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Chapter 21

Neutralization
21.1 Neutralization
Lesson Objectives
The student will:

explain what is meant by a neutralization reaction and give an example of one.


write a balanced equation for the reaction that occurs when an acid reacts with a base.
describe the formation of a salt in terms of the Arrhenius denitions of acids and bases.
predict the salt that will be produced from the neutralization reaction between a given acid and base.
identify acidic, basic, and neutral salts from a neutralization reaction.

Vocabulary

acidic salt
basic salt
neutral salt
neutralization

Introduction
Neutralization is a reaction between an acid and a base that produces water and a salt. The general
reaction is shown below:
acid + base salt + water
After reviewing the concept of ionic compounds, we will examine neutralization reactions and look at the
dierent types of salts that can be formed from acids and bases as they react with one another.

Neutralization Reactions
Acids are a combination of a hydrogen cation and a nonmetal anion. Examples include HCl, HNO3 , and
HC2 H3 O2 . Many bases are a combination of metal cations and nonmetal anions. Examples include NaOH,

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KOH, and Mg(OH)2 . According to the Arrhenius denitions of acids and bases, the acid will contribute
an H+ ion that will react to neutralize the OH ion contributed by the base, producing neutral water
molecules.
All acid-base reactions produce salts. The anion from the acid will combine with the cation from the base
to form the ionic salt. Examples are shown below.
HClO4(aq) + NaOH(aq) NaClO4(aq) + HOH(l)
H2 SO4(aq) + 2KOH(aq) K2 SO4(aq) + 2HOH(l)
(Note: HOH = H2 O)
No matter what the acid or the base may be, the products of this type of reaction will always be a salt
and water. Aside from the fact that the H+ ion will neutralize the OH ion to form water, we also know
that these reactions are double displacement reactions, because they consist of cations exchanging anions.
We can write this as a total ionic equation:
+ ClO4(aq) + H2 O(l)
H+
+ ClO4(aq) + Na+
+ OH(aq) Na+
(aq)
(aq)
(aq)
However, since Na+ and ClO4 are spectator ions, the net ionic equation is:
H+
+ OH(aq) H2 O(l)
(aq)
This is the net ionic equation for all neutralization reactions.

Salt Hydrolysis
When a salt is dissolved in water, it is possible for the solution to be neutral, acidic, or basic. If a solution
is to be acidic, it must contain more hydrogen ions than hydroxide ions. For the solution to be basic, it
must contain more hydroxide ions than hydrogen ions. Consider the solution produced when the salt KBr
dissolves in water. There will be four ions present in the solution.
K+ + Br + H+ + OH
When potassium ions in the solution come into contact with hydroxide ions, the KOH ion pair could
potentially form. However, since KOH is a strong base, it would immediately dissociate back into ions.
Similarly, if the bromide ions come into contact with hydrogen ions, the molecule formed would be HBr,
a strong acid, so they would immediately dissociate back into ions. Thus, having potassium and bromide
ions in a water solution would not cause a reaction.
Now consider the solution produced when the salt NH4 Cl is dissolved in water. There will be four ions
present in the solution.

+
NH+
4 + Cl + H + OH

When hydrogen ions come into contact with chloride ions, if they join together, the resultant molecule
would be HCl, which is a strong acid. Therefore, the HCl would immediately dissociate back into the ions.

When NH+
4 ions come into contact with OH ions, however, the resultant molecule would be NH4 OH,
which is a weak base and does not dissociate very much. Therefore, when ammonium chloride is dissolved
in water, a reaction occurs.
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+
+
NH+
4 + Cl + H + OH NH4 OH(aq) + Cl + H

The ammonium hydroxide dissociates very little, so we would have mostly un-dissociated ammonium
hydroxide molecules in solution with hydrogen and chloride ions. The hydrogen ions in this nal solution
would cause the solution to be acidic. Thus, dissolving ammonium chloride in water produces an acidic
solution.
By a similar process, dissolving sodium acetate, NaC2 H3 O2 , in water will produce a basic solution. When
the sodium acetate is dissolved in water, four ions will be present in the solution.
Na+ + C2 H3 O2 + H+ + OH
If sodium ions contact hydroxide ions, the substance formed would be a strong base which would immediately dissociate. If hydrogen ions contact acetate ions, however, the molecule formed would be acetic acid,
which is a weak acid and the ions would NOT dissociate. Therefore, when sodium acetate is dissolved in
water, a reaction will occur as shown below.
Na+ + C2 H3 O2 + H+ + OH HC2 H3 O2(aq) + Na+ + OH
The resultant solution has excess of hydroxide ions, so it is basic. Dissolving sodium acetate in water
produces a basic solution.

Neutral, Acidic, and Basic Salts


Table 21.1 shows all of the strong acids and bases that we have encountered so far. You can assume that
any other acids and bases we will look at are weak.
Table 21.1: Strong Acids and Bases
Strong Acid

Formula

Strong Base

Formula

Hydrochloric Acid
Hydrobromic Acid
Hydroiodic Acid
Nitric Acid
Perchloric Acid
Sulfuric Acid

HCl
HBr
HI
HNO3
HClO4
H2 SO4

Lithium Hydroxide
Sodium Hydroxide
Potassium Hydroxide
Rubidium Hydroxide
Cesium Hydroxide
Calcium Hydroxide
Strontium Hydroxide
Barium Hydroxide

LiOH
NaOH
KOH
RbOH
CsOH
Ca(OH)2
Sr(OH)2
Ba(OH)2

The information in the table helps us to determine what type of salt is formed in an acid-base reaction.
For example, a reaction between a strong acid and a strong base will form a neutral salt. It is like a
power struggle between the acid and the base. Since both are strong, neither overpower the other, so the
salt ends up being neutral. If, however, we have a reaction between a weak acid and a strong base, the
result would be a basic salt.
HC2 H3 O2(aq) + NaOH(aq) NaC2 H3 O2(aq) + H2 O(l)
Acetic acid is a weak acid and sodium hydroxide is a strong base. Therefore, the salt formed, sodium

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acetate, is a basic salt.


