3.

0 Aqueous Reactions and Solution

chemistry

4-1
 Definitions

Solution A homogeneous mixture of two or more

substances.

Solute The substance present in a smaller

amount

Solvent The substance present in a larger amount

Aqueous The solute initially is a liquid or a solid and the

solutions solvent is water

4-2
 Solution Stoichiometry

• Many reactions occur in solution.

• A solution consists of one or more solutes dissolved in a
solvent.
• The concentration of a solution is given by the quantity
of solute present in a given quantity of solution.
• Molarity (M) is often used to express concentration.

Molarity = moles solute mol solute

M=
liters of solution L soln

4-3
 Sample Problem 3.22 Calculating the Molarity of a Solution

PROBLEM: What is the molarity of an aqueous solution that contains

0.715 mol of glycine (H2NCH2COOH) in 495 mL?

PLAN: SOLUTION:
Molarity is the number of moles of
solute per liter of solution.
0.715 mol glycine x 1000 mL
mol of glycine
495 mL soln 1L
divide by volume

concentration in mol/mL = 1.44 M glycine

103 mL = 1 L

molarity of glycine

4-4
 Figure 3.13 Summary of mass-mole-number-volume
relationships in solution.

4-5
 Sample Problem 3.23 Calculating Mass of Solute in a Given
Volume of Solution
PROBLEM: How many grams of solute are in 1.75 L of 0.460 M
sodium monohydrogen phosphate buffer solution?

PLAN: Calculate the moles of solute using volume of solution

the given molarity and volume. multiply by M
Convert moles to mass using the
molar mass of the solute. moles of solute
multiply by M

SOLUTION: grams of solute

1.75 L x 0.460 moles

= 0.805 mol Na2HPO4
1L

0.805 mol Na2HPO4 x 141.96 g Na2HPO4 = 114 g Na2HPO4

1 mol Na2HPO4

4-6
 Figure 3.14 Laboratory preparation of molar solutions.

A
•Weigh the solid needed.
C Add solvent until the solution
•Transfer the solid to a
reaches its final volume.
volumetric flask that contains
about half the final volume of
solvent.
B Dissolve the solid
thoroughly by swirling.

4-7
 Figure 3.15 Converting a concentrated solution to a dilute solution.

4-8
 Sample Problem 3.24 Preparing a Dilute Solution from a
Concentrated Solution
PROBLEM: “Isotonic saline” is a 0.15 M aqueous solution of NaCl. How
would you prepare 0.80 L of isotonic saline from a 6.0 M
stock solution?
PLAN: To dilute a concentrated solution, we add only solvent, so the
moles of solute are the same in both solutions. The volume and
molarity of the dilute solution gives us the moles of solute.
Then we calculate the volume of concentrated solution that
contains the same number of moles.
volume of dilute soln
multiply by M of dilute soln
moles of NaCl in dilute soln =
mol NaCl in concentrated soln
divide by M of concentrated soln
L of concentrated soln

4-9
 Sample Problem 3.24

Mdil x Vdil = # mol solute = Mconc x Vconc

SOLUTION:
Using the volume and molarity for the dilute solution:

0.80 L soln x 0.15 mol NaCl = 0.12 mol NaCl

1 L soln

Using the moles of solute and molarity for the concentrated solution:

0.12 mol NaCl x 1 L soln

= 0.020 L soln
6.0 mol NaCl

A 0.020 L portion of the concentrated solution must be

diluted to a final volume of 0.80 L.

4-10
 Sample Problem 3.25 Visualizing Changes in Concentration

PROBLEM: The beaker and circle represents a unit volume of

solution. Draw the solution after each of these changes:

(a) For every 1 mL of solution, 1 mL of

solvent is added.
(b) One third of the volume of the solution
is boiled off.

PLAN: Only the volume of the solution changes; the total number of
moles of solute remains the same. Find the new volume and
calculate the number of moles of solute per unit volume.

4-11
 Sample Problem 3.25

SOLUTION: Ndil x Vdil = Nconc x Vconc

where N is the number of particles.

