphine) gas is added to boron trichloride gas: PH3 + BCl3 → H3P-BCl3 Released Exam 2007 Questions Question 4 (b) (i) Excess nitric acid is added to solid calcium carbonate. New York: Harper Collins. 4th ed. L. E. 2006. J. Rayner-Canham. H. Bibliography Brown..H. Salzberg. and T. H. 1993. Descriptive Inorganic Chemistry. Overton. 12 . DC: American Chemistry Society. A. W. 5th ed. T. New York: W. 1991. From Caveman to Chemist. Inorganic Chemistry. 1991. and R. E. Washington. and B. 2 H+ + CaCO3 → Ca2+ + H2O + CO2 (ii) Briefly explain why statues made of marble (calcium carbonate) displayed outdoors in urban areas are deteriorating. 4th ed. G.SPECIAL FOCuS: Acids and Bases Released Exam 2006 Questions Question 4 (c) A solution of ethanoic (acetic) acid is added to a solution of barium hydroxide: HC2H3O2 + OH... Bursten. Keiter. NJ: Prentice Hall. L. E. Keiter.. E.

the concentration of the hydronium ion is equal to the initial concentration of HCl in the solution.Weak Acids and Bases Valerie Ferguson Moore High School Moore. the conjugate base. However. Strong acids and bases are strong electrolytes in water solutions. The particle that donates a proton is the acid and the particle accepting the proton is the base. and are almost totally ionized.in acid. Since all of the HCl molecules are converted to H3O+ and Cl-. Strong acids and bases are not thought of as establishing equilibria since the reaction essentially goes to completion. Some of the substances ionize completely and others only partially ionize.” The equilibrium autodissociation of water is always present and operative in any aqueous solution even though the conjugate ion concentration (OH. Weak acid and base solutions are partially ionized. The Brønsted-Lowry definition describes many acid and base interactions as a proton transfer from one particle to another. The reaction depicted below of a strong acid in water occurs with all of the HCl molecules in water. The acid and its product. equilibria never “turn off. . The products of these reactions are called conjugate acids and conjugate bases. Oklahoma Many substances dissolve in water to cause a change in the pH of pure water. are a conjugate acid–base pair. H3O+ in base) is extremely small.

is a weak acid in water. The Ka expression for HOCl is shown above.SPECIAL FOCuS: Acids and Bases Conjugate acid–base pairs are two substances whose formulas differ by a proton. Opportunities for such practice occur several times during the course. Brønsted-Lowry bases are proton acceptors. Hypochlorous acid. HOCl(aq) + H2O(l) ↔ OCl-(aq) + H3O+(aq) Teaching Tips Students need to practice writing equations for the reactions of weak acids and bases in water. The illustration below shows the Brønsted-Lowry reaction of a weak base.2 x 10-8 1. Questions on the AP Chemistry Exam commonly ask students to demonstrate their knowledge of writing these equations. ammonia. The example below illustrates a Brønsted-Lowry reaction with acetic acid in water. 14 . (a) Write a chemical equation showing how HOCl behaves as an acid in water. HOCl. Examples from Prior AP Chemistry Examinations (2005 Form B) Ka = [H3O+][OCl-]/[HOCl] = 3. in water.

NH4+ acts as (A) (B) * (C) (D) (E) a catalyst both an acid and a base the conjugate acid of NH3 the reducing agent the oxidizing agent (1994) HSO4. H2O III. In the equilibrium represented above.+ H2O ↔ H3O+ + SO4222. the reaction represented above occurs. In liquid ammonia.Weak Acids and Bases (2002) 2 NH3 ↔ NH4+ + NH222. In the reaction. SO42(A) II only (B) III only (C) I and II (D) I and III * (E) II and III 15 . HSO4II. the species that act as bases include which of the following? I.

16 . (D) The equilibrium constant will increase with an increase in temperature. (C) The conjugate base of CN-(aq) is C2H3O2-(aq). (E) The pH of a solution equimolar amounts of CN-(aq) and HC2H3O2(aq) is 7. (1999) HC2H3O2(aq) + CN-(aq) ↔ HCN(aq) + C2H3O2-(aq) 62 . (B) HCN(aq) is a stronger acid than HC2H3O2(aq). The relative strengths of the various weak acids can be described in different ways: the value of the acid dissociation.0. Stronger acids and bases tend to react with each other to produce their weaker conjugates. it is in higher concentrations in the solution. The weaker species will be in greater concentration when equilibrium is established. or the position of the dissociation.The reaction represented above has an equilibrium constant equal to 3. The conjugates are very weak and less likely to react with water. Since the weaker species is less likely to react. Which of the following can be concluded from this information? * (A) CN (aq) is a stronger base than C2H3O2 (aq).SPECIAL FOCuS: Acids and Bases (1989) 34. strength of the conjugate base compared to water. The weaker acids have stronger conjugate bases. All of the following species can function as Brønsted-Lowry bases in solution EXCEPT (A) H2O (B) NH3 (C) S2+ * (D) NH4 (E) HCO3* Proton acceptors must have a lone pair of electrons.7 x 104. Ka. in aqueous solutions. The position of the equilibrium depends on the strength of the acid and/or base. in comparison to water. the [H+] compared to the initial [HA]. The strong acids and bases are essentially totally ionized. the conjugates are less likely to react and are thus weaker. Since the stronger species are more likely to react. Brønsted-Lowry reactions are reversible and will establish a chemical equilibrium between the forward and reverse reactions.

Weak Acids and Bases (1989) H2PO4. The equilibrium constant for the reaction represented by the equation above is greater than 1.> H2PO4(C) H2PO4.+ HBO32. Which of the following gives the correct relative strengths of the acids and bases in the reaction? Acids * (A) H2PO4 > H2BO3 (B) H2BO3.> HBO32HPO42.> HPO42HPO42. The graphic below represents the reaction of a binary acid in water.> H2PO4(E) H2PO4.= H2BO3and and and and and Bases HBO32.> HPO42HBO32.> H2BO3(D) H2BO3. The strength of a binary acid increases from top to bottom within the same group.0. Binary hydroacids—those that contain only hydrogen and a nonmetal—tend to increase in strength from left to right across the periodic table within the same period.> HBO32HPO42.+ H2BO355. 17 .↔ HPO42. Each of the following can act as both a Brønsted acid and a Brønsted base EXCEPT (A) HCO3(B) H2PO4+ * (C) NH4 (D) H2O (E) HSPeriodic trends are observed in the relative strength of acids.= HBO32- (1984) 49.

The strength of an oxoacid depends upon the ease with which the hydrogen ion is released from the O-H group. the electrons are pulled to the central atom and away from the O-H bond. oxygen. the strength of the oxoacid increases from top to bottom within a group and from left to right across a period. Oxoacids are composed of a central atom with one or more O-H groups attached to it.5 × 10-9 < < 3.5 HOI Ka=2.0 HOC 2. The more readily the hydrogen ion is released. When the number of oxygens is held constant. As the electronegativity of the central atom increases. and some other element are called oxoacids or oxyacids. 18 .SPECIAL FOCuS: Acids and Bases Electronegativity of E increases Acid strength increases 2. For the same central atom. The probability that H+ will be released is increased. the stronger the acid.9 × 10-8 Acids composed of hydrogen.3 × 10-11 < < 2. the stronger acids contain more oxygen atoms.8 HOBr 2. The other atoms in the molecule affect the polarity of the O-H bond.

the weaker the O-H bond as the electrons are pulled away from the O-H bond. These compounds are weak acids called carboxylic acids. An important group of oxoacids is the carboxylic acids. 1 point earned for a correct explanation. Only the O-H bond is polar enough so the hydrogen is readily donated as a hydrogen ion. attached.Weak Acids and Bases (2002) 1(e). Most carboxylic acids react in a similar fashion. Its reaction with water is shown on page 1. HOBr is a weaker acid than HBrO3. Acetic acid 19 . -COOH. Acetic acid is an example of a simple carboxylic acid. These organic compounds are characterized by containing a chain of carbon atoms with one or more carboxyl groups. Many students found it helpful to draw a structural formula to help answer this question. Teaching Tips Students need to demonstrate an understanding of the strength of the O-H bond as related to the strength of the acid. Account for this fact in terms of molecular structure. The H-O bond is weakened or increasingly polarized by the additional oxygen atoms bonded to the central bromine atom in HBrO3. The greater the number of electronegative atoms in the molecule.

the greater the effect on acid strength by weakening the O-H bond.+ H2O The strength of the carboxylic acids is affected by the substitution of one or more hydrogen atoms with electronegative atoms. complete the equation by drawing the complete Lewis structures of the reaction products. reacts with water to produce an acidic solution. In the space provided above. Show below are the complete Lewis structures of the reactants. More electronegative atoms pull the electron density away from the O-H bond and cause an increase in acid strength. 20 . OH. bases and buffer solutions.+ HC2H3O2 → C2H5O2. (a) Lactic acid. The closer the electronegative atoms are to the O-H bond. HC3H5O3. Write the net ionic equation for the following reaction: Solutions of potassium hydroxide and propanoic acid are mixed. Answer the following questions about laboratory solutions involving acids. Write the net ionic equation for the following reaction: Ethanoic acid (acetic acid) is added to a solution of barium hydroxide.+ H2O (2005 Form B) 4(d).SPECIAL FOCuS: Acids and Bases (2007 Form B) 5. (2001) 4(d). C2H5COOH + OH.→ C2H5COO.

NH3. Amines react as bases similar to reactions of NH3. The amines act as Brønsted-Lowry bases and are proton acceptors.Weak Acids and Bases I—CH2CH2COOH 3-ledopropanoic acid Cl—CH2CH2COOH 3-Chloropropanoic acid CH3CHCLOOH 2-Chloropropanoic acid CH3CCL2COOH 2. reacts with water according to the reaction represented above.0 x 10-4 < Ka = 1.4 x 10-3 < Ka = 8. CH3NH2 + H2O → CH3NH3+ + OH- (2003) C6H4NH2(aq) + H2O(l) ↔ C6H5NH3+(aq) + OH-(aq) 1. NH3(aq) + H2O(aq) ↔ NH4+(aq) + OH-(aq) H3CNH2(aq) + H2O(l) ↔ H3CNH3+(aq) + OH-(aq) Teaching Tips The equation for the reaction of ammonia with water is compared to the equation for the reaction of methylamine with water. Examples of other amines. a weak base. 21 . (1999) 4(f).7 x 10-3 Amines are organic compounds that act as weak bases. The proton attaches to the nitrogen in the amine group. The structure is an ammonia molecule. Aniline. Write the net ionic equation for the following reaction: Methylamine gas is bubbled into distilled water.3 x 10-5 Increasing acid strength < Ka = 1. with one hydrogen substituted by a hydrocarbon group.2-Dichloropropanoic acid Ka = 8. In each reaction the water acts as a BrønstedLowry acid and ammonia or methylamine as a Brønsted-Lowry base.

Students should be encouraged to develop an understanding of the similarity of amine reactions to those of ammonia. In question 1 from 2003. BF3 + NH3 → BF3NH3 (2006) 4(f). PH3 + BCl3 → H3PBCl3 CO2(g) + OH-(aq) → HC03-(aq) Lewis acid-base theory represents the movement of electrons in this reaction as follows. Students need to have a background of the behavior of amines as weak bases. The discussion of weak acids and bases is a good time to include some organic chemistry. 22 . students were asked to demonstrate an understanding of the characteristics of an amine equilibrium. Lewis acids can be described as electron-pair acceptors and Lewis bases as electron-pair donors. Write the net ionic equation for the following reaction: Boron trifluoride gas is added to ammonia gas. Write the net ionic equation for the following reaction: Hydrogen phosphide (phosphine) gas is added to boron trichloride gas. as in compounds such as BF3. Sometimes the Lewis acid has fewer than eight electrons. (2005) 4(f).SPECIAL FOCuS: Acids and Bases Teaching Tips The examples above demonstrate the inclusion of amines on past AP Exams.

SO2 + H2O → H2SO3 Hydrated metal ions can act as acids in water. 23 .Weak Acids and Bases (1999) 4(g). Write the net ionic equation for the following reaction: carbon dioxide gas is passed over hot. The smaller metal ions with greater charge have a greater charge density and produce more acidic solutions. Write the net ionic equation for the following reaction: Sulfur dioxide gas is bubbled into distilled water. CO2 + Na2O → Na2CO3 (2001) 4(a). solid sodium oxide.

htm. Write the net ionic equation for the following reaction: Excess concentrated potassium hydroxide solution is added to a solution of nickel(II) chloride.SPECIAL FOCuS: Acids and Bases (2004 Form B) 4(g). Michael Abraham.edu/CCLI/ Startup. OH– + Ni2+ → [Ni(OH)4]2.(some other products were accepted) (2003) 4(e). Write the net ionic equation for the following reaction: Excess concentrated aqueous ammonia is added to solid silver chloride.html 24 . and Kirk Haines. Gelder. which can be found at: genchem1. Write the net ionic equation for the following reaction: Excess saturated sodium fluoride solution is added to a solution of aluminum sulfate.iastate.okstate.edu/group/Greenbowe/sections/projectfolder/ animationsindex.chem. located at: www. • The second is part of a collaboration of John I. Which of the following ions is the strongest Lewis acid? (A) Na+ (B) Cl(C) CH3COO(D) Mg2+ 3+ * (E) Al I highly suggest using the following Web sites with simulations of weak acid and weak base behavior: • The first is the work of Thomas Greenbowe of Iowa State University. F– + Al3+ → [AlF6]3- (2003 Form B) 4(g).chem. AgCl + NH3 → Ag(NH3)2+ + Cl- (1984) 48.

Larry M. Chemistry: Matter and Its Changes. 8th ed. LeMay. and Fred Senese. Brown. Ralph H. 2000.. Upper Saddle River. Peck. 7th ed. Chemistry. 2nd ed. 2005. Silberberg. McCreary. CA: Thomson/Brooks/Cole. Perry. 2007. Belmont. Boston: Houghton Mifflin. Zumdahl..Weak Acids and Bases Bibliography Brady. Davis. Zumdahl. Martin S. New York: McGraw-Hill Higher Education. Steven S. Upper Saddle River.. Theodore E. 2003. Kenneth W. NJ: Wiley. Raymond E. Bursten. and Bruce E. 2006. James E. NJ: Pearson/Prentice-Hall. Petrucci. Chemistry: The Central Science. Chemistry: The Molecular Nature of Matter and Change. Chemistry. 25 . and Susan A.. and Scott S. Whitten. 4th ed. Hill. 4th ed.. 10th ed. Stanley. John W. Eugene H . Terry W. NJ: Pearson/Prentice-Hall. General Chemistry. 2007. and George G. Hoboken.

4th ed. John W. 706.. 703. and Scott S. 2006. Petrucci.. NJ: Pearson/PrenticeHall. Petrucci. John W. LeMay. Perry.. Upper Saddle River. NJ: Pearson/PrenticeHall. 621... Theodore E.. 4th ed. Terry W. Ralph H. NJ: Wiley. 622. Chemistry: The Central Science.. Bursten. NJ: Pearson/Prentice-Hall.. James E. Upper Saddle River. (Picture 8) Hill. 4th ed. (Picture 7) Brady. NJ: Pearson/PrenticeHall. 2006. Chemistry: Matter and Its Changes. General Chemistry. Petrucci. 617.. Upper Saddle River. 2005. (Picture 2) Hill. Eugene H. and Scott S. (Picture 10) Brown. Perry. LeMay. and Scott S. General Chemistry.. 2005. Ralph H. Terry W. Terry W. Theodore E. Chemistry: The Central Science. Hoboken.. NJ: Pearson/Prentice-Hall. Upper Saddle River. and Fred Senese.. and Bruce E. 2003. Ralph H. 4th ed. LeMay. General Chemistry. Eugene H. and Scott S. Upper Saddle River.. 2005.SPECIAL FOCuS: Acids and Bases Graphics Index (Picture 1) Brady. McCreary. and Bruce E. Ralph H. Terry W. Petrucci. Ralph H. 10th ed. 10th ed. John W.. 738. Chemistry: The Central Science. 705. John W. Upper Saddle River. General Chemistry.. and Scott S. McCreary. 2005.. McCreary.. Perry. Perry. NJ: Pearson/Prentice-Hall. (Picture 6) Hill. (Picture 9) Brown. Theodore E. McCreary. 622. and Fred Senese. NJ: Wiley. Upper Saddle River.. 4th ed. 2006. Bursten. 2005.. John W. 10th ed. (Picture 4) Hill. 748. (Picture 3) Hill. 4th ed. Upper Saddle River. James E. Terry W. McCreary. (Picture 5) Brown. Petrucci. Bursten. Eugene H.. NJ: Pearson/Prentice-Hall. 4th ed. and Bruce E. Perry. General Chemistry. 2003. 617. NJ: Pearson/Prentice-Hall. Hoboken. Chemistry: Matter and Its Changes. 26 .

. and Fred Senese. James E.. 2000. New York: McGraw-Hill Higher Education.. 4th ed. 752. Terry W. General Chemistry. (Picture 12) Silberberg. 2nd ed. 4th ed. NJ: Wiley. New York: McGraw-Hill Higher Education. 623. 2003. Martin S. Upper Saddle River. (Picture 13) Brady.. Perry. NJ: Pearson/Prentice-Hall. 792. Chemistry: Matter and Its Changes. 2000. 2005... 2nd ed.. Chemistry: The Molecular Nature of Matter and Change.. Martin S. Chemistry: Matter and Its Changes. 751. Chemistry: The Molecular Nature of Matter and Change. and Scott S. 27 . (Picture 15) Silberberg. 2003. 2nd ed.Weak Acids and Bases (Picture 11) Hill. Hoboken. Martin S. 4th ed. and Fred Senese. McCreary. Hoboken. (Picture 16) Silberberg. 786. (Picture 14) Brady. John W. Ralph H. NJ: Wiley. 2000. 780.. Chemistry: The Molecular Nature of Matter and Change. Petrucci. James E. New York: McGraw-Hill Higher Education.

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6 kJ ∕mol . . ΔGº298K = -79.8 kJ ∕mol The negative sign of ΔGº298K .0 × 1014 1. the symbol H+(aq)” is a convenient and suitable representation.2 = 1.0 M H+ and 1. The symbol “H+(aq)” is a shorthand representation of the hydrated proton. it is probably most accurately represented as “H2n+1On+(aq).” Because the number of water molecules coordinated to a single proton varies with time.0 M OH-.-79. In aqueous solutions. The state of equilibrium is quantitatively described by the equilibrium constant expression.” where “n” represents the number of water molecules. “H3O+(aq).pH and the Properties of [H+] in Aqueous Solution Lew Acampora St. ΔHº = -55. Because the concentration of the pure water is unaffected by the progress of the reaction. Rather than proceeding to completion. when used correctly.→ H2O . In terms of calculations. Francis School Louisville. and experience tell us that the reaction proceeds spontaneously from standard initial concentrations of 1.00831 K eq = e .are present. Keq: K eq = 1 [ H ] ⋅ OH− + The value of Keq can be readily calculated as: . it is omitted from the equilibrium constant expression. where the concentration of one or both of the reactants is completely exhausted. Kentucky The neutralization of a strong acid with a strong base occurs according to the net ionic equation1: Equation 1: H+ + OH.nG o RT = e kJ ⋅298 K mol ⋅K = e32.8 kJ mol 0. the acidic proton is undoubtedly coordinated to several water molecules through and is often written as the hydronium ion. the reaction does attain a state of equilibrium in which small but measurable concentrations of both H+ and OH.

or buffer solution containing solutes of reasonable concentration.020 -0. In pure water2: [ H+ Η + = 0Hˉ. In any case.0 × 10-14 The implication of this calculation is that even in the purest sample of water at 25 oC. Solutes that have this effect on the relative concentrations of H+ and OH. which represents the autoionization of water. The symbol Kw represents the specific equilibrium constant that refers to the auto-ionization of water.0 × 10-14 = = 2.0 × 10-14 1. base.0 x 10-14. For example. and the [OH-] is subsequently calculated using Equation 2.] ] = [ OH = 1.0 × 10-14 OH− = 1. The [OH-] ion determined from Equation 2: H+ ⋅ OH− = 1.020 M. [H+] [OH-] = 1. is used to determine the [H+] and [OH-] in aqueous solutions.020 + Cl-(aq) 0 +0. the reverse reaction of Equation 1.0 × 10-14 = 1. In determining the [H+] and the [OH-] in an acid.020 The [H+] = 0.. the contribution from the autoionization of water can be neglected. In this case: Equation 2: H2O  H+ + OH. the value of Kw at 25oC is commonly used. In a solution of an acid. ΔGº298K = +79.0 × 10-7 M While the [H+] = [OH-] in pure water.0 × 10-13 M + H 0.020 0.SPECIAL FOCuS: Acids and Bases While the magnitude of the value of Keq reflects the observation that the equilibrium state of this reaction lies far to the right. there are small but measurable concentrations of H+ and OH. Kw = [ H+ ] ∙ [ OH– ] = 1.020 0 → H+(aq) ~0 +0.8 kJ ∕mol . the [H+] can be determined directly from the concentration and strength of the acid. Commonly. the [H+] ion in a 0. any substance that increases the [H+] must also decrease the [OH-] in order to satisfy the equilibrium relation. many solutes (acids or bases) will change the relative concentrations of these ions.020 0. Like all equilibrium constants. Conversely. Therefore.020 2. In terms of calculations expected on the AP Chemistry Examination. will remain applicable in any aqueous solution at 25 oC.are called acids. its value is a function of the temperature.020 M solution of the strong acid hydrochloric acid is readily determined as follows: Equation 3: [ ]o Δ[ ] [ ]f HCl(g) 0. the equilibrium mixture will maintain small but measurable concentrations of both hydrogen ion and hydroxide ion.ion. bases are substances that will increase the [OH-] and will decrease the [H+]. 30 . the equilibrium relation.

00.10 The [OH-] = 0. In fact.10 The preceding examples illustrate that both the [H+] and the [OH-] in aqueous solutions vary over a range that is greater than 14 orders of magnitude.0 × 10-14 H+ = 1.0 x 10-14 at standard temperature of 25 oC. and the pH of pure. translates to a pH range from 14. the pOH of an aqueous solution is defined as pOH = -log10 [OH–].020 M HCl(aq) solution is pH = -log10 0.050 +0.050 M Ba(OH)2(aq) solution is pH = -log10 1. Solutions of weak acids only. is temperature dependent. The [H+] ion determined from Equation 2: H+ ⋅ OH− = 1. The range of values for [H+] in aqueous solutions. the above relationships among [H+]. but no additional information is conveyed by the pH of the solution that is not already indicated by the [H+].0 × 10-14 = = 1.0 × 10-13 M − OH 0. the value of Kw = 1. approximately 1. Solutions of strong bases only. Referring to the previous examples. 3.050 0 ~0 -0.0 x 10-14 M < [H+] < 1.3 Calculation of these values for aqueous solutions will depend on the type of solute.020 = 1. 31 . and five types of calculations can be identified: • • • • Solutions of strong acids only. and [OH–] = 10-pOH. Analogously. pH. and subsequently the [H+] can be determined. Algebraically.00 to 0.050 0. the pH of the 0. [OH-]. the [OH-] is directly calculated.0 M .70.050 +0. The pH scale is commonly used as an alternative expression to the [H+].pH and the Properties of [H+] in Aqueous Solution For an aqueous solution of a base. The logarithmic pH scale conveniently represents the [H+] over the 14 orders of magnitude. where pH is defined as pH = -log10[H+].10 0 0. neutral water is then pH = -log10 1. The value of Kw.10 M. and pOH imply that the value of any one of these will fix the values of the others. Solutions of weak bases only. and shows that the pH value is the negative of the exponent of 10 when the concentration is expressed as a power of 10.050 M solution of barium hydroxide are determined as: Equation 4: [ ]o Δ[ ] [ ]f Ba(OH)2(s) → Ba2+(aq) + 2 OH-(aq) 0.0 x 10-7 =7.0 × 10-14 1. the concentrations of each ion in a 0.0 x 10-13 = 13.00. like all equilibrium constants. For example. the pH of the 0. this is equivalent to [H+] = 10-pH.00. While the relation: Kw = [H+] [OH-] is generally true.

Though the technical details vary by instrument. defined as –log10 Ka. the test electrode and the reference electrode are combined into the same body. Conversely. the fundamental operation of a pH meter is to measure the electrochemical potential difference between a glass membrane electrode. for Ka. and the pH meter is simply a high impedance voltmeter that is calibrated to reflect the pH of the solution. and the solution will have the color of the base form of the indicator. its pH. laboratory pH meters are routinely capable of making accurate pH measurements to ±0. With careful calibration using standard buffer solutions. The laboratory determination of the [H+] of an aqueous solution. The indicator will then ionize according to the equation: H-In ← H+ + In→ The acid dissociation constant of the indicator is written as K a. In >> [H+]. [ H − In ] In− K a. An indicator is itself a weak acid whose color is different from that of its conjugate base. the pKa of the indicator. In . so that a negligible concentration of the indicator is added to the solution – sufficiently dilute so that it does not have an appreciable effect on the [H+] of the solution. referred to as a combination electrode. In practice. and the color of the solution changes from that of the acid form to the color of the base form as the pH of the solution changes from (pKa – 1) to (pKa + 1). can be done in two ways. [In-] >> [H-In]. either in solution or adsorbed onto pH paper.In = + .4 The measured potential depends on the [H+] in the external solution.In = . whose electrochemical potential is sensitive to the [H+] in the solution being measured. H+ ⋅ In− 32 . [In-] << [H-In] and the solution will have the color of the acid form of the indicator. In practice. More precise pH measurements are made with a pH meter. For Ka. The use of indicators. is compared to the pH of the solution. 4. and the [H+] in the solution. and an internal reference electrode. affords a crude determination of the pH of a sample. In << [H+]. Examples of these calculations are described elsewhere in this manual. or equivalently. Indicators with different pKa’s can be used to measure different ranges of pH values. A chart of commonly used indicators and their transition point (pKa’s) can be found in most textbooks. of the indicator.SPECIAL FOCuS: Acids and Bases • Buffer solutions (containing appreciable concentrations of a weak acid and its conjugate base). The indicator is intensely colored.01 pH unit. showing that the ratio of the This equation can be rearranged as [ H − In ] H concentration of the conjugate base form to the acid form depends on the value of Ka.