When the basic salt is dissolved in water, a reaction takes places in which extra hydroxide ions, OH , are
produced from the salt and the water molecules. A similar situation will occur when we have a strong acid
reacting with a weak base. When a strong acid reacts with a weak base, an acidic salt is formed.
HCl(aq) + NH4 OH(aq) NH4 Cl(aq) + H2 O(l)
Hydrochloric acid is a strong acid and ammonium hydroxide is a weak base. Therefore, the salt formed,
ammonium chloride, is an acidic salt. The salt will react with water molecules to produce hydrogen ions,
H+ , so it is referred to as an acidic salt.
Example:
Complete the following neutralization reactions and identify the type of salt produced.
1. H2 SO4 + Ba(OH)2 ?
2. HCOOH + Ca(OH)2 ?
Solution:
1. H2 SO4 + Ba(OH)2 BaSO4 + 2 H2 O; A strong acid reacts with a strong base and produces a neutral
salt.
2. 2 HCOOH + Ca(OH)2 Ca(HCOO)2 + 2 H2 O; A weak acid reacts with a strong base and produces
a basic salt.
By determining which acid and base were used to form the salt, you can gure out if the salt is acidic,
basic, or neutral. For example, lets say you are looking at calcium nitrate, Ca(NO3 )2 . Remember that
there is a double displacement reaction that forms the salt, so we can write out the reaction:

Therefore, the neutralization reaction would have been:


2 HNO3 + Ca(OH)2 Ca(NO3 )2 + 2 HOH
This salt would have been produced from a strong acid-strong base reaction, so it is neutral.
Lets try another. Consider the salt copper(II) chloride (CuCl2 ).
The copper would have come from the base, Cu(OH)2 , which is a weak base. The chloride would have
come from the acid, HCl, which is a strong acid.
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2 HCl + Cu(OH)2 CuCl2 + 2 HOH


The reaction is a strong acid weak base reaction, so the salt should be acidic.

This video is an overview of endothermic and exothermic reactions and includes a demonstration of an
exothermic reaction (7b): http://www.youtube.com/watch?v=sAyPDTQHEeE (2:31).

Figure 21.1: (Watch Youtube Video)


http://www.ck12.org/exbook/embed/view/413

Lesson Summary
A neutralization reaction between an acid and a base will produce a salt and water.
In a neutralization reaction, the acid will produce H+ ions that react to neutralize the OH- ions
produced by the base, forming neutral water. The other product will be an ionic salt.
A strong acid + a strong base in an acid/base neutralization reaction will form a neutral salt.
A strong acid + a weak base in an acid/base neutralization reaction will form an acidic salt.
A weak acid + a strong base in an acid/base neutralization reaction will form a basic salt.

Further Reading / Supplemental Links


The following link shows a video of a neutralization reaction.
http://www.youtube.com/watch?v=_P5hGzA6Vb0

Review Questions
1. How do an acid and a base t the denition of an ionic compound? Use examples in your answer.
2. Explain neutralization reactions in terms of Arrhenius theory. Use an example in your answer.
3. Which salt will form a basic solution when dissolved in water?
(a)
(b)
(c)
(d)

KNO3
CaCl2
NaClO4
NaNO2

4. Which salt will form an acidic solution when dissolved in water?


(a) copper(II) sulfate
(b) sodium acetate

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(c) potassium chloride


(d) sodium cyanide
5. Milk of magnesia is a common over-the-counter antacid that has magnesium hydroxide as its main
ingredient. It is used by the public to relieve acid indigestion. Acid indigestion is caused by excess
stomach acid being present. Write the balanced chemical equation for the reaction between milk of
magnesia and hydrochloric acid. What type of reaction is this? What type of salt is formed?
6. Complete the following neutralization reactions and identify the type of salt produced.
(a)
(b)
(c)
(d)
(e)

H2 SO4(aq) + NaOH(aq)
HNO3(aq) + NH4 OH(aq)
HF(aq) + NH4 OH(aq)
CH3 COOH(aq) + KOH(aq)
HCl(aq) + KOH(aq)

21.2 Titration
Lesson Objectives
The student will:

explain what an acid/base indicator is.


explain how acid-base indicators work.
explain the dierence between natural and synthetic indicators.
explain how indicators are used in the lab.
explain what a titration is.
describe how titrations can be used to determine the concentration of an acid or a base in solution.
explain the dierence between the equivalence point and the end point.
dene a standard solution in terms of acid-base titrations.
calculate the concentration of an acid or base solution using a standard solution.
calculate the concentration of unknown acid or base when given the concentration of the other and
the volume needed to reach the equivalence point in a titration.