(a) Ndil = Nconc x Vconc = 8 particles x 1 mL = 4 particles

Vdil 2 mL
(b) N Vdil
conc = N dil x = 8 particles x 1 mL = 12 particles
Vconc 2 mL
3

(a) (b)

4-12
 Sample Problem 3.26 Calculating Quantities of Reactants and
Products for a Reaction in Solution
PROBLEM: A 0.10 M HCl solution is used to simulate the acid
concentration of the stomach. How many liters of “stomach
acid” react with a tablet containing 0.10 g of magnesium
hydroxide?
PLAN: Write a balanced equation and convert the mass of Mg(OH)2 to
moles. Use the mole ratio to determine the moles of HCl, then
convert to volume using molarity.

mass Mg(OH)2
divide by M
mol Mg(OH)2
use mole ratio
mol HCl L HCl
divide by M

4-13
 Sample Problem 3.26

SOLUTION:

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

0.10 g Mg(OH)2 x 1 mol Mg(OH)2 = 1.7x10-3 mol Mg(OH)2

58.33 g Mg(OH)2

= 1.7x10-3 mol Mg(OH)2 x 2 mol HCl

= 3.4x10-3 mol HCl
1 mol Mg(OH)2

3.4x10-3 mol HCl x 1L HCl soln = 3.4x10-2 L HCl

0.10 mol HCl

4-14
 Sample Problem 3.27 Solving Limiting-Reactant Problems for
Reactions in Solution
PROBLEM: In a simulation mercury removal from industrial wastewater,
0.050 L of 0.010 M mercury(II) nitrate reacts with 0.020 L of
0.10 M sodium sulfide. How many grams of mercury(II)
sulfide form? Write a reaction table for this process.
PLAN: Write a balanced chemical reaction. Determine limiting reactant.
Calculate the grams of mercury(II) sulfide product.

volume of Hg(NO3)2 soln volume of Na2S soln

multiply by M multiply by M
mol of Hg(NO3)2 mol of Na2S
mole ratio mole ratio
mol of HgS mol of HgS
select lower number of moles of HgS
multiply by M
mass of HgS
4-15
 Sample Problem 3.27

SOLUTION: Hg(NO3)2 (aq) + Na2S (aq) → HgS (s) + 2NaNO3 (aq)

0.050 L Hg(NO3)2 x 0.010 mol Hg(NO3)2 x 1 mol HgS

1 L Hg(NO3)2 1 mol Hg(NO3)2
= 5.0x10-4 mol HgS

0.020 L Na2S x 0. 10 mol Na2S x 1 mol HgS = 2.0x10-3 mol HgS

1 L Na2S 1 mol Na2S

Hg(NO3)2 is the limiting reactant because it yields less HgS.

5.0 x 10-4 mol HgS x 232.7 g HgS = 0.12 g HgS

1 mol HgS

4-16
 Sample Problem 3.27

The reaction table is constructed using the amount of Hg(NO3)2 to

determine the changes, since it is the limiting reactant.

Amount Hg(NO3)2 (aq) + Na2S (aq) → HgS (s) + 2NaNO3 (aq)

Initial 5.0 x 10-4 2.0 x 10-3 0 0
Change -5.0 x 10-4 -5.0 x 10-4 +5.0 x 10-4 +1.0 x 10-3

Final 0 1.5 x 10-3 5.0 x 10-4 +1.0 x 10-3

4-17
 Figure 3.16 An overview of amount-mass-number
stoichiometric relationships.

4-18
 Water as a Solvent

• Water is a polar molecule

– since it has uneven electron distribution
– and a bent molecular shape.
• Water readily dissolves a variety of substances.
• Water interacts strongly with its solutes and often plays
an active role in aqueous reactions.

4-19
 Figure 4.1 Electron distribution in molecules of H2 and H2O.

A. Electron charge distribution

in H2 is symmetrical. B. Electron charge distribution
in H2O is asymmetrical.

C. Each bond in H2O is polar.

D. The whole H2O molecule is polar.
4-20
 Figure 4.2 An ionic compound dissolving in water.

4-21
 Figure 4.3 The electrical conductivity of ionic solutions.

4-22
 Sample Problem 4.1 Using Molecular Scenes to Depict an Ionic
Compound in Aqueous Solution

PROBLEM: The beakers shown below contain aqueous solutions of

the strong electrolyte potassium sulfate.

(a) Which beaker best represents the compound in solution?

(H2O molecules are not shown).
(b) If each particle represents 0.10 mol, what is the total
number of particles in solution?

4-23
 Sample Problem 4.1

PLAN: (a) Determine the formula and write and equation for the
dissociation of 1 mol of compound. Potassium sulfate is a
strong electrolyte; it therefore dissociates completely in
solution. Remember that polyatomic ions remain intact in
solution.
(b) Count the number of separate particles in the relevant
beaker, then multiply by 0.1 mol and by Avogadro’s number.

