Reactions in Aqueous

Solutions
Chapter 4

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 Solutions
A solution is a homogenous mixture of 2 or more
substances.
The solute is (are) the substance(s) present in the
smaller amount(s).
The solvent is the substance present in the larger
amount.

Solution Solvent Solute

Soft drink (l) Sugar,
Air (g) , Ar,
Soft solder (s) Pb Sn
aqueous solutions of
KMnO4 2
 Electrolytes
An electrolyte is a substance that, when dissolved in water,
results in a solution that can conduct electricity.
A nonelectrolyte is a substance that, when dissolved, results in
a solution that does not conduct electricity.

nonelectrolyte weak electrolyte strong electrolyte

3
 Electrolytes (2)
Conduct electricity in solution?
Cations (+) and Anions (-)

Strong Electrolyte – 100% dissociation

−
+ ¿ ( 𝑎𝑞 ) + Cl ( 𝑎𝑞 ) ¿
NaCl ( 𝑠 ) H 2 O Na
→

Weak Electrolyte – not completely dissociated

− +¿ (𝑎𝑞 )¿
CH 3 COOH ⇄ CH 3 CO O ( 𝑎𝑞 ) + H
4
 Electrolytes (3)
Ionization of acetic acid
− +¿ (𝑎𝑞 )¿
CH 3 COOH ⇄ CH 3 CO O ( 𝑎𝑞 ) + H

⇄ A reversible reaction. The reaction can

occur in both directions.

Acetic acid is a weak electrolyte because its

ionization in water is incomplete.
5
 Hydration
Hydration is the process in which an ion is surrounded
by water molecules arranged in a specific manner.

d-

d+
H2O 6
 Electrolytes (4)
Nonelectrolyte does not conduct electricity?
No cations (+) and anions (-) in solution
C 6 H 12 O 6 ( 𝑠) H 2 O C 6 H 12 O 6 (𝑎𝑞 )
→
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Table 4.1 Classification of Solutes in Aqueous Solution

Strong Electrolyte Weak Electrolyte Nonelectrolyte
(urea)
(methanol)
(ethanol)
(glucose)
(sucrose)

Ionic compounds
*H2S04 has two ionizable H+ ions, but only one of the H+ ions is totally ionized. 7
Pure water is an extremely weak electrolyte.
†
 Precipitation Reactions
Precipitate – insoluble solid that separates from solution
precipitate

Pb ( NO 3 )2 ( 𝑎𝑞 ) +2 NaI ( 𝑎𝑞 ) → PbI 2 ( 𝑠 ) +2 NaNO 3(𝑎𝑞)

molecular equation
−
+¿ +2 N O ¿
− + ¿ + 2 I → PbI 2 ( 𝑠 )+ 2 Na
− 3
¿
2+ ¿ +2 NO 3 + 2 Na ¿
Pb
ionic equation
−
2+¿ +2 I → PbI 2( 𝑠 ) ¿
Pb
net ionic equation
Na+ and are spectator ions
8
PbI2
 Precipitation of Lead Iodide

PbI 2
−
2+¿ +2 I → PbI 2( 𝑠 ) ¿
Pb
9
 Solubility
Solubility is the maximum amount of solute that will dissolve in
a given quantity of solvent at a specific temperature.
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Table 4.2 Solubility Rules for Common Ionic Compounds in Water at

Soluble Compounds Insoluble Exceptions
Compounds containing alkali metal
ions (, , , , ) and the ammonium ion
()
Nitrates (), acetates (), bicarbonates
(), chlorates (), and perchlorates ()
Halides (, , ) Halides of Ag+, , and
Sulfates () Sulfates of , , , , , and
Insoluble Compounds Soluble Exceptions
Carbonates (), phosphates (), Compounds containing alkali metal ions and the
chromates (), sulfides () ammonium ion
Hydroxides ()
Compounds containing alkali metal ions and the
ion

10
Examples of Insoluble Compounds

CdS PbS ¿ (OH )2Al (OH )3 11

Example 4.1

Classify the following ionic compounds as soluble or insoluble:

(a) silver sulfate ()

(b) calcium carbonate ()

(c) sodium phosphate ().