1 x 10 -9 M 1.00 0. the concentrations of these ions in such solutions are often critically important.13 8.10 M CH3COOH [Ka = 1.0 x 10 -3 M 13. Because chemical properties of the solution are sensitive to variations in the concentrations of these ions.30 2.ion is an important step that will allow students to go further in their mastery of the material.8 x 10 -5] 0.10 M CH3COOH [Ka = 1.8 x 10 -5] & 0.12 7.70 pOH 13.0 x 10 -6 M 1.0 x 10 -14 M [OH-] 2. Exercises Complete the following table: Solute and Concentration ? M HCl 0.8 x 10 -5] & ? M CH3COO Pure Water 0.0 x 10 -3 M 0.050 M 1.87 5.10 M NH3 [Kb = 1.10 M CH3COOH [Ka = 1.ions in any aqueous solution determines much of the chemistry of the solutions.3 x 10 -3 M 1.12 [H+] 0. the equilibrium that exists between H+ ions and OH.5 x 10 -12 M 8.00 5.25 M Ba(OH)2 [H+] 0.95 11. the role of pH as a measure of the concentration of not only the H+ ion but also the OH.00 13.0 x 10 -11 M 2.8 x 10 -5] ? M Ba(OH)2 1.05 3.88 7. Though these equilibrium concepts are sometimes difficult for students to master.8 x 10 -5] 0.056 M NH3 [Kb = 1.8 x 10 -5] & 0.050 M [OH-] pH pOH Answer: Solute and Concentration 0.8 x 10 -8 M 1.050 M HCl 0.70 5.0 x 10 -7 M 1.70 11.20 M NH4+ ? M NH3 [Kb = 1.0 x 10 -7 M 9.30 33 .24 M CH3COO Pure Water 0.10 M NH3 [Kb = 1.00 8.8 x 10 -5] & 0.8 x 10 -5] 0.20 M NH4+ 0.2 x 10 -5 M 1.pH and the Properties of [H+] in Aqueous Solution In closing.50 M pH 1.10 M CH3COOH [Ka = 1.0 x 10 -13 M 7.

the same concentration of a weak base would have to have a lower pH value.1-molar ammonia is approximately (A) 1 (B) 4 (C) 7 * (D) 11 (E) 14 Students should recognize that ammonia is a weak base and that a solution of a weak base will have a pH > 7.10 M HCl. d.10 M HCl is a solution of a strong acid: H+ f = [ HCl ]o = 0. A solution prepared by mixing 45. A solution prepared by mixing 50. 3.0 mL of distilled water. and there will be excess base remaining: 34 .10 M NaOH.00 with 50.00 H+ f = 0.0 mL of 0. Find the pH of each of the following: a.10 M × = 0. Because a 0. a [H+] ion = 1 x 10-13 M and pH = 13.0 mL of 0. 0. 0. A solution prepared by mixing 10.0010 M c.10 = 1. Solution of a strong acid: 10 mL 990 mL + 10 mL pH = −log10 0. The strong acid and strong base will neutralize.0010 = 3. Choice (D) is the only choice that matches these constraints.0 mL of a solution of 0.1-molar solution of a strong base would have a [OH-] = 0.10 M HCl with 55.10M pH = −log 10 0. 3.0 mL of distilled water. b.1 M. The pH of 0. c. Answers: a.SPECIAL FOCuS: Acids and Bases AP Exam Questions – Past Exams (1984) 2.0 mL of a buffer of pH 4.00 b.10 M HCl with 990.

00 .0 mL sample of an aqueous solution of pure benzoic acid is titrated using standardized 0.150 M NaOH.0 × 10-10 M 35 .0010 H 2O 0 +0.010 M 0. Q1aii) Ka = 6.pH and the Properties of [H+] in Aqueous Solution Rxn: molo ∆mol molf H+ + 0. [OH-]. [HA] >> [H+].00 pH = 14.00 = 12. (2006B.47.0045 0. pH = 4. (i) [H+] in the solution (ii) [OH-] in the solution 2.47 = 9. and pOH easily.4. [A-].53 = 3.00 . pH. Benzoic acid. dissociates in water as shown in the equation above.4 × 10 pOH = pK w . [OH-].0055 -0. the ratio [ HA ] will not be affected by dilution and the pH will remain unchanged.10 L pOH = −log 10 0.0045 0 OH− f = OH. C6H5COOH.0 × 10-10 M -5 3. Answers: Students should be able to convert among [H+]. Because solution (d) is a buffer solution.0 × 10-14 = 3.pH = 14. Calculate each of the following.46x 10-5 C6H5COOH(s) ← C6H5COO-(aq) + H+(aq) → 2.0 mL of the 0.150 M NaOH. A 25. (a)(i) H+ = 10-pH = 10-4.4 × 10-5 M (a)(ii) OH− = or Kw H+ = 1. (a) After addition of 15.0045 -0.00 (assuming that after dilution.53 OH− = 10-pOH = 10-9.47 = 3.2.00 A− d.010 = 2.0045 0. Q1ai.0045 0.→ 0. the pH of the resulting solution is 4.0010 M = 0.

10M HF K = a H3O+ F− [ HF ] [ HF ]× K a H3O (e) + = F − = 0.0 mL of 0.0 mL of 0.40 mol L−1) − (0. Assume that volumes are additive.8 × 10-4 M pH = -log10 (4.15 M . HF(aq) reacts with NaOH(aq) according to the reaction represented below.010 mol − 0.40 M NaOH(aq) is added to 25. Answers: (c) mol HF(aq) = initial mol HF(aq) − mol OH−(aq) added = (0.015 L)(0.e) HF(aq) + H2O(l) ← H3O+(aq) + F– (aq) → Ka = 7. A volume of 15. 2.14 + log .SPECIAL FOCuS: Acids and Bases (2007.025 L)(0. HF(aq). (d) Calculate the molar concentration of F– (aq) in the solution.15 M = 4.40 M HF(aq) solution. HF(aq) + OH-(aq) ← H2O(l) + F– (aq) → 2.004 mol (d) [HF] = . Q1c .8 × 10-4 ) = 3.32 [ HF ] 36 .0060 mol = 0. (e) Calculate the pH of the solution. dissociates in water as represented by the equation above.2 × 10-4 ) 0.2x 10-4 Hydrofluoric acid.040L = 0.40mol L−1) = 0.32 OR pH = pK a + log F− = 3.10 M × (7.10 M = 3. (c) Calculate the number of moles of HF(aq) remaining in the solution.004 mol HF .

Emphasize that both H+ and OH. pH. but they are not available for the multiple-choice questions. Emphasize the mathematical relationships among [H+]. only strong base. only weak acid. be sure that students can identify the type of solution that they are dealing with: • • • • • strong acid.pH and the Properties of [H+] in Aqueous Solution Teaching Strategies Introduce the auto-ionization of pure water as the reverse of the neutralization reaction of a strong acid and a strong base. given the value of any one of these data. Remind students that the relevant equations are provided on the insert for the free-response section of the AP Chemistry Examination. [OH-].are present in any aqueous solution. and pOH for aqueous solutions and that. and that the concentration of either particle will fix the concentration of the other. only buffer solution containing both a weak acid and its conjugate base Students should understand which principles/equations are applicable to each of these instances. values for the remaining are fixed and can easily be determined. In determining the [H+] in an aqueous solution. only weak base. 37 .

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a chemical indicator is added to signal the point at which the two reactants have been combined in just the right ratio to give a complete reaction.25 M sodium hydroxide will it take to be equivalent to 20 mL of 0. Once the amount is known. the equivalence point may be determined using a pH meter to follow the progress of the reaction. In any event. The titration procedure generally involves the addition of carefully measured portions of a “standard” solution of known concentration to a measured mass or volume of an unknown. for example. In many acid–base titrations. This is sometimes called the stoichiometric point or. Alternatively.Acid–Base Titrations Cheri Smith Yale Secondary School Abbotsford. more commonly. such as the concentration of the solution or the molar mass of the solute. the equivalence point. Simple problems should involve the idea of “matching” equivalent amounts of strong acids and strong bases in solutions. (For . Approaching Titration Problems with an AP® Chemistry Class AP students may or may not be already familiar with introductory titration problems such as those involving the determination of an unknown solution’s concentration or finding the volume of a solution required to react with a standard solution. other quantities may be discerned. how many mL of 0. For students who have done little lab. British Columbia Titration is an important type of volumetric analysis usually used to determine the number of moles of solute in a certain amount of aqueous solution. the AP Chemistry teacher would be wise to briefly review some simple problems before using a more sophisticated lecture and laboratory approach. from their first course in chemistry. a good introduction may be to titrate HCl with NaOH by drop counting in a well tray using phenolphthalein indicator.50 M hydrochloric acid.

buffer use. buffer calculations. including the applications of Kw and/ or pKw. more important for AP Chemistry.2 M HCl?) Examples of more sophisticated lecture topics and labs that should be done in AP Chemistry include: Determination of the molar mass of a unknown monoprotic acid.1 mol/L acetic acid. and NaHSO3 are good unknowns to use in lab as their masses vary significantly from one another. Weak–strong curves are the source of a wealth of review. • Calculation of pH in a Theoretical Titration Curve— Use of the ICF Table Most AP Chemistry students are able to handle the calculation of pH in a solution containing only one dissolved species. formic acid and propanoic acids are good unknowns for lab use as their Ka values differ by a full order of magnitude. Calculating the pH at various points during a theoretical titration is an extremely valuable exercise for AP Chemistry students. they find the problem considerably more difficult. however. and strong acids or bases in excess. hydrolysis problems.SPECIAL FOCuS: Acids and Bases example. how many drops of 0. including weak acid and base pH problems (ICE table calculations). Included should be titrations of a strong acid with a strong base and.1M NaOH are equivalent to 10 drops of 0.) • Back titrations to determine the strength of antacid products.) • Determination of the Ka value for an unknown monoprotic acid. The teacher may elect to include diprotic titrations and should certainly consider the selection of appropriate acid–base indicators. as it requires the application of virtually every type of pH problem encountered in the acid–base unit. (KHP. One of the biggest issues is the 40 . KHSO4. he or she can move on to the determination of pH experimentally and mathematically at different points during a titration. as well as the use of pH meters or probeware. When two solutions are combined. a strong acid or base with a weak acid or base. or at least teacher demonstration of actual variation of pH during titrations. thus reviewing the determination of the pH of strong acids and bases alone and in combination with one or the other in excess. and hydrolysis reactions. (Approximately 0. An AP Chemistry teacher would find it beneficial to begin with strong–strong titration curves. Once the teacher has reviewed and reinforced the students’ basic understanding of titration. These should be reinforced by either student run pH mater/probe use.

to list any information they can 41 . Because one (or both) of the reacting species is strong.” for “equilibrium” in an ICE chart. is replaced by an “F” that stands for “final” quantities following a reaction that goes to completion in one direction. FIGuRE 1 pH Providing such a curve for the titration of 25 mL of 0. with no further information.0 mL of 0. the reaction goes virtually to completion. the AP Chemistry teacher might ask the class members to take several minutes. The ICF table is a valuable tool for AP Chemistry teachers and students facing problems that involve chemical reactions such as neutralization with limiting and excess reactants. It is similar to the ICE chart used for equilibrium problems in that the “I” represents “initial” concentrations or numbers of moles and the “C” is the “change” in the initial quantities during the reaction.100 mol/L HCl. working alone or collaboratively. Such a reaction in a titration curve calculation will involve neutralization by a strong acid or base.” Such a reaction is said to be quantitative and is useful for analytic calculations.100 mol/L HCl with NaOH. The traditional “E. hence “F” replaces “E. Consider the curve that describes the titration of 25. Strong Acid–Strong Base Titrations Though the pH at various points during the titration of a strong acid with a strong base (or vice versa) is relatively easy to determine. pre-AP and AP Chemistry teachers alike would be wise to apply the ICF technique early as it will build student confidence for its application to more difficult problems later.Acid–Base Titrations organization of the increased amount of information given in such problems.

0 • The volume of base required to reach equivalence = 23. • The moles NaOH = moles OH.106 mol/L AP Chemistry teachers should reinforce the importance of beginning titration calculations with a balanced chemical equation. or a titration curve for a strong monoprotic acid being titrated with a strong base. during. Any AP Chemistry text will contain a sample curve to which teachers can refer.00250 mol NaOH are required to reach equivalence.100 mol HCl x 1 mol NaOH = 1000 mL 1 mol HCl 0.1 mol/L • The acid is strong as the initial [H+] = the initial [HCl] indicates 100% ionization. Example 1 Calculate the pH of the 25.0 mL x 0.0 mL sample of 0. Once students have examined a pH profile. 42 .5 mL.00250 mol x 23. • The reaction is represented by: HCl + NaOH → NaCl + H2O • The initial pH = 1. however.0 = 0. • The [NaOH] = 0. Production of the curve could be done after. This leads to a proper mole ratio that is most likely to be correct when units include the formula of the species they refer to.5 mL 1000 mL 1L = 0. • The pH at equivalence = 7.100 mol/L solution of HCl being titrated in the profile above. or even before the calculations.= 25. the AP Chemistry teacher can discuss the calculation of pH at various points throughout the curve. Sample student responses might include: • Base is being added to acid.0 • The initial [HCl] = [H+] = 10-pH = 10-1.SPECIAL FOCuS: Acids and Bases determine about the titration from the pH profile. ideally in molecular form. the teacher might prefer to produce a curve using probeware (such as that available from Vernier or Pasco) or to use a variety of simulations available commercially or on the Internet (see suggestions in the laboratory section at the end of this chapter).

100 mol/L (25. students must recognize that the concentration of a solution is affected by the addition of water or another solution as both of these cause dilution. Solution: [HCl]in = 0.0 mL is irrelevant to the problem at this point.0 mL) Neutralization in ICF shows: HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) I: 0. H2SO4 is only nearly completely ionized for its first ionization) as there is no table of acid ionization constants included with the AP Chemistry Exam.000 Example 2 Calculate the pH of the 25. The dilution factors are 25/35ths and 10/35ths. HClO4. this is what we’ve determined for our example.0303 F: 0.0 mL) = 0. Step one is to dilute.Acid–Base Titrations Strategy: The student should recognize that pH = . Strong acids such as HCl.106 mol/L = 0.log (0.0714 mol/L [NaOH]in = 0.0303 mol/L (10. Step two is to neutralize by applying the ICF table.log [HCl] = .100 mol/L) = 1.0303 M 0M C: -0.0 mL sample of HCl following the addition of 10. Step three is to examine the bottom line of the ICF table to determine what affects the pH. and H2SO4 (HClO3 is included in some texts. (AP Chemistry students must be aware of the “BIG 6” strong acids: HCl. Strategy: The ICF table is very useful for helping students keep track of everything necessary to solve this problem.respectively. 25.0 mL) (35. although it ionizes less than 100%). HI. [H+] = [HCl].0714 M 0.) Solution: pH = .log [H+] and that the concentration of a solution is independent of its volume.0 mL of 0.0 mL) (35.0303 +0. Hence. however.log [H+] = . If concentrations are to be used (which may be preferable because pH depends upon concentration rather than moles).0303 43 . ionize completely. Note that a “rounder” concentration of base might be used for introduction.0303 -0. HNO3.106 mol/L NaOH. hence.0411 0 0. HBr.

as [H+][OH-] must always = 10-14 = Kw (at 25oC).0515 M 0. following the neutralization.0515 mol/L Neutralization in ICF shows: I: 0.0515 0. HCl.5 mL) = 0. If [H+] = [OH-].0411) = 1. Na+ and an anion. hence. though it can never actually equal 0.0515 mol/L = 0.5 mL of a 0.0515 mol/L solution of NaCl. impossible. Cl.5 mL) HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) 0 M+0.0 mL) [NaOH]in = 0.5 mL of 0.00106 moles. dilute and neutralize.386 (Note that moles might have been used by multiplying the molarity of each reactant by its volume and using the moles in the “I” line.10638 mol/L (48.0515 F: 0 0 (23. the same pH as shown. [OH-] = [NaOH] at equivalence is negligible and approaches 0.) One final note that should be mentioned is that the ICF table indicates that the [NaOH]final = 0 mol/L. Strategy: As in example 2. then each = √ 10-14 = 10-7. then examine the bottom line of the ICF table. pH = .log (0. which is very small compared to the molarity numbers on the problem.0 mL sample of HCl following the addition of 23.0515 -0.SPECIAL FOCuS: Acids and Bases The bottom line indicates a [HCl] = [H+] = 0. As the conjugate base of the strong acid.log [H+] = . The changes would then have been 0. Example 3 Calculate the pH of the 25. of course. Cl-.0515 This process shows that the pH of 7 at the equivalence point is due to the formation of 48. Determination of the pH at some point beyond 44 .0515 M C: -0. The final moles of acid divided by a total volume of 0.106 mol/L NaOH. and so ≈ 0.is too weak to accept any appreciable quantity of protons from the water it is dissolved in and hence. This is.100 mol/L (25. which dissociates to form the neutral cation.5 mL) (48. it too is neutral.0411 mol/L. Solution: [HCl]in = 0.0350 L would give the same concentration and consequently. Hence.

10638 mol/L (55.90. Example 4 Calculate the pH of the 25. Strategy: As in example 2. such as ethanoic (acetic) acid or methanoic (formic) acid.log (0.0 mL of 0.0455 +0.0 x 10-13) = 12.0 mL) (55.00 at 25oC.0125) = 1.log [OH-] = -log[NaOH] = . NaCl.Acid–Base Titrations equivalence in the same fashion is helpful as it involves the application of Kw and/or pKw along with the ICF table. the salt. The application of Kw and/or pKw will be required to convert the [OH-]. as pKw = pH + pOH = 14.0455 M 0. is completely neutral and does not affect the pH at all. pH = .0125 = 8.0 mL) Neutralization in ICF shows: HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) I: 0. dilute and neutralize. or titration curve for a weak monoprotic acid being titrated with a strong base. the AP Chemistry teacher can compare the calculation of pH at various points throughout the curve with that of a strong–strong titration. However. the [NaOH]excess is very significant.0 mL) = 0.0 mL sample of HCl following the addition of 30.106 mol/L NaOH solution. it becomes evident that the pOH = . Solution: [HCl]in = 0.0455 mol/L = 0. the pH = 14.log (8.10.0455 -0. Consequently.0580 mol/L (30.00 – 1.0455 F: 0 0. with a strong base.0 mL) [NaOH]in = 0.100 mol/L (25. The alternative approach would be to recognize that [H+] = Kw/[OH-] = 10-14/0.0125 0. From this number. Once students have examined a pH profile.0 x 10-13 M. Weak–Strong Titrations A classic weak–strong titration involves the titration of a weak carboxylic acid.0580 M 0 MC: -0. 45 .0455 As explained in example 3. then examine the bottom line of the ICF table. Hence.90 = 12.10.

with no further information. with emphasis on any obvious differences they notice between this curve and the earlier strong–strong one. • The volume of base required to reach equivalence = 23.9 = 0. The reaction is represented by: CH3COOH + NaOH→ NaCl + H2O. • The initial pH approximates 2. the AP Chemistry teacher might ask the class to take several minutes. to list any information they can determine about the titration from the pH profile. This is typical of a weak acid. Sample student responses might include: • • Base is being added to acid. • The % ionization = 0. • This is a particularly significant point for students to recognize and it should be emphasized that the strength of an acid has no bearing on the volume 46 .5 mL (same value). • The pH at equivalence is between 8 and 9 (above the neutral value of 7).0013 x 100% = 1. for the titration of 25 mL of 0.9 (higher than the strong acid). working collaboratively with a partner. • The net ionic reaction is CH3COOH + OH.→ H2O + CH3COO-. • The acid is not as strong as the initial [H+] << the initial [CH3COOH] indicates less than 100% ionization.100 • The pH rises more quickly during a weak–strong titration. 0.3%.0013 mol/L.SPECIAL FOCuS: Acids and Bases FIGuRE 2 pH ml NaOH added Providing such a curve.100 mol/L acetic acid. • The initial [H+] = 10-pH = 10-2.

00250 mol 1000 mL 1 mol HA required to reach equivalence.5 mL 1L • The same sources suggested for strong–strong curves may be relied upon for weak–strong curves.Acid–Base Titrations of base required to neutralize it. One mole of monoprotic acid requires one mole of base to neutralize it completely whether the acid is strong or weak.) Strategy: The student should recognize that acetic acid is a weak acid. x may be considered negligible compared with the initial concentration. resulting in the following equilibrium: CH3COOH + H2O ↔ H3O+ + CH3COOI: 0. Example 5 Calculate the pH of the 25.100 x x For weak acids that ionize less than 5%.100 M 0M 0M C: -x +x + x [H+] formed is defined as x E: ~ 0. It is important for students to consider the chemical composition of the solution being titrated as well as the process for calculating its pH at any particular point. the AP Chemistry teacher can discuss the calculation of pH at various points throughout the curve. 23. or titration curve for a weak monoprotic acid being titrated with a strong base. hence an ICE table type of calculation is required to determine the [H3O+]. AP Chemistry teachers should stress the review of weak acid. weak base.106 mol/L. and hydrolysis calculations as they arise. The ICF table is particularly useful for students attempting to deal with the additional complexity of these problems. Once students have examined a pH profile. an acid will donate a proton to the base it is dissolved in. (Given the Ka of acetic acid = 1. only a small percentage of the molecules will donate protons. buffer.00250 mol x 1000 mL = 0. Solution: According to the Brønsted-Lowry definition. • The moles NaOH = 25. The [NaOH] = 0.0 mL sample of a 0.100 mol HA x 1 mol NaOH = 0.0 mL x 0. 47 . Because this acid is weak.100 mol/L solution of CH3COOH being titrated in the profile above.8 x 10-5.

4 x 10-5) = 4. The pH of this solution may be calculated as a weak acid with conjugate base present as a common ion: Ka = [H3O+] [CH3COO-] = [H3O+] (0.4 x 10-5 mol/L.8 x 10-5 [CH3COOH] 0. pH = . The student should recognize the presence of a weak conjugate pair with significant quantities of both the conjugate acid and base present.8 x 10-5 Since [H3O+] = 2.0303 M -0.0 mL sample of CH3COOH following the addition of 10.0714 mol/L = 0.SPECIAL FOCuS: Acids and Bases Ka = [H3O+] [CH3COO-] = x2 = 1.100 M (25.log (1.0 mL) = 0.3 x 10-3) = 2. The AP Chemistry teacher should point out that such a solution constitutes a buffer.log [H3O+] = .0303 mol/L Neutralization in ICF shows: CH3COOH(aq) + NaOH(aq) → NaCH3COO(aq) + H2O(l) I: 0.0303 M. Strategy: The ICF table may be used in an identical series of steps to those used for example 2 for the strong–strong titration shown previously.106 mol/L NaOH.0411 M and a [CH3COO-] = [CH3COO-] = 0.0 mL) (35.3 x 10-3 mol/L and pH = .0714 M C: -0.0303 F: 0.0411 = 1.0 mL) [NaOH]in = 0.0303 The bottom line indicates a [CH3COOH] = 0. Example 6 Calculate the pH of the 25.log (2.87.0303 0.0411 0.0 mL) (35.61. Solution: [CH3COOH]in = 0. The pH of a buffer may also be calculated using the Henderson-Hasselbalch equation: 48 .0 mL of 0.106 M (10.0303 0 0M +0.100 Simple algebra reveals x = [H3O+] = 1.0303) [CH3COOH] 0.