SOLUTION:

(a) The formula is K2SO4, so the equation for dissociation is:

K2SO4 (s) → 2K+ (aq) + SO42- (aq)

4-24
 Sample Problem 4.1

There should be 2 cations for every 1 anion;

beaker C represents this correctly.

(b) Beaker C contains 9 particles, 6 K+ ions and 3 SO42- ions.

6.022x1023 particles
9 x 0.1 mol x = 5.420x1023 particles
1 mol

4-25
 Sample Problem 4.2 Determining Amount (mol) of Ions in Solution

PROBLEM: What amount (mol) of each ion is in each solution?

(a) 5.0 mol of ammonium sulfate dissolved in water

(b) 78.5 g of cesium bromide dissolved in water
(c) 7.42x1022 formula units of copper(II) nitrate dissolved in water
(d) 35 mL of 0.84 M zinc chloride

PLAN: Write an equation for the dissociation of 1 mol of each

compound. Use this information to calculate the actual
number of moles represented by the given quantity of
substance in each case.

4-26
 Sample Problem 4.2

SOLUTION:
(a) The formula is (NH4)2SO4 so the equation for dissociation is:
(NH4)2SO4 (s) → 2NH4+ (aq) + SO42- (aq)

5.0 mol (NH4)2SO4 x 2 mol NH4+

= 10. mol NH4+
1 mol (NH4)2SO4

5.0 mol (NH4)2SO4 x 1 mol SO42- = 5.0 mol NH4+

1 mol (NH4)2SO4

4-27
 Sample Problem 4.2

SOLUTION:

(b) The formula is CsBr so the equation for dissociation is:

CsBr (s) → Cs+ (aq) + Br- (aq)

+
78.5 g CsBr x 1 mol CsBr x 1 mol Cs = 0.369 mol Cs+
212.8 g CsBr 1 mol CsBr

There is one Cs+ ion for every Br- ion, so the number of
moles of Br- is also equation to 0.369 mol.

4-28
 Sample Problem 4.2

SOLUTION:
(c) The formula is Cu(NO3)2 so the formula for dissociation is:
Cu(NO3)2 (s) → Cu2+ (aq) + 2NO3- (aq)

7.42x1022 formula units Cu(NO3)2 x 1 mol

6.022x1023 formula units

= 0.123 mol Cu(NO3)2

0.123 mol Cu(NO3)2 x 1 mol Cu2+

= 0.123 mol Cu2+ ions
1 mol Cu(NO3)2

There are 2 NO3- ions for every 1 Cu2+ ion, so there are
0.246 mol NO3- ions.

4-29
 Sample Problem 4.2

SOLUTION:
(d) The formula is ZnCl2 so the formula for dissociation is:
ZnCl2 (s) → Zn2+ (aq) + 2Cl- (aq)

35 mL soln x 1 L x 0.84 mol ZnCl2 = 2.9x10-2 mol ZnCl2

103 mL 1 L soln

2.9x10-2 mol ZnCl2 x 2 mol Cl-

= 5.8x10-2 mol Cl-
1 mol ZnCl2

There is 1 mol of Zn2+ ions for every 1 mol of ZnCl2, so

there are 2.9 x 10-2 mol Zn2+ ions.

4-30
 Writing Equations for Aqueous Ionic Reactions

The molecular equation shows all reactants and products

as if they were intact, undissociated compounds.
This gives the least information about the species in solution.

2AgNO3 (aq) + Na2CrO4 (aq) → Ag2CrO4 (s) + 2NaNO3 (aq)

When solutions of silver nitrate and sodium chromate mix, a

brick-red precipitate of silver chromate forms.

4-31
 The total ionic equation shows all soluble ionic
substances dissociated into ions.
This gives the most accurate information about species in solution.

2Ag+ (aq) + 2NO3- (aq) → Ag2CrO4 (s)

+ 2Na+ (aq) + CrO42- (aq) + 2Na+ (aq) + NO3- (aq)

Spectator ions are ions that are not involved in the actual
chemical change. Spectator ions appear unchanged on
both sides of the total ionic equation.