Example 4.1 (1)
Strategy Although it is not necessary to memorize the
solubilities of compounds, you should keep in mind the
following useful rules: all ionic compounds containing alkali
metal cations; the ammonium ion; and the nitrate, bicarbonate,
and chlorate ions are soluble. For other compounds, we need to
refer to Table 4.2.

Solution
(a) According to Table 4.2, is insoluble.

(b) This is a carbonate and Ca is a Group 2A metal. Therefore,

is insoluble.

(c) Sodium is an alkali metal (Group 1A) so is soluble.

 Writing Net Ionic Equations

1. Write the balanced molecular equation.

2. Write the ionic equation showing the strong electrolytes
completely dissociated into cations and anions.
3. Cancel the spectator ions on both sides of the ionic
equation.
4. Check that charges and number of atoms are balanced in
the net ionic equation.

14
Example 4.2
Predict what happens when a potassium phosphate solution is
mixed with a calcium nitrate solution. Write a net ionic equation
for the reaction.
Example 4.2 (1)
Strategy
From the given information, it is useful to first write the
unbalanced equation

What happens when ionic compounds dissolve in water?

What ions are formed from the dissociation of and ?

What happens when the cations encounter the anions in

solution?
Example 4.2 (2)
Solution In solution, dissociates into and ions and
dissociates into and ions.

According to Table 4.2, calcium ions and phosphate ions () will

form an insoluble compound, calcium phosphate , while the
other product, is soluble and remains in solution.

Therefore, this is a precipitation reaction. We follow the

stepwise procedure just outlined.

Step 1: The balanced molecular equation for this reaction is

Example 4.2 (3)
Step 2: To write the ionic equation, the soluble compounds are
shown as dissociated ions:

Step 3: Canceling the spectator ions ( and ) on each side of the

equation, we obtain the net ionic equation:

Step 4: Note that because we balanced the molecular equation

first, the net ionic equation is balanced as to the number
of atoms on each side and the number of positive (+6)
and negative (−6) charges on the left- hand side is the
same.
 Properties of Acids
Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.
Cause color changes in plant dyes.

React with certain metals to produce

hydrogen gas.

2 HCI ( 𝑎𝑞 ) +Mg ( 𝑠 ) → MgCI 2 ( 𝑎𝑞 )+H2 ( 𝑔 )

React with carbonates and bicarbonates
to produce carbon dioxide gas.

2 HCI ( 𝑎𝑞 )+CaCO3 ( 𝑠 ) →CaCI 2 ( 𝑎𝑞 ) +CO2 ( 𝑔 )+H2 O ( 𝑙 )

Aqueous acid solutions conduct electricity.
19
 Properties of Bases
Have a bitter taste.

Feel slippery. Many soaps contain bases.

Cause color changes in plant dyes.

Aqueous base solutions conduct electricity.

20
 Arrhenius Acids and Bases
Arrhenius acid is a substance that produces in water.

Arrhenius base is a substance that produces in water.

21
Hydronium ion, hydrated proton,

22
 Brønsted Acids and Bases
A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor

base acid acid base

A Brønsted acid must contain at least one ionizable

proton!
23
 Types of Acids
Monoprotic acids
−
+¿ + CI ¿
HCI → H −
Strong electrolyte, strong acid
+¿ + N O 3 ¿
HN O 3 → H Strong electrolyte, strong acid
−
+¿+CH 3 COO ¿
CH 3 COOH ⇄ H Weak electrolyte, weak acid

Diprotic acids
−

H 2 SO 4 → H +¿ + HS O 4 ¿
Strong electrolyte, strong acid
2−
− +¿ +S O4 ¿
HS O ⇄ H
4
Weak electrolyte, weak acid

Triprotic acids
−
+¿+ H 2 P O4 ¿
H 3 PO 4 ⇄ H 2−
Weak electrolyte, weak acid
− +¿ + HP O 4 ¿
H 2 PO ⇄ H 4 Weak electrolyte, weak acid
2−
2− +¿ + P O 4 ¿
HP O 4 ⇄H Weak electrolyte, weak acid
24
Common Acids
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for reproduction or display.