Vocabulary

endpoint
equivalence point
natural indicator
standard solution
synthetic indicator
titrant
titration
titration curve

Introduction
The typical laboratory procedure for determining the concentration of acid and/or base in a solution is to
complete a titration. There are three main types of titration experiments. As we go through this lesson,
we will take apply the knowledge we have obtained about acids and bases, chemical reactions, and molarity
calculations to the concept of titrations.
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Indicators
Recall from the chapter on Acids-Bases that an indicator is a substance that changes color at a specic
pH and is used to indicate the pH of the solution. One example of an indicator is litmus paper. Litmus
paper is paper that has been dipped in a substance that will undergo a color change when it is exposed to
either an acid or a base. If red litmus paper turns blue, the solution is basic (pH > 7), and if blue litmus
turns red the solution is acidic (pH < 7).
A natural indicator is an indicator that is a naturally occurring substance. For example, the juice from
red cabbage can be used to prepare an indicator paper. It contains the chemical anthrocyanin, which is
the active ingredient in the indicator. Red beets, blueberries, and cranberries are other great examples
of naturally occurring indicators. These are all due to the same anthocyanin molecule found in the red
cabbage.
Some owers are also natural indicators. Hydrangea is a common garden plant with owers that come in
many colors, depending on the pH of the soil. A hydrangea plant with blue owers indicates that the soil
is acidic, while creamy white owers mean the soil is neutral and pink owers mean the soil is basic.

Figure 21.2: A hydrangea plant with blue owers. What does the ower color indicate about the pH of
the soil?

Synthetic indicators are compounds created in a chemistry lab rather than compounds found in nature.
Both naturally occurring indicators and synthetic indicators are weak organic acids or bases. For example, a
common synthetic indicator used in most chemistry laboratories is phenolphthalein. The chemical structure
of phenolphthalein is shown in the gure below.

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This indicator changes color at a pH of 8.2. Below 8.2 it is colorless, and above 8.2 it is bright pink. There
are many common synthetic indicators that are useful in the chemistry laboratory. When dealing with a
more acidic range, chemistry students may use methyl orange. The structure for methyl orange is shown
below.

Methyl orange changes color from pH 3.2 to 4.4. Below 3.2, the color of the indicator is red. Above 4.4,
the color of the indicator is yellow. In between 3.2 and 4.4, there are various shades of orange, hence the
name.
There are two requirements for a substance to function as an acid-base indicator: 1) the substance must
have an equilibrium aected by hydrogen ion concentration, and 2) the two forms of the compound on
opposite sides of the equilibrium must have dierent colors. Most indicators function in the same general
manner and can be presented by a generic indicator equation. In the equation below, we represent in the
indicator ion with a hydrogen ion attached as HIn, and we represent the indicator ion without the hydrogen
attached as In .

Since the indicator itself is a weak acid, the equilibrium between the protonated form and the anionic form
is controlled by the hydrogen ion concentration. For the example above, the protonated form is colored
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red and the anionic form is colored yellow. If we add hydrogen ion to the solution, the equilibrium will be
driven toward the reactants and the solution will turn red. If we add base to the solution (reduce hydrogen
ion concentration), the equilibrium will shift toward the products and the solution will turn yellow. It is
important to note that if this indicator changes color at pH = 5, then at all pH values less than 5, the
solution will be red and at all pH values greater than 5, the solution will be yellow. Therefore, putting this
indicator into a solution and having the solution turn yellow does NOT tell you the pH of the solution, it
only tells you that the pH is greater than 5. At pH values less than 5, the great majority of the indicator
molecules are in the red form and the solution will be red. At pH values greater than 5, the great majority
of the indicator particles will be in the yellow form and the solution will be yellow. The equilibrium between
these indicator particles is such that the particles will be 50% red form and 50% yellow form at exactly
pH = 5. Therefore, at pH = 5, the actual color of the solution will be a 50-50 mixture of red and yellow
particles and the solution will be orange, as demonstrated in the gure below.

Many indicators are available to help determine the pH of solutions. A list of the most common indicators is
found in Table 21.2, along with their respective color change pH valuess and corresponding color changes.
Table 21.2: Colors and pH Ranges for Common Indicators
Indicator

pH Range

Color Change

Methyl Violet
Thymol Blue
Orange IV
Methyl Orange
Bromophenol Blue
Congo Red
Bromocresol Green
Methyl Red
Litmus
Chlorophenol Red
Bromothymol Blue
Phenol Red
Thymol Blue
Phenolphthalein
Alizarin Yellow R
Methyl Blue
Indigo Carmine

0.0 1.6
1.2 2.8
1.3 3.0
3.2 4.4
3.0 4.7
3.0 5.0
3.8 5.4
4.8 6.0
5.0 8.0
4.8 6.2
6.0 7.6
6.4 8.2
8.0 9.6
8.2 10.0
10.1 12.0
10.6 13.4
11.4 13.0

Yellow - Blue
Red - Yellow
Red - Yellow
Red - Orange
Orange/Yellow - Violet
Blue - Red
Yellow - Blue
Red - Yellow
Red - Blue
Yellow - Red
Yellow - Blue
Yellow - Red/Violet
Yellow - Blue
Colorless - Pink
Yellow - Red
Blue - Pale Violet
Blue - Yellow

There are many more indicators than are shown in Table 21.2, but these are ones that you may nd in
common chemistry classroom laboratories. One example of an indicator not found in the table is known
as the universal indicator. The universal indicator is a solution that has a dierent color for each pH from
014. Universal indicator is produced by creatively mixing many of the individual indicators together so
that a dierent color is achieved for each dierent pH. It is used for many types of experiments to determine

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if solutions are acids or bases and where on the pH scale the substance belongs. The chart below indicates
the colors of universal indicator for dierent pH values.

