Reactions in Aqueous Solutions

Chapter 4

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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) H2O Sugar, CO2
Air (g) N2 O2, Ar, CH4
Soft solder (s) Pb Sn aqueous solutions of
KMnO4
2
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
 Conduct electricity in solution?

Cations (+) and Anions (-)

Strong Electrolyte – 100% dissociation

H 2O
NaCl (s) Na+ (aq) + Cl- (aq)

Weak Electrolyte – not completely dissociated

CH3COOH CH3COO- (aq) + H+ (aq)

4
 Ionization of acetic acid

CH3COOH CH3COO- (aq) + H+ (aq)

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




H2O 6
Nonelectrolyte does not conduct electricity?

No cations (+) and anions (-) in solution

H2 O
C6H12O6 (s) C6H12O6 (aq)

7
 Precipitation Reactions
Precipitate – insoluble solid that separates from solution
precipitate

Pb(NO3)2 (aq) + 2NaI (aq) PbI2 (s) + 2NaNO3 (aq)

molecular equation

Pb2+ + 2NO3- + 2Na+ + 2I- PbI2 (s) + 2Na+ + 2NO3-

ionic equation

Pb2+ + 2I- PbI2 (s)

PbI2
net ionic equation
Na+ and NO3- are spectator ions
8
Precipitation of Lead Iodide

Pb2+ + 2I- PbI2 (s) PbI2

9
Solubility is the maximum amount of solute that will dissolve
in a given quantity of solvent at a specific temperature.

10
Examples of Insoluble Compounds

CdS PbS Ni(OH)2 Al(OH)3 11

Example 4.1

Classify the following ionic compounds as soluble or insoluble:

(a)silver sulfate (Ag2SO4)

(b)calcium carbonate (CaCO3)

(c)sodium phosphate (Na3PO4).

Example 4.1
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
•According to Table 4.2, Ag2SO4 is insoluble.

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

CaCO3 is insoluble.

(c) Sodium is an alkali metal (Group 1A) so Na3PO4 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 (K 3PO4)
solution is mixed with a calcium nitrate [Ca(NO 3)2] solution. Write a
net ionic equation for the reaction.
Example 4.2
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 K3PO4 and

Ca(NO3)2?

What happens when the cations encounter the anions in

solution?
Example 4.2
Solution In solution, K3PO4 dissociates into K+ and ions
and Ca(NO3)2 dissociates into Ca2+ and ions.

According to Table 4.2, calcium ions (Ca2+) and phosphate ions

( ) will form an insoluble compound, calcium phosphate
[Ca3(PO4)2], while the other product, KNO3, 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
Step 2: To write the ionic equation, the soluble compounds are
shown as dissociated ions:

Step 3: Canceling the spectator ions (K+ 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.
 Chemistry In Action:
An Undesirable Precipitation Reaction

Ca2+ (aq) + 2HCO-3 (aq) CaCO3 (s) + CO2 (aq) + H2O (l)
CO2 (aq) CO2 (g)

19
 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.
2HCl (aq) + Mg (s) MgCl2 (aq) + H2 (g)

React with carbonates and bicarbonates

to produce carbon dioxide gas.

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

Aqueous acid solutions conduct electricity.

20
 Properties of Bases
Have a bitter taste.

Feel slippery. Many soaps contain bases.

Cause color changes in plant dyes.

Aqueous base solutions conduct electricity.

Examples:

21
Arrhenius acid is a substance that produces H+ (H3O+) in water.

Arrhenius base is a substance that produces OH- in water.