2Ag+ (aq) + 2NO3- (aq) → Ag2CrO4 (s)

+ 2Na+ (aq) + CrO42- (aq) + 2Na+ (aq) + 2NO3- (aq)

4-32
 The net ionic equation eliminates the spectator ions and
shows only the actual chemical change.

2Ag+ (aq) + CrO42- (aq) → Ag2CrO4 (s)

4-33
 Figure 4.4 An aqueous ionic reaction and the three types
of equations.

4-34
 Precipitation Reactions

• In a precipitation reaction two soluble ionic compounds

react to give an insoluble products, called a precipitate.

• The precipitate forms through the net removal of ions

from solution.

• It is possible for more than one precipitate to form in

such a reaction.

4-35
 Figure 4.5 The precipitation of calcium fluoride.

2NaF (aq) + CaCl2 (aq) → CaF2 (s) + 2NaCl (aq)

2 Na+ (aq) + 2 F- (aq) + Ca2+ (aq) + 2 Cl- (aq) → CaF2(s) + 2 Na+ (aq) + 2 Cl- (aq)

2 NaF(aq) + CaCl2 (aq) → CaF2(s) + 2 NaCl (aq)

4-36
 Figure 4.6 The precipitation of PbI2, a metathesis reaction.

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

2Na+(aq) + 2I- (aq) + Pb2+ (aq) + 2NO3- (aq)

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

Precipitation reactions are also called

double displacement reactions or
metathesis.

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

Ions exchange partners and a precipitate forms, so there

is an exchange of bonds between reacting species.
4-37
 Predicting Whether a Precipitate Will Form

• Note the ions present in the reactants.

• Consider all possible cation-anion combinations.
• Use the solubility rules to decide whether any of the ion
combinations is insoluble.
– An insoluble combination identifies the precipitate that will form.

4-38
 Table 4.1 Solubility Rules for Ionic Compounds in Water

Soluble Ionic Compounds

1. All common compounds of Group 1A(1) ions (Li+, Na+, K+, etc.) and
ammonium ion (NH4+) are soluble.
2. All common nitrates (NO3-), acetates (CH3COO- or C2H3O2-) and most
perchlorates (ClO4-) are soluble.
3. All common chlorides (Cl-), bromides (Br-) and iodides (I-) are soluble,
except those of Ag+, Pb2+, Cu+, and Hg22+. All common fluorides (F-) are
soluble except those of Pb2+ and Group 2A(2).
4. All common sulfates (SO22-) are soluble, except those of Ca2+, Sr2+, Ba2+,
Ag+, and Pb2+.
Insoluble Ionic Compounds

1. All common metal hydroxides are insoluble, except those of Group 1A(1)
and the larger members of Group 2A(2)(beginning with Ca2+).
2. All common carbonates (CO32-) and phosphates (PO43-) are insoluble,
except those of Group 1A(1) and NH4+.
3. All common sulfides are insoluble except those of Group 1A(1), Group
2A(2) and NH4+.
4-39
 Sample Problem 4.3 Predicting Whether a Precipitation Reaction
Occurs; Writing Ionic Equations

PROBLEM: Predict whether or not a reaction occurs when each of the

following pairs of solutions are mixed. If a reaction does occur,
write balanced molecular, total ionic, and net ionic equations,
and identify the spectator ions.
(a) potassium fluoride (aq) + strontium nitrate (aq) →
(b) ammonium perchlorate (aq) + sodium bromide (aq) →

PLAN: Note reactant ions, write the possible cation-anion

combinations, and use Table 4.1 to decide if the combinations
are insoluble.
Write the appropriate equations for the process.

4-40
 Sample Problem 4.3

SOLUTION: (a) The reactants are KF and Sr(NO3)2. The possible

products are KNO3 and SrF2. KNO3 is soluble, but
SrF2 is an insoluble combination.

Molecular equation:
2KF (aq) + Sr(NO3)2 (aq) → 2 KNO3 (aq) + SrF2 (s)

Total ionic equation:

2K+ (aq) + 2F- (aq) + Sr2+ (aq) + 2NO3- (aq) → 2K+ (aq) + 2NO3- (aq) + SrF2 (s)

K+ and NO3- are spectator ions

Net ionic equation:

Sr2+ (aq) + 2F- (aq) → SrF2 (s)

4-41
 Sample Problem 4.3

SOLUTION: (b) The reactants are NH4ClO4 and NaBr. The

possible products are NH4Br and NaClO4. Both are
soluble, so no precipitate forms.