0515 M -0.0515 mol/L solution of the salt.100 M (25. Solution: [CH3COOH]in = 0.5 mL) (48.10638 M (23.” It is particularly instructive for the AP Chemistry teacher to point out that exactly half way to equivalence. Substitution into each of the equations above. [H+] < Ka and so pH exceeds pKa.61 (0.74 + log (0.0411) This portion of the curve is referred to as the “buffer zone.5 mL of a 0. the quantity of excess weak acid exactly equals the quantity of conjugate base formed by the neutralization. [H+] = Ka and pH = pKa.0303) = 4. shows: Ka =[H3O+] [CH3COO-] = [H3O+] and pH = pKa + log [CH3COOH] [CH3COO-] = pKa+ log(1) = pKa [CH3COOH] The teacher should encourage AP Chemistry students to use either or both of these equations to recognize and to verify the changes that occur during the buffer zone portion of a weak–strong titration curve: • halfway to equivalence. dilute and neutralize.0 mL) [NaOH]in = 0. Strategy: As in example 6.0515 M C: -0.5 mL of 0.0 mL sample of CH3COOH following the addition of 23. 49 . [H+] exceeds Ka and so pH < pKa. NaCH3COO.5 mL) (48. • prior to halfway.0515 mol/L =0.106 mol/L NaOH.0515 0 0M +0. then examine the bottom line of the ICF table. in turn.0515 mol/L Neutralization in ICF shows: CH3COOH(aq) + NaOH(aq) → NaCH3COO(aq) + H2O(l) I: 0.5 mL) =0.0515 F: 0 0.Acid–Base Titrations pH = pKa + log [CH3COO-] [CH3COOH] = 4. Example 7 Calculate the pH of the 25.0515 - The bottom line shows that the basic pH at the equivalence point is due to the formation of 48. • past halfway and before equivalence.0515 0.

dilute and neutralize.0M +x x 0M + x [OH-] formed is x defined as x hence. Strategy: As in example 7.0 mL) (55.0455 0 0.0 mL) = 0.0580 M -0.3 x 10-6) = 5.0455 M -0.27 = 8.10638 M (30. Kb = [CH3COOH][OH-] = Kw = 10-14 = 5. and pH = 14 – 5.0455 0. Na+ and the weakly basic anion.73 Example 8 Calculate the pH of the 25.8 x 10-5 0.SPECIAL FOCuS: Acids and Bases which dissociates to form the neutral cation.106 mol/L NaOH solution.0515 x = [OH-] = 5. CH3COO-(aq) + H2O(l) → CH3COOH(aq) + OH-(aq) I: C: E: 0.0455 mol/L = 0. then examine the bottom line of the ICF table.0580 mol/L Neutralization in ICF shows: CH3COOH(aq) + NaOH(aq) ↔ NaCH3COO(aq) + H2O(l) I: C: F: 0.0515 M -x ~ 0. As the conjugate base of the weak acid. it forms hydroxide ions by hydrolysis. the [NaOH]excess is much more significant.3 x 10-6 mol/L and pOH = . the salt.log(5.0125 0M +0. NaCH3COO. However.0 mL) (55. CH3COO.0515 .0 mL) [NaOH]in = 0. Solution: [CH3COOH]in = 0.0 mL sample of CH3COOH following the addition of 30. CH3COOH. In fact. is weakly basic due to hydrolysis.100 M (25. As in the strong–strong example 4 shown previously.27.0 mL of 0.6 x 10-10 = x2 [CH3COO-] Ka 1.0455 - As explained in example 7.0455 0. the hydroxide 50 . the application of Kw and/or pKw will be required to convert the [OH-].is strong enough to accept an appreciable quantity of protons from the water it is dissolved in and hence. CH3COO-.

The [OH-] = [NaOH]excess for all intents and purposes.log (0. the pOH = .0 x 10-13 M. FIGuRE 3 Such a titration would include the calculation of pH by: • The use of the ionization constant of a weak base. 51 . as pKw = pH + pOH = 14. Hence. • The use of a Kb expression or Henderson-Hasselbalch during the buffer zone. of course.0125 = 8. Hence. In this portion of the curve the solution contains the weak conjugate pair ammonia and ammonium ion.log (8.10. Initially one is determining the pH of a solution of ammonia.10. A classic example might be the titration of ammonia with hydrochloric acid. Consequently.00 – 1.0125) = 1.log [OH-] = .00 at 25oC.0 x 10-13) = 12. The alternative approach would be to recognize that [H3O+] = Kw/[OH-] = 10-14/0.Acid–Base Titrations ion from the NaOH forces the hydrolysis reaction so far left that its contribution to the [OH-] may be completely ignored. the titration of a weak base with a strong acid.90 = 12. the pH = 14. The alternative to titrating a weak acid with a strong base is. therefore it is a basic buffer.90. Kb. pH = .

SPECIAL FOCuS: Acids and Bases • The use of the acid ionization constant of a weak acid. ammonium chloride. the acid will donate protons to the indicator. • The application of the standard definition of pH applied to the excess [H3O+] present in a solution of ammonium chloride once excess strong acid has been added and the titration proceeds beyond equivalence. Thus. When indicators are in the middle of their color change. which undergoes cationic hydrolysis. endpoints should occur exactly at equivalence. It has a pKa of approximately 9. A stronger base will pull protons from the indicator. Many indicators were originally isolated from organic plants or foods. On the other hand. during the color change (at the indicator’s endpoint).form (and color). Substitution into familiar equations shows: Ka = [H3O+] [In-] = [H3O+] and pH = pKa + log [ In-] = pKa+ log(1) = pKa [HIn] [HIn] Hence. Ka at equivalence due to the formation of an acidic salt.1.73. The general form for the equation that represents the equilibrium for an indicator is: HIn(aq) + H2O(l) ↔ H3O+(aq) + In-(aq) acid form base form (color one) (color two) If the indicator is placed in a stronger acid. Since indicators are actually weak acids. the pH of the system will equal the indicator’s pKa. producing the HIn form (and color).2 and 10. This is called the endpoint or transition point for the indicator. an indicator will reach its endpoint and change color when the [H3O+] in the system equals the indicator’s Ka. different types of titrations will require different indicators. Some have been used as dyes. Ideally. producing the In.0. Similarly. in this case. they do have Ka and consequently pKa values. it would be absolutely wrong for use in the titration of ammonia with hydrochloric acid because the pH at equivalence for that titration 52 . Selection of an Appropriate Acid-Base Indicator An acid–base indicator is a chemical species that has an acid and a base form with one or both forms being visibly colored. hence it would be quite appropriate for the acetic acid titration because example 7’s calculated equivalence point was pH 8. the [HIn] = [In-] and the color shown will be a combination of the acid and base form colors. Phenolphthalein changes color between pH 8.

as shown in the third curve (Figure 3). an indicator’s pKa need not exactly match the pH expected at equivalence. Rather. The titration curve below shows that phenolphthalein or methyl red along with many other indicators would be appropriate for determining the equivalence point for a strong–strong titration. It is often a significant topic in the free-response portion of the examination.4. Problem number 53 . AP Chemistry teachers can demonstrate this dramatically through the use of a pH meter or probe ware (such as that available from Vernier or Pasco) or a variety of simulations available commercially or on the Internet (see suggestions in the laboratory section at the end of this chapter). Because of this rapid change. the indicator must simply complete its entire color change during the vertical part of the titration curve. One significant point demonstrated by each of the curves we’ve studied is the rapid change in pH that suddenly occurs at equivalence. FIGuRE 4 Sample Questions from Previous AP Chemistry Exams The topic of titration appears on virtually every AP Chemistry exam. This means that phenolphthalein might be selected ahead of an indicator having a pKa closer to the pH at equivalence simply because its change from colorless to pink is so clearly visible and easy to detect.Acid–Base Titrations would be around 5.

is a weak acid that dissociates in water.115 M Ba(OH)2(aq) needed to reach the equivalence point when titrated into a 65. Account for this fact in terms of molecular structure.8 x 10-5 M (1.00 ´ 10–9 M.3 x 10-9 X x = [HOBr] = 0. This problem centers on an acid–base equilibrium nearly every other year. (e) HOBr is a weaker acid than HBrO3. Explain.8 x 10-5)2 = 2.1 x 10-5 mol/L (b) Ka = [H+][OBr] = 2.160 M HOBr to produce a buffer solution with [H+] = 5.146 M HOBr(aq). as represented by the equation above. (d) Calculate the number of moles of NaOBr(s) that would have to be added to 125 mL of 0. Hypobromous acid.14 M 54 + . (i) Calculate the volume of 0. [H+] = 10-4. Assume that volume change is negligible. then calculate the concentration of HOBr(aq) in an HOBr solution that has [H+] equal to 1.0 mL sample of 0. or greater than 7.8 x 10-5 M. equal to 7. HOBr. 2002 Operational Exam HOBr(aq) ↔ H+(aq) + OBr–(aq) Ka = 2.3 x 10-9 [HOBr] [H+] = [OBr–] = 1. (c) A solution of Ba(OH)2 is titrated into a solution of HOBr. Such problems require student confidence with acid–base calculations of the sort discussed in this chapter.95. Solution: (a) pH = –log[H ] . (b) Write the equilibrium constant expression for the ionization of HOBr in water.SPECIAL FOCuS: Acids and Bases one of the three required problems is always an equilibrium problem.3 x 10-9 1. (ii) Indicate whether the pH at the equivalence point is less than 7. (a) Calculate the value of [H+] in an HOBr solution that has a pH of 4.95 = 1.

(b) A sample of aniline is dissolved in water to produce 25.0 mL of the acid has been titrated.3 ′ 109) = 0.0736 M 5. O Br — O – H O 2003 Operational Exam C6H5NH2(aq) + H2O(l) ↔ C6H5NH3+(aq) + OH–(aq) 1.3 mL 0. for the reaction represented above. The pH of the solution is 8. 55 . (c) The solution prepared in part (b) is titrated with 0. Calculate the equilibrium constant. Which of the indicators listed is most suitable for this titration? Justify your answer.736 mol OBr– x 1000 mL 1 mol OBr– (e) very electronegative oxygen is able to draw electrons away from the bromine and weaken the O–H bond.10 M HCl. a weak base. for this reaction.115 mol Ba(OH)2 (ii) pH > 7. making it easier for the hydrogen ion to be donated. (e) The pKa values for several indicators are given below.82.146 mol HOBr x 1 mol H+ x 1 mol OHˉ x 1 mol Ba(OH)2 1000 mL 1 mol HOBr 1mol H+ 2 mol OHˉ 1000 mL x = 41.160)(2.0 mL of 0.00 ′ 109 1 mol NaOBr = 0.0 mL x 0. Kb.Acid–Base Titrations (c) (i) 65.00920 mol NaOBr 125 mL x 0. reacts with water according to the reaction represented above. Calculate the pH of the solution when 5. Aniline.10 M solution. salt of a weak acid is a weak base (hydrolysis of OBr-) (d) pH = pKa + log [A ] [HA] – or [A–] = [HA]Ka [H+] [OBr–] = (0. (a) Write the equilibrium constant expression. (d) Calculate the pH at the equivalence point of the titration in part (c). Kb.

SPECIAL FOCuS:

Acids and Bases

Indicator Erythrosine Litmus Thymolphthalein

pKa 3 7 10

Solution
(a) Kb =

C6H5 NH+ OH− 3

[ C6H5 NH2 ]

(b) pOH = 14 – pH = 14 – 8.82 = 5.18 –log[OH–] = 5.18; [OH–] = 6.61×10–6 M [OH-] = [C6H5NH3+] = 4.4×10–10 0.10 – 6.61× 10−6 0.1mol (c) 25 mL x = 2.5 mmol C6H5NH2 1L 0.1mol 5 mL × = 0.5 mmol H+ added 1L 2.0 mmol base remains in 30.0 mL solution (may determine from ICF)
0.50mmol  30.0ml    4.4 × 10−10  20.0mmol   30.0mL    –9 – X = 1.80×10 = [OH ] 1 × 10−14 [H+] = = 5.6×10–6; pH = 5.26 1.8 × 10−9

Kb =

(6.61×10−6 )

2

[ X ] X + 

(d) When neutralized, there are 2.5 mmol of C6H5NH3+ in 50.0 mL of solution, giving a [C6H5NH3+] = 0.050 M (may determine from ICF.) This cation will partially ionize according to the following equilibrium: C6H5NH3+(aq) ↔ C6H5NH2(aq) + H+(aq) at equilibrium, [C6H5NH2] = [H+] = X [C6H5NH3+] = (0.050–X)
X2 = Ka = 2.3×10–5 (0.050 − X )

X = 1.06×10–3 = [H+] pH = –log[H+] = 2.98

56

Acid–Base Titrations

(e) Erythrosine; the indicator will change color when the pH is near its pKa, since the equivalence point is near pH 3, the indicator must have a pKa near this value. The lab-based essay question has focused on acid-base titrations. Occasionally, the core concepts of titrimetry will be tested in an essay question that is not lab based. The following is an example of a lab-based acid–base essay question:

1998 Operational Exam
Lab-Based Question
An approximately 0.1–molar solution of NaOH is to be standardized by titration. Assume that the following materials are available. • • • • • • Clean, dry 50 mL buret 250 mL Erlenmeyer flask Wash bottle filled with distilled water Analytical balance Phenolphthalein indicator solution Potassium hydrogen phthalate, KHP, a pure solid monoprotic acid (to be used as the primary standard)

(a) Briefly describe the steps you would take, using the materials listed above, to standardize the NaOH solution. (b) Describe (i.e., set up) the calculations necessary to determine the concentration of the NaOH solution. (c) After the NaOH solution has been standardized, it is used to titrate a weak monoprotic acid, HX. The equivalence point is reached when 25.0 mL of NaOH solution has been added. In the space provided at the right, sketch the titration curve, showing the pH changes that occur as the volume of NaOH solution added increases from 0 to 35.0 mL. Clearly label the equivalence point on the curve.

57

SPECIAL FOCuS:

Acids and Bases

FIGuRE 5

pH

Volume of NaOH Solution Added (mL)

(d) Describe how the value of the acid–dissociation constant, Ka, for the weak acid HX could be determined from the titration curve in part (c). (e) The graph below shows the results obtained by titrating a different weak acid, H2Y, with the standardized NaOH solution. Identify the negative ion that is present in the highest concentration at the point in the titration represented by the letter A on the curve.
FIGuRE 6

pH

Volume of NaOH Solution Added

58

• Rinse the buret with the NaOH solution and fill. • With mixing. the acid is halfneutralized and the pH = pKa. at the 12. (b) mass of KHP molar mass KHP = moles of KHP. since KHP is monoprotic. • Add a few drops of phenolphthalein to the flask.Acid–Base Titrations Solution: (a) • Exactly mass a sample of KHP in the Erlenmeyer flask and add distilled water to dissolve the solid. moles of NaOH = molarity of NaOH L of titrant FIGuRE 7 equivalence point pH Volume of NaOH Solution Added (mL) (d) From the titration curve.5 mL volume point. • Repeat to check your results. • Record end volume of buret. Ka = 10-pKa (e) Y2– 59 . titrate the KHP with the NaOH solution until it just turns slightly pink. this is the number of moles of NaOH. • Record starting volume of base in buret.

the efficiency of an antacid or the concentration of a diprotic acid. based on conductivity of. Virtual Labs There are a number of laboratory exercises that may be done virtually. 14G and 14 H). Essential Experiments in Chemistry by Morrison and Scodellaro. the first experiment should involve the preparation of a primary standard that could be used to standardize a base that might be used to determine a molar mass.SPECIAL FOCuS: Acids and Bases Recommended Laboratory Exercises Related to Acid–Base Titration Wet Labs Of the 22 recommended laboratory experiments for AP Chemistry. Laboratory Investigations: AP Chemistry by Hostage and Fossett. HCl and second. The second experiment should involve the development of experimental titration curves to be graphed and interpreted by the students. As suggested earlier. 2006). the moles of water of hydration. the Central Science. Other possibilities include the titration of a weak base such as NH3 with HCl or a polyprotic acid. An even simpler experiment (titration by drops) may be useful for students who have not encountered any form of titration in a previous class. such as H3PO4 with NaOH. Additionally Chemistry and Computers by Holmquist and Volz. Peoples Publishing Group. This disc includes several lab exercises that students may perform virtually. One of the more popular is the Virtual Chemlab disc provided with the text. on the computer. 2005. There are a number of excellent resources for laboratories such as these. Some of them are commercially available on DVD or CD. SMG Lab Books. contains five of these labs (#23–#27) each with specific direction for use of probe ware. The third experiment involves the determination of appropriate indicators for different acid–base titrations. Ba(OH)2 with H2SO4 is another possibility. 10th edition. to list a few possibilities. The classic two curves are. 2005. a Ka value. A potentiometric titration. contains two of them (#8 and #10). including a titration 60 . Such an experiment will help bridge students’ pre-AP or general chemistry skills to those required for AP Chemistry. 2003. LeMay and Bursten (Prentice Hall. three involve acid–base titrimetry. by Brown. the titration of first. for example. includes all three of these labs (14A. of course. Chemistry. CH3COOH with NaOH as examples of strong acid–strong base and weak acid–strong base curves.

The data they collect may be presented in tabular and/or graphic form. A fantastic source of Flash-based chemistry simulations has been prepared by Tom Greenbowe from Iowa State. Bridging to the Lab by Jones and Tasker. Freeman and Company.iastate. one of which uses an acid-base titration to determine the pKa of a food preservative.chem.html to actually plot a titration curve that may be used to determine the concentration and/or the pKa of a variety of weak acids. one of two possible indicators. 61 . Another great Web site for curves was prepared by Yue-Wing Long from Wake Forest University. there are some Web sites whose authors have graciously provided their lab exercises free of charge. and four different bases that may be placed in the buret. includes 11 different virtual lab exercises.H. Students may select from several weak or strong acids.wfu. W. Visit www. In addition to the commercial lab exercises.edu/group/Greenbowe/sections/projectfolder/ flashfiles/to select a titration simulation that is very easy to use.Acid–Base Titrations lab that allows them to select various reagents to use in a variety of titrations. This site is particularly useful as it allows students to alter the strength of the acid they use by selecting various Ka or concentration values for the acids they titrate. 2002.edu/~ylwong/chem/titrationsimulator/index. Start at www. Students produce a titration curve and use it to determine the pKa of a weak acid as well as its concentration and finally its molar mass.

.

and the energy of hydration of the X . dissolves into water and reaches a state of dynamic equilibrium in which a fraction of the HF molecules will be ionized at any instant. A Lewis acid is an electron-pair acceptor. the strength of the intermolecular forces between the HX molecule and the water molecules. The extent to which a species donates a proton is a measure of the acidity of the species and is ultimately determined by the electronic structure of the particle. Kentucky According to Brønsted-Lowry formalism. Francis School Louisville. defines acids and bases in terms of their capacity to accept or donate pairs of electron. This state of equilibrium is indicated by the double arrows and leads to the classification of hydrofluoric acid as a weak acid: HF(aq) + H2O(l)  H3O+(aq) + F-(aq) or HF(aq)  H+(aq) + F-(aq) The difference in the behavior of HCl and HF can be traced to such factors as the relative strength of the H-X bond. The more general definition of acids. most quantitative problems in AP Chemistry can be approached using the Brønsted-Lowry formalism. . imbues acids with their familiar properties. Lewis.ion. 5. it is classified as a strong acid: HCl(aq) + H2O(l) → H3O+(aq) + Cl-(aq) or HCl(aq) → H+(aq) + Cl-(aq) Hydrogen fluoride. N. attributed to G. the converse statement—that all hydrogen-containing compounds act as acids—is not generally true.5 The common and unique reactivity of the proton. Though all Brønsted-Lowry acids contain hydrogen. For example. also represented as the H+ ion. an acid is defined as a proton donor.Polyprotic Acids Lew Acampora St. however. Though this definition is more general. because gaseous hydrogen chloride dissolves and ionizes completely in aqueous solutions.

the hydrogen atoms that are directly bonded to carbon are not ionized in aqueous solution. CH3COOH. SO42-. the hydrogen sulfate ion. Thus. The presence of more than one acidic hydrogen per molecule will affect the stoichiometry of reactions of those polyprotic acids. triprotic. and finally the sulfate ion. there are two additional factors or considerations that should be noted. the sulfuric acid molecule can lose both protons sequentially to become. and will have ramifications in terms of the acid strength. etc. with subsets including diprotic. HSO4-. though each molecule contains four hydrogen atoms. A general schema for such a reaction with a monoprotic acid is: HA + B →A. the tendency to donate each proton will be different.SPECIAL FOCuS: Acids and Bases Hydrochloric acid and hydrofluoric acid are examples of monoprotic acids because each molecule contains only one ionizable hydrogen. For example. one of the most common diprotic acids is sulfuric acid. and such substances are generally referred to as polyprotic acids. Many substances contain more than one ionizable hydrogen atom.+ HB+ 64 . it is only the carboxylic hydrogen that is ionized in aqueous solution: CH3COOH(aq)  H+(aq) + CH3COO-(aq) Because of the covalent character of the C – H bond. A structural diagram for sulfuric acid shows that both hydrogen atoms are directly bonded to oxygen atoms. however. is another example of a monoprotic acid because. In these substances. Additionally. The Brønsted-Lowry formalism considers an acid–base reaction as simply a proton transfer reaction between a proton donor (the acid) and a proton acceptor (the base). H2SO4. FIGuRE 1 The underlying principles of reactivity that govern the behavior of monoprotic acids are generally true for polyprotic acids. and the character of these O-H bonds leads to the acidity of both hydrogen atoms. each acidic hydrogen can be donated. first. Acetic Acid.

only half as many moles of the diprotic acid are required: H2A + 2 B → A2. H3PO4. for polyprotic acids. for example. 7. 65 . H+ + PO4 3- 4. As protons are removed from the substance. then each mole of acid will contribute two moles of protons. any remaining ionizable protons are more strongly bonded because a positively charged proton will be more strongly attracted to the more negatively charged particle. H3PO4.10 M H 2SO4 solution would be considered 0. In order to neutralize a given quantity of base. This is reflected in the values of the acid dissociation constants. where the “n” refers to the nth proton donated by the molecular species.6 The tendency of a particular species to donate a proton—the acid strength—is ultimately traced to the electronic structure of the acid and its conjugate base. and Ka3.3 x 10 -3 H2PO4 . The resulting species is a weaker acid than the original particle. or 0. The acid dissociation constants for polyprotic acids are generally denoted as Kan. then. a 0. Steps in the complete ionization of phosphoric acid and the values of the acid dissociation constants are shown here: Reaction Equation H3PO4  H+ + H2PO4 - Equilibrium Constant Expression H +  ⋅ H 2PO4 −   K a1 =    [H3PO4 ] Equilibrium Constant Value 7.+ 2 HB+ or ½ H2A + B →½ A2. the triprotic weak phosphoric acid. H+ + HPO42- H +  ⋅ HPO4 2−   Ka2 =    − H 2PO4    H +  ⋅ PO4 3 −  K a 3 =    2−  HPO4    6.2 x 10 -8 HPO42.7 Kan. Normality in this context is defined as “moles of ionizable protons per liter of solution. the normality is simply twice the molarity. successive ionizations of a polyprotic acid are generally weaker.20 N. a triprotic acid would have Ka1. If the reactant is a diprotic acid. Ka2. For this reason. The concept of “normality” has fallen somewhat out of favor and can be omitted from the AP Chemistry course. would be 0. but it still may be useful in describing the stoichiometry of acid–base reactions. Consider.Polyprotic Acids The stoichiometry of the reaction shows that acid and base are consumed in equimolar quantities. Similarly. a 0.+ HB+ While 1 mole of hydrochloric acid will completely neutralize 1 mole of sodium hydroxide. which decrease in value for successive ionizations. Thus.10 M solution of the triprotic phosphoric acid. the same neutralization would require only ½ mole of sulfuric acid.8 x 10 -13 6.20 normal. A diprotic acid would have different values of Ka1 and Ka2.30 N.” For a diprotic acid.

the H-O bonds in H2PO4. Though these terms are not strictly synonymous. for the purposes of the AP Chemistry curriculum.20 M sodium hydroxide are mixed.are stronger than those in H3PO4. Other examples of such species include the monohydrogen phosphate ion.+ H2O  H3PO4 + OH - K b1 = [H PO ] ⋅ OH  3 4 − H 2PO4    −   1.+ OH - Equilibrium Constant Expression HPO4 2−  ⋅ OH −     Kb3 =  PO4 3 −    - Equilibrium Constant Value 2.10 M phosphoric acid and 0.+ H2O  HPO 42. Net Ionic Equation H3PO4 + OH .is a weaker acid.10 M sodium hydroxide are mixed. and H2PO4. The observation that successive protons are increasingly difficult to remove from polyprotic acids implies that these polyprotic acids ionize stepwise when reacting with strong bases. Equal volumes of 0.+ 2 H2O Since phosphoric acid. acting as an acid. the following net ionic equations apply: Reaction Description Equal volumes of 0.3 x 10 -12 Again. These bases are listed in order of increasing base strength. which can either donate a proton. and the hydrogen carbonate or bicarbonate ion.+ H2O H3PO4 + 2 OH . 66 .10 M phosphoric acid and 0.→ PO4 3. they can be considered interchangeable. the following net ionic equations can be written: 8. still contains two ionizable protons and is itself an acid. Equal volumes of 0.30 M sodium hydroxide are mixed. For phosphoric acids. acting as a base.1 x 10 -2 HPO4 + H2O  H2PO4 + OH 2- H 2PO4 −  ⋅ OH −     Kb2 =  HPO4 2−    1. HCO3-. the dihydrogen phosphate ion H2PO4-. HPO42-. is termed amphiprotic or amphoteric.+ 2 H2O H3PO4 + 3 OH .8 Because of its overall negative charge and the bond electron density. monohydrogen phosphate. and the values of the respective base dissociation constants reflect this: Reaction Equation PO4 3. their respective conjugate bases are dihydrogen phosphate. and phosphate ion. A species such as H2PO4-.10 M sodium dihydrogen phosphate and 0.20 M sodium hydroxide are mixed.→ HPO42.SPECIAL FOCuS: Acids and Bases The phosphoric acid molecule H3PO4 is the strongest acid among the substances listed. or accept a proton. Equal volumes of 0.+ 3 H2O H2PO4 .→ H2PO4 .10 M phosphoric acid and 0.6 x 10 -7 H2PO4 .+ 2 OH . since the bases will accept protons stepwise. Its conjugate base. and monohydrogen phosphate ion can each act as acids.→ PO4 3. dihydrogen phosphate ion.