22
Hydronium ion, hydrated proton, H3O+

23
 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!
24
Monoprotic acids
HCl H+ + Cl- Strong electrolyte, strong acid

HNO3 H+ + NO3- Strong electrolyte, strong acid

CH3COOH H+ + CH3COO- Weak electrolyte, weak acid

Diprotic acids
H2SO4 H+ + HSO4- Strong electrolyte, strong acid

HSO4- H+ + SO42- Weak electrolyte, weak acid

Triprotic acids
H3PO4 H+ + H2PO4- Weak electrolyte, weak acid
H2PO4- H+ + HPO42- Weak electrolyte, weak acid
HPO42- H+ + PO43- Weak electrolyte, weak acid
25
26
Example 4.3

Classify each of the following species in aqueous solution as a

Brønsted acid or base:

(a)HBr

(b)

(c)
Example 4.3

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
Solution
(a)We know that HCl is an acid. Because Br and Cl are both
halogens (Group 7A), we expect HBr, like HCl, to ionize in water
as follows:

Therefore HBr 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

(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) + H2O

H+ + Cl- + Na+ + OH- Na+ + Cl- + H2O
H+ + OH- H2O

31
Neutralization Reaction Involving a Weak
Electrolyte

weak acid + base salt + water

HCN (aq) + NaOH (aq) NaCN (aq) + H2O

HCN + Na+ + OH- Na+ + CN- + H2O
HCN + OH- CN- + H2O

32
Example 4.4

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

(a) hydrobromic acid(aq) + barium hydroxide(aq)

(b) sulfuric acid(aq) + potassium hydroxide(aq)

Example 4.4
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
Solution
(a)Molecular equation:
2HBr(aq) + Ba(OH)2(aq) BaBr2(aq) + 2H2O(l)
Ionic equation:

2H+(aq) + 2Br−(aq) + Ba2+(aq) + 2OH−(aq)

Ba2+(aq) + 2Br−(aq) + 2H2O(l)
Net ionic equation:
2H+(aq) + 2OH−(aq) 2H2O(l)
or
H+(aq) + OH−(aq) H2O(l)
Both Ba2+ and Br− are spectator ions.
Example 4.4
(b) Molecular equation:

H2SO4(aq) + 2KOH(aq) K2SO4(aq) + 2H2O(l)

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 + CO2

2HCl (aq) + Na2CO3 (aq) 2NaCl (aq) + H2O +CO2

2H+ + 2Cl- + 2Na+ + CO32- 2Na+ + 2Cl- + H2O + CO2

2H+ + CO32- H2O + CO2

37
 Oxidation-Reduction Reactions
(electron transfer reactions)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)
2Mg + O2 + 4e- 2Mg2+ + 2O2- + 4e-
2Mg + O2 2MgO 38
39
 Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)

Zn Zn2+ + 2e- Zn is oxidized

Zn is the reducing agent

Cu2+ + 2e- Cu Cu2+ is reduced

Cu2+ is the oxidizing agent

40
 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, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1. 41
4.4
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,
O2-, is –½.

42
Example 4.5

Assign oxidation numbers to all the elements in the following

compounds and ion:

(a)Li2O

(b)HNO3

(c)
Example 4.5

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
Solution
(a)By rule 2 we see that lithium has an oxidation number of +1
(Li+) and oxygen’s oxidation number is −2 (O2−).

(b)This is the formula for nitric acid, which yields a H+ ion and a
N 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
x + 3(−2) = −1
x = +5
Example 4.5
(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
2(y) + 7(−2) = −2
y = +6

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

47
Types of Oxidation-Reduction Reactions

Combination Reaction
A+B C
0 0 +3 -1
2Al + 3Br2 2AlBr3

Decomposition Reaction
C A+B

+1 +5 -2 +1 -1 0
2KClO3 2KCl + 3O2
48
Types of Oxidation-Reduction Reactions

Combustion Reaction

A + O2 B
0 0 +4 -2
S + O2 SO2

0 0 +2 -2
2Mg + O2 2MgO

49
 Types of Oxidation-Reduction Reactions

Displacement Reaction
A + BC AC + B
0 +1 +2 0
Sr + 2H2O Sr(OH)2 + H2 Hydrogen Displacement
+4 0 0 +2
TiCl4 + 2Mg Ti + 2MgCl2 Metal Displacement
0 -1 -1 0
Cl2 + 2KBr 2KCl + Br2 Halogen Displacement

50
The Activity Series for Metals

Hydrogen Displacement Reaction

M + BC MC + B
M is metal
BC is acid or H2O
B is H2
Ca + 2H2O Ca(OH)2 + H2
Pb + 2H2O Pb(OH)2 + H2

51
The Activity Series for Halogens
F2 > Cl2 > Br2 > I2

Halogen Displacement Reaction

0 -1 -1 0
Cl2 + 2KBr 2KCl + Br2

I2 + 2KBr 2KI + Br2

52
 Types of Oxidation-Reduction Reactions
Disproportionation Reaction
The same element is simultaneously oxidized and
reduced.