Molecular equation:
NH4ClO4 (aq) + NaBr (aq) → NH4Br (aq) + NaClO4 (aq)

Total ionic equation:

NH4+ (aq) + ClO4- (aq) + Na+ (aq) + Br- (aq) → NH4+ (aq) + Br- (aq) +
Na+ (aq) + ClO4- (aq)

All ions are spectator ions and there is no net ionic equation.

4-42
 Sample Problem 4.4 Using Molecular Depictions in
Precipitation Reactions
PROBLEM: The following molecular views show reactant solutions for a
precipitation reaction (with H2O molecules omitted for clarity).

(a) Which compound is dissolved in beaker A: KCl, Na2SO4, MgBr2, or

Ag2SO4?
(b) Which compound is dissolved in beaker B: NH4NO3, MgSO4,
Ba(NO3)2, or CaF2?

4-43
 Sample Problem 4.4

PLAN: Note the number and charge of each kind of ion and use
Table 4.1 to determine the ion combinations that are soluble.

SOLUTION:
(a) Beaker A contains two 1+ ion for each 2- ion. Of the choices
given, only Na2SO4 and Ag2SO4 are possible. Na2SO4 is
soluble while Ag2SO4 is not.
Beaker A therefore contains Na2SO4.

(b) Beaker B contains two 1- ions for each 2+ ion. Of the choices
given, only CaF2 and Ba(NO3)2 match this description. CaF2 is
not soluble while Ba(NO3)2 is soluble.
Beaker B therefore contains Ba(NO3)2.

4-44
 Sample Problem 4.4

PROBLEM: (c) Name the precipitate and spectator ions when solutions A
and B are mixed, and write balanced molecular, total
ionic, and net ionic equations for this process.
(d) If each particle represents 0.010 mol of ions, what is the
maximum mass (g) of precipitate that can form (assuming
complete reaction)?

PLAN: (c) Consider the cation-anion combinations from the two

solutions and use Table 4.1 to decide if either of these is
insoluble.

SOLUTION: The reactants are Ba(NO3)2 and Na2SO4. The possible

products are BaSO4 and NaNO3. BaSO4 is insoluble
while NaNO3 is soluble.

4-45
 Sample Problem 4.4

Molecular equation:
Ba(NO3)2 (aq) + Na2SO4 (aq) → 2NaNO3 (aq) + BaSO4 (s)

Total ionic equation:

Ba2+ (aq) + 2NO3- (aq) + 2Na+ (aq) + SO42- (aq) → 2Na+ (aq) + 2NO3- (aq)
+ BaSO4 (s)

Na+ and NO3- are spectator ions

Net ionic equation:

Ba2+ (aq) + SO42- (aq) → BaSO4 (s)

4-46
 Sample Problem 4.4

PLAN: (d) Count the number of each kind of ion that combines to
form the solid. Multiply the number of each reactant ion by
0.010 mol and calculate the mol of product formed from
each. Decide which ion is the limiting reactant and use this
information to calculate the mass of product formed.

SOLUTION: There are 4 Ba2+ particles and 5 SO42- particles depicted.

2+
4 Ba2+ particles x 0.010 mol Ba x 1 mol BaSO4 = 0.040 mol BaSO
4
1 particle 1 mol Ba2+

2-
4 SO42- particles x 0.010 mol SO4 x 1 mol BaSO4 = 0.050 mol BaSO4
1 particle 1 mol SO42-

4-47
 Sample Problem 4.4

Ba2+ ion is the limiting reactant, since it yields less BaSO4.

0.040 mol BaSO4 x 233.4 g BaSO4 = 9.3 g BaSO

4
1 mol BaSO4

4-48
 Acid-Base Reactions

An acid is a substance that produces H+ ions when

dissolved in H2O.
H2O
HX → H+ (aq) + X- (aq)

A base is a substance that produces OH- ions when

dissolved in H2O.
H2O
MOH → M+ (aq) + OH- (aq)

An acid-base reaction is also called a neutralization reaction.

4-49
 Figure 4.7 The H+ ion as a solvated hydronium ion.

H+ interacts strongly with H2O, forming H3O+ in aqueous solution.