Table 4.3
Some Common Strong and
Weak Acids

Strong Acids Formula

Hydrochloric acid

Hydrobromic
acid
Hydroiodic acid

Nitric acid

Sulfuric acid

Perchloric acid

Weak Acids Formula

Hydrofluoric acid

Nitrous acid

Phosphoric acid

Acetic acid
25
Example 4.3

Classify each of the following species in aqueous solution as a

Brønsted acid or base:

(a)

(b)

(c)
Example 4.3 (1)

Strategy
What are the characteristics of a Brønsted acid?

Does it contain at least an H atom?

With the exception of ammonia, most Brønsted bases that you

will encounter at this stage are anions.
Example 4.3 (2)
Solution
(a) We know that is an acid. Because Br and Cl are both
halogens (Group 7A), we expect , like , to ionize in water as
follows:

Therefore is a Brønsted acid.

(b) In solution the nitrite ion can accept a proton from water to
form nitrous acid:

This property makes a Brønsted base.

Example 4.3 (3)

(c) The bicarbonate ion is a Brønsted acid because it ionizes in

solution as follows:

It is also a Brønsted base because it can accept a proton

to form carbonic acid:

Comment The species is said to be amphoteric because it

possesses both acidic and basic properties. The double arrows
show that this is a reversible reaction.
 Neutralization Reaction

acid +base → salt + water

HCl ( 𝑎𝑞 ) + NaOH ( 𝑎𝑞 ) → NaCl ( 𝑎𝑞 ) + H 2 O

−
+ ¿ +Cl +H O ¿
− + ¿ + OH −
→ Na 2
¿
+ ¿ + Cl + Na ¿
H
−
+¿ + O H → H O ¿
H 2

30
 Neutralization Reaction Involving a Weak
Electrolyte

weak acid +base → salt + water

HCN ( 𝑎𝑞 ) + NaOH ( 𝑎𝑞 ) → NaCN ( 𝑎𝑞 ) + H 2 O

−
− + ¿ + CN +H2 O¿
+¿ +OH → Na ¿
HCN + Na
− −
HCN +OH →C N +H 2O

31
Example 4.4

Write molecular, ionic, and net ionic equations for each of the
following acid-base reactions:

(a)
Example 4.4 (1)
Strategy
The first step is to identify the acids and bases as strong or
weak.

We see that HBr is a strong acid and H2SO4 is a strong acid for
the first step ionization and a weak acid for the second step
ionization.

Both Ba(OH)2 and KOH are strong bases.

Example 4.4 (2)
Solution
(a) Molecular equation:

Ionic equation:

Net ionic equation:

or

Both and are spectator ions.

Example 4.4 (3)
(b) Molecular equation:

Ionic equation:

Net ionic equation:

Note that because is a weak acid and does not ionize

appreciably in water, the only spectator ion is K+.
 Neutralization Reaction Producing a Gas

acid +base → salt + water + CO 2

2 HCl ( 𝑎𝑞 ) +Na 2 CO3 ( 𝑎𝑞 ) → 2 NaCl ( 𝑎𝑞 ) +H 2O+CO 2

−
+ ¿+ 2 Cl +H O+ C O ¿
− + ¿ +CO 2−
→2 Na 2 2
¿
+¿ + 2Cl +2 Na ¿
2H
3

2−
+¿ +C O → H O +C O ¿
2 H 3 2 2

36
 Oxidation-Reduction Reactions
(electron transfer reactions)

−
2+¿+ 4 e ¿
2 Mg → 2 Mg Oxidation half-reaction (lose e-)
O 2 + 4 e − → 2 O 2 − Reduction half-reaction (gain e-)
2− −
− 2+ ¿ +2 O +4 e ¿
2 Mg +O 2 +4 e → 2 Mg
2 Mg + O 2 → 2 MgO 37
Oxidation-Reduction Reactions (1)

