Reactions in Aqueous Solution

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

NaCl (s) H2O 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.

d-

d+
H2O 6
Nonelectrolyte does not conduct electricity?

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

H 2O
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)

net ionic equation
Na+ and NO3- are spectator ions
8
PbI2
Solubility is the maximum amount of solute that will dissolve
in a given quantity of solvent at a specific temperature.

9
Examples of Insoluble Compounds

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

10
Example 1

Classify the following ionic compounds as soluble or insoluble:

(a) silver sulfate (Ag2SO4)

(b) calcium carbonate (CaCO3)

(c) sodium phosphate (Na3PO4).

 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.

12
Example 2
Predict what happens when a potassium phosphate (K3PO4)
solution is mixed with a calcium nitrate [Ca(NO3)2] solution.
Write a net ionic equation for the reaction.
Example
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
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.
 Practice Reactions
• Complete the following precipitation reactions. (Write the
balanced molecular equation, the complete ionic and the
net ionic equations).
– Reaction between
• a solution of Al(NO3)3 and a solution of NaOH
• a solution of BaCl2 and a solution of ZnSO4
• a solution of potassium sulfide and a solution of
copper (II) chloride

16
 Properties of Acids
• Have a sour taste. Vinegar owes its taste to acetic acid. Citru
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.

17
 Properties of Bases
• Have a bitter taste.

• Feel slippery. Many soaps contain bases.

• Cause color changes in plant dyes.

• Aqueous base solutions conduct electricity.

18
Arrhenius acid is a substance that produces H+ (H3O+) in water.

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

19
 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!
20
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
21
22
Example 3

Classify each of the following species in aqueous solution as a

Brønsted acid or base:

(a) HBr

(b)

(c)
 Neutralization Reactions

acid + base salt + water

HCl (aq) + NaOH (aq) NaCl (aq) + H2O

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

24
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

25
Example 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
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
(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

29
Oxidation – Reduction Reactions
(electron transfer reactions)

30
31
 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

Copper wire reacts with silver nitrate to form silver metal.

What is the oxidizing agent in the reaction?

Cu (s) + 2AgNO3 (aq) Cu(NO3)2 (aq) + 2Ag (s)

Cu Cu2+ + 2e-
Ag+ + 1e- Ag Ag+ is reduced Ag+ is the oxidizing agent

32
 Oxidation-Reduction 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 33
 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. 34
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.

35
Example 5

Assign oxidation numbers to all the elements in the following

compounds and ion:

(a) Li2O

(b) HNO3

(c)
Example
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
(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?
 Practice Problems
• Assign oxidation numbers to all the elements in following
compounds/ions:

1. CO2 C ____ O _______

2. PF3 P _______ F _______
3. MnO4- Mn______ O _______
4. KClO3 K ______ Cl _____ O ________
5. SF6 S _____ F ______
6. O2 O ____
7. NO2 N _____ O ____
8. CuCl2 Cu ______ Cl _____

39
The Oxidation Numbers of Elements in their Compounds

40
 Oxidation and Reduction half – reactions

• Sr + O2 → SrO
- Sr → Sr2+ + 2e- (Sr is oxidized)

-O 2
+
4 e- → 2O2- (O2 is reduced)
(Each O atom gains 2e-)

# e- lost = # e- gained

(Sr → Sr2+ + 2e-) x 2 = 2 Sr → 2 Sr2+ + 4e-

4e- transferred

2 Sr → 2 Sr2+ + 4e-
O2 + 4 e- → 2O2-

→ 41
2Sr + O2 2 Sr2+ 2O2-
 Practice Problems

• For each of the following reactions,

Assign the oxidation numbers to all the elements; determine
what is oxidized and what is reduced; write the oxidation and
reduction half-reactions; determine the number of electrons
transferred; balance the reaction.

1. Mg + O2 → MgO
2. Mg + N2 → Mg3N2
3. Fe + O2 → Fe2O3
4. Na + S → Na2S
42
 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
43
 Types of Oxidation-Reduction Reactions

Combustion Reaction

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

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

44
 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

45
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

46
The Activity Series for Halogens
F2 > Cl2 > Br2 > I2

Halogen Displacement Reaction

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

I2 + 2KBr 2KI + Br2

47
 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

48
 Practice Problems

Classify the following reactions

Fe + H2SO4 → FeSO4 + H2

49
 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

50
Example 6

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
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
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
Preparing a Solution of Known Concentration

54
 Practice problems
1. What is the molarity of 85.0 mL ethanol (C2H5OH)
solution containing 1.77 g of C2H5OH.

2. What volume in mL of a 0.315 M NaOH contains 6.22 g of

NaOH?

3. How many moles of chloride ions are present 60.0 mL of

0.100 M MgCl2 solution?

55
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 56
Example 7

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

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
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),

 Practice Questions

1. Water is added to 25.0 mL of a 0.866 M KNO3 solution

until the volume is 500. mL. What is the concentration of
the final solution?

2. A 46.2 mL of 0.568 M calcium nitrate solution is mixed

with 80.5 mL of 1.396 M calcium nitrate solution. Calculate
the concentration of the final solution.

60
 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
61
Titrations can be used in the analysis of

Acid-base reactions

H2SO4 + 2NaOH 2H2O + Na2SO4

Redox reactions

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

62
Example 8

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
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:
What volume of a 1.420 M NaOH solution is required
to titrate 25.00 mL of a 4.50 M H2SO4 solution?

WRITE THE CHEMICAL EQUATION!

H2SO4 + 2NaOH 2H2O + Na2SO4

M rxn M
volume acid moles red moles base volume base
acid coef. base

4.50 mol H2SO4 2 mol NaOH 1000 ml soln

25.00 mL x x x = 158 mL
1000 mL soln 1 mol H2SO4 1.420 mol NaOH
65
Example 9
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
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
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
The concentration of the FeSO4 solution in moles of FeSO4 per
liter of solution is
 Practice Problems

• 18.68 mL of KOH is required to neutralize 0.4218 g of

KHP. What is the concentration of KOH in molarity?
• 43.79 mL of a 0.1172 M NaOH is required to titrate 25.00
mL of H2SO4. What is the concentration of H2SO4?
2 NaOH + H2SO4 → Na2SO4 + 2H2O
• How many mL of 0.206 M of HI are required to reduce
22.5 mL of a 0.374 M KMnO4?
10HI + 2KMnO4 + 3H2SO4 → 5I2 + 2 MnSO4 + K2SO4 + 8H2O

70