4-50
 Table 4.2 Selected Acids and Bases

Acids Bases
Strong Strong

hydrochloric acid, HCl sodium hydroxide, NaOH

hydrobromic acid, HBr potassium hydroxide, KOH
hydriodic acid, HI calcium hydroxide, Ca(OH)2
nitric acid, HNO3 strontium hydroxide, Sr(OH)2
sulfuric acid, H2SO4 barium hydroxide, Ba(OH)2
perchloric acid, HClO4

Weak Weak
hydrofluoric acid, HF ammonia, NH3

phosphoric acid, H3PO4

acetic acid, CH3COOH (or HC2H3O2)

4-51
 Figure 4.8 Acids and bases as electrolytes.

Strong acids and strong bases dissociate completely into ions in

aqueous solution.
They are strong electrolytes and conduct well in solution.

4-52
 Figure 4.8 Acids and bases as electrolytes.

Weak acids and weak bases dissociate very little into ions in aqueous
solution.
They are weak electrolytes and conduct poorly in solution.

4-53
 Acid-Base Titrations

• In a titration, the concentration of one solution is used to

determine the concentration of another.
• In an acid-base titration, a standard solution of base is
usually added to a sample of acid of unknown molarity.
• An acid-base indicator has different colors in acid and
base, and is used to monitor the reaction progress.
• At the equivalence point, the mol of H+ from the acid
equals the mol of OH- ion produced by the base.
– Amount of H+ ion in flask = amount of OH- ion added
• The end point occurs when there is a slight excess of
base and the indicator changes color permanently.

4-54
 Figure 4.11 An acid-base titration.

4-55
 Sample Problem 4.8 Finding the Concentration of Acid from a
Titration

PROBLEM: A 50.00 mL sample of HCl is titrated with 0.1524 M NaOH.

The buret reads 0.55 mL at the start and 33.87 mL at the end
point. Find the molarity of the HCl solution.
PLAN: Write a balanced equation for the reaction. Use the volume of
base to find mol OH-, then mol H+ and finally M for the acid.
volume of base
(difference in buret readings)
multiply by M of base
mol of OH-
use mole ratio as conversion factor

mol of H+ and acid

divide by volume (L) of acid
molarity (M) of acid
4-56
 Sample Problem 4.8

SOLUTION: NaOH (aq) + HCl (aq) → NaCl (aq) + H2O (l)

volume of base = 33.87 mL – 0.55 mL = 33.32 mL

33.32 mL soln x 1L x 0.1524 mol NaOH = 5.078x10-3 mol NaOH

103 mL 1 L soln

Since 1 mol of HCl reacts with 1 mol NaOH, the amount of HCl
= 5.078x10-3 mol.

5.078x10-3 mol HCl x 103 mL

= 0.1016 M HCl
50.00 mL 1L

4-57
 Oxidation-Reduction (Redox) Reactions

Oxidation is the loss of electrons.

The reducing agent loses electrons and is oxidized.

Reduction is the gain of electrons.

The oxidizing agent gains electrons and is reduced.

A redox reaction involves electron transfer

Oxidation and reduction occur together.

4-58
 Figure 4.12 The redox process in compound formation.

4-59
 Table 4.3 Rules for Assigning an Oxidation Number (O.N.)

General rules

1. For an atom in its elemental form (Na, O2, Cl2, etc.): O.N. = 0
2. For a monoatomic ion: O.N. = ion charge
3. The sum of O.N. values for the atoms in a compound equals zero. The
sum of O.N. values for the atoms in a polyatomic ion equals the ion’s charge.

Rules for specific atoms or periodic table groups

1. For Group 1A(1): O.N. = +1 in all compounds
2. For Group 2A(2): O.N. = +2 in all compounds
3. For hydrogen: O.N. = +1 in combination with nonmetals
4. For fluorine: O.N. = -1 in combination with metals and boron
5. For oxygen: O.N. = -1 in peroxides
O.N. = -2 in all other compounds(except with F)
6. For Group 7A(17): O.N. = -1 in combination with metals, nonmetals
(except O), and other halogens lower in the group

4-60
 Sample Problem 4.9 Determining the Oxidation Number of Each
Element in a Compound (or Ion)

PROBLEM: Determine the oxidation number (O.N.) of each element in

these species:
(a) zinc chloride (b) sulfur trioxide (c) nitric acid

PLAN: The O.N.s of the ions in a polyatomic ion add up to the charge
of the ion and the O.N.s of the ions in the compound add up
to zero.

SOLUTION:
(a) ZnCl2. The O.N. for zinc is +2 and that for chloride is -1.

(b) SO3. Each oxygen is an oxide with an O.N. of -2.