38
 Oxidation-Reduction Reactions (2)
Zn ( 𝑠 )+ Cu SO 4 (𝑎𝑞)→ ZnS O 4 ( 𝑎𝑞 ) +Cu (𝑠 )

−
2+¿ + 2 e ¿ Zn is oxidized
Zn → Zn
Zn is the reducing agent

−
2 +¿ +2 e →Cu ¿ Cu2+ is reduced
Cu
Cu2+ is the oxidizing agent

39
 Oxidation Number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation

number of zero.

Na , Be , K , Pb , H 2 ,O 2 , P4 =0
2. In monatomic ions, the oxidation number is equal to
the charge on the ion.
2 −
3+ ¿ , Fe = +3 ; O , O= − 2¿
+ ¿ , Li= +1 ; Fe ¿
Li
3. The oxidation number of oxygen is usually –2. In and
it is –1. 40
4.4
 Oxidation Number (1)
4. The oxidation number of hydrogen is +1 except when it
is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.

5. Group IA metals are +1, IIA metals are +2 and fluorine

is always –1.
6. The sum of the oxidation numbers of all the atoms in a
molecule or ion is equal to the charge on the molecule
or ion.

7. Oxidation numbers do not have to be integers. The

oxidation number of oxygen in the superoxide ion, ,
is .

41
Example 4.5

Assign oxidation numbers to all the elements in the following

compounds and ion:

(a)

(b)

(c)
Example 4.5 (1)

Strategy
In general, we follow the rules just listed for assigning oxidation
numbers.

Remember that all alkali metals have an oxidation number of

+1, and in most cases hydrogen has an oxidation number of +1
and oxygen has an oxidation number of −2 in their compounds.
Example 4.5 (2)
Solution
(a)By rule 2 we see that lithium has an oxidation number of +1
and oxygen’s oxidation number is −2 .

(b)This is the formula for nitric acid, which yields a H+ ion and
a ion in solution. From rule 4 we see that H has an oxidation
number of +1. Thus the other group (the nitrate ion) must have
a net oxidation number of −1. Oxygen has an oxidation
number of −2, and if we use x to represent the oxidation
number of nitrogen, then the nitrate ion can be written as

so that
Example 4.5 (3)
(c) From rule 6 we see that the sum of the oxidation numbers in
the dichromate ion must be − 2. We know that the oxidation
number of O is − 2, so all that remains is to determine the
oxidation number of Cr, which we call y. The dichromate ion
can be written as

so that

Check In each case, does the sum of the oxidation numbers of

all the atoms equal the net charge on the species?
The Oxidation Numbers of Elements in their Compounds

46
Types of Oxidation-Reduction Reactions

Combination Reaction
A+ B → C
0 0 +3 -1
2 Al + 3 Br 2 → 2 Al Br 3

Decomposition Reaction
C → A + B
+1 +5 -2 +1 -1 0
2 KCl O 3 → 2 KCl + 3 O 2
47
Types of Oxidation-Reduction Reactions (1)

Combustion Reaction

A + O2 → B
0 0 +4 -2
S +O 2 → SO 2

0 0 +2 -2
2 Mg + O 2 → 2 MgO

48
Types of Oxidation-Reduction Reactions (2)

Displacement Reaction
A + BC → AC + B
0 +1 +2 0
Sr +2 H 2 O → Sr (OH )2 + H 2 Hydrogen Displacement
+4 0 0 +2
Ti Cl 4 +2 Mg → Ti+ 2 Mg Cl 2 Metal Displacement
0 -1 -1 0
Cl 2 +2 KBr → 2 KCl + Br 2 Halogen Displacement