10 M sodium monohydrogen phosphate are mixed. the values of the relevant acid dissociation constants are sufficiently diverse that the solution chemistry is usually dominated by one ionization.+ H+ → HPO42PO4 3. Equal volumes of 0. Fortunately.30 M hydrochloric acid and 0. a solution of 0.5 × 10–3 = 67 . The [H+] of the resulting solution can be determined from the ionization of the first proton: H3PO4 [ ]o ∆[ ] [ ]eq Ka1= 0. In principle. H2PO4-. Equal volumes of 0.10 M sodium phosphate are mixed. Consider. Net Ionic Equation PO4 3.Polyprotic Acids Reaction Description Equal volumes of 0.024 M 7. in addition to the H+ and OH. H+ + HPO42and HPO42. the solution contains the species H3PO4.10 M sodium phosphate are mixed. for example. calculations to determine the concentration of each species may seem intractable.10 M phosphoric acid.10 M hydrochloric acid and 0. Equal volumes of 0. the chemistry of the solution is dominated by the ionization reaction of the first proton: H3PO4  H+ + H2PO4Ionization of subsequent protons: H2PO4.+ 3 H+ → H3PO4 HPO 42.10 M -x 0.10 M hydrochloric acid and 0.10 – x [H3PO4]  H+ ~0 +x x + H2PO40 +x x [H+] ∙ [H2PO4–] x∙x 0.+ 2 H+ → H2PO4 PO4 3. H+ + PO43will have a negligible effect on the [H+] in the solution.ions.10 M sodium phosphate are mixed. and the concentrations of each species can be determined from straightforward calculation.20 M hydrochloric acid and 0. In practice.10 – x + [H ] = [H2PO4–] = x = 0.+ H+ → H2PO4 - Because a solution of a polyprotic acid or its conjugate base(s) may contain several species related by different equilibrium reactions and constants. and PO43-. HPO42-.

8 × 10−13 = PO 4 3− = x = 1. Each of the ionizable protons is lost from the acid sequentially with increasing pKa values.024 M) 6. Similarly. illustrates 68 . The graph of pH vs. volume base added.2 ×10−8 M) 4. the relatively small [HPO42-] implies that the second ionization occurs to a negligible extent and has no measurable effect on the [H+] or the [H2PO4-]. above. the calculated [PO43-] is extremely small. the [PO43-] can be determined using previously calculated concentrations: K a3 = H+ ⋅ PO 4 3− HPO 4 2− (0.2 × 10−8 = HPO 4 2− = x = 6.SPECIAL FOCuS: Acids and Bases The resulting [H+] and [H2PO4-] can be used to determine the [HPO42-]: K a2 = H+ ⋅ HPO 4 2− H 2 PO 4− (0.2 × 10−18 M Not surprisingly.024 M) ⋅ x (0.024 M) ⋅ x (6. FIGuRE 2 The behavior of polyprotic acids in acid–base titrations reflects the same considerations.2 × 10−8 M As expected.

are equal to the moles of HA initially present. 2 HA The fundamental principles of acid–base chemistry remain valid for acids that have many ionizable protons. At the half-equivalence point. volume base shows two buffering regions corresponding to the sequential ionization of each proton from the acid when a solution of a weak diprotic acid is titrated with a strong base. As in the case of the monoprotic acid. 2 [ H2 A ] At the half-equivalence point corresponding to the second ionization. the equilibrium constants for each ionization may be determined from the pH values at each half-equivalence point. half of the initial moles of weak acid remain. and K a1 = 10 a1 . and K a = 10 a . and K a = = H+ . At the first half-equivalence point in the titration curve. Important points on the graph are the equivalence point. monoprotic acid is titrated with a strong base. 2 .Polyprotic Acids what happens when a solution of a weak. and the half-equivalence point. and a solid understanding of the chemistry of monoprotic acids and bases is essential for students before they can grasp the details of the chemistry of polyprotic species. [H2A] = [HA-] and: H+ ⋅ HA− -pK K a1 = = H+ . [HA-] = [A2-] and H+ ⋅ A 2K a2 = = H+ . and half have been converted to the conjugate base. 69 . [HA] = H+ ⋅ A − -pK [A-]. and K a 2 = 10-pK a 2 . where the moles of added OH. Pt. 2 [ HA ] FIGuRE 3 The graph of pH vs. 1 . Pt. At this point in the titration. so pK a2 = pH 1 Eq. so pK a1 = pH 1 Eq. Pt. so pK a = pH 1 Eq.

Oxalic acid. H2C2O4. The graph below shows the results obtained by titrating a different weak acid. H2Y.9 x 10-10 (E) 1.K = K1 x K2 = 2.SPECIAL FOCuS: Acids and Bases Examples from Prior AP Chemistry Examinations (1994) H2C2O4 + 2 H2O  2 H3O+ + C2O4231.+ H2O  H3O+ + C2O42K1 = 5.3 x 10-5. Answer: A270 . Identify the negative ion that is present in the highest concentration at the point in the titration represented by the letter “A” on the curve.9 x 10-13 31. with the standardized NaOH solution.3 x 10-5 H2C2O4 + 2 H2O  2 H3O+ + C2O42.8 x 10-6 (1998) 5(e).36 x 10-2 (B) 5. Answer: (C) From Hess’s Law H2C2O4 + H2O  H3O+ + HC2O4HC2O4. FIGuRE 4 5(e).36 x 10-2 and K 2 = 5.3 x 10-5 (C) 2.36 x 10-2 K2 = 5. is a diprotic acid with K1 = 5. For the reaction above. what is the equilibrium constant? (A) 5.8 x 10-6 (D) 1.

Calculate the [C2O42-] in the resulting solution.32)2 = 6. is 6.56 × 10-10 = -5 K a2 6.(equilibrium constant = K1) HC2O4. for the reaction that occurs when solid Na2C2O4 is dissolved in water.78 × 10-6 ) × (0. K1. The overall dissociation of oxalic acid.015-molar solution of oxalic acid. (c) To a 0.40 × 10 71 .400-molar NaOH is required to neutralize completely a 5. The overall dissociation constant is also indicated.400M (b) There are two successive dissociations: H2C2O4  H+ + HC2O4. H+ + C2O42.+ H2O  HC2O4. (Assume the change in volume is negligible.K = 3.00 ×10−3mol) H+ = 1.0 × 10-7 M (d) C2O42.40 × 10-5 H+ = 10-0.00 × 10−2 mol OH− = 0.00 × 10-14 = 1.015) (0.+ OHKb = Kw 1. H2C2O4  2 H+ + C2O42.00 ×10−2mol OH− 1.0250 L = 25.40 x 10-5.00 x 10-3-mole sample of pure oxalic acid? (b) Give the equations representing the first and second dissociations of oxalic acid. K2. H2C2O4.015 M K = H+ ⋅ C 2 O 4 2− 2 [ H 2C 2O 4 ] C 2 O 4 2− = K ⋅[ H 2C 2O 4 ] H + 2 = (3. Answers: (a) 5.5 Because K << 1.Polyprotic Acids (1997) 1.78 x 10-6 (a) What volume of 0. Calculate the value of the first dissociation constant.00 ×10−3 mol H2C2O4 = 2 ×(5. Kb. a strong acid is added until the pH is 0.78 × 10-4 = = 5. is represented below. for oxalic acid if the value of the second dissociation constant.5 = 0.(equilibrium constant = K2) K = K1 × K 2 K1 = K 3.91 × 10-2 K2 6.0 mL 0.32 M (c) pH = 0. [H2C2O4]eq ≈ 0.00 ×10−2 mol H+ = 1.5.) (d) Calculate the value of the equilibrium constant.

(a) Write the two net ionic equations for the formation of the major species. showing the shape of the titration curve that results when 100. (b) Identify the species that acts as both a Brønsted acid and as a Brønsted base in the equations in (a). milliliters of 0.2000-molar HCl is added dropwise to 100. Answers: (a) H+ + PO43. HPO42H+ + HPO42. (d) Write the equation for the reaction that occurs if a few additional milliliters of HCl solution are added to the solution resulting from the titration in (c). 7. milliliters of the HCl solution is added slowly from a buret to the Na3PO4 solution. H2PO4(b) HPO42- 72 . milliliters of 0.100-molar Na3PO4 solution.SPECIAL FOCuS: Acids and Bases (1994) 7. Account for the shape of the curve. A chemical reaction occurs when 100. (c) Sketch a graph using the axis provided. Draw the Lewis electron-dot diagram for this species.

Polyprotic Acids (c) (d) H+ + H2PO4. H3PO4 73 .

.

Salts and Buffers Adele Mouakad St. CH3COO. but in many instances it dissolves in water to form a solution that is acidic or basic. Notable examples are: (i) The reaction of the acetate ion with water. the expression for Ka is: Ka = [H3O+][NH3] [NH4+] . you can write an expression for Kb. John’s School San Juan. which shows that some ions can act as acids or bases. Since this solution has the form of a base ionization. NH4+ + H2O → NH3 + H3O+ This resulting solution would be acidic due to the presence of the hydronium ion. Kb = [OH-][CH3COOH] [CH3COO-] (ii) The reaction of the ammonium ion with water. Puerto Rico Acid–Base Properties of Salt Solutions A salt is an ionic compound that can be considered to be the product of the reaction between an acid and a base. This can be clearly explained from the Brønsted-Lowry theory. The salt that is produced is sometimes neutral.+ H2O → CH3COOH + OHThis resulting solution would be basic due to the presence of the hydroxide ion. Hydrolysis is the reaction of an ion with water to produce the conjugate acid and hydroxide ion or the conjugate base and hydronium ion. These ions can act as acids or bases because they react with water. Since the resulting solution has the form of an acid ionization. This reaction with water is called hydrolysis.

So we can generalize that the cations of weak bases are acidic. it produces acetic acid. the H2O molecules in Cu(H2O)42+ are acidic. Br-. I -. Let us examine the cation conjugate to a weak base. Many of these ions form hydrated metal ions. copper (II) ion forms the Cu(H2O)42+ ion. we can say that anions of weak acids will be basic. Cu(H2O)42+ (aq) + H2O (l) ↔ Cu(H2O)3(OH)+(aq) + H3O+(aq) We can summarize this in the following tables: IONS OF NEuTRAL SALTS Cations Na+. usually hydrolyze by acting as acids. these anions do not hydrolyze.from HCl) have very little basic character. NO3 - Anions Some Common Basic Ions FHCO3 SO42ClO2CH3COO CO32HPO42NO2S2PO4 3CN HS ClO - 76 . it does not ionize readily).. Aqueous metal ions. such as the ammonium + (NH4 ) ion. Ca2+. On the other hand. This means that the acetate ion holds fairly strongly to the proton (i. and the water molecule becomes a hydroxide as shown in the reaction below. which we used in our example above. As a result. basic or neutral? When the acetate ion hydrolyzes. In general. It is clearly seen that it behaves like an acid. For example. ClO4 -.. Cl. the anions of strong acids (e.5. So we can say that the acetate ion acts as a base.. that are not those of the alkali or alkaline earth metals. in turn. K+. The Cu2+ ion acts as a Lewis acid. which is a weak acid. BrO4 -.g. tend to draw electrons from the O – H bonds. Sr 2+.SPECIAL FOCuS: Acids and Bases How can you predict whether a salt will be acidic. Because the electrons are drawn away from the oxygen atoms by the Cu atom. forming bonds with a lone pair of electrons in the O atoms of H2O. reducing the charge of the ion by 1. the cations of strong bases (alkali metal cations and alkaline earth metal cations) have hardly any acidic character. making them increasingly polar and weaker. Cs+ Mg2+. Copper (II) salts tend to have a pH around 3.e. Cu(H2O)42+ hydrolyzes by donating a proton to a free water molecule. the O atoms. In other words. ClO3 . On the other hand. Ba2+ Cl -. Rb+. One of the water molecules loses a proton.

it does not hydrolyze) K2CO3: K+ + H2O → No reaction. Let us examine the following exercise from the 1981 AP Exam.. Conclusions regarding acid or basic hydrolysis can be made by examining the Ka or Kb values in the literature for the species involved. or basic.+ OHNaHSO4: 77 . However. neutral. Exercise 1 Al(NO3)3 K2CO3 NaHSO4 NH4Cl (a) Predict whether a 0. CO32. Cu2+) To predict whether the salt solution is acidic. or neutral you need to know whether the ions comprising the salt are acidic or basic or do not hydrolyze. basic. This salt is composed of the potassium ion.g. the CN. Therefore. so Na+ does not hydrolyze. is basic.+ H2O ↔ HCO3. CN-.10 molar solution of each of the salts above is acidic. Na+ and the cyanide ion. A salt of sodium cyanide is expected to be basic. write a balanced chemical equation for a reaction occurring with water that supports your prediction. the cyanide ion. a weak acid.+ H2O →No reaction (conjugate base of a strong acid. Sodium is an alkali metal. In other words. CN-. Solution: (a) Al(NO3)3 = acidic NaHSO4 = acidic K2CO3 = basic NH4Cl = acidic (b) Al(NO3)3: Al(H2O)63+ + H2O ↔ H3O+ + Al(H2O)5(OH)2+ NO3-.is the conjugate base of a weak acid.Salts and Buffers Some Common Acidic Ions NH4+ HSO4- CH3NH3+ H2PO4- Al3+ Pb2+ Transition metal ions (e. hydrocyanic acid. you have to determine the acidity or basicity of the ions comprising the salt. NaCN. Consider sodium cyanide. (b) For each of the solutions that is not neutral.

4. In this case both ions hydrolyze. If 0.01 mol of HCl is added to 1. Composition: A buffer contains a weak acid and its conjugate base or a weak base and its conjugate acid. A salt of a weak acid and a strong base. If the Ka > Kb. This is very important because many aquatic organisms are very sensitive to changes in pH.4. 3. If the Kb > Ka. Buffers Definition: A buffer solution is one that resists changes in pH when small quantities of an acid or a base are added to it. the pH changes by only 0.+ H2O → No reaction (conjugate base of strong acid. Cu2+. The salt does not have any ions that will hydrolyze. Zn2+.38. The pH of mammalian blood is also maintained at a pH of close to 7. A salt of a strong acid and a strong base. so it hydrolyzes producing an acidic solution. so it hydrolyzes giving a basic solution.0 L of ocean or sea water. A salt of a weak acid and weak base. etc. the pH changes from 7. Obviously. On the other hand. if this same amount of hydrochloric acid is added to 1.5 to 8. (e. The anion is the conjugate base of a weak acid.0 to 2.1 unit. A salt of a strong base and a weak acid. sea water has other substances present that maintain the pH of sea water at a fairly constant level. 2. Thus a buffer solution contains both an acid species and a 78 .g.SPECIAL FOCuS: Acids and Bases Na+ + H2O → No reaction HSO4. so it will be neutral. the solution will be acidic. it does not hydrolyze) NH4+ + H2O ↔ NH3 + H3O+ One of the things to note from the above exercise is that students need to be aware that the transition metal ions and other metallic ions mentioned above do form complex ions with water. such as Al3+. the solution will be basic.0 L of sodium chloride solution.0. A few basic rules would be: 1. the acidity or basicity depends on the Ka and Kb of the conjugate acids and bases respectively.+ H2O ↔ H3O+ + SO42NH4Cl: Cl. The pH of sea water ranges from 7. Students need to know the coordination number for the more common ions. The cation of this salt is the conjugate of a weak base. NaCl).

0050 moles of acetate ion/0. Adding a base to the buffer solution: Bases contain hydroxide ions or react to form them.(a) A buffer made of 50. • The equilibrium reaction is CH3COOH(aq) + H2O(l) ↔ CH3COO-(aq) + H3O+(aq).0050 moles of acid/0. the pH of the buffer changes very little. Either carbonic acid or bicarbonate ion reacts: H2CO3(aq) + OH-(aq) ↔ HCO3-(aq) + H2O(l) HCO3-(aq) + OH-(aq) ↔ CO32-(aq) + H2O(l) Since most of the hydroxide has been removed. • The total volume of the buffer is 100. and 50. Adding an acid to the buffer: The buffer solution must remove most of the new hydrogen ions otherwise the pH would drop markedly.10 M sodium acetate. 79 . so the buffer solution must remove most of these ions. to maintain the pH of the juice. The pH of a buffer is determined by the relative amounts of acid and conjugate base that are present in the solution and the Ka of the acid.0 mL. CH3COOH. H2CO3. 1.Salts and Buffers base species. The buffer in sea water is mostly due to the presence of carbonic acid. The pH of a buffer: The pH of buffers can vary from being in the acid range of the pH scale all the way to the basic range. This is similar to one of citric acid and sodium citrate that is often found in commercial fruit juices. The hydrogen ions will combine with the bicarbonate ion to make carbonic acid: HCO3-(aq) + H+(aq) ↔ H2CO3(aq) Even though the reaction is reversible.100 L = 0.7 x 10-5. both the carbonate and phosphate buffers are present. In blood. But because the reaction is reversible. Let us compare the pH of two different buffer solutions. and its conjugate base. There are two ways in which the carbonic/bicarbonate buffer can remove the hydroxide ion. Let us examine a buffer made of acetic acid and sodium acetate. so the pH won’t change very much. • The Ka of acetic acid is 1. the pH will decrease a very small amount. • The concentration of the acetate ion is 0. • The concentration of acetic acid is 0.10 M solution of acetic acid. most of the new hydrogen ions have been removed.0 mL of a 0. CH3COONa.050 M.0 mL of a 0.050 M.100L = 0. the bicarbonate ion HCO3-.

050 M.7 x 10-5 M pH = . We substitute the equilibrium concentrations in the above equation. The pH of this buffer can be altered by adjusting the relative concentrations of the acid and the conjugate base. we get [H3O+] = (1. Substituting in the above equation we can see that the ratio [HA]/[A-] = 0. In doing so we can assume that X is small compared with 0.050 M + X H3O + 0 +X X In this solution Ka = [H3O+ ] [CH3COO-] / [CH3COOH]. the concentration of hydronium ion is [H3O+] = Ka [HA]/ [A-].25. 80 .025 M.7 x 10-5 = [X] [0. It is slightly more basic than the previous solution. A conclusion from the above problem: If the ratio [HA]/[A-] = 1 then the pH of the resulting solution will be equal to pKa If the ratio [HA]/[A-] > 1 then the resulting solution will be more acidic than pKa.025/0. and the resulting [H3O+] = 5. is less than 1.76 which is in the acid range Now in this example the concentrations of the acid and the conjugate base are equal and the concentration of the hydronium ion is equal to Ka.050 M) [H3O+] = 1.7 x 10-5 ) (0.050 M – X H 2O CH3COO0. If the ratio [HA]/[A-] < 1 then the resulting solution will be more basic than pKa.7 x 10-5M] = 4.070 M and the equilibrium concentration of the acetic acid is 0.67 x 10-5 has a pH of 5.050 M +X 0. So the net equation is: 1.070.050 M] After rearranging. if the equilibrium concentration of the acetate ion is 0.log [1.050 M]/ [0. but still well within the acid range.SPECIAL FOCuS: Acids and Bases Filling in the ICE concentration table: CH3COOH Initial Change Equilibrium 0. (b) For example.050 M)/ (0.050 M -X 0.

050 M.050 M.050 M + X H3O + 0 +X X Now Ka = [H3O+] [NH3]/ [NH4+]. Let us examine this.0 mL of 0.3. A buffer solution is made up of 50. The final concentration of [NH3] = 0. we can clearly see that the pH of the buffer will be determined mainly by the value of Ka. Filling in the ICE concentration table: NH4+ Initial Change Equilibrium 0. For a buffer with a pH of 9.10 M NH4+ and 50. 4.56 x 10-10 = (X) (0.0 mL of 0.050 M +X 0.Salts and Buffers 2. we choose an acid/conjugate base combination that has a pKa close to 3.56 x 10-10 M • pH = -log [5. a. When water is added to a buffer solution. the pH remains unchanged. The final volume is 100 mL. which is in the basic range.050 M .8 x 10-5 Ka = 5.050 M – X H 2O NH3 0.050 M) • We can see that X = [H3O+] = 5.56 x 10-10] This gives a pH of 9.050 M -X 0. The addition of water affects a buffer solution (dilutes of a buffer). 3. we choose an acid/conjugate base combination that has a pKa close to 9. From studying the two different buffers.10 M NH3. so the final concentration of [NH4+] = 0. The Ka of ammonium ion is Kw/ Kb Ka = 1 x 10-14 / 1. For a buffer with pH 3. Substituting we get: • 5. b.56 x 10-10 The equilibrium reaction is NH4+(aq) + H2O(l) ↔ NH3(aq) + H3O+. HA ↔ H+ + AKa = [H+] [A-] / [HA] 81 .050 M) / (0. We can assume that X is small compared to 0.

10 M nitrous acid and 0. This analysis does not consider new effects that appear if the solution becomes extremely dilute.019 – 0.00050 moles of acid is produced and 0. • The moles of H3O+ = (0.10 M hydrochloric acid.0 mL of 0. Suppose we have a buffer consisting of 0. This first part is a stoichiometric calculation where we assume that all the H3O+ from the strong acid reacts with the nitrite ion forming nitrous acid. The second part is an equilibrium problem where the concentrations from the first part are used.SPECIAL FOCuS: Acids and Bases Rearranging this.0095 moles.(aq) → HNO2 (aq) + H2O(l) Because the nitrous acid is a weak acid.5 x 10-4. nitrous acid and nitrite ions in the solution before the reaction.10 M.0185 mol. A buffer resists change to pH when small amounts of acid or base are added. • Moles of nitrite ion remaining = (0. since the same amount of water is being added to both.00050 moles of nitrite ion is used up. we must calculate amounts of hydrogen ions. the hydrogen ion concentration is equal to the molarity of the acid.00050 moles.= (0. • The moles of NO2. • HCl is 0. The Ka of nitrous acid is 4. If this ratio remains unchanged. Solution Part 1—Stoichiometric Calculation When a hydronium ion is added to the buffer it reacts with the nitrite ion: H3O+(aq) + NO2.005L) = 0. We assume that all the H3O+ added reacts with the nitrite ion. 5. Because HCl is a strong acid.019 moles. To 95. 0. we can see that: [H+] = Ka [HA] / [A-]. The addition of more water to the buffer does not change the ratio [HA]/[A-].10 moles/L) (0.20 M sodium nitrite.095L ) = 0. This type of problem becomes a two-part problem. 82 . the pH stays the same. First.00050) mol = 0.095L) = 0.0 mL of this buffer solution we add 5. Therefore. We are now going to examine this quantitatively. therefore the concentration of H3O+ is 0. we assume that the reaction goes to completion.20 moles/L) (0.10 M. • The moles of HNO2 = (0.10 moles/L) (0.

Beula B.185 M +X 0.61.185 + X The equilibrium constant equation is: Ka = [H3O+] [NO2-] / [HNO2] Substituting.04 units The buffer pH changed much less than 0. says he would mix NH3 and NaOH solutions. the pH after the addition of the 5.010 mol. • [NO2-] = 0.10 M -X 0. Describe the components and the composition of effective buffer solutions.10 M.00050) mol = 0. Part 2—Equilibrium Problem Using the concentration found in Part 1.185) /0.5 units. 83 . 2(b). which is considered the maximum change that a buffer should have and continue to be effective at pH control.10 M HCl(aq) is 3.43 x 10-4 The pH of the original buffer was 3.10 L = 0.185M .5 x 10-4 = [ X ] [0. says he would mix acetic acid and sodium acetate solutions.10 – X H3O+ (mol/L) 0 +X X NO2. • [HNO2] = 0.10 [H3O+] = X = 2. Archie A.Salts and Buffers • Moles of nitrous acid after reaction = (0. So the pH changed by only 0.10 – X] Assuming that X is small enough that 0. An employer is interviewing four applicants for a job as a laboratory technician and asks each how to prepare a buffer solution with a pH close to 9.0185 moles/ 0. you get: 4.0 mL of 0. Specify the properties of a buffer solution.010 mol/0.0095 + 0. says she would mix NH4Cl and NH3 solutions. Examples from Prior AP Chemistry Examinations (1983) 2(a).185 and 0.185 + X] / [0.10 – X ≈ 0. says she would mix NH4Cl and HCl solutions.65. you construct the following ICE table: HNO2 (mol/L) Initial Change Equilibrium 0.1855 + x ≈ 0.(mol/L) 0. x 10-4 = (X) (0.10L = 0. Dexter D.10. Carla C.