Example:
If the pH of the solution is 4.8, what would be the color of the solution if the following indicators were
added?
1. Universal indicator
2. Bromocresol Green
3. Phenol red
Solution:
1. Universal indicator = Orange to orange-yellow
2. Bromocresol Green = green (midway pH = 4.6)
3. Phenol red = yellow
Example:
A solution found in the laboratory was tested with a number of indicators. These were the results:

Phenolphthalein was colorless


Bromocresol green was blue
Methyl red was yellow
Phenol red was yellow

What was the pH of the solution?


Solution:

Phenolphthalein was colorless, pH < 8.0


Bromocresol green was blue, pH > 5.4
Methyl red was yellow, pH > 6.0
Phenol red was yellow, pH < 6.4

Therefore, the pH of the solution must be between 6.0 and 6.4.

The Titration Process


One of the properties of acids and bases is that they neutralize each other. In the laboratory setting,
an experimental procedure where an acid is neutralized by a base (or vice versa) is known as titration.
Titration is the addition of a known concentration of base (or acid), also called the titrant, to a solution
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of acid (or base) of unknown concentration. Since both volumes of the acid and base are known, the
concentration of the unknown solution is then mathematically determined.
When doing a titration, you need to have a few pieces of equipment. A burette like the one shown below is
used to accurately dispense the volume of the solution of known concentration. An Erlenmeyer ask is used
to hold a known volume of the solution whose concentration is unknown. A few drops of the indicator are
added to the ask before you begin the titration. The endpoint is the point where the indicator changes
color, which tells us that the acid is neutralized by the base. The equivalence point is the point where
the number of moles of acid exactly equals the number of moles of base.

Some laboratories have pH meters that measures this point more accurately than the indicator. The
diagram below shows a simplied version of a pH meter with the probe from the meter immersed in a
mildly alkaline solution (pH = 8.03). The two knobs on the meter are used to calibrate the instrument.

An example of a typical electronic pH meter with the attached probes is shown below. The main purpose
of a pH meter in this experiment is to measure the changes in pH as the titration goes from start to nish.

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A typical titration setup is shown below. The burette is upright and ready to drip the solution into the
ask holding the solution of unknown concentration and the few drops of indicator. When the indicator
changes color, the number of moles of acid equals the number of moles of base and the acid (or base) has
been neutralized.

There are three types of titrations that are normally performed in the laboratory in order to determine
the unknown concentration of the acid or base. These three types are:
1. Strong acid vs. Strong base
2. Strong acid vs. Weak base
3. Weak acid vs. Strong base
In these titrations, a pH meter may be used to measure the changes in the pH as the titration goes to
completion. If so, a titration curve can be constructed. A titration curve is a graph of the pH versus the
volume of titrant added. Lets take a look at how each of these types of titrations diers in terms of their
pH curves and their pH at the equivalence point.
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(1) Strong Acid vs. Strong Base


For a strong acid vs. a strong base titration, lets assume the strong base is the titrant. Therefore, the
Erlenmeyer ask contains the strong acid and a few drops of your indicator. The initial pH of the solution
in the ask will likely be low since the solution is a strong acid. As the base is added, the acid is slowly
neutralized. At rst the change in pH is minimal. This is due to the fact that the ask has a much greater
number of H3 O+ ions than OH ions available from the added titrant.
As more and more base is added, more OH ions are added and thus more H3 O+ ions get neutralized.
Lets stop here and look at the reaction. The equation below shows the total ionic equation of a reaction
between a strong acid and a strong base:
H+
+ Cl(aq) + Na+
+ OH(aq) Na+
+ Cl(aq) + H2 O(l)
(aq)
(aq)
(aq)
The next equation shows the net ionic equation for the reaction between the strong acid and the strong
base:
H+
+ OH(aq) H2 O(l)
(aq)
As we add more OH ions, more H3 O+ (or H+ ) ions are being neutralized. Since these two ions react to
form water, a neutral solution will eventually be formed. For a strong acid and a strong base, this means
the pH = 7.0 at the point of neutralization. If we continue to add the titrant (containing OH ions) after
all of the H3 O+ ions have been neutralized, the pH will continue to rise as more base is added and there
are excess OH ions.
Now that we know what happens in a strong acid-strong base titration, what does the titration curve look
like? The main points described above are shown in the titration curve below.

The points A through D sum up the description of the events that take place during the titration. Point
A is the start of the titration. Point B is the midpoint, the point where half of the H+ ions have been
neutralized. Point D is the equivalence point.
(2) Strong Acid vs. Weak Base
What would happen if we were to titrate a strong acid with a weak base or vice versa? The titration curve
for a weak base-strong acid titration is shown below. Try to determine what is happening in the titration
just by looking at the graph.