49
The Activity Series for Metals

Hydrogen Displacement Reaction

M + BC → MC + B
M is metal
BC is acid or
B is
Ca+2 H 2 O→ Ca(OH )2+ H 2
Pb+2 H 2 O→ Pb(OH )2+ H 2

50
 The Activity Series for Halogens
F 2 > Cl 2 > Br 2 > I 2

Halogen Displacement Reaction

0 -1 -1 0
Cl 2 +2 KBr → 2 KCl + Br 2

I 2 +2 KBr → 2 KI + Br 2

51
Types of Oxidation-Reduction Reactions (3)
Disproportionation Reaction

The same element is simultaneously oxidized and

reduced.

Example: reduced

0 +1 -1
Cl 2 +2 O H − → Cl O − +Cl − + H 2 O

oxidized

52
Example 4.6
Classify the following redox reactions and indicate changes in
the oxidation numbers of the elements:

(a)

(b)

(c)

(d)
Example 4.6 (1)
Strategy Review the definitions of combination reactions,
decomposition reactions, displacement reactions, and
disproportionation reactions.

Solution
(a)This is a decomposition reaction because one reactant is
converted to two different products. The oxidation number of N
changes from +1 to 0, while that of O changes from −2 to 0.

(b)This is a combination reaction (two reactants form a single

product). The oxidation number of Li changes from 0 to +1
while that of N changes from 0 to −3.
Example 4.6 (2)
(c) This is a metal displacement reaction. The Ni metal
replaces (reduces) the ion. The oxidation number of Ni
increases from 0 to +2 while that of Pb decreases from
+2 to 0.

(d) The oxidation number of N is +4 in and it is +3 in and

+5 in . Because the oxidation number of the same
element both increases and decreases, this is a
disproportionation reaction.
 Solution Stoichiometry

The concentration of a solution is the amount of solute

present in a given quantity of solvent or solution.

moles of solute
𝑴 =𝒎𝒐𝒍𝒂𝒓𝒊𝒕𝒚 =
liters of solution

56
Preparing a Solution of Known Concentration

57
Example 4.7

How many grams of potassium

dichromate (K2Cr2O7) are
required to prepare a 250-mL
solution whose concentration is
2.16 M?

A K2Cr2O7 solution.
Example 4.7 (1)
Strategy
How many moles of does a 1-L (or 1000 mL) 2.16 M solution
contain?

A 250-mL solution?

How would you convert moles to grams?

Example 4.7 (2)
Solution The first step is to determine the number of moles of
in 250 mL or 0.250 L of a 2.16 M solution. Rearranging
Equation (4.1) gives

Thus,
Example 4.7 (3)
The molar mass of is 294.2 g, so we write

Check As a ball-park estimate, the mass should be given by

or . So the answer is reasonable.
Example 4.8

In a biochemical assay, a chemist needs to add 3.81 g of

glucose to a reaction mixture. Calculate the volume in milliliters
of a 2.53 M glucose solution she should use for the addition.
Example 4.8 (1)
Strategy
We must first determine the number of moles contained in
3.81 g of glucose and then use Equation (4.2) to calculate the
volume.

Solution
From the molar mass of glucose, we write
Example 4.8 (2)
Next, we calculate the volume of the solution that contains
mole of the solute. Rearranging Equation (4.2) gives

Check One liter of the solution contains 2.53 moles of .

Therefore, the number of moles in 8.36 mL or L is or mol.
The small difference is due to the different ways of rounding
off.
71
 Dilution
Dilution is the procedure for preparing a less concentrated
solution from a more concentrated solution.

Dilution
Add Solvent

Moles of solute
before dilution (i) ¿ Moles of solute
after dilution (f)
𝑀 i 𝑉 i= 𝑀 f 𝑉 f 73
Example 4.9

Describe how you would prepare of a 1.75 M

solution, starting with an 8.61 M stock solution of .
Example 4.9 (1)

Strategy
Because the concentration of the final solution is less than that
of the original one, this is a dilution process.