6 x 10–10) Answer: 2(a). but the following acidity constants may be helpful: acetic acid. (a) Calculate the hydronium ion concentration of a 0. • Carla has the correct buffer.0 x 10–8M 84 .0 x 10–5M (b) HOCl + H2O ↔ H3O+ + OClX ‹‹ 0. (NH4+) and its conjugate base (NH3). So he does not have the correct buffer. since she has a weak acid (NH4+) and a strong acid (HCl). HOCl.050 molar solution of HOCl. but it does not have the correct pH since the pKa is close to 5. Explain what is wrong with the erroneous procedures. • Beula does not have a buffer. Preparation of a buffer: Mix a weak acid with the conjugate base of the acid.050 molar HOCl and 0. • Dexter does not have a buffer since he has mixed a weak base and a strong base. NH4+. Archie has a buffer solution: he has a weak acid and its conjugate base.8 x10–5.050 X = [H3O+] = 4. NaOCl. (1977A) 3. since the pKa is close to 9.010 X = [H3O+] = 8. A buffer solution resists changes in pH when small amounts of an acid or a base are added. Answer: (a) HOCl + H2O ↔ H3O+ + OClX << 0. Ka. is 3. (b) Calculate the concentration of hydronium ion in a solution prepared by mixing equal volumes of 0.020 molar sodium hypochlorite. She has a weak acid. for hypochlorous acid. 2(b).1 X 10 –8. referring to your discussion in part (a). She also has the correct pH.SPECIAL FOCuS: Acids and Bases Which of these applicants has given an appropriate procedure? Explain your answer. The value of the ionization constant. (No calculations are necessary. Ka = 5. Ka= 1.

ionizes in water according to the equation above.265 – X = [HC3H5O2] 85 + .265 – X ≈ 0. calculate each of the following. then [C3H5O2–] = 0. and this is more than thousands of times larger than the propanoate ions from the acid.00188 M = [H ] [you can assume that 0.103 = [C3H5O2–] 0. then X = [C3H5O2–] = [H+] 0.265 M solution of propanoic acid.Salts and Buffers (2005A) HC3H5O2(aq) ↔ C3H5O2–(aq) + H+(aq) Ka = 1. NaC3H5O2.0 mL sample of a 0.103 M 0.265 – X X = 0.50L since each sodium propanoate dissociates completely when dissolved. HC3H5O2 . (i) The concentration of the propanoate ion.496 g sample of sodium propanoate.73 1mol 96.0g (c) (i) = 0. (b) Calculate the pH of a 0. (c) A 0.496g × (ii) let X be the amount that ionizes. then: X = [H+] X + 0.265 in order to simplify your calculations] pH = –log[H+] = 2. producing 1 propanoate ion for every sodium propanoate.34 × 10–5 Propanoic acid.34 x10–5 0. C3H5O2–(aq) in the solution (ii) The concentration of the H+(aq) ion in the solution Answer: (a) [C3H5O2-][H+] = Ka [HC3H5O2] (b) let X be the amount of acid that ionizes.103 M 0.265 – X = [HC3H5O2] X2 = Ka = 1.265 M solution of propanoic acid. (a) Write the equilibrium constant expression for the reaction. is added to a 50. Assuming that no change in the volume of the solution occurs.

265 – X ≈ 0. They will resist change to pH when only small amounts of acid or base added.] Buffer capacity is the amount of acid or base that can be added to a buffer solution before a major pH change (more than +.) The students can see the importance of a natural buffer such as is present in seawater and also study the buffering capacity of seawater.50 M NaCl solution.5 units) occurs. A buffer with a large capacity has a large concentration of HA and of A-. All buffers have a buffer capacity. science. “The Buffer Capacity of Sea Water”. The pH of a buffered solution is determined by the ratio [HA]/[A-]. A good laboratory activity to do with the students is to study the buffering capacity of seawater as compared to that of a 0.” University of Waterloo.103 ≈ 0.265 – X X = 3. and Norris Rakestraw. The Biological Bulletin 65 (December 1933): 437–451. then the buffer’s capacity is exceeded and a major pH change will occur.uwaterloo. (This concentration ≈ the concentration of NaCl in seawater.html (accessed January 2008). General Chemistry.103 + X) = Ka = 1. The capacity of a buffer is determined by the magnitude of [HA] and [A-]. “Hydrolysis of Metal Salts.ca/~cchieh/cact/c123/salts. in order to simplify calculations. 86 . The buffer’s capacity is determined by the amount of acid and conjugate base. so that it can absorb a relatively large amount of H3O+ or OH-. Ebbing. and Steve Gammon.43 x 10–5 M = [H+] [We can assume that 0. 8th ed. Bibliography Cyberspace Chemistry. Boston: Houghton Mifflin Company. If large amounts of acid or base are added.34 x 10–5 0.265 and X + 0. Philip. Mitchell. Darrell.103.0. http://www. 2005.SPECIAL FOCuS: Acids and Bases (X) (0.

or when the oxide is reacted directly with an acid or a base. hence forming an acidic solution and in effect acting as a proton donor. cesium. calcium. strontium. and can be studied more closely as follows: (1) An alternative view of the basic oxides is that these are mostly ionic compounds (with a high degree of ionic character) and can be thought of as . In this case the oxides are classified as basic oxides. and the halogens. These are among the most electronegative elements or nonmetals group. Idaho The oxides of the elements form an interesting group of acidic and basic compounds. hence forming a basic solution. sulfur. nitrogen.+ H2O → M—O—H + OHHere the oxide is a proton acceptor from water leaving an excess of hydroxide ion in solution. These are among the least electronegative elements or metals group. Oxides behaving in this way include those of carbon.Acidic and Basic Reactions of Oxides Marian DeWane Centennial High School Boise. (2) X = O + H2O → -O—X—O. sodium. These reactions are obviously oversimplified.+ 2H+ Here the oxide is an oxygen acceptor from water. The combination of element X with the highly electronegative oxygen results in a polarized bond (in every instance except two oxygen atoms bonding to form O2). which releases hydrogen ions into the solution. Such oxides are classified as acidic oxides. potassium. Two types of reactions can result: (1) M – O. phosphorous. Oxides behaving in this way include those of lithium. and barium. which then can be a reaction site when the oxide is added to water to form an aqueous solution.

+ H2O → 2 OH. For example: SO3 + H2O → HSO4 . each O2. K2O. CaO.. hence the highly basic nature of the resulting solution. For example. the nonmetal atom readily forms covalent bonding with the oxygen. it is these ions that act as proton acceptors as follows: O2. SO3 + 2NH3 + H2O → (NH4)2SO4 88 . Thus it is the ionic structure of the metal oxides that best explains their reaction in aqueous solution. This weakens the O-H bond in water.→ SO4 2. (2) In the acidic oxides.ion reacting to form two hydroxide ions. So. While this uses some electron density of the central atom. The combination of the highly electronegative oxygen atom with the low electronegativity atom of a typical metal produces the ionic bond in metal oxides.+ H+ HSO4 . sodium oxide can react with hydrochloric acid to form sodium chloride and water in a typical acid–base reaction forming a salt and water: Na2O + 2HCl → 2 NaCl + H2O However. sulfur trioxide can react with ammonia to form ammonium sulfate. when an acidic oxide reacts with some bases water must be present to provide the oxygen transferred to the central atom. the more electronegative atoms in the nonmetals still have sufficient remaining electron density to form additional bonding with oxygen atoms in water molecules. Cl2O. MgO. releasing H+ ion. for example. NO2.+ H+ Direct reactions of oxides can occur without water being an obvious reagent. The complete reaction may take place in two steps to release two H+ ions. SO3. The electronegative oxygen is easily able to attract the most weakly bonded electron away from a metal atom to form the ionic bond. etc. for example.SPECIAL FOCuS: Acids and Bases containing ions in the solid state. When added to water. Typical oxides are Na2O. Two electrons can be taken from an alkaline earth element such as magnesium to form Mg2+O2-. as in common examples such as CO2. Water has to be included as a reagent to provide the oxygen transferred.

but it can be dissolved by reacting in strong HCl. BaO + H2O → Ba2+ + 2OH2002 Question 4 (c): Solid cesium oxide is added to water. CaO + H2O → Ca2+ +2OH89 . can act as an acid or a base. neutralizing the hydrochloric acid. Aluminum oxide is a compact strong structure relatively insoluble in water. SrO + H2O → Sr2+ +2OH1999 Question 4 (a) Calcium oxide powder is added to distilled water.+ 2Na+ AP Exam Examples of Free-Response Questions: Free-response questions about oxides are usually in the equations section.Acidic and Basic Reactions of Oxides Amphoteric Oxides As in all other areas of chemistry. With hydrogen as an exception (water is clearly an example of an amphoteric oxide). Here the aluminum oxide is acting as a base. as can SiO2. depending on the circumstances. and oxides are no exception. there are chemical behaviors that fall in between two extremes. Cs2O + H2O → 2Cs+ +2OH2000 Question 4 (g): Powdered strontium oxide is added to distilled water. question 4. Al2O3. metals in the center of periods and semimetals tend to form such oxides. as represented in the reaction below: Al2O3 + 6HCl → Al2Cl6 + 3H2O However. The question now requires students to provide a balanced net equation and answer a question about the reaction. Amphoteric oxides can act as acids or bases. Metal oxide plus water examples: 2004 Form B Question 4 (f): Powdered barium oxide is mixed with water. no additional questions were asked. aluminum oxide also dissolves in strong sodium hydroxide solution acting as an acid neutralizing the sodium hydroxide. The year these questions were given. This reaction can be represented by the equation: Al2O3 + 2NaOH + 3H2O → 2Al(OH)4. For example aluminum oxide.

G. J. H. New York: Freeman. and N. G. New York: Saunders. 6th ed. Wilkinson. Nachtrieb. Senese. A. 1999.. 2001 Question 4 (a): Sulfur dioxide gas is bubbled into distilled water. Advanced Inorganic Chemistry. SO3 + H2O → H+ + HSO42002 Form B Question 4 (e): Sulfur dioxide gas is bubbled into a beaker of water.. D. and F. Descriptive Inorganic Chemistry.Nonmetal oxide plus water examples: 2003 Question 4 (h): Solid dinitrogen pentoxide is added to water. SO2 + H2O → H+ + HSO3SO2 + H2O → H2SO3 was also accepted. Bibliography Brady. Principles of Modern Chemistry. 4th ed. 1990. New York: John Wiley and Sons. F. Oxtoby. 2004. and M. N2O5 + H2O → 2H+ + 2NO32003 Form B Question 4 (f): Sulfur trioxide gas is bubbled into water. Rayner-Canham. 1998. Chemistry: Matter and Its Changes. 2nd ed. Carlos Murillo.. New York: John Wiley and Sons. W. SO2 + H2O → H+ + HSO3SO2 + H2O → H2SO3 was also accepted. 2nd ed. . Cotton. Bochmann.

Restating the question also does not answer the question.” Others reflect misunderstanding of material presented within the AP class or read from the textbook. These are often termed “preconceptions. or distracters.” they would not survive long in their jobs. Many may reflect prior thinking brought to the AP class.” or “justify. Yet that is the format a considerable number of students exhibit when providing an explanation on the AP Chemistry Exam.Misconceptions in Chemistry Demonstrated on AP Chemistry Examinations George E. Frequently. Irvine Irvine. perhaps the most common misconception demonstrated is a lack of understanding of the words “explain. California Misconceptions and misunderstandings are often demonstrated by students on both multiple-choice and free-response portions of the AP Chemistry Examination. which will help the student make the correct selection. Miller University of California. “It was because team X scored more points. frequent misconceptions are often included by the item writers as possible wrong answers.” This persists even when the examination question tries to provide guidance as to what is expected. . The teacher can then proceed to help the student correct the misconception in their thinking. misunderstandings arise from a lack of depth and/or accuracy of thinking about a topic or question. If a sportswriter or commentator explained why team X won the game against team Y by stating. Use of familiar examples is helpful. Teachers should always ask students to explain why they selected a particular distracter. On multiple-choice questions. Students who select these answers are showing they have that misconception. In free-response questions.

8 x 10 -9 Incorrect response (1): The table shows there is a difference between the Ka values of HClO and HBrO. For example. Student and teacher dialogue (almost more than demonstrations. so master Brønsted-Lowry or proton transfer systems before even thinking about anything else. (No nonaqueous systems are dealt with in AP Chemistry. explain the difference in K a values for HClO and HBrO.8 x 10-9 is larger than 3 x 10-8 . Mathematical errors even creep in as a result of carelessness or real misunderstandings of conceptual algebra. Bases. 92 .SPECIAL FOCuS: Acids and Bases For example. and Aqueous Equilibria There is confusion on a number of issues relating to acids and bases. Incorrect response (2): HBrO has a larger Ka because 2. To foster correct thinking.0 x 10 -8 Electronegativity of halogen 3. as noted below. the following question and answer might have appeared in AP: Using the information given in the following table. or exponential notation (as seen above). The largest numbers of molecules present in solutions are therefore water molecules. which also can easily be misconstrued) is key. Acid HClO HBrO Ka 3. teachers should encourage students to always answer the question qualitatively before plugging in any numbers. arguing somewhat as follows: 1. Reflective conceptual thinking would always look for responses where numerator and denominator values moved in the same direction. The remaining document addresses selected topics where frequent misunderstandings are demonstrated.) Lewis acids are barely mentioned. 2. Reactions of acids and bases occur in water. students may transcribe K = [H][A] / [HA] ≅ [H]2 /[HA] incorrectly as [H] = √ K/[HA]. Misconceptions Regarding Acids.8 2. together with some hints for instructors.0 2. The answer is to start with basic principles.

and some not OK. strong bases have a high K value for the reaction B + H2O ↔ B+ + OH-. In one system at equilibrium. there can only be ONE value of a species concentration (e. An acid with a high K value (K value > 10-1) for the reaction HA + H2O ↔ A. Correspondingly. Most will be attached to water molecules in the form of H(H2O)n+ where n is 1-4. If you jump into a crowded swimming pool. if it is at equilibrium. putting a lot of any chemical in water makes it “strong. Thus.g. Some texts still may use the term “dissociation” based on the idea that HA becomes H+ and A. To the lay public. However. This is a semantic problem caused by the unfortunate choice of terms by chemists. all possible equilibria and the corresponding equilibrium constant expressions must be simultaneously satisfied.+ H3O+ is a strong acid.” Strong coffee or strong lemonade has a high concentration of those chemicals. Water is amphiprotic and amphoteric. acid–base chemistry is almost exclusively (>99%!) the study of proton transfer reactions all of which are equilibrium reactions and each of which has a well-defined equilibrium constant that only varies with temperature. this is abbreviated to H+. So we simply must list all possible reactions of any given system in water and ask: “Is the system at equilibrium?” If not. therefore.Misconceptions in Chemistry Demonstrated on AP Chemistry Examinations 3. One cannot have some OK. 9. Acid–base “strength” is related to acid–base concentration. Generally. but the corresponding idea for a base also exists. The solution cannot track what H+ came from what source to create separate values. So what are the misconceptions. Thus. the chances are that you will hit water molecules first! 4. The obvious species for anything to react with is.. water. In most texts. 7. 5. This is often stated in terminology regarding the “degree of ionization. 1. then what do we know about all the possible equilibrium constants? 8. and why do they exist? The following examples are given mostly for an acid. one value of [H+] or [OH-]. 6. first-cut reactions are water reactions. acids and bases are defined as strong or weak solely on the basis of their equilibrium constants in reaction with water. Free protons do not exist in water solutions—they must be attached to something.by simple dissociation.” Conversely. so its reactions are to accept a proton or donate a proton. then consider reactions that happen as they go to equilibrium. it is now recognized that proton 93 .

” In many problems with high or medium concentrations of acids. so the result is strongly basic. This concentration expression is the same for either a strong or a weak acid. a “neutral” solution of pH = 7. All reactions must be allowed to proceed to equilibrium before the equilibrium mixture is analyzed. and vice versa.with Ka = 1. or the corresponding values for a base. 94 . What is the end result? Beginning students who have learned to correctly write an equilibrium constant for the weak acid in water as HAc + H2O ↔ H+ + Ac. it is not at equilibrium. leaving the remainder in solution.” So a weak acid cannot react to neutralize a strong base. we assume complete transfer.8 x 10-6) or 1. “Acids are the only source of protons in water. The “concentration” of a solution of an acid in water strictly refers to the formal concentration which is the same as [HA] + [A-] .8 x 10-5 frequently will argue that since [H+] = [Ac-]. so the true value is close to 1 x 10-7 + 1 x 10-10 or 1 x 10-7 M. there are circumstances where the contribution of the “autoionization” or “autoprotolysis” of water according to H2O + H2O ↔ H(H2O)+ + OHcannot be ignored. Weaker students find this quite difficult. However. one can have a high concentration of a weak acid. so [H+] from HCl is 1 x 10-10 M. the ICE tabulation method can be used to obtain a result. When the solution is mixed.1) and the concentration of hydrogen ion is now only √ (1.8 x 10-5 = [H+]2 / (0. which leads to a third order equation for [H+]. A good student will recognize this as nonsense since this is a basic solution. It is the K value for the transfer to water that determines whether an acid is classified as strong or weak. With this in mind. Thus. For example: 5 mL of 0.1 M NaOH is added to 10 mL of 0.3 x 10-3 moles of OH-. The water is contribution 1 x 10-7. so often neglecting water as a source works.1 M acetic acid. The classic catch question is: What is the [H+] of a 1 x 10-10 M solution of HCl in water? Since HCl is a strong acid. (pH = 10).3 x 10-3 M. this is approximately true. Thus the reaction can only consume 1. The full treatment of this. but a class of 40 weak students is still a weak class. or a small concentration of a strong acid. now 1. 2. 3. “Reaction to completion can only occur as the K value will allow. is usually given in college analytical chemistry courses. A class of one strong student is a strong class.SPECIAL FOCuS: Acids and Bases transfer reactions to water are what actually takes place.

or at least a frequent repetition of the mantra pH + pOH ALWAYS = 14 (at normal room temperature) could help. Much practice in writing reaction equations with water as reagent and seeking the K values for the reactions in tables will help students learn how to classify more correctly. bases are compounds containing OH. Unfortunately. but these are rarely dealt with in any significant way in AP or first-year college chemistry courses. Accepting a proton from water creates a basic solution (larger [OH-] than [H+]). 5.Misconceptions in Chemistry Demonstrated on AP Chemistry Examinations Usually the examination committee for AP has tried to set problems on the freeresponse section where the water contribution can be ignored and approximations are simple. 4. this defines NH3 as an acid. [H+] and [OH-] values are independent of each other. 95 . A small but significant number of students fail to apply the water equilibrium in acid–base solutions.to be written to correctly identify ammonia as a (weak) base. Acids and bases are defined according to their ability to donate or accept protons. Acids are compounds containing H atoms. This enables reactions such as NH3 + H2O ↔ NH4+ + OH. Thus they are comfortable to report a pH of 4 and a pOH of 4 (or the equivalent concentrations values) in the same solution. almost exclusively (for AP) in reaction with water. Perhaps a focus during discussions on the need to satisfy the water equilibrium. Of course there are nonaqueous systems.

.

However. Trends in acidity as a function of molecular structure in the gas phase can often be more easily understood.ions. which are absent in the gas phase (Barntmess. As a consequence. HBr. (Recall from the discussion of Brønsted-Lowry acids and bases that reactions with H+ ions involve competitions . This article will address acid–base chemistry beyond water and. HClO4. Zipp SUNY Cortland Cortland. McIver 1979).Acid–Base Chemistry Beyond AP® Arden P. all stronger acids (or bases) are made to appear as if they are of equal strength.will abstract protons from H2O to leave OH. thus. where the relative tendency of a molecule to donate or accept a proton can be measured. and H2SO4 (first proton). the use of water as a solvent limits the species that can act as acids or bases and restricts the range of reactions that can be legitimately considered as acid–base reactions. while bases that are stronger than OH. as many trends in solution depend on solvation energy considerations. Scott. beyond the usual considerations of AP. these differences are not apparent in water because H2O molecules attract the H+ from the various anions so strongly that all the acid is converted into H3O+ and the corresponding anion. Although the Ka of these substances actually varies from 101 to 1011. Leveling Effect of Water It is well known that H2O ionizes into H+ (or H3O+) and OH-. which appear equally strong in water. A further extension is provided by acidity and basicity measurements in the gas phase. This occurs because H2O molecules are stronger bases toward H+ than any of the anions in these acids. Acids that are stronger than H3O+ will donate protons to H2O to form H3O+ ions. New York Most of the acid–base behavior discussed in AP Chemistry occurs in water. so the differences in anion attraction for the H+ are not apparent. HI. HNO3. This is the situation with HCl.

) Nominally. As an example of this behavior. it is possible to measure the relative amounts of the ionized and un-ionized acids. 98 . and to relate these values to aqueous solutions. alcohols (ROH) contain hydroxyl (-OH) groups but exhibit neither acidic nor basic properties in H2O. 1010. which would lead to them being leveled in water as discussed above. 109.(e.g. In this way. Rourke. and liquid HF. HClO4 and HI have been found to be 101.in water. C2H5O. a less basic solvent than water (one with a more negative pKa value) can be used. H-. and 1011. to calculate their ionization constants. acids with Ka values that range from 100 to 10-14 (pKas from 0 to 14) can be studied in water and substances with values outside this range must be investigated in other solvents.or S2-) because they react with an H+ from water to form H2. H2SO4. the Ka values of HNO3.as the predominant anion in solution. HCl. Thus. The Ka for a typical alcohol is about 10-18 (pKa = 18). respectively. and Armstrong 2006. The opposite effect occurs for very weak acids (or bases). leaving OH. HBr. the acids do not ionize completely. HCOOH. respectively.. or HS-. Two examples of such solvents are liquid methanoic (formic) acid. (There is virtually no tendency for an alcohol to behave as a base by either gaining an H+ or losing an OH. Because these solvent molecules have less attraction for H+ than does H2O.) The same “leveling” phenomenon occurs with bases that are stronger than OH. Note: Saying that alcohols are very weak acids is equivalent to stating that their conjugate bases (RO-) are very strong. which are not strong enough to exhibit their acid or base properties in water. 102. Weller. 117).SPECIAL FOCuS: Acids and Bases between two bases. C2H5OH. 107. pKa Ranges of pure Solvents Relative to Water H2SO4 HF HCOOH H 2O (CH3)2SO NH3 -20 -10 0 10 20 Effective pKa in water 30 40 In order to discriminate among the acidities of the six strong acids mentioned above. One way to compare the useful ranges of different solvents is to graph their effective pKa ranges relative to H2O as depicted below (Atkins. Overton.

oxoacids). Such substances ionize according to the equation: HxY <=> H+ + H(x-1)Y. Although the specific structural factors depend on the acid category (hydroacids vs. which can even protonate hydrocarbons! At the other extreme are super bases. Hydroacids These acids can be represented by the general formula H xY and include species in which an atom of a nonmetal is attached directly to one or more hydrogen atoms. which can remove H+ ions from virtually anything including many hydrocarbons.e. 99 . acids that are stronger than 100% sulfuric acid. bases stronger than OH.. the fact that acid strengths can be correlated with structures for a given category of acids provides a very powerful organizational tool. which can be done both theoretically and experimentally. a variety of other acid–base reactions can be observed. In the case of very weak bases a more acidic solvent than H2O is needed in order to protonate the basic site more effectively and for very weak acids a more basic solvent must be employed to help remove H+. which have pKa values greater than 14..can be distinguished by using solvents such as liquid dimethyl sulfoxide. The opposite strategy applies to the task of distinguishing among very weak acids (or bases). For a series of alcohols their relative strengths could potentially be determined by studying them in either dimethylsulfoxide or ammonia. with the extent of this reaction dependent on the ease with which the bond between H+ and H(x-1)Y. which do not show acidic properties under other circumstances. Relative Acid Strengths Although it is common to classify acids as either strong or weak. Consideration of acid strength from gas phase species. such as butyllithium—LiC4H9. there is a great deal of variation among the species in each category. can lead to interestingly different results as solvation effects are removed (Bartmess and Hinde 2005).Acid–Base Chemistry Beyond AP On the other hand.” i. The Ka values for the compounds in groups 14 to 17. Once the constraints of an aqueous solution have been eliminated. (CH3)2SO. Chemists have developed “super acids. or liquid NH3. These variations can be accounted for on the basis of the structures of the molecules involved.can be broken.