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As the acid (the titrant) is added, the pH decreases as the H3 O+ ions begin to neutralize the OH ions.
Point D is the equivalence point. Notice that for a weak base and a strong acid titration, the pH at
equivalence point is acidic. The equation for the reaction between NH3 , a weak base, and HCl, a strong
acid, is shown below:
NH3(aq) + HCl(aq) NH4 Cl(aq) + H2 O(l)
The ionic equation is:
NH3(aq) + H+
+ Cl(aq) NH+
+ Cl(aq) + H2 O(l)
(aq)
4(aq)
(3) Weak Acid vs. Strong Base
The third type of titration is that of a weak acid with a strong base. When we follow through with the
same procedure as the previous two titrations, we can determine a great deal of information simply by
looking at the pH curve. For example, lets consider the titration of a solution of acetic acid, HC2 H3 O2 ,
with a solution of potassium hydroxide, KOH. We can write the chemical reaction for this acid-base
neutralization and begin to draw a rough sketch of a titration curve:
H+
+ C2 H3 O2(aq) + K+
+ OH(aq) K+
+ C2 H3 O2(aq) + H2 O(l)
(aq)
(aq)
(aq)

The points on the curve represent the same points as with the other two titration curves. Look, however, at
the equivalence point. Notice how the pH for the equivalence point of the weak acid-strong base titration
is above 7.0.
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Example:
Draw a rough sketch of the titration curve between nitric acid and ethylamine, CH3 NH2 . Assume the acid
is in the burette. What is the estimated pH at the equivalence point?
Solution:

The <H at the equivalence point is approximately 4.6 from this graph.
The titrant is the solution of known concentration. For accuracy reasons, this titrant is normally titrated
to nd its exact concentration before beginning the desired titration. The purpose of this initial titration
is to determine, with as much accuracy as possible, the exact concentration of the solution in the burette.
To determine the exact concentration of the titrant, we use a standard solution. A standard solution
is a solution whose concentration is known exactly. Standard solutions have this property because these
chemicals are normally found in pure, stable forms. Examples of chemicals used to prepare standard
solutions are potassium hydrogen phthalate, KHC8 H4 O4 (sometimes referred to as KHP), and sodium
carbonate, Na2 CO3 .
When using a standard solution, the standard is rst prepared by dissolving the solid in a known volume
of water, adding a few drops of indicator, and titrating with the solution that you want to standardize.
Example:
What is the concentration of a sodium hydroxide solution if 32.34 mL is required to neutralize a solution
prepared by dissolving 1.12 g of KHC8 H4 O4(s) in 25.00 mL of H2 O?
Solution:
Step 1: Find the moles of KHC8 H4 O4 .
moles KHC8 H4 O4 =

mass
molar mass

1.12g
204.2 g/mol

= 5.48 103 mol

Step 2: Use mole ratio from the reaction to nd the moles of NaOH.
KHC8 H4 O4(aq) + NaOH(aq) KNaC8 H4 O4(aq) + H2 O(l)
Since the reaction is 1:1, 1 mole of KHP reacts with every mole of NaOH.
mol NaOH = 5.48 103 mol
Step 3: Determine the concentration of NaOH.
[NaOH] =

5.48103 mol
0.03234 L

= 0.170 M

Therefore, the exact concentration of the sodium hydroxide solution used in the titration is 0.170 mol/L.

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Choosing an Appropriate Indicator


To choose an appropriate indicator for a titration, a titration curve is useful. Knowing the pH at equivalence
for the dierent types of titrations (see Table 21.3) is also necessary.
Table 21.3: pH at Equivalence for Titrations
Type of Titration

pH at Equivalence

Strong Acid Strong Base


Strong Acid Weak Base
Weak Acid Strong Base

pH = 7
pH < 7
pH > 7

Choosing an indicator close to the equivalence point is essential to see the point where all of the H+ ions
and OH ions have been neutralized. The color change should occur on or around the equivalence point.
So, for example, with a strong acid-strong base titration, the pH at equivalence is 7.0. Indicators such as
bromothymol blue (pH range = 6.0 - 7.6) and phenol red (pH range = 6.6 - 8.0) are common. Notice the
midpoint color (green) for bromothymol blue would appear at a pH = 6.8, which is close to 7.0. For phenol
red, the midpoint color (orange) would appear at pH = 7.3, again close to 7.0.
The same process is used for other titration types. For a strong acid-weak base titration where the pH
at equivalence is less than 7, the indicators normally chosen are methyl red (pH range = 4.8 - 6.0) and
chlorophenol red (pH range = 4.8 - 6.2). For a weak acid-strong base titration, where the pH at equivalence
is greater than 7, the indicators normally chosen are phenolphthalein (pH range = 8.2 - 10) and thymol
blue (pH range = 8.0 - 9.6). As with strong acid-strong base titrations, the visual observation of the
indicators midpoint color should signal close proximity to the equivalence point.
Example:
Look at the graph below and determine the appropriate indicator.

Solution:
We rst look at the graph and mark the vertical stretch of the titration curve in order to nd the half-way
mark on this vertical stretch. Looking at the graph, when we follow this half-way mark over to the y-axis,
we can see that the equivalence point occurs at approximately pH = 8.8. The indicator appropriate to use
would be phenolphthalein pH range = 8.2 - 10). As soon as the pink color forms, we are at the equivalence
point.
There is an interesting observation about the endpoint that has yet to be mentioned. The endpoint was
dened earlier as the point where the indicator changes color. In an acid-base neutralization reaction, this
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point may not be the point where all of the H+ ions have been neutralized by OH ions, or vice versa. The
experimenter continues titration until the indicator changes color, that is, the endpoint has been reached.
The equivalence point is the point where the moles of hydrogen ion and the moles of hydroxide ion are
equal. It requires knowledge by the experimenter to select an indicator that will make the endpoint as
close as possible to the equivalent point.