Keep in mind that in dilution, the concentration of the solution

decreases but the number of moles of the solute remains the
same.
Example 4.9 (2)
Solution We prepare for the calculation by tabulating our data:

Substituting in Equation (4.3),

Example 4.9 (3)

Thus, we must dilute 102 mL of the 8.61 M solution with

sufficient water to give a final volume of in a 500-mL
volumetric flask to obtain the desired concentration.

Check The initial volume is less than the final volume, so the
answer is reasonable.
 Titrations
To determine the concentration of a particular
solute in a solution, chemists often carry out a
titration, which involves combining a solution
where the solute concentration is not known with a
reagent solution of known concentration, called a
standard solution.

Just enough standard solution is added to

completely react with the solute in the solution of
unknown concentration.

83
 Titrations
In a titration, a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.
Equivalence point – the point at which the reaction is complete
Indicator – substance that changes color at (or near) the
equivalence point

Slowly add base

to unknown acid
UNTIL
the indicator
changes color
84
Knowing the volumes of both solutions and the
concentration of the standard solution, we can
calculate the concentration of the unknown
solution as diagrammed in ▼ Figure 4.19.
 Titrations (1)

Titrations can be used in the analysis of:

Acid-base reactions

Redox reactions

87
Example 4.11

In a titration experiment, a student finds that 23.48 mL of a

solution are needed to neutralize 0.5468 g of . What is the
concentration (in molarity) of the solution?
Example 4.11 (1)
Strategy We want to determine the molarity of the solution.
What is the definition of molarity?

need to
mol NaOH find
molarity of NaOH =
L soln

want to given
calculate

The volume of solution is given in the problem. Therefore, we

need to find the number of moles of to solve for molarity. From
the preceding equation for the reaction between and shown in
the text we see that 1 mole of neutralizes 1 mole of . How
many moles of are contained in 0.5468 g of ?
Example 4.11 (2)
Solution First we calculate the number of moles of consumed
in the titration:

Because , there must be of in 23.48 mL of solution. Finally,

we calculate the number of moles of in 1 L of the solution or
the molarity as follows:
Example 4.12

How many milliliters (mL) of a 0.610 M solution are needed to

neutralize 20.0 mL of a 0.245 M solution?
Example 4.12 (1)
Strategy We want to calculate the volume of the solution.
From the definition of molarity [see Equation (4.1)], we write
need to
mol NaOH find
L soln =
molarity

want to given
calculate
From the equation for the neutralization reaction just shown, we
see that 1 mole of neutralizes 2 moles of .
How many moles of are contained in 20.0 mL of a 0.245 M
solution?
How many moles of would this quantity of neutralize?
Example 4.12 (2)
Solution
First we calculate the number of moles of in a 20.0 mL solution:

From the stoichiometry we see that . Therefore, the number of

moles of reacted must be
, or .
Example 4.12 (3)

From the definition of molarity [see Equation (4.1)], we have

or

or
Example 4.13
A 16.42-mL volume of 0.1327 M solution is
needed to oxidize 25.00 mL of a solution in
an acidic medium. What is the concentration
of the solution in molarity? The net ionic
equation is
Example 4.13 (1)
Strategy We want to calculate the molarity of the solution.
From the definition of molarity need to
find
mol Fe SO 4
molarity of Fe SO 4 =
L soln
want to
given
calculate
The volume of the solution is given in the problem. Therefore,
we need to find the number of moles of to solve for the
molarity.
From the net ionic equation, what is the stoichiometric
equivalence between and ?
How many moles of are contained in 16.42 mL of 0.1327 M
solution?
Example 4.13 (2)
Solution The number of moles of in 16.42 mL of the solution is

From the net ionic equation we see that 5 mol Therefore, the
number of moles of oxidized is
Example 4.13 (3)
The concentration of the solution in moles of per liter of
solution is