There are two factors that influence the ease with which the H-Y bond can be broken. H2SO4. therefore. which would increase the acidity. acid strength in the same directions. their strengths as represented by their Ka (or pKa) values are found to fall into different categories depending on the number of unprotonated oxygen atoms. 314).8 2. Thus. increasing the polarity of the bond. The increase in acidity going across the periodic table can be accounted for by the change in EN. HNO3. decreasing down the table. H2CO3. HNO2. Oxoacids This group of acids is more extensive and diverse than the hydroacids discussed above. HClO3. and H3PO4. are bonded to the central atom Y.74 7. HClO4. there is a large increase in atomic size descending in any group. 100 . Because the atomic size does not vary appreciably across a period. HClO2.SPECIAL FOCuS: Acids and Bases most of which had to be measured in solvents other than water. However. H2SO3. the electron pair in the H-Y bond will be drawn closer to Y. its electrostatic attraction for H+ decreases. the structure of HClO is actually HOCl. reflecting an increase in Ka values and. As the EN of Y increases across the period.6 HF HCl HBr HI 3. the change in EN is the major factor affecting the acidity. because the EN changes in the wrong direction. As the size of an anion increases. These are the electronegativity (EN) and the size of the atom Y.45 -7 -9 -11 The pKa values of these substances decrease down the periodic table and from left to right. which emphasizes the fact that the ionizable protons are bonded to oxygen atoms. This is shown in the table below (Bowser 1993. which. while that of HClO2 is HOClO and that of H2SO4 is (HO)2SO2. cover a range of 10 60 (from 10-49 to 1011) as reflected in the pKas given in the table below (Bowser 1993. regardless of the number of ionizable H’s in the molecule. Despite this variability in formula. pKa for Hydroacids CH4 SiH4 GeH4 49 35 25 NH3 39 PH3 27 AsH3 23 H 2O H2S H2Se H2Te 15. all of the acids in this group can be represented by the general formula (HO)mYOn. with changes in both the central atom and the number of oxygen and/or hydrogen atoms as shown in the list of several of the more common oxoacids: HClO. however. 314).05 3. The increase in the acidity down the table cannot be explained in terms of the EN. When these species are compared in this manner. in turn.

accepting a share of a pair of electrons from appropriate donors.44 -3 1.66 (H0)mYO3 Very Strong pKa < 5 HOClO3 -7. Second. changes in the electronegativity of the central atom represent a small effect on the attraction for the H+ compared to the influence of the greater EN effects of one or more (more electronegative) oxygen atoms.89 2. An increase in the number of such electron-attracting oxygen atoms will withdraw electrons more effectively from the H in the O-H bond.77 (H0)mYO Weak pKa 2 – 5 HOClO HONO (HO)2CO (HO)2SO (HO)2SeO (HO)3PO (HO)3AsO 1. However. One of the most common electron pair donors is the H2O molecule. Sr2+ and Ba2+) with H2O goes no further.62 2.Acid–Base Chemistry Beyond AP pKa Table for Oxoacids (HO)mY Very weak pKa > 7 HOCl HOBr (HO)3As (HO)4Si 7. First. This can be accounted for by the fact that the ionizable H+ is always attached to an oxygen atom whose size doesn’t change and.60 1.3 Several points are notable about the data in this table. any change in the size of the central atom has little effect on the size of the anion as a whole. This increases the polarity of the bond and makes the H atom more H+-like.54 8.49 9. Similarly.21 (H0)mYO2 Strong pKa < 1 HOClO2 HONO2 (HO)2SO2 (HO)2SeO2 -2. Acidity of Metal Ions Metal ions behave as Lewis acids.0 -1. the acid strength increases with the number of unprotonated oxygen atoms in the molecule.18 9. the acid strength changes little with variations in atomic size or electronegativity in contrast to the behavior observed for the hydroacids discussed above. further. many metal ions attract the electron pairs of the coordinated H2O molecules so strongly that one or more molecules may actually be torn apart.94 3.15 2. especially in aqueous solutions.20 3. where most metal ions exist as octahedral species as shown by the equation: Mx+ + 6H2O --> M(H2O)6x+ The interaction of some metal ions (most notably alkali metal ions and larger alkaline earth metal ions such as Ca2+. releasing H+ and making the solution acidic as represented in the equation: M(H2O)6x+ --> M(H2O)5OHx-1 + H+ 101 .

SPECIAL FOCuS:

Acids and Bases

The tendency of metal ions to behave in this manner depends primarily on two factors: charge and size, as shown in the table below where the pKa values for several metal ions participating in this reaction are given along with their radii (Wulfsberg 1991, 25).
pKa values and Radii of Common Metal Ions
Ion pK Radius (nm) Na+ 14.2 0.116 Ca2+ 12.8 0.114 Pu3+ 7.0 0.114 Mg2+ 11.4 0.086 Ca2+ 12.8 0.114 Ba2+ 13.5 0.149

The radius and charge can be combined into a single quantity called the charge density. (It is not necessary to consider the details of calculating this quantity but only to deal with it qualitatively, where it increases with an increase in charge and/or a decrease in ionic radius.) As a first approximation, solutions containing metal ions become more acidic as the charge density of the metal ion increases. As the charge density of metal ions increases, this reaction may proceed further, to the precipitation of metal hydroxides: M(H2O)6x+ --> M(OH)x + xH+ + (6-x) H2O The pH at which this reaction is initiated decreases as the charge density of the metal ion increases, as shown by the pH values for the formation of the following hydroxides, which are characterized by a decrease in size and/or an increase in the charge of the cation (Masterton and Hurley 2006, 427). Ca(OH)2 pH 12.3 Fe(OH)2 pH 8.67 Fe(OH)3 pH 4.49

For species with extremely high charge densities, the potential cations may exist as oxoanions. This is illustrated by the ions VO43-, CrO42- and MnO4-, in which the charges on the nonexistent cations would be +5, +6, and +7, respectively.

Hard and Soft Acids and Bases (HSAB)
This concept represents one of the most significant developments in acid–base theory in recent years. It represents an extension of the Lewis theory and was developed to account for the results obtained when a variety of electron-pair acceptors were reacted with several electron pair donors. Specifically, it was found that a cation such as Ag+ reacts with halide ions in the order I- > Br- > Cl- > F-, whereas (as was pointed out above) H+ reacts with this same series of ions in the opposite order: F- > Cl- > Br- > I- .

102

Acid–Base Chemistry Beyond AP

To account for this difference in behavior, the electron-pair acceptors (Lewis acids) H+ and Ag+ were labeled as hard and soft, respectively, while the halide ions F-, Cl-, Br-, and I- were assumed to progress from hard to soft. Hard acids and bases are species that interact in an electrostatic manner, whereas soft acids and bases exhibit covalent interactions. A fundamental principle of this theory is that hard acids interact preferentially with hard bases. Thus, hard H+ reacts more strongly with hard F- (to form the weak acid HF) than with the soft I- (since HI is a strong acid) and the soft Ag+ interacts more strongly with soft I- (to form the less soluble AgI) than with harder F- (AgF is more soluble). The HSAB theory has provided the basis to account for a wide range of chemical phenomena. For example, it offers explanations for the strengths of the hydrohalic acids and the solubilities of the silver halides as described above. Further, however, it provides the basis to understand the distribution of metal ions in nature between sulfides (soft species such as Ag+, Hg2+, Pt2+) and oxides (hard species Fe2+/3+, Cu2+).

Activities
(1) Determine the pKa value of an acid with a Ka = 1.2 x 102. (2) Give the formula for the acidic and basic species in CH3COOH. (3) Organic amines behave as weak bases in aqueous solutions when an H+ ion reacts with the lone pair of electrons on the N atom. a. Predict the relative strength of an organic amide (RCONH2) behaving as a weak base. b. Give the formula of an appropriate solvent in which an amide would behave this way. (4) Give an approximate pK for the hydroacid stibine (SbH3). (5) The oxoacid pyrosulfuric acid (H2S2O7) is produced when SO3 is bubbled into H2SO4. Write the formula in the (HO)mEOn style, determine the number of free O atoms per S atom and predict its strength relative to that of H2SO4. (6) Use the charge density to a. Account for the fact that the reaction of alkali metal ions and H2O goes only to M(H2O)6+. b. Identify the alkali metal ion that would be most likely to go beyond this stage.

103

SPECIAL FOCuS:

Acids and Bases

(7) Copper can form the ions Cu+ and Cu2+. State and explain which of these is more likely to react with the hard base F-.

Conclusion
This essay has attempted to present several aspects of acid–base theory beyond those discussed in earlier selections (or in the average AP Chemistry course). The topics covered here were chosen in the hope that they would further the understanding and appreciation of the topics usually found in AP courses.

Bibliography
Atkins, P. W., T.L. Overton, J.P. Rourke, M.T. Weller, and F.A. Armstrong. Inorganic Chemistry, 4th ed., Oxford, UK: Oxford University Press, 2006, 117. Bartmess, J. E., J. A. Scott, and R. T. McIver Jr. “Scale Of Acidities in the Gas Phase from Methanol to Phenol.” Journal of American Chemistry Society 101 (1979): 6046–56. Bartmess, J. E., and Robert J. Hinde. “The Gas-Phase Acidities of the Elemental Hydrides are Functions of Electronegativity and Bond Length.” Canadian Journal of Chemistry 83(11) (2005): 2005–12. Bowser, J. R. Inorganic Chemistry. Pacific Grove, CA: Brooks/Cole Publishing, 1993, 312–14. Masterton, W. L., and C. N. Hurley. Chemistry: Principles and Reactions, 5th ed. Pacific Grove, CA: Brooks/Cole Publishing, 2006, 427. Wulfsberg, G. Principles of Descriptive Inorganic Chemistry. Mill Valley, CA: University Science Books, 1991, 25.

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5th edition. This may be disconcerting to some who would prefer to follow the textbook in the order it is presented. etc. and Lewis) and associated concepts Review strong/weak acids and bases as well as additional classifications of acids (monoprotic. Guyer High School Denton. This past year. Be that as it may. but that would be dependent on when I teach acids and bases. It brings back familiar concepts and calculations to second-year students. General Outline Day 1: • • • Review characteristics and examples of acids and bases Review acid/base theories (Arrhenius. The text provided to students is Zumdahl’s Chemistry. and twelfth-grade students enroll in AP Chemistry with an Algebra II minimum math co-requisite. as well as a wealth of laboratory activities to keep them engaged. eleventh-. but may not work for you. You may find my problem selections in the study guide odd. polyprotic.) . Brønsted-Lowry. we as a district moved equilibrium into the first semester with the acid–base unit following directly after it. since we teach the first year of chemistry to freshmen. oxy acids. from the Houghton Mifflin Company. here is a basic outline of what I would cover in my acid–base unit in years where I did not teach the pre-AP class and was unsure of the students’ background. Tenth-. Texas This is one of my favorite units of the year. ternary.Acid–Base Lesson Plans Heather Hattori John H. I teach on an A/B day 90-minute block schedule so some activities are done during class while others are done outside (either after school or on Saturdays). It works for us. diprotic.

dilute) and calculations (molarity) Review acid–base reactions including acid–base formation from acid–base anhydrides • Review pH scale. [OH-]. and associated strong acid–base calculations ([H3O+]. pH Determination) • Assign Study Guides for Chapters 14 and 15. Including a Weak Acid or Weak Base) Day 4: (this lab has been done outside the school day) • % Acetic Acid in Vinegar Lab Day 5: • • • Weak acid–base equilibria—revisiting K Calculating the pH of a weak acid or base Use past AP free-response questions for practice Day 6: • • 106 Common-ion Effect Buffers . logarithms. and pOH) • Pre-lab: Determining the pH of a Substance (fits AP suggested lab topic: Determination of Appropriate Indicators for Various Acid–Base Titrations. pH. • • Day 2: • • • Determining the pH of a substance lab Discussion of titration curves Pre-lab: Titration Curves of Weak and Strong Acids and Bases Day 3: • Titration Curves of Weak and Strong Acids and Bases Lab • Review titration problems • Pre-lab: % Acetic Acid in Vinegar (fits AP suggested lab topic: Determination of Concentration by Acid–Base Titration.SPECIAL FOCuS: Acids and Bases Review concentration terms (concentrated.

2007. 1995. and Martin Fossett.Acid–Base Lesson Plans • Pre-lab: Preparation of a Buffer Solution at a Given pH or A Resistance to Change (fits AP suggested lab topic: Preparation and Properties of Buffer Solutions) Day 7: (this lab has been done outside the school day) • Preparation of a Buffer Solution at a Given pH Lab Day 8: (If time permits. If not. OR: Vernier Software & Technology. • Acids and Bases Introduction-Review Notes • Titration Notes • Calculating the pH of a Weak Acid or Base Notes • Common Ion Effect and Buffers Notes • Determining the pH of a Substance. Heather R. Saddle Brook. Hattori. Hattori. Heather R. 5th edition. • Acid-Bases. 2001. 2005. Jack Randall.” in Laboratory Investigations: AP Chemistry. 107 . and Titration Calculation Review Worksheet. Heather R. Inc. David. Beaverton. Reactions. Hattori.. 2000. In Chemistry with Calculators.. NJ: The Peoples Publishing Group. then skip to Day 9) • Complex Ion Equilibria Day 9: • Unit Assessment Additional Attachments: • Study Guides to Accompany Zumdahl’s Chemistry. • Dissociation and pH Practice. Hattori. Bibliography Holmquist Dan D. Hostage. 2006. Heather R. and Don Volz. “Finding the Mass Percent of Acetic Acid in Vinegar.

NJ: The Peoples Publishing Group. “A Resistance to Change. 2003. and Zumdahl. Moore. and Martin Fossett. 2006. McGraw-Hill.. and Richard Langley. Laboratory Investigations: AP Chemistry. John T. David. Pasco Scientific. CA: PASCO Scientific. 5 Steps to a 5 AP Chemistry. Zumdahl. Saddle Brook. 108 .. Steven S. Roseville.SPECIAL FOCuS: Acids and Bases Hostage.” in PasPort Explorations in Chemistry. Chemistry. Houghton Mifflin Company. 5th ed. 2004. 2000.

oranges. Vinegar contains acetic acid. Soft drinks contain carbonic and phosphoric acids.0 • Are corrosive Bases • Taste bitter • Turn red litmus paper blue • Have a pH > 7.Appendix A Review Notes on Acids and Bases Introduction Common Acids and Bases Where do I find acids? • • • • Fruits (lemons. Where do I find bases? • Cleaners contain ammonia. • Milk of magnesia contains magnesium hydroxide. etc. Characteristics of Acids and Bases • Acids • Taste sour • Turn blue litmus paper red • Have a pH < 7.) contain citric acid. • Drano contains sodium hydroxide.0 • Are caustic • . Rain water contains sulfuric acid.

the hydroxide ion could accept a hydrogen ion from the ammonium and become water. bases accept H+ (hydrogen ions) in solution.(aq) H3PO4 (aq) + 3H2O (l) → 3 H3O1+ (aq) + PO43.(aq) Ca(OH)2 (aq) → Ca2+ (aq) + 2OH1.(aq) Bases are proton acceptors.(aq) H3PO4 (aq) → 3 H1+ (aq) + PO43. Bases are electron-pair donors in solution. NH3 (aq) + H2O (l) → NH41+ (aq) + OH1. acids donate H+ (hydrogen ions) in solution. In other words.(aq) Brønsted-Lowry Model Acids are proton donors.(aq) CaO (s) + H2O (l) → Ca(OH)2 (aq) The first equation sets up two interesting relationships. NaOH (aq) → Na1+ (aq) + OH1. BF3(aq) + :NH3 (aq) → F3B:NH3 110 .(hydroxide ions) in solution. Not only does the ammonia accept a hydrogen ion to become the ammonium ion. Lewis Theory Acids are electron-pair acceptors in solution.SPECIAL FOCuS: Acids and Bases Three Acid–Base Theories The following theories are where we get our definitions of what acids and bases are: • • • Arrhenius Concept Brønsted-Lowry Model Lewis Theory Arrhenius Concept Acids produce H+ (hydrogen ions) in solution.(aq) Bases produce OH. In other words. These two relationships make the ammonia/ammonium ion and the water/hydroxide ion conjugate acid/base pairs. HCl(aq) → H1+ (aq) + Cl1. HCl(aq) + H2O (l) → H3O1+ (aq) + Cl1.

0 X 10-7 ∴ [H3O1+] = 1.is made. so: [H3O1+][OH1-] = 1.0 X 10-14 x = 1. Remember that: H2O (l) ↔ H+1 (aq) + OH-1 (aq) (Arrhenius concept) According to the Arrhenius concept water (in the equation above) is acting as an acid by producing hydrogen ions as well as a base by producing hydroxide ions. one OH1. sometimes it is hard to compare the [H3O1+]. The water molecule that is accepting the hydrogen ion is acting as the base. The pH scale was developed to make it easier to recognize if a substance was acidic or basic.0 X 10-14 always at 25°C We can solve for the [H3O1+] or [OH1-] based on the above equation. For every H3O1+ produced. The amphoteric nature of pure water contributes to its neutral nature. then the solution is acidic [H1+] < [OH1-].0 X 10-7 M = [OH1-] In solutions when the: [H1+] > [OH1-]. Since concentrations can be large or small. then the solution is basic [H1+] = [OH1-].Appendix A The pH Concept pH represents the relative acidity of a solution based on hydrogen ion or hydronium ion concentration and can be found using either of the following equations: pH = -log[H+] or pH = -log[H3O+]. This means that water can act as an acid or a base due to the concept known as autoionization shown in the following two examples. 2H2O (l) ↔ H3O+1 (aq) + OH-1 (aq) (Brønsted-Lowry model) According to the Brønsted-Lowry model one water molecule (in the equation above) is acting as an acid by donating a hydrogen ion to the other molecule of water forming a hydronium ion. If we write the equilibrium expression for this we get: Kw = [H3O1+][OH1-] = 1.0 X 10-14 x2 = 1.2 X 10-13 M. then the solution is neutral 111 .0 X 10-14 becomes [x][x] = 1. such as 12 M or 4.

4 X 10-7M? By combining all three of the previous formulas: Kw = [H3O1+][OH1-] = 1. Let’s look at a hydrated aluminum hydroxide ion as an example.SPECIAL FOCuS: Acids and Bases Based on this and the fact that [H1+] and [OH1-] can be calculated if you know one or the other. pOH = -log [OH1-] 4. or neutral). 0 Acidic pH = -log[H+] or 7 Neutral pH = -log [H3O+] 14 Basic 3. Given the [H3O1+] = 1. Substances other than water can also be amphoteric.0 X 10-9 M? A similar formula can be used to calculate the pOH (relative basicity) if you know the [OH1-]. basic. [Al(H2O)4(OH)2]1+ + HCl ↔ [Al(H2O)5OH]2+ + Cl1When a hydroxide from [Al(H2O)4(OH)2]1+ accepts the hydrogen ion to create the fifth water of hydration. basic. Examples 1. it is acting as a Brønsted-Lowry acid. What is the pOH of a solution with a [OH1-] = 2. Given the [OH1-] = 1. What is the pH of a solution with a [H+] = 1. 2. the pH scale was developed. [Al(H2O)4(OH)2]1++ NaOH ↔ Al(H2O)3(OH)3 + OH1When a water of hydration from [Al(H2O)4(OH)2]1+ donates the hydrogen ion to becomes the third hydroxide ion.0 X 10-14 pH = -log [H3O1+] 112 . or neutral).0 X 10-2M. it’s time to solve some problems. it is acting as a Brønsted-Lowry base. solve for the [H3O1+] and determine the solution’s nature (acidic. pH scale Based on logarithms. solve for the [OH1-] and determine the solution’s nature (acidic.0 X 10-5M.

which describe the amount of dissociation.8. and HClO4. 113 . Strong bases include: LiOH. KOH. HI. NaOH.Appendix A pOH = -log [OH1-]. HBr. 5. • • Strong acids include: HCl. which describe the solution concentration. A strong acid or base is one that completely dissociates in water or has 100% ionization. What is the pOH of a solution that has a pH of 10. HNO3. All others are considered weak. [H3O1+]. What are the pOH. Mg(OH)2. we can derive the formula: pH + pOH = 14. and Ba(OH)2.0? Vinegar has a pH of 2. weak or strong. and [OH1-] of a vinegar solution? Relative Strengths of Acids and Bases Acids and bases can be concentrated or dilute. All others are considered weak. Sr(OH)2. A weak acid or base is one in which only a small portion of the particles dissociate or one that only partially ionizes. Do not confuse the first two. Ca(OH)2. H2SO4. with the last two.

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oranges. etc.0 • are caustic .Appendix B Review Notes on Acids and Bases— Teacher’s Edition Common Acids and Bases Where do I find acids? • Fruits (lemons. • Rain water contains sulfuric acid. • Milk of magnesia contains magnesium hydroxide. Where do I find bases? • Cleaners contain ammonia. • Soft drinks contain carbonic and phosphoric acids. Characteristics of Acids and Bases Acids: • • • • taste sour turn blue litmus paper red have a pH < 7. • Vinegar contains acetic acid. • Drano contains sodium hydroxide.) contain citric acid.0 are corrosive Bases: • taste bitter • turn red litmus paper blue • have a pH > 7.

(aq) Bases are proton acceptors. Not only does the ammonia accept a hydrogen ion to become the ammonium ion. where n may be 1–6.(hydroxide ions) in solution. 116 . bases accept H+ (hydrogen ions) in solution.(aq) H2PO4. NaOH (aq) → Na+ (aq) + OH.(aq) CaO (s) + H2O (l) → Ca(OH)2 (aq) The first equation sets up two interesting relationships. as shown in some of the examples below. the hydroxide ion could accept a hydrogen ion from the ammonium ion and become water. usually to water. For convenience. HCl(aq) → H+ (aq) + Cl.(aq) Ca(OH)2 (aq) → Ca2+ (aq) + 2OH. In other words. In other words.(aq) H3PO4 (aq) → H+ (aq) + H2PO4.(aq) Bases produce OH. this species is usually abbreviated to H+ except when a balanced equation is desired. The reaction goes both ways and so reaches equilibrium.(aq) + H2O (l) → H3O+ (aq) + PO43. These are hydrated to form H(H2O)n+. HCl(aq) + H2O (l) → H3O+ (aq) + Cl.SPECIAL FOCuS: Acids and Bases Three Acid–Base Theories The following theories are where we get our definitions of what acids and bases are: • Arrhenius Concept • Brønsted-Lowry Model • Lewis Theory Arrhenius Concept Acids produce H+ (hydrogen ions) in solution. NH3 (g) + H2O (l) → NH4+ (aq) + OH.(aq) Brønsted-Lowry Model Acids are proton donors.(aq) H3PO4 (aq) + H2O (l) → H3O+ (aq) + H2PO4. acids donate H+ (hydrogen ions) in solution.(aq) HPO42.(aq) + H2O (l) → H3O+ (aq) + HPO42. These two relationships make the ammonia/ammonium ion and the water/hydroxide ion conjugate acid–base pairs.

0 X 10-14 117 .0 X 10-14 becomes [x][x] = 1.Bases are electron pair donors in solution.(aq) (Brønsted-Lowry model) According to the Brønsted-Lowry model.0 X 10-14 at 25°C We can solve for the [H3O+] or [OH-] based on the above equation. such as 12 M or 4. The water molecule that is accepting the hydrogen ion is acting as the base. is acting as an acid by producing hydrogen ions as well as a base by producing hydroxide ions. with no other substances present. Since concentrations can be large or small. the symbol [H+] is used to represent the concentration of H+ ions in moles per liter. which is shown in the following two examples.2 X 10-13 M. one water molecule in the equation above is acting as an acid by donating a hydrogen ion to the other molecule of water forming a hydronium ion. Remember that: H2O (l) ↔ H+ (aq) + OH.Appendix B Lewis Theory Acids are electron pair acceptors in solution. pH represents the relative acidity of a solution based on hydrogen ion or hydronium ion concentration and can be found using either of the following equations: pH = -log[H+] or pH + -log[H+] . sometimes it is hard to compare the [H+]. BF3(aq) + :NH3 (aq) → F3B:NH3 The pH Concept Conventionally. water. The amphoteric nature of pure water contributes to its neutral nature. H2O (l) + H2O (l) ↔ H3O+ (aq) + OH. If we write the equilibrium expression for this we get: Kw = [H3O+][OH-] = 1. The pH scale was developed to make it easier to recognize if a substance was acidic or basic. In pure water.is made so [H3O+] = [OH-] = x [H3O1+][OH1-] = 1. for every H3O+ produced. This means that water can act as an acid or a base by accepting or donating protons. Water also undergoes a process called auto-ionization. in the equation above. one OH.(aq) (Arrhenius concept) According to the Arrhenius concept.

0 X 10-14 [OH-] = 1.0 X 10-14 [H3O+] = 1.0 X 10-7 M = [OH-] In solutions when the: [H+] > [OH-]. it is acting as a Brønsted-Lowry base. or neutral).0 X 10-7 ∴ [H3O+] = 1.0 X 10-12 M which is less than the [H3O+] so 1. Kw = [H3O+][OH-] = 1. basic. Based on this and the fact that [H+] and [OH-] can be calculated using Kw if you know one or the other. Given the [H3O+] = 1. it’s time to solve some problems.0 X 10-14 [1. Examples 1. [H+] = [OH-].0 X 10-2M.0 X 10-9 M which is less than the [OH-] so the 1. [Al(H2O)4(OH)2]++ NaOH ↔ Al(H2O)3(OH)3 + OHWhen a water of hydration from [Al(H2O)4(OH)2]+ donates the hydrogen ion to becomes the third hydroxide ion it is acting as a Brønsted-Lowry acid.0X 10-2 M the solution is basic. 118 . basic. then the solution is basic.0X 10-5 M solution is basic. solve for the [H3O+] and determine the solution’s nature (acidic. or neutral).0X 10-2 M][OH-] = 1.0 X 10-14 M2 = 1.0 X 10-14 [H3O+] [1. then the solution is acidic.0 X 10-14 M2 = 1. Let’s look at a hydrated aluminum hydroxide ion as an example.0X 10-5] = 1. solve for the [OH-] and determine the solution’s nature (acidic.SPECIAL FOCuS: Acids and Bases x2 = 1. Given the [OH-] = 1. [Al(H2O)4(OH)2]+ + HCl ↔ [Al(H2O)5OH]2+ + ClWhen a hydroxide from [Al(H2O)4(OH)2]+ accepts the hydrogen ion to create the fifth water of hydration. then the solution is neutral. [H+] < [OH-].0 X 10-5M. Kw = [H3O+][OH-] = 1. 2.0 X 10-14 x = 1. Substances other than water can also be amphoteric.

we can derive the formula: pH + pOH = 14 4.0 X 10-14 pH = -log [H+] pOH = -log [OH-]. [H+].8 = -log[H+] [H+] = 2 X 10-3 M pOH = -log[OH-] 11.2 = -log[OH-] [H+] = 6 X 10-12 M 119 .0 + pOH = 14 pOH = 4.2 pH = -log[H+] 2.00 A similar formula can be used to calculate the pOH (relative basicity) if you know the [OH-]. the pH scale was developed. 0 Acidic pH = -log[H+] or 7 Neutral pH = -log [H3O+] 14 Basic 3.8.0X10-9 M) pH = 9.0 pOH = 6.0 X 10-9 M? pH = -log[H+] pH = -log(1.62 Vinegar has a pH = 2.4 X 10-7 M) By combining all three of the previous formulas: Kw = [H+][OH-] = 1. What are the pOH. and [OH-] of a vinegar solution? pH + pOH = 14 2.0? pH + pOH = 14 10.Appendix B pH scale Based on logarithms. What is the pOH of a solution that has a pH of 10.4 X 10-7M? pOH = -log [OH-] pOH = -log(2.8 + pOH = 14 pOH = 11. pOH = -log [OH-] What is the pOH of a solution with a [OH-] = 2. What is the pH of a solution with a [H+] = 1.