The Mathematics of Titration


For the calculations involved here, we will only use our acid and base examples where the stoichiometric
ratio of H+ and OH is 1:1. To determine the volume required to neutralize an acid or a base, or in other
words, to reach the equivalence point, we will use a formula similar to the dilution formula:
Ma Va = Mb Vb
where Ma is the molarity of the acid, Va is the volume of the acid, Mb is the molarity of the base, and Vb
is the volume of the base. Note that if the acid and base do not neutralize each other in a 1:1 ratio, this
equation does not hold true.
Example:
When 10.0 mL of a 0.125 mol/L solution of hydrochloric acid, HCl, is titrated with a 0.100 mol/L solution
of potassium hydroxide, KOH, what is the volume of the hydroxide solution required to neutralize the
acid? What type of titration is this?
Solution:
Step 1: Write the balanced ionic chemical equation.
H+ + Cl + K+ + OH K+ + Cl + H2 O
Step 2: Use the formula and ll in all of the given information.
Ma Va = Mb Vb
Ma = 0.125 mol/L
Va = 10.0 mL
Mb = 0.100 mol/L
Vb =?
Ma Va = Mb Vb
(0.125 mol/L)(10.0
a
Vb = MaMV
=
0.100 mol/L
b

mL

= 12.5 mL

Therefore, for this strong acid-strong base titration, the volume of base required is 12.5 mL.

This video shows the technique for performing a titration using an indicator: http://www.youtube.com/
watch?v=9DkB82xLvNE (5:03).

Lesson Summary
An indicator is a substance that changes color at a specic pH and is used to indicate the pH of the
solution relative to that point.

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Figure 21.3: (Watch Youtube Video)


http://www.ck12.org/exbook/embed/view/414

A natural indicator is an indicator that is a naturally occurring substance.


Indicators are normally weak organic acids or bases with complicated structures.
Universal indicator is a mixture of indicators that produces a dierent color for each pH from 0 14.
A titration is the addition of a known concentration of base (or acid) to a solution of acid (or base)
of unknown concentration.
The titrant is the solution of known concentration. This solution is normally in the burette.
The endpoint is the point in the titration where the indicator changes color.
The equivalence point is the point in the titration where the number of moles of acid equals the
number of moles of base.
The three types of titrations usually performed in the laboratory are: strong acid vs. strong base,
strong acid vs. weak base, and weak acid vs. strong base.
A titration curve is a graph of the pH versus the volume of titrant added.
For a strong acid vs. strong base titration, the pH at equivalence is 7.0. For a strong acid vs. weak
base titration, the pH at equivalence is less than 7.0. For a weak acid vs. strong base titration, the
pH at equivalence is greater than 7.0.
A standard solution is a solution whose concentration is known exactly and is used to nd the exact
concentration of the titrant.
For titrations where the stoichiometric ratio of mol H+ to mol OH is 1:1, the concentrations or
volumes for the unknown acid or base can be calculated with the formula Ma Va = Mb Vb.

Further Reading / Supplemental Links


The following link is to a video about acid-base neutralization and titration.
http://link.brightcove.com/services/player/bcpid9113583001?bctid=1405713919
The video at the link below shows the lab techniques needed for titration.
http://chem-ilp.net/labTechniques/TitrationVideo.htm
This video is a ChemStudy lm called Acid Base Indicators. The lm is somewhat dated but the information is accurate.
http://www.youtube.com/watch?v=yi8QrjmV6Sw

Review Questions
1. Why do you think there would be more experimental error when using an indicator instead of a pH
meter during a titration?
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528

2. Which of the following denitions best suits that of an endpoint?


(a) The stoichiometric point where the number of moles of acid equals the number of moles of base.
(b) The visual stoichiometric point where the number of moles of acid equals the number of moles
of base.
(c) The midpoint of the vertical stretch on the titration curve.
(d) None of the above
3. In the following titration curve, what pair of aqueous solutions would best represent what is shown
to be happening in the curve?
(a)
(b)
(c)
(d)

HCOOH(aq) + NH3(aq)
HCOOH(aq) + NaOH(aq)
H2 SO4(aq) + Ba(OH)2(aq)
HClO4(aq) + NH3(aq)

4. What would be the best indicator to choose for the pH curve shown in question 3?
(a)
(b)
(c)
(d)

Methyl red
Litmus
Phenolphthalein
Phenol red

5. What is the best indicator to use in the titration of benzoic acid with barium hydroxide?
(a)
(b)
(c)
(d)
(e)

Methyl violet, range = 0.0 1.6


Bromothymol blue, range = 3.0 4.7
Phenolphthalein, range = 8.2 10.0
Methyl blue, range = 10.6 13.4
Indigo carmine, range = 11.4 13.0

6. If 22.50 mL of a sodium hydroxide solution is necessary to neutralize 18.50 mL of a 0.1430 mol/L


HNO3 solution, what is the concentration of NaOH?
(a)
(b)
(c)
(d)

0.1176 mol/L
0.1430 mol/L
0.1740 mol/L
2.64 mol/L

7. Calculate the concentration of hypochlorous acid if 25.00 mL of HClO is neutralized by 32.34 mL of


a 0.1320 mol/L solution of sodium hydroxide.

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21.3 Buers
Lesson Objectives
The student will:

dene and give an example of a buer.


explain the eect of a strong acid or base on a buer system.
explain the mechanism by which a buer solution resists changes in pH.
given appropriate information, calculate the pH of a buer.
describe how to make a buer solution.