Example: reduced

0 +1 -1
Cl2 + 2OH- ClO- + Cl- + H2O

oxidized

53
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
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
(c) This is a metal displacement reaction. The Ni metal
replaces (reduces) the Pb2+ 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 NO2 and it is +3 in HNO2

and +5 in HNO3. Because the oxidation number of the
same element both increases and decreases, this is a
disproportionation reaction.
 Chemistry in Action: Breath Analyzer
+6
3CH3CH2OH + 2K2Cr2O7 + 8H2SO4

+3
3CH3COOH + 2Cr2(SO4)3 + 2K2SO4 + 11H2O

57
 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

58
Preparing a Solution of Known Concentration

59
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
Strategy
How many moles of K2Cr2O7 does a 1-L (or 1000 mL) 2.16 M
K2Cr2O7 solution contain?

A 250-mL solution?

How would you convert moles to grams?

Example 4.7
Solution The first step is to determine the number of moles of
K2Cr2O7 in 250 mL or 0.250 L of a 2.16 M solution. Rearranging
Equation (4.1) gives

moles of solute = molarity × L soln

Thus,
Example 4.7
The molar mass of K2Cr2O7 is 294.2 g, so we write

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

by [molarity (mol/L) × volume (L) × molar mass (g/mol)] or
[2 mol/L × 0.25 L × 300 g/mol] = 150 g. 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
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
Next, we calculate the volume of the solution that contains 2.114
× 10−2 mole of the solute. Rearranging Equation (4.2) gives

Check One liter of the solution contains 2.53 moles of C6H12O6.

Therefore, the number of moles in 8.36 mL or 8.36 × 10−3 L
is (2.53 mol × 8.36 × 10−3) or 2.12 × 10−2 mol. The small
difference is due to the different ways of rounding off.
Dilution is the procedure for preparing a less concentrated
solution from a more concentrated solution.

Dilution
Add Solvent

Moles of solute Moles of solute

before dilution (i) = after dilution (f)

MiVi = MfVf 67
Example 4.9

Describe how you would prepare 5.00 × 102 mL of a

1.75 M H2SO4 solution, starting with an 8.61 M stock
solution of H2SO4.
Example 4.9

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
Solution We prepare for the calculation by tabulating our data:

Mi = 8.61 M Mf = 1.75 M
Vi = ? Vf = 5.00 × 102 mL

Substituting in Equation (4.3),

Example 4.9

Thus, we must dilute 102 mL of the 8.61 M H2SO4 solution with

sufficient water to give a final volume of 5.00 × 102 mL 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.
 Gravimetric Analysis
1. Dissolve unknown substance in water
2. React unknown with known substance to form a precipitate
3. Filter and dry precipitate
4. Weigh precipitate
5. Use chemical formula and mass of precipitate to determine
amount of unknown ion

72
Example 4.10

A 0.5662-g sample of an ionic compound containing chloride

ions and an unknown metal is dissolved in water and treated
with an excess of AgNO3. If 1.0882 g of AgCl precipitate forms,
what is the percent by mass of Cl in the original compound?
Example 4.10
Strategy
We are asked to calculate the percent by mass of Cl in the
unknown sample, which is

The only source of Cl− ions is the original compound. These

chloride ions eventually end up in the AgCl precipitate.