The O.N. of sulfur must therefore be +6.

(c) HNO3. H has an O.N. of +1 and each oxygen is -2.

The N must therefore have an O.N. of +5.

4-61
 Sample Problem 4.10 Identifying Redox Reactions

PROBLEM: Use oxidation numbers to decide whether each of the following

is a redox reaction or not.
(a) CaO (s) + CO2 (g) → CaCO3 (s)
(b) 4 KNO3 (s) → 2 K2O(s) + 2 N2(g) + 5 O2(g)
(c) NaHSO4 (aq) + NaOH (aq) → Na2SO4 (aq) + H2O (l)

PLAN: Use Table 4.3 to assign an O.N. to each atom. A change in

O.N. for any atom indicates electron transfer.

SOLUTION: (a) CaO(s) + CO2(g) → CaCO3(s)

+2 +2 +2 -2
-2 -2 +2

This is not a redox reaction, since no species change O.N.

4-62
 Sample Problem 4.10

(b) 4 KNO3 (s) → 2 K2O(s) + 2 N2(g) + 5 O2(g)

+1 -2 +1 0 0
+5 -2

This is a redox reaction.

N changes O.N. from +5 to 0 and is reduced.
O changes O.N. from -2 to 0 and is oxidized.

4-63
 Sample Problem 4.10

(c) NaHSO4 (aq) + NaOH (aq) → Na2SO4 (aq) + H2O (l)

+1 -2 +1 +1 -2 +1 -2
+1 -2 +6
+6 +1

This is not a redox reaction since no species change O.N.

4-64
 Figure 4.13 A summary of terminology for redox reactions.

4-65
 Sample Problem 4.11 Identifying Oxidizing and Reducing
Agents

PROBLEM: Identify the oxidizing agent and reducing agent in each

of the following reactions:
(a) 2Al (s) + 3H2SO4 (aq) → Al2(SO4)3 (aq) + 3H2(g)
(b) PbO (s) + CO (g) → Pb (s) + CO2 (g)
(c) 2H2 (g) + O2 (g) → 2H2O (g)

PLAN: Assign an O.N. to each atom and look for those that change during
the reaction.
The reducing agent contains an atom that is oxidized (increases in
O.N.) while the oxidizing agent contains an atom that is reduced
(decreases in O.N.).

4-66
 Sample Problem 4.11

SOLUTION:

(a) 2Al(s) + 3H2SO4(aq) → Al2(SO4)3(aq) + 3H2(g)

0 +1 +3 0
+6 -2 +6
-2 +1 -2

Al changes O.N. from 0 to +3 and is oxidized.

Al is the reducing agent.
H changes O.N. from +1 to 0 and is reduced.
H2SO4 is the oxidizing agent.

4-67
 Sample Problem 4.11

SOLUTION:

(b) PbO (s) + CO (g) → Pb (s) + CO2 (g)

+2 +2 0
-2 +4
-2 -2

Pb changes O.N. from +2 to 0 and is reduced.

PbO is the oxidizing agent.
C changes O.N. from +2 to +4 and is oxidized.
CO is the reducing agent.

4-68
 Sample Problem 4.11

SOLUTION:

(c) 2H2 (g) + O2 (g) → 2H2O (g)

0 0 +1

-2

H2 changes O.N. from 0 to +1 and is oxidized.

H2 is the reducing agent.
O changes O.N. from 0 to -2 and is reduced.
O2 is the oxidizing agent.

4-69
 Balancing Redox Equations
(oxidation number method)
1. Assign O.N.s to all atoms.
2. Identify the reactants that are oxidized and reduced.
3. Compute the numbers of electrons transferred, and
draw tie-lines from each reactant atom to the product
atom to show the change.
4. Multiply the numbers of electrons by factor(s) that make
the electrons lost equal to the electrons gained.
5. Use the factor(s) as balancing coefficients.
6. Complete the balancing by inspection and add states of
matter.

4-70
 Sample Problem 4.12 Balancing Redox Equations by the
Oxidation Number Method

PROBLEM: Use the oxidation number method to balance the following

equations:

(a) Cu (s) + HNO3 (aq) → Cu(NO3)2 (aq) + NO2 (g) + H2O (l)

SOLUTION:
Assign oxidation numbers and identify oxidized and reduced species:

(a) Cu (s) + HNO3 (aq) → Cu(NO3)2 (aq) + NO2 (g