All others are considered weak. Ca(OH)2. and HClO4. Do not confuse the first two. and Ba(OH)2. HI. Strong acids include: HCl. which describe the amount of dissociation. Sr(OH)2. H3PO4 . which describe the solution concentration. 120 . A strong acid or base is one that completely dissociates in water or has 100% ionization. with the last two.SPECIAL FOCuS: Acids and Bases Relative Strengths of Acids and Bases Acids and bases can be concentrated or dilute. or one that only partially ionizes. H2SO4. weak or strong. A weak acid or base is one in which only a small portion of the particles dissociate. HBr. NaOH. Mg(OH)2. All others are considered weak. HNO3. Strong bases include: LiOH. KOH.

Common indicators used in acid–base titrations include phenolphthalein (clear to pink pH = 8-10) and bromothymol blue (yellow to blue pH = 6-8). the indicator experiences a color change at the endpoint of the titration. Titration curves are a way to visually represent the change in pH during a titration. the endpoint and the equivalence point (when there are equal amounts of acid and base) occur at nearly the same time.Appendix C Titration Notes A titration is the experimental procedure used to determine the concentration of an unknown acid or base. Acid–Base Reactions When an acid reacts with a base a neutralization reaction occurs. The necessary chemical components of a titration include a standard solution. The same thing happens when a base reacts with an acid. The equivalence point can be visually determined from the titration curve. and solution of unknown concentration. An acid–base reaction is a double displacement reaction. During a titration. Examples HCl + NaOH → NaCl + HOH H2SO4 + KOH → . Titrations and titration curves tell you many things about a reaction. It is the area in which the slope of the line approaches infinity (or is nearly vertical). AB + CD → AD + CB The products of an acid–base reaction are a salt (metal/nonmetal compound) and water. and an indicator. If the best indicator is chosen.

0 mL of 2. the goal of a titration is to calculate the concentration of one of the reactants. A 10.0 M KOH.0 mL sample of H2SO4 was neutralized by 13. What volume of 1.0 mL sample of HCl was titrated to the endpoint with 15.05M Ca(OH)2 solution to the endpoint? 122 . This can be done using a balanced equation and stoichiometry.5 mL of 1.50 M NaOH is necessary to neutralize 20.5M H3PO4? 4. How much 0.5M HNO3 is necessary to titrate 25. 1.0 mL of 0. What was the molarity of the acid? 3.SPECIAL FOCuS: Acids and Bases H3PO4 + LiOH → Hydrobromic acid + calcium hydroxide HBr + Ca(OH)2 → CaBr2 + 2H2O Hydrofluoric acid + aluminum hydroxide HF + Al(OH)3→ AlF3 + 3H2O Titration Problems Often. What was the molarity of the acid? 2.0 mL of 2.0 M NaOH. A 25.

During a titration. . An acid–base reaction is a double displacement reaction. the endpoint and the equivalence point (when equivalent amounts of acid and base have been added) occur at nearly the same time. Acid–Base Reactions When an acid reacts with a base. The same thing happens when a base reacts with an acid. a neutralization reaction occurs. Titration curves and the progress of titrations can also be followed by using a pH meter or probe. a solution of unknown concentration.Appendix D Titration Notes – Teacher’s Edition A titration is the experimental procedure used to determine the concentration of an unknown acid or base. The necessary chemical components of a titration include a standard solution. The equivalence point can be visually determined from the titration curve. It is the area where the slope of the line approaches infinity (or is nearly vertical). and may include a colored indicator. AB + CD → AD + CB The overall products of an acid–base reaction are a salt (metal/nonmetal compound) and water. Titrations and titration curves tell you many things about a reaction. Common indicators used in acid–base titrations include phenolphthalein (clear to pink pH = 8–10) and bromothymol blue (yellow to blue pH = 6–8). Titration curves are a way to visually represent the change in pH during a titration. the indicator experiences a color change at the endpoint of the titration. If the best indicator is chosen.

What was the molarity of the acid? H2SO4 + 2KOH → K2SO4 + 2H2O 13. which can be mol/L or millimoles/mL.0 mol NaOH × 1 L NaOH 1 mol HCl × 1 mol NaOH 1 25. A 25.0 mL H3PO4 × 2.SPECIAL FOCuS: Acids and Bases Examples HCl + NaOH → NaCl + HOH (which also can be written H2O) H2SO4 + 2KOH → K2SO4 + 2H2O H3PO4 + 3LiOH → Li3PO4 + 3H2O Hydrobromic acid + calcium hydroxide HBr + Ca(OH)2 → CaBr2 + 2H2O Hydrofluoric acid + aluminum hydroxide HF + Al(OH)3 → AlF3 + 3H2O Titration Problems Often.0 mol KOH × 1 mol H2 SO4 × 1000 mL H2 SO4 1000mL 1L 2 mol KOH 1 L H2SO4 × 1 = 0.0 mL NaOH × 1 L NaOH × 1000mL NaOH 2. 1.5M H3PO4? Note: M is molarity.00 × 102mL NaOH 124 .0 mL of 2.68 M H2SO4 10. What volume of 1.5 mL KOH × 1 L KOH × 1.0 mL HCl × 1000 mL 1 L HCl = 1.0 mL sample of H2SO4 was completely reacted by 13.0 mL H2SO4 3. A 10.0 mL of 2.2 M HCl 2. the goal of a titration is to calculate the concentration of one of the reactants. What was the molarity of the acid? HCl + NaOH → NaCl + H2O 15.0 mL sample of HCl was titrated to the equivalence point with 15.50mmol NaOH = 1.5 mL of 1.0 mL H3PO4 3 mmol NaOH 1 mmol H3PO4 × 1mL NaOH 1.50 M NaOH is necessary to completely react with 20.0 M NaOH.0 M KOH. H3PO4 + 3NaOH → Na3PO4 + 3H2O 20.5 mmol H3PO4 × 1. This can be done using a balanced equation and stoichiometry.

05 mmol Ca(OH)2 × 1 mL Ca(OH)2 2 mmol HNO3 1 mmol Ca(OH)2 × 1mL HNO3 0.0 mL Ca(OH)2 × 0.05M Ca(OH)2 solution to the equivalence point? 2HNO3 + Ca(OH)2 → Ca(NO3)2 + 2H2O 25.0 mL of 0.5M HNO3 is necessary to titrate 25. How much 0.00 mL HNO3 125 .Appendix D 4.5 mmol HNO3 = 5.

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8 X 10-5 [ 0. We begin by writing the equilibrium expression: Ka Ka = [H3O1+ ][ C2H3O 21.Appendix E Calculating the pH of a Weak Acid or Base When working with weak acids.8 X 10-5. This becomes an equilibrium problem instead of a simple stoichiometry problem (like it would if it were a strong acid).100M . Acetic acid is a weak acid and thus. the case of calculating the pH of a 0. or buffer systems.100M -x 0.(aq). weak bases.34 X 10−3 = [ H 3O 1+ ] .100M is negligible because of the large difference (power difference > 10-3 units) in concentration and Ka. only a small percentage of it dissociates.x H3O1+ 0 +x x C2H3O210 +x x Substituting into the equilibrium expression we get: Ka = [x][x] = 1.8 X 10−6 x = 1. for example. one must take into account the fact that many species exist in the reaction vessel.100 M acetic acid solution whose Ka = 1. The reaction: HC2H3O2 (aq) + H2O (l) ↔ H3O1+ (aq) + C2H3O21.100M -x ] Assuming the effect of x on 0. Take.] [ HC2H3O 2 ] Next we need to look at the conditions during the reaction: HC2H3O2 Initial Change Equilibrium 0. solving for x we get: x2 x 2 = 1.

78. A. 2. 11.00M -x ] Assuming the effect of x on 2.8 X 10-5.30 B. If you chose answer B. 128 .87.x NH41+ 0 +x x OH10 +x x Substituting into the equilibrium expression we get: [x][x] Kb = = 1. Kb = −10 5.8 X 10-5 [ 2.22. pH = 14 – 2. If you chose answer C. 8. The reaction is NH3(aq) + H2O(l) ↔ NH41+(aq) + OH1-(aq) Kw Since Kw = Ka Kb = 1.6 X 10−6 x x = 6.71 X 10 NH3 Initial Change Equilibrium 2. Example 1 Calculate the pH of a 2.SPECIAL FOCuS: Acids and Bases Now we can solve for pH using the equation: pH = -log[H3O1+] and find the pH to be 2.71 X 10-10 for your Kb value instead of 1.00M is negligible because of the large difference (power difference > 10-3 units) in concentration and Kb. Since pH + pOH = 14.94 D. If you chose answer A. solving for x we get: x 22 = 3.22 C.71 X 10-10 @ 25°C.00 M -x 2.00M ammonia solution with a K a = 5. you only used the initial concentration of ammonia and substituted it into the pH = -log[H3O1+] assuming that the concentration of ammonia was equal to the hydronium ion concentration. -0. you selected the value that was equal to the pOH.8 X 10−5 M .78 Solution: The correct answer is D.0 X 10-14 so Kb = substituting in values we get: Ka 1.22. you used 5. and the pH = 11.0 X 10−3 = [OH 1− ] Now we can solve for pOH using the equation: pOH = -log[OH1-] and find the pOH to be 2.00 .0 X 10−14 = 1.

the equilibrium shifts to relieve the stress this is an application of . . If NaF is added to HF: HF ↔ H+ + F NaF ↔ Na+ + F More fluoride ions are added to the solution. If NH4Cl is added to NH3: NH3 + H2O ↔ NH4+ + OH NH4Cl ↔ NH4+ + Cl More ammonium ions are added to the solution. This shifting process is called the common ion effect.Appendix F Applications of Aqueous Equilibria Notes Different Constants (to hopefully clear confusion) Kb Kf k Kw Ka Kb Kc Kp Ksp Kd Kf molal boiling point constant molal freezing point constant rate constant ionization constant for water acid dissociation constant base dissociation constant equilibrium constant for concentrations equilibrium constant based on pressures equilibrium constant for solubility product equilibrium constant for decomposition reactions equilibrium constant for formation reactions ∆tb = K bm ∆tf = Kfm Rate = k [reactants] Kw = Ka Kb = 1.0 X 10 -14 @ 25°C Ka = [H+][A -]/[HA] Kb = [X+][OH -]/[XOH] The Effect of Common Ions When a salt is added to an acid or base containing similar ions. The equilibrium shifts to the left. The equilibrium shifts to the left. This complicates the equilibrium by providing an additional source for ions.

d.100 M HC3H5O2 and 0. be sure to look at the stoichiometry before setting up the equilibrium. b. Determine the pH after the following quantities of base have been added to the acid solution and draw the resulting titration curve.00 mL 49. Problems like this have appeared in the past on the AP Exam.0 mL sample of 0. e.150 M HNO2 (pKa = 3.00 mL Indicators and Titrations Common indicators used in acid base titrations are: phenolphthalein (clear to pink pH =8-10) bromothymol blue (yellow to blue pH = 6-8) universal indicator (red to purple pH = 1-13) 130 .100 M NaC3H5O2.00 L of solution versus the pH of the ammonia alone? Kb = 1. When working with buffers.SPECIAL FOCuS: Acids and Bases Example 1 Calculate the pH of a mixture containing 0.00 mL 55.35) was titrated with 0.300 M NaOH. the pH of the mixture can be calculated. A 100. a. 0.50 mL 50.81 X 10-5 The Henderson-Hasselbalch equation can also be used to solve for pH.00 mL 75.3 x 10-5 Buffers Combinations of weak acids or weak bases with their salts form buffers.00 mol of ammonium chloride in 1. f.00 mol of ammonia and 3. pH = pKa + log ([A-]/[HA]) pOH = pKb + log ([X+]/[WB]) Solution: Titrations are laboratory procedures used to determine the concentration of acids or bases. Along the way. Example 2 What is the difference in pH of a solution containing 2. Ka = 1. Buffers are solutions that resist changes in pH when hydrogen or hydroxide ions are added.00 mL 25. c.

then [A-] = 0. [ A− ] 6.8 X 10 ) + log [HA] -5 A−  6.Appendix F To prepare a buffer with a specific pH (part of pre-lab discussion): = pK a + pH = pKa + log [ A− ] [HA] [ A− ] 6.0 = p(1.2 X 10-2 4. then as the water molecules collide with the salt and interact with the intermolecular forces. you would choose HOAc and NaOAc since the pKa of HOAc is closest to 6.74 + log   [HA ] 1.055 = [HA] If [HA] = 0.3 X 10-7 5. the formula units of the salt begin to dissolve.2 X 10-2 Large 1.0 = pK a + 6. none is dissolved. the equilibrium involved is the solubility equilibria. for a buffer with pH = 6.6 X 10-11 1. Solubility Equilibria When solids dissolve to form aqueous solutions.2 X 10-8 4.0055M.3 X 10-3 6.0 = pKa + log [HA] Acids to choose from: H2SO3 HOAc H3PO4 H2CO3 HSO41H2SO4 Their Ka values 1. When a salt is added to water at first.1 M. Eventually the maximum amount of 131 .26 = [ A− ] [HA] [ A− ] [HA] [ A− ] 0.0 X 10-7 1.5 X 10-2 1.0 = 4.8 X 10-13 So if I am not mistaken.8 X 10-5 7.26 = log 10−1.

132 . that solubility and the solubility product are not the same. Ksp problems are much like Ka and Kb problems. RICE diagrams are very useful in demonstrating this affect. then their Ksp values can be used to determine their solubilities relative to each other.20 M solution of potassium sulfate. Do realize. BaCO3 (s) ↔ Ba2+ (aq) Ksp = [Ba2+] [CO32-] = 1.2 X 10-5. the less soluble it is. We would expect this since barium carbonate is not considered soluble in water based on what we have learned from solubility rules.SPECIAL FOCuS: Acids and Bases solid that can dissolve at that particular temperature does dissolve and equilibrium is reached.(aq) Why is the BaCO3 not included in the K sp expression? Notice that the K value is very small. At 25°C.14 X 10-4 mol/L Al(OH)3 has a Ksp of 2 X 10-32 at 25°C. If the salts produce different numbers of ions when they dissolve. then you have to calculate the solubilities from the Ksp values. The smaller the Ksp. however. Calculate the solubility of silver sulfate in a 0. Solubility is a position that changes with temperature and the concentration of common ions present in the solution. as in the previous example.what is the Ksp of PbSO4? What is its solubility of PbSO4 at 25°C? Relative Solubilities If salts produce the same number of ions when they dissolve. The Common Ion Effect on Solubility A common ion affects the solubility of a solid.6 X 10-9 + CO32. generally reducing the amount that dissolves by providing an initial concentration of one of the ions. Example 3 The Ksp of silver sulfate is 1. Calculating Ksp from solubility Calculating solubility from Ksp PbSO4 has a measured solubility of 1. The solubility product is a constant value for a particular temperature (usually room temperature when you look it up in a chart).

the equilibrium shifts to relieve the stress this is an application of LeChatlier’s Principle If NaF is added to HF: HF ↔ H+ + F NaF ↔ Na+ + F More fluoride ions are added to the solution.0 X 10 -14 @ 25°C Ka = [H+][A -]/[HA] Kb = [X+][OH -]/[XOH] The Effect of Common Ions When a salt is added to an acid or base containing similar ions. The equilibrium shifts to the left. .Appendix G Applications of Aqueous Equilibria Notes – Teacher’s Edition Different Constants (to hopefully clear confusion) Kb Kf k Kw Ka Kb Kc Kp Ksp Kd Kf molal boiling point constant molal freezing point constant rate constant ionization constant for water acid dissociation constant base dissociation constant equilibrium constant for concentrations equilibrium constant based on pressures equilibrium constant for solubility product equilibrium constant for decomposition reactions equilibrium constant for formation reactions ∆tb = Kbm ∆tf = Kfm Rate = k [reactants] Kw = Ka Kb = 1. If NH4Cl is added to NH3: NH3 + H2O ↔ NH4+ + OH NH4Cl ↔ NH4+ + Cl More ammonium ions are added to the solution. This complicates the equilibrium by providing an additional source for ions. The equilibrium shifts to the left. This shifting process is called the common ion effect.

00 mol of ammonium chloride in 1.81 X 10-5 2.] Ka = [x][0.3 X 10-5M = [H+] pH = -log[H+] pH = -log(1.(aq) NH3 Initial Change Equilibrium 2.100M .00M . Buffers are solutions that resist changes in pH when hydrogen or hydroxide ions are added.100M -x] =1.00 mol of ammonia and 3.(aq) 2.x NH41+ 0 3.100 + x] [0.3 X 10-5 If you consider x to be negligible. then this simplifies to : K K aa = [0.100M -x 0. which is consistent with a weak acid.3 X 10−5 and [ 0. be sure to look at the stoichiometry before setting up the equilibrium.00 mol NH4Cl NH3 + H2O(aq) ↔ NH4+(aq) + OH .00M .SPECIAL FOCuS: Acids and Bases Example 1 Calculate the pH of a mixture containing 0.x H1+ 0 +x x C3H5O210 x + 0.00 mol NH3 only NH3 + H2O(aq)  NH4+(aq) + OH .100x] = 1. Buffers Combinations of weak acids or weak bases with their salts form buffers.00 M -x 2.89.3X10-5) pH = 4. When working with buffers. Ka = 1. Example 2 What is the difference in pH of a solution containing 2.00 M -x 2.00 mole NH3 + 3.100 [The 0.3 x 10-5 HC3H5O2(aq)  H+(aq) + C3H5O2-(aq) HC3H5O2 Initial Change Equilibrium 0.00 + x x OH1- 0 x x 134 .x NH41+ 0 +x x OH10 +x x NH3 2.00 L of solution versus the pH of the ammonia alone? Kb = 1.100M] x = 1.100 comes from the NaC3H5O2.100 x + 0.100 M NaC3H5O2.100 M HC3H5O2 and 0.

Appendix G
[x][x] [2.00M -x] [3.00M + x][x] [2.00M -x]

Ka =

= 1.81 X 10 -5

Ka =

= 1.81 X 10 -5

Considering x to be negligible:
x = 2.00 M × (1.81 X 10 )
2 -5

Considering x to be negligible:
3x = 2.00 M × 1.81 X 10 -5 x = 1.21 × 10 -5 M = [OH -] pOH = -log[OH -] pOH = 4.917 pH + pOH = 14 pH + 4.917 = 14 pH = 9.083

x= 6.01 × 10 -3 M = [OH -] pOH = -log[OH -] pOH = 2.221 pH + pOH = 14 pH + 2.221 = 14 pH = 11.779

The Henderson-Hasselbalch equation can also be used to solve for pH. pH = pKa + log ([A-]/[HA]) pOH = pKb + log ([X+]/[WB])

Titrations are laboratory procedures used to determine the concentration of acids or bases. Along the way, the pH of the mixture can be calculated. Problems like this have appeared in the past on the AP Exam. A 50.0 mL sample of 0.300 M HNO2 (pKa = 3.35) was titrated with 0.450 M NaOH. Determine the pH after the following quantities of base have been added to the acid solution and draw the resulting titration curve: a. b. c. d. e. f. 0.00 mL 16.5 mL 32.0 mL 33.3 mL 35.0 mL 50.0 mL pKa = -log(Ka) 3.35 = -log(Ka)

a. HNO2(aq)  H+(aq) + NO2-(aq) Ka = 4.5 × 10-4
KKa = a [H+ ][NO 2- ] =4.55X 10-4−4 = 4. X 10 [HNO 2 ]

135

SPECIAL FOCuS:

Acids and Bases

[HNO2]
Initial Change Equilibrium 0.300 M -x 0.300 M - x

[H1+]
0 +x x

[NO21-]
0 +x x

Ka =

[x][x] =4.5 × 10 [0.300M -x]

x = 1.2 × 10-2M = [H+] pH = -log[H+] pH = 1.92 b. HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O 50.0 mL HNO2 × 1L/1000mL × 0.300 M = 0.0150 mol HNO2 16.5 mL NaOH × 1L/1000mL × 0.450 M = 0.00743 mol NaOH 0.0150 mol – 0.007425 mol = 0.07575 mol HNO2 left after reaction 50.0mL + 16.5mL = 66.5 mL or 0.0665 L HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O
[HNO2]
Initial Change Equilibrium 0.0150 mol -0.0743mol 0.0757 mol

[NaOH]
0.0743 mol -0.0743 mol 0

[Na1+]
0 + 0.0743 mol 0.0743 mol

[NO21-]
0 + 0.0743mol 0.0743 mol

pH = pKa + log ([A-]/[HA]) pH = 3.35 + log(0.0743 mol/0.0665 L ÷ 0.0757 mol/0.0665 L) pH = 3.34 c. HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O 50.0 mL HNO2 × 1L/1000mL × 0.300 M = 0.0150 mol HNO2 32.0 mL NaOH × 1L/1000mL × 0.450 M = 0.0144 mol NaOH 0.015 mol – 0.014 mol = 0.001 mol HNO2 left after reaction 50.0mL + 32.0mL = 82.0 mL or 0.0820 L HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O
[HNO2]
Initial Change Equilibrium 0.0150 mol -0.0144 mol 0.0006 mol

[NaOH]
0.0144 mol -0.0144 mol 0

[Na1+]
0 + 0.0144 mol 0.0144 mol

[NO21-]
0 + 0.0144 mol 0.0144 mol

136

Appendix G

pH = pKa + log ([A-]/[HA]) pH = 3.35 + log(0.0144 mol/0.0820 L ÷ 0.0006 mol/0.0820 L) pH = 4.73 d. HNO2(aq) + NaOH(aq) Na+(aq) + NO2-(aq) + H2O 50.0 mL HNO2 × 1L/1000mL × 0.300 M = 0.0150 mol HNO2 33.3 mL NaOH × 1L/1000mL × 0.450 M = 0.0150 mol NaOH 0.0150 mol – 0.0150 mol = 0.00 mol HNO2 left after reaction 50.0mL + 33.3mL = 83.3 mL or 0.0833 L HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O
[HNO2]
Initial Change Equilibrium 0.0150 mol 0.0150 mol 0

[NaOH]
0.0150 mol 0.0150 mol 0

[Na1+]
0 + 0.0150 mol 0.0150 mol

[NO21-]
0 + 0.0150 mol 0.0150 mol

0.0150 mol NO21- = 0.180 M 0.0833 L NO2- is the conjugate base of a weak acid so pKa + pKb = 14.0 pKb = 14.0 – 3.35 = 10.65 NO2- (aq) + H2O (l)  OH- (aq) + HNO2(aq)
[NO2-] Initial Change Equilibrium 0.180M -x 0.180M-x [H2O] [OH -] 0 +x x [HNO2] 0 +x x

pKb = -log(Kb)

Kb = 2.24 × 10-11

[OH− ][HNO 2 ] KKb = = 2.24 X 10−11 b [NO 2 ] x2 = (0.180M) × 2.24 × 10-11 x = 2.01 ×10-6 = [OH-] pOH = -log[OH-] pOH = 5.697 14 - pOH = pH

pH = 8.303

e. HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O 50.0 mL HNO2 × 1L/1000mL × 0.300 M = 0.0150 mol HNO2 35.0 mL NaOH × 1L/1000mL × 0.450 M = 0.0158 mol NaOH
137

0225 mol 0.0008 mol [Na1+] 0 + 0.0075M) pOH = 2.0 mL or 0.0158 mol – 0.SPECIAL FOCuS: Acids and Bases 0.0075 mol NaOH left after reaction 50.0150 mol 0.0008 mol NaOH left after reaction 50.0 mL NaOH × 1L/1000mL × 0.0 mL + 35.0150 mol Here the concentration of NaOH controls the pH since it is a strong base.300 M = 0.0150 mol 0. HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O 50.0mL = 100.0075 mol [Na1+] 0 + 0.450 M = 0.0150 mol 0 [NaOH] 0.0150 mol 0 [NaOH] 0. pOH = -log[OH-] pOH = -log(0.0150 mol 0.0158mol 0.0 mL HNO2 × 1L/1000mL × 0.0150 mol 0.125 pH + pOH = 14 pH = 14 – pOH pH = 11.0mL + 50.0150 mol = 0.0150 mol [NO21-] 0 + 0.0150 mol 0.0850 L HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O [HNO2] Initial Change Equilibrium 0.0225 mol NaOH 0.0 mL = 85.0150 mol 0.0 mL or 0.0150 mol 0. pOH = -log[OH-] pOH = -log(0.0150 mol HNO2 50.0150 mol = 0.0150 mol Here the concentration of NaOH controls the pH since it is a strong base.0150 mol 0.0225 mol – 0.0008 M) pOH = 3 pH + pOH = 14 pH = 14 – pOH pH = 11 f.875 Indicators and Titrations Common indicators used in acid base titrations are: • • • phenolphthalein (clear to pink pH = 8-10) bromothymol blue (yellow to blue pH = 6-8) universal indicator (red to purple pH = 1-13) To prepare a buffer with a specific pH (part of pre-lab discussion) pH = pKa + log pK a 138 [ A− ] [HA] .1000 L HNO2(aq) + NaOH(aq)  Na+(aq) + NO2-(aq) + H2O [HNO2] Initial Change Equilibrium 0.0150 mol [NO21-] 0 + 0.