Vocabulary
buer

Introduction
There are many situations in which it is desirable to keep the pH of a solution close to a particular value
even though quantities of acids and/or bases are added to the solution. Many organic and biochemical
reactions require acids or bases, but if the pH goes too high or too low, the products will be destroyed.
For these reactions, it is necessary to keep the pH within a very small range even while acids or bases
are added to the reaction. Chemists use mixtures called buers to keep the reaction solutions within the
necessary pH range. Buers are mixtures of chemicals that cause a solution to resist changes in pH.
Buers are very important to many biological reactions. Human blood is a substance whose function is
very dependent on the function of buers. Human blood must maintain a nearly constant pH between 7.3
and 7.5. A change of just 0.2-0.4 pH units outside this range could cause loss of consciousness or even
death. The pH of human blood can change slightly depending on foods we eat and the rate at which we
inhale and exhale CO2 . Fortunately, the human blood stream has buers that are able to resist these pH
changes.

Buers
A buer is a solution that maintains the pH level when small amounts of acid or base are added to the
system. Buer solutions contain either a weak acid and its conjugate base or a weak base and its conjugate
acid. A common procedure for producing a buer in the lab is to make a solution containing both a weak
acid and a salt of its conjugate base.
For example, you could make a buer by preparing a solution containing acetic acid and sodium acetate.
This common buer would contain acetic acid, CH3 COOH, and the acetate ion, CH3 COO . The solution
will remain in the pH range of 3.7 5.8 even if small amounts of acids or bases are added. Another example
3
is a solution of hydrogen phosphate, HPO2
4 , plus the phosphate, PO4 . This will buer a solution in the
pH range of 11.3 - 13.3.
How is it possible that a solution will not change its pH when an acid or base is added? Lets examine the
acetic acid/acetate ion buer. The ionization equation for acetic acid is shown below.
HC2 H3 O2(aq) H+ + C2 H3 O2
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If acid (H+ ions) is added to this solution, the equilibrium will shift toward the reactants to use up some of
the added hydrogen ions. Equilibrium will be re-established in the solution with dierent concentrations
of the three species in the reaction. Although the H+ concentration will be higher than its initial value,
the change will be partially corrected due to the presence of C2 H3 O2 ions. Similarly, if a base is added
to this solution, the base will remove hydrogen ions and the equilibrium will shift to the right to partially
counteract the stress. Again, equilibrium will be re-established with new concentrations. The existence of
large quantities of both undissociated acid molecules and acetate ions in the solution is what allows the
buer to consume quite a large amount of added acid or base without the pH changing signicantly.
Examine what happens to 1.00 liter of pure water to which 0.100 mole of gaseous HCl is added. The
original concentration of hydrogen ion in the pure water is 1.00/times107 M and therefore, the pH is 7.
After the 0.100 mole of HCl is added, the concentration of hydrogen ions will be 0.100 M (plus the original
1.00 107 M, which can be neglected as insignicant). This new concentration of hydrogen ions will
produce a pH = 1. So, the addition of the 0.100 mole of gaseous HCl caused the pH of the pure water to
change from 7 to 1.
Lets now see what happens if this same amount of gaseous HCl is added to an acetic acid-acetate ion
buer. Lets say we made this solution to contain 0.50 M acetic acid and 0.50 M acetate ion (0.50 M
sodium acetate which fully dissociated). The acetic acid dissociation equation will reach equilibrium at its
Ka is 1.8 105 .
Ka =

[H+ ][C2 H3 O2 ]
[HC2 H3 O2 ]

= 1.8 105

We know both the acetic acid and the acetate ion concentrations will be 0.50 M, so we can plug these
values into the expression and solve for [H+ ].
[H+ ] =

(1.8105 )[HC2 H3 O2 ]
[C2 H3 O2 ]

(1.8105 )(0.50)
(0.50)

= 1.8 105 M

Then we can insert the hydrogen ion concentration into the pH formula and determine the original pH of
the buer solution.
pH = log(1.8 105 ) = 4.74
Next, we will add the same 0.100 mole of gaseous HCl to this buer solution and calculate the pH of the
solution after the acid has been added and equilibrium has been re-established.
When we add 0.100 mole HCl gas to this solution, the added hydrogen ion will combine with acetate ion
to produce more undissociated acid. A small amount of the newly formed acetic acid may dissociate again,
but the amount is minimal and can be neglected. The new [HC2 H3 O2 ] will equal 0.60 M (the original
0.50 M plus the added 0.10 M) and the new [C2 H3 O2 ] will equal 0.40 M (the original 0.50 M minus the
0.10 M that reacted with the added hydrogen ions). We can now plug these values into the Ka expression,
calculate the new [H+ ], and nd the new pH.
[H+ ][C2 H3 O2 ]
= 1.8 105
[HC2 H3 O2 ]
5
(1.810 )[HC2 H3 O2 ]
(1.8105 )(0.60)
[H+ ] =
=

(0.40)
[C2 H3 O2 ]
pH = log(2.7 105 ) = 4.57

Ka =

= 2.7 105 M

The same quantity of HCl gas that changed the pH of pure water from 7 to 1 has changed the pH of this
buer from 4.74 to 4.57. The change in pH is only 0.17, which is a function of the buer. Buers resist

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change to pH. We could do this same calculation by adding a base instead of an acid and show that the pH
increases by this same slight amount. We will leave this as an exercise for you to complete on your own.
Example:
Which of the following combinations would you expect to make a useful buer solution:
1. HClO4 /ClO4
2. CH3 NH2 /CH3 NH+
3
Solution:
1. HClO4 /ClO4 :HClO4 is a strong acid and buers are made from weak acids and their conjugate bases
or weak bases and their conjugate acids. Therefore, this cannot be made into a buer.
+
2. CH3 NH2 /CH3 NH+
3 :CH3 NH2 is a weak base and CH3 NH3 is the conjugate acid of this base. Therefore, this can be made into a buer solution.