Can we calculate the mass of the Cl− ions if we know the

percent by mass of Cl in AgCl?
Example 4.10
Solution The molar masses of Cl and AgCl are 35.45 g and
143.4 g, respectively. Therefore, the percent by mass of Cl in
AgCl is given by

Next, we calculate the mass of Cl in 1.0882 g of AgCl. To do so

we convert 24.72 percent to 0.2472 and write
Example 4.10
Because the original compound also contained this amount of
Cl− ions, the percent by mass of Cl in the compound is

Check AgCl is about 25 percent chloride by mass, so the

roughly 1 g of AgCl precipitate that formed corresponds to
about 0.25 g of chloride, which is a little less than half of the
mass of the original sample. Therefore, the calculated percent
chloride of 47.51 percent is reasonable.
 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
77
Titrations can be used in the analysis of

Acid-base reactions

H2SO4 + 2NaOH 2H2O + Na2SO4

Redox reactions

5Fe2+ + MnO4- + 8H+ Mn2+ + 5Fe3+ + 4H2O

78
Example 4.11

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

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

need to
find

want to given
calculate
The volume of NaOH solution is given in the problem. Therefore,
we need to find the number of moles of NaOH to solve for
molarity. From the preceding equation for the reaction between
KHP and NaOH shown in the text we see that 1 mole of KHP
neutralizes 1 mole of NaOH. How many moles of KHP are
contained in 0.5468 g of KHP?
Example 4.11
Solution First we calculate the number of moles of KHP
consumed in the titration:

Because 1 mol KHP ≏ 1 mol NaOH, there must be 2.678 × 10−3

mole of NaOH in 23.48 mL of NaOH solution. Finally, we
calculate the number of moles of NaOH in 1 L of the solution or
the molarity as follows:
Example 4.12

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

needed to neutralize 20.0 mL of a 0.245 M H2SO4 solution?
Example 4.12
Strategy We want to calculate the volume of the NaOH solution.
From the definition of molarity [see Equation (4.1)], we write

need to
find

want to given
From the equation for the neutralization reaction just shown, we
calculate
see that 1 mole of H2SO4 neutralizes 2 moles of NaOH.

How many moles of H2SO4 are contained in 20.0 mL of a 0.245

M H2SO4 solution?

How many moles of NaOH would this quantity of H 2SO4

neutralize?
Example 4.12
Solution
First we calculate the number of moles of H2SO4 in a 20.0 mL
solution:

From the stoichiometry we see that 1 mol H2SO4 ≏ 2 mol NaOH.

Therefore, the number of moles of NaOH reacted must be
2 × 4.90 × 10−3 mole, or 9.80 × 10−3 mole.
Example 4.12

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

or
Example 4.13
A 16.42-mL volume of 0.1327 M KMnO4
solution is needed to oxidize 25.00 mL of a
FeSO4 solution in an acidic medium. What is
the concentration of the FeSO4 solution in
molarity? The net ionic equation is
Example 4.13
Strategy We want to calculate the molarity of the FeSO4
solution. From the definition of molarity
need to
find

want to given
calculate
The volume of the FeSO4 solution is given in the problem.
Therefore, we need to find the number of moles of FeSO4 to solve
for the molarity.
From the net ionic equation, what is the stoichiometric
equivalence between Fe2+ and ?
How many moles of KMnO4 are contained in 16.42 mL of 0.1327
M KMnO4 solution?
Example 4.13
Solution The number of moles of KMnO4 in 16.42 mL of the
solution is

From the net ionic equation we see that 5 mol Fe2+ ≏1 mol
Therefore, the number of moles of FeSO4 oxidized is
Example 4.13
The concentration of the FeSO4 solution in moles of FeSO4 per
liter of solution is
 Chemistry in Action: Metals from the Sea
CaCO3 (s) CaO (s) + CO2 (g)

CaO (s) + H2O (l) Ca2+ (aq) + 2OH - (aq)

Mg2+ (aq) + 2OH -(aq) Mg(OH)2 (s)

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

Mg2+ + 2e- Mg
2Cl- Cl2 + 2e-
MgCl2 (aq) Mg (l) + Cl2 (g)

90