When a salt is added to water at first.0 pK a 6.0 X 10-7 6.26 10 = [HA] [ A− ] 0.0 = 4.1 M. you would choose HOAc and NaOAc since the pKa of HOAc is closest to 6. for a buffer with a pH of 6.8 X 10-5 ) + log 6. 139 .2 X 10-2 H2SO4 Large So if I am not mistaken. Solubility Equilibria When solids dissolve to form aqueous solutions.74 + log [ A− ] [HA] [ A− ] −1. BaCO3 (s) ↔ Ba2+ (aq) + CO32.0 = pKa + log [ A− ] [HA] Their Ka values 1.3 X 10-7 HSO411.Appendix G 6.(aq) Ksp = [Ba2+] [CO32-] = 1. then as the water molecules collide with the salt and the intermolecular forces interact with the water. the formula units of the salt begin to dissolve.3 X 10-3 H2CO3 4. none is dissolved. 6.0055M.6 X 10-9 Why is the BaCO3 not included in the K sp expression? Barium carbonate is a solid and solids are not found in equilibrium expressions.0 = p(1.055 = [HA] 1. then [A-] = 0.2 X 10-8 5.2 X 10-2 4. the equilibrium involved is the solubility equilibria.8 X 10-5 H3PO4 7.5 X 10-2 HOAc 1.8 X 10-13 Acids to choose from: H2SO3 1. the maximum amount of solid that can dissolve at that particular temperature does dissolve and equilibrium is reached.6 X 10-11 1. Eventually.26 = log [ A− ] [HA] [ A− ] [HA] If [HA] = 0.

that solubility and the solubility product are not the same. Calculating Ksp from solubility PbSO4 has a measured solubility of 1. based on what we have learned from solubility rules. . the less soluble it is.Notice that the K value is very small. however.14 × 10-4)2 Ksp = 1. generally reducing the amount that dissolves by providing an initial concentration of one of the ions.14 X 10-4 mol/L What is the Ksp of PbSO4? PbSO4(s)  Pb2+(aq) + SO42-(aq) Ksp = [Pb2+][SO42-] Ksp = (x)(x) Ksp = (1. The smaller the Ksp. RICE diagrams are very useful in demonstrating this effect. The solubility product is a constant value for a particular temperature (usually room temperature when you look it up on a chart). Ksp problems are much like Ka and Kb problems. then their Ksp values can be used to determine their solubilities relative to each other. Do realize. If the salts produce different numbers of ions when they dissolve.30 × 10-8 Calculating solubility from Ksp Al(OH)3 has a Ksp of 2 X 10-32 at 25°C Al(OH)3(s)  Al3+(aq) + 3OH-(aq) Ksp = [Al3+][OH-]3 2 X 10-32 = (x)(3x)3 x = 5 × 10-9 M Relative Solubilities If salts produce the same number of ions when they dissolve. then you have to calculate the solubilities from the Ksp values. Solubility is a position that changes with temperature and the concentration of common ions present in the solution. The Common Ion Effect on Solubility A common ion affects the solubility of a solid. We would expect this since barium carbonate is not considered soluble in water. as in the previous example.

20 +x 0. Ag2SO4 (s)  2Ag1+(aq) + SO42-(aq) Ksp = [Ag1+]2[SO42-] The K2SO4 solution contributes 0. selective precipitation.9 × 10-3 M [Ag1+] = 2x = 7.20 M of SO42[Ag1+] Initial Change Equilibrium 0 +2x 2x [SO42-] 0. Read about it if you have time. otherwise.20 M solution of potassium sulfate.2 × 10-5.7 × 10-3 M The rest of Chapter 15 discusses qualitative analysis.20 + x 1. Calculate the solubility of silver sulfate in a 0. 141 .20 + x) x = 3. and complex ion equilibria—topics that generally receive very little attention on the AP Exam.2 × 10-5 = (2x)2(0.Appendix G Example 3 The Ksp of silver sulfate is 1. we will come back to it after all the other AP material has been covered or after the AP Exam.

.

Appendix H Study Guides and Worksheets Chapter 14 Answer the following questions. Water is amphoteric. Make a chart comparing the definitions of an acid and a base according to the Arrhenius concept. how do you determine the number of significant digits in your answer? 11. basic solutions. How does calculating the pH of a strong acid differ from calculating the pH of a weak acid? 12. Give examples of salts that produce acidic solutions. What is a diprotic acid? Give an example. and neutral solutions. Why? Read through the In-Class Discussion Questions. and the Lewis acid–base model. Hydrofluoric acid is the only weak acid consisting of a halogen. What is Ka? 5. Due date: 1. What does that mean? 9. What is a conjugate acid–base pair? Give an example. in order. the Bronsted-Lowry model. What is Kw? What is its value at 25 °C? 10. . 7. When calculating pH from [H+]. 15. Organic acids are generally strong or weak? Why? 8. How do you calculate the pH of a strong base? 14. 2. What is a hydronium ion? 3. 4. on notebook paper. They may be used for warm-ups. How do you calculate percent dissociation? 13. What is the difference between a strong and weak acid? 6.

What is qualitative analysis? 14. from pages 712–717. 95–96. 18–19. 115–118. 89. 71–72. 51–53. What is a buffered solution? What does it do? What substance in our body is considered a buffered solution? 4. and 153) Chapter 15 Answer the following questions. 103–04. 69. 21–23. and 123) 144 . When dealing with a strong acid or strong base being added to a buffer. 31–32. 88. 49–54. 109–10. what do you do before setting up the ICE chart? 5. What is the common ion effect? 10. What is the Henderson-Hasselbalch equation? When can you use it? 6. 55. 97–99. 119–121. How do common ions affect equilibrium? 3. 37–38. What is the ion product? How is it related to Ksp and precipitation? 12. 106. in order. Draw the pH curves for a strong acid/strong base titration. in order. (13–14.SPECIAL FOCuS: Acids and Bases Complete the following problems. (19. 81. 129. 84–85. 123. How are pH and solubility related? 11. 43–46. 92. What is a ligand? Read through the In-Class Discussion Questions. in order. 61. 138. 23–24. 29. a weak acid– strong base titration. What is selective precipitation and what is it used for? 13. 64. 142–143. What is a common ion? 2. 79–82. 8. 33 –36. What is the solubility product? 9. 40. Due date: 1. from pages 781–789. 63. What is buffer capacity and how is it calculated? 7. They may be used for warm-ups. on notebook paper. and a weak base–strong acid titration. What is a complex ion? 15. 27. 61. 57–60. Complete the following problems.

Calculate the molarity of the vinegar solution.00 mL sample of vinegar (acetic acid solution) with 38. barium hydroxide and sulfuric acid b. and the [H3O+]? 3. Write and balance the chemical equation for the reaction between: a. the [H3O+]. How many mL of 1. aluminum hydroxide and nitric acid c.50 M phosphoric acid? 6. d. What are the pOH. Write and balance the chemical equation for the reaction.50M magnesium hydroxide are necessary to titrate 25. The approximate pH of oranges is 3.39 3. b. c. Reactions. a.23 X 10 -2 M 8. Complete the following table.25 mL of 0.020 M acetic acid solution? 7. The approximate pOH of tomatoes is 9. and the [OH-]? 4.0 mL is neutralized by 7. the [OH-].0 mL of 2. How many grams of acetic acid would be in 1. phosphoric acid and potassium hydroxide 5. What are the pH. [H3O+] 7.5. and Titration Calculation Review Worksheet 1. A student reacted a 25.5 mL of a 0.89 X 10 -7 M 10. Show all work on a separate sheet of paper.500 M sodium hydroxide.3 9.19 X 10 -10 M [OH-] pH pOH 2. What is the molarity of a lithium hydroxide solution if 15.00 g/mL)? 145 .00 L of the vinegar? What is the percent by mass of acetic acid in the vinegar solution (assume a density of 1.Appendix H Acid–Bases.99 X 10 -5 M 1.8.

39 4. The approximate pOH of tomatoes is 9.5.19 X 10 -10 3.38 × 10 -13M 8. the [OH-].SPECIAL FOCuS: Acids and Bases Acid–Bases. phosphoric acid and potassium hydroxide H3PO4 + 3KOH → K3PO4 + 3H2O 5.399 4.5mL Mg(OH)2 146 . How many mL of 1. What are the pH.949 10. Show all work on a separate sheet of paper.38 × 10 -13M 1. [H+] =3 × 10-4M 3.50 mol H3PO4 × 3 mol Mg(OH)2 × 1L Mg(OH)2 × 1000mLMg(OH)2 11000mL H3PO4 1L H3PO4 2 mol H3PO4 1. pOH = 10.38 × 10 -13M 1.61 9.38 × 10 M -13 2. [OH-] = 2 × 10-10M 4.0 mL H3PO4 × 1 L H3PO4 × 2.8. and Titration Calculation Review Worksheet— Teacher’s Edition 1.23 X 10 -2 M 1. pH = 4.924 pOH 12.141 7.40 × 10 M -5 M 2.0 mL of 2.50 M phosphoric acid? 3Mg(OH)2 + 2H3PO4 → Mg3(PO4)2 + 6H2O 25. Reactions.2 b. barium hydroxide and sulfuric acid Ba(OH)2 + H2SO4 → BaSO4 + 2H2O b.51 × 10 -10M 1.50 mol Mg(OH)2 1L Mg(OH)2 = 62.89 X 10 M -7 pH 1. and the [OH-]? a. [H+] 7.50M magnesium hydroxide are necessary to completely titrate 25.12 × 10 M -8 [OH-] 1. aluminum hydroxide and nitric acid Al(OH)3 + 3HNO3 → Al(NO3)3 + 3H2O c. Complete the following table.7 9. the [H+]. and the [H+]? a.38 × 10 M -13 1.859 6.99 X 10 -5 M 8.051 3. Write and balance the chemical equation for the complete reaction between: a. What are the pOH.076 1.5 b. The approximate pH of oranges is 3.3 4. [H+] = 6× 10-5M c. [OH-]=3 × 10-11M c.601 9.

Appendix H

6. What is the molarity of a lithium hydroxide solution if 15.0 mL is completely titrated by 7.5 mL of a 0.020 M acetic acid solution? LiOH + HC2H3O2 → LiC2H3O2 + H2O
7.5 mL HC2H3O2 × 0.020 mmol HC2H3O2 × 1 mmol LiOH × 1 1mL HC2H3O2 1mmol HC2H3O2 1 = 0.010M LiOH 15.0 mL LiOH

7. A student reacted a 25.00 mL sample of vinegar (acetic acid solution) with 38.25 mL of 0.500 M sodium hydroxide. a. Write and balance the chemical equation for the reaction. HC2H3O2 (aq)+ NaOH(aq)→ NaC2H3O2 (aq) + H2O b. Calculate the molarity of the vinegar solution.
38.25 mL NaOH × 1mL NaOH 0.500 mmol NaOH 1mmol NaOH × 1 mmol HC2H3O2 25.00 mL HC2H3O2 × 1 1 = 0.765M HC2H3O2

c. How many grams of acetic acid would be in 1.00 L of the vinegar?
1.00 L HC2H3O2 1 × 0.765M HC2H3O2 1L HC2H3O2 × 60.05 g HC2H3O2 1mol HC2H3O2 = 45.9 g HC2H3O2

d. What is the percent by mass of acetic acid in the vinegar solution (assume a density of 1.00 g/mL)?
45.9 g HC2H3O2 1L HC2H3O2 × 1L HC2H3O2 × 1000mL HC2H3O2 1 mL HC2H3O2 1.00 g HC2H3O2 × 100 = 4.59% HC2H3O2

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Appendix I Dissociation and pH Practice
Weak Acid or Weak Base Systems
The ionization constant (or equilibrium constant) is very important here. Only ions contribute. Water, which is usually the solvent, does not participate in any major way here. The general form for a reaction containing an acid is: HA + 2H2O ↔ H3O+ + A- so: Ka = HA is an acid because it begins with hydrogen or because it donates a proton to form H3O+. The A- is the element or polyatomic ion portion of the acid with a negative charge. Write the Ka for the dissociation of chlorous acid, HClO2, and formic acid, HCOOH. Ka = Ka =

Weak polyprotic acids dissociate (break apart) stepwise. Each step is written as a different reaction. Generally there is a different value for K a each time an acid loses a hydrogen ion. H3PO4 + H2O ↔H3O+ + H2PO41H2PO41- + H2O ↔ H3O+ + HPO42HPO42- + H2O ↔ H3O+ + PO43Ka1 = Ka2 = Ka3 =

Examples:
Write the dissociation reactions for sulfuric acid and carbonic acid. H2SO4 H2CO3

This also holds true for weak bases like ammonia.

Ka or Kb. Solve for the concentrations.75 X 10-5 1) NH3 (aq) + H2O (l) ↔ NH41+ (aq) + OH1.SPECIAL FOCuS: Acids and Bases Write the K b for NH3 + H2O ↔ NH4+ + OHKb = Steps for calculating the pH of a weak acid or base: 1) 2) 3) 4) 5) 6) Write and balance the equation if it is not already done for you. Determine the equilibrium expression.(aq) 2) Kb = 3) NH3 Initial Change Equilibrium NH41+ OH1- 4) Kb = 5) pOH = -log[OH1-] pH + pOH = 14 150 .00M acetic acid solution with a K a = 1.500M ammonia solution with a K b = 1.(aq) 2) Ka = 3) HC2H3O2 Initial Change Equilibrium H3O1+ C2H3O21- 4) Ka = 5) pH = -log[H3O1+] Try this one: Calculate the pH of a 0. Develop the ICE table. Substitute the final values into the equilibrium expression.8 X 10-5 1) HC2H3O2 (aq) + H2O (l) ↔ H3O1+ (aq) + C2H3O21. Solve for pH or pOH based on the [H+] or [OH-]. Calculate the pH of a 1.

+ H2O ↔ H3O+ + PO43Ka1 = [H3O+][ H2PO4-] [H3PO4] Ka2 = [H3O+][ HPO42-] [H2PO4-] Ka3 = [H3O+][ PO43-] [HPO42-] . Write the Ka for the dissociation of chlorous acid. HCOOH. The general form for a reaction containing an acid is: HA + 2H2O ↔ H3O+ + A. does not participate in any major way here. HClO2. which is usually the solvent. H3PO4 + H2O ↔ H3O+ + H2PO4H2PO4. Water. and formic acid.is the element or polyatomic ion portion of the acid with a negative charge.Appendix J Dissociation and pH Practice—Teacher’s Edition Weak Acid or Weak Base Systems The ionization constant (or equilibrium constant) is very important here. Each step is written as a different reaction. The A.so: Ka = [H3O+][A-] [HA] HA is an acid because it begins with hydrogen or because it donates a proton to form H3O+. Only ions contribute. Ka = [H+][ClO2-] Ka = [H+][COOH-] [HClO2] [HCOOH] Polyprotic acids dissociate (break apart) stepwise.+ H2O ↔ H3O+ + HPO42HPO42. Generally there is a different value for Ka each time an acid loses a hydrogen ion.

8 X 10-5 1) HC2H3O2 (aq) + H2O (l) ↔ H3O+ (aq) + C2H3O2.00 M . Determine the equilibrium expression.+ H2O ↔ H3O+ + SO42HCO3.00M acetic acid solution with a K a = 1. H2SO4 H2CO3 H2SO4 + H2O ↔ H3O+ + HSO4H2CO3 + H2O ↔ H3O+ + HCO3HSO4. Ka or Kb.SPECIAL FOCuS: Acids and Bases Practice Write the dissociation reactions for sulfuric acid and carbonic acid. Substitute the final values into the equilibrium expression.500M ammonia solution with a K b = 1.00 M -x 1.8×10-5 [1.x [H3O+][C2H3O2-] [HC2H3O2] [H+] 0 +x x [C2H3O2-] 0 +x x 4) Ka = [x][x] = 1. Examples: Calculate the pH of a 1.+ H2O ↔ H3O+ + CO32Equilibrium expressions also can be written for weak bases like ammonia. Develop the ICE table.00-x] 5) x = 4. Solve for pH or pOH based on the [H+] or [OH-].75 X 10-5 152 . Write the Kb for NH3 + H2O ↔ NH4+ + OHKb = [NH4+][OH-] [NH3] Steps for calculating the pH of a weak acid or base: 1) 2) 3) 4) 5) 6) Write and balance the equation if it is not already done for you.87 Calculate the pH of a 0. Solve for the concentrations.(aq) 2) Ka = 3) [HC2H3O2] Initial Change Equilibrium 1.2×10-3M = [H+] 6) pH = -log[H+] = 2.

96×10-3M = [OH-] 6) pOH = -log[OH-] pOH = 2.75×10-5 5) x = 2.529 pH + pOH = 14 pH = 14 – pOH pH = 11.500-x] = 1.(aq) 2) K b = [NH4+][OH-] [NH3] 3.471 153 .500-x [NH4+] 0 +x x [OH-] 0 +x x 4) Kb = [x][x] [0.Appendix J 1.) [NH3] Initial Change Equilibrium 0.500 M -x 0.) NH3 (aq) + H2O (l) ↔ NH4+ (aq) + OH.

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0 red-orange 4.Appendix K Lab: Determining the pH of a Substance Introduction Many classification systems for compounds exist.6 8.8-6. To estimate the pH of some common household products using these reactions. .0 orange 5. 2.0 blue-green 9.0 violet Objectives 1. The use of an indicator.0 yellow 6.2-7.5 6.0 green 8.0 Bromothymol blue Phenolphthalein Universal indicator: changes colors at different pH values as follows 3.0-7.0 green-yellow 7. a weak organic acid that changes colors. Different indicators work in different pH ranges. To observe typical reactions of several indicators when treated with acids and bases. is another way to measure the hydrogen ion concentration. One way to classify substances is based on the relative amount of acid present. The pH scale was developed to measure the amount of hydrogen ions present in a solution. Use the following table as a reference: Indicators Methyl red Litmus Color at a bottom of range Red Red Yellow Clear Color at top of range Yellow Blue Blue Pink pH range 4.0 blue-gray 10. An acid produces hydrogen ions in an aqueous solution according to the Arrhenius concept.0-10.0 5.

Part 2: 1. Record in the data table. 3. Add 1–3 drops of each product across a row in wells according to data table 2. 5. Add 1 drop of indicator down the wells according to data table 2. Record the colors observed for each reaction in the data table. Add 1–3 drops of each standard across a row in wells according to data table 1. 2. 2. Obtain a set of standard solutions and a set of indicators. 4. 6. Record the pH value in the data table. Rinse out the spot plate with deionized water. Obtain a set of household products. Part 3: (To be done after you estimate the pH of each household substance based on the indicator colors. Submerge the probe tip in a small amount of the first solution to be measured. 3. Go to a station set up for measuring the pH of the products. Estimate the pH of each solution. Record in the data table. 156 . 5. 4.SPECIAL FOCuS: Acids and Bases Procedure Part 1: 1.) 1. Repeat steps 3–5 with each household product to be tested. 3. Rinse out the spot plate with deionized water. Add 1 drop of indicator down the wells according to data table 1. 2. Rinse the probe thoroughly with deionized water. 6. 5. 6. 4. Estimate the pH of each solution. Follow the directions for calibrating your pH probe. Record the colors observed for each reaction in the data table.

1 M NaOH Data Table 2: Product aspirin bleach detergent eggs lemon juice milk milk of magnesia clear soft drink tea Methyl Red Litmus Indicator Bromthymol Blue Phenolphthalein universal Indicator Estimated pH 157 .1 M acetic acid distilled water 0.1 M NH3 (ammonia) 0.Appendix K Data Table 1: Standard Solution 0.1 M HCl Methyl Red Litmus Indicator Bromthymol Blue Phenolphthalein universal Indicator Estimated pH 0.

Where they as you expected? Does one indicator work better than another? If so. Based on your observations. find the strengths of the listed acids and bases. Conclusions Describe your results. how does the estimated pH of ammonia compare to the estimated pH of sodium hydroxide? 3. or even in an office. your home.SPECIAL FOCuS: Acids and Bases Analysis: 1. how does the estimated pH of the hydrochloric acid compare to the estimated pH of the acetic acid? 2. which one and in what cases? 158 . Indicators also can come from objects found in nature. Based on your observations. Using your textbook. How does your estimated pH values compare to the rankings of these substances? 4. Locate one such indicator through research and explain how you could tell the difference between an acid and a base using this indicator.

what would you expect to happen as you add 10.0 mL of hydrochloric acid in a beaker.0 mL of NaOH? 20. add a couple drops of methyl red and a couple drops of phenolphthalein. which one(s)? Why do you think this might have been the case? If you start with 15.Appendix K Was it difficult to determine the color of the indicator in any particular substance? If so.0 mL of NaOH? 159 .0 mL of sodium hydroxide? 15.

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and Question Leader at the AP Chemistry Exam Reading. For the last 16 years he has taught AP Chemistry at independent schools across the country. Table Leader. Puerto Rico. She has served as a Reader and Table Leader for the AP Chemistry Examination. Valerie Ferguson teaches AP Chemistry at Moore High School in Moore. and is a National Leader for the College Board. She has been a Reader and Table Leader for the AP Chemistry Examination. Francis School in Louisville.About the Editor Marian DeWane teaches AP Chemistry at Centennial High School in Boise. He is a consultant for the College Board and serves on the ACS Exams Institute Advanced High School Committee. president of the Oklahoma Science Teachers Organization. John’s School in San Juan. She has been teaching AP Chemistry since 1983. She also works as a consultant for the College Board and teaches Summer Institutes for AP Chemistry teachers. She has also served as a consultant for the College Board. and has been a member of the Woodrow Wilson Foundation Teacher Outreach Program and a Dreyfus Master Teacher. and Presidential Scholar Teacher. Smith has contributed to numerous 161 . conducting AP workshops worldwide. She has served as chair of the Oklahoma ACS. Adele Mouakad is an award-winning teacher at St. About the Authors Lew Acampora currently teaches AP Chemistry at the St. She has a long list of accomplishments including Teacher of the Year. National Board Certification in Chemistry. She has won the Presidential Award for Excellence in Science Teaching. British Colombia in Canada. he has served as a Reader. Since 1995. She also serves on the ACS Exams Institute Advanced High School Committee and National Chemistry Olympiad Task Force. Oklahoma. Idaho. and was co-organizer of the Teaching AP Chemistry symposium at the 14th Biennial Conference on Chemistry Education. Cheri Smith is an award-winning teacher of AP Chemistry at Yale Secondary School in Abbotsford. She is currently a Question Leader for the AP Chemistry Examination and has also served as a Reader and Table Leader. She has also been a Reader for the AP Chemistry Examination and a member of the National Chemistry Olympiad Task Force. Kentucky.

D. and Question Leader for AP Chemistry over a period of 20 years. Table Leader. Austin State University in 1991 and is currently attending the University of North Texas in pursuit of a Ph. Arden Zipp is a distinguished faculty member at State University of New York College at Cortland in Cortland. but has been taking a break to raise Arabian horses and most recently attend graduate school in her spare time. He has served in every capacity for the College Board in the development and scoring of the AP Examination: He has been a Reader. Guyer High School in Denton. She has been teaching AP Chemistry and/or AP Environmental Science since 2000 and has been an AP Chemistry Reader since 2005.publications and served as a reviewer for the AP Vertical Teams® Guide for Science and the Pre-AP®: Topics for Vertical Teams in Science workshop. He has been a Reader.and weeklong workshops for AP and general chemistry teachers. Chief Reader. New York. . Questions Leader. Texas. and pre-AP physics at John H. Miller is a senior lecturer emeritus in the Chemistry department at the University of California Irvine. He is also involved in the development and scoring of the IB Chemistry Program. and instrumental analysis. He has more than 60 publications in analytical chemistry and in science education. He was member and chair of the AP Chemistry Development Committee and a member of the College Board Subject Test in Chemistry Committee. Heather Hattori teaches AP Chemistry. and has presented both day. analytical chemistry. Hattori received her bachelor’s degree in chemistry and English from Stephen F. in chemistry. and has taught freshman chemistry. AP Environmental Science. and is chair of the National Chemistry Olympiad Examination Task Force. He has been on the chemistry faculty at UCI since 1965. and Development Committee member and chair. pre-AP chemistry. where he is also principal scientist and supervisor of the nuclear reactor facility and responsible for K–12 science teacher professional development. Table Leader. George E. radiochemistry. Hattori was a College Board consultant in the mid-90s.

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