The rst video considers the mathematics of buer solutions and the second video shows a laboratory
example of buering (5g; 1l I&E Stand.): http://www.youtube.com/watch?v=O_QlZe4fv4g (10:18),
(5g) http://www.youtube.com/watch?v=g_ZK2ABUjvA (2:39).

Figure 21.4: (Watch Youtube Video)


http://www.ck12.org/exbook/embed/view/415

Figure 21.5: (Watch Youtube Video)


http://www.ck12.org/exbook/embed/view/416

The Buer in Blood


The primary buer found in your bloodstream is carbonic acid, H2 CO3 . The carbonic acid is present due
to carbon dioxide from your respiratory system dissolving in water.
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CO2(g) + H2 O(l)
H2 CO3(aq)
The amount of carbonic acid in your bloodstream is aected by the rate of your respiration. If you breathe
rapidly, you reduce the amount of CO2 in your bloodstream, and the equilibrium shown above shifts
toward the reactants, thus lowering the amount of H2 CO3 . If you breathe slowly, the amount of CO2
in your bloodstream increases, and the equilibrium shifts toward the products, increasing the amount of
H2 CO3 in your system.
Once the H2 CO3 is produced by dissolving carbon dioxide, the carbonic acid dissociates in your blood as
shown below:
H2 CO3(aq)
H+ + HCO3
The buering system in your blood is composed of the weak acid, H2 CO3 , and its conjugate base, HCO3 .
Any changes in blood pH that could be caused by food intake will be buered by this equilibrium system.
If acid is added to your blood, the equilibrium will shift toward the reactants, using up the hydrogen ions.
If base were added to your blood, thus reacting with hydrogen ions, the equilibrium will shift toward the
products to generate more hydrogen ions. This buer in your blood is very eicient at keeping your blood
pH in the necessary range.
Some people, when they get nervous, begin breathing very fast or very slow. Breathing too fast is called
hyperventilating, and breathing too slow is called hypoventilating. Your respiratory rate is normally
controlled by the amount of carbon dioxide in the blood. Your body receives instructions to breathe faster
or slower to adjust the amount of carbon dioxide in your blood in order to properly regulate the buer
system. When people breathe too fast or too slow because of other reasons, the CO2 content of the blood
becomes incorrect and the pH of the blood rises or lowers outside the acceptable range of 7.3 - 7.5. When
this happens, the person can pass out. People who hyperventilate when excited or nervous are sometimes
advised to carry a lunch sack or something similar to breathe into when they are feeling light-headed.
Breathing into a sack returns air with the same concentration of carbon dioxide that was exhaled. This
keeps the amount of carbon dioxide in the blood up and prevents a loss of consciousness.

Lesson Summary
A buer is a solution of a weak acid and its conjugate base or a weak base and its conjugate acid
that resists changes in pH when an acid or base is added to it.
Adding a strong acid to a buer only decreases the pH by a small amount.
Adding a strong base to a buer only increases the pH by a small amount.

Further Reading / Supplemental Links


The following link is to a video lecture about acid-base buers.
http://www.youtube.com/watch?v=O_QlZe4fv4g
To see a short animated video showing concentration changes as strong acid or base is added to a buer,
follow the link below.
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/buffer12.swf

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Review Questions
1. Dene a buer solution.
2. One of the following statements of buers is incorrect. Which one?
(a) A buer may be prepared from a weak acid and its conjugate base salt.
(b) A buer may be prepared from a weak base and its conjugate acid salt.
(c) A buer is a solution that can resist changes in pH when any amount of acid or base is added
to it.
(d) A buer is a solution that can resist changes in pH when a small amount of acid or base is added
to it.
3. Which of the following pairs of aqueous 1.0 mol/L solutions could be chosen to prepare a buer: i.
NH4 HSO4(aq) and H2 SO4(aq) , ii. HNO2(aq) and NaNO2(aq) , iii. NH4 Cl(aq) and NH3(aq) ?
(a)
(b)
(c)
(d)

i and iii only


ii and iii only
i, ii, and iii
None of these solutions is a buer.

4. Which of the following would form a buer solution if combined in appropriate amounts?
(a)
(b)
(c)
(d)

HCl and NaCl


HCN and NaCN
H2 S and NaSH
HNO3 and NaNO3

5. A buer is made up of a weak acid and a conjugate base. A small amount of acid is added to the
buer. What happens to the resulting solution?
(a)
(b)
(c)
(d)

The
The
The
The

acid dissociation constant goes up.


concentration of the weak acid in the buer goes down.
pH of the solution goes up.
pH remains almost the same.

Image Sources
(1) David Kauman. Hydrangeas. Public domain.
All images, unless otherwise stated, are created by the CK-12 Foundation and are under the Creative
Commons license CC-BY-NC-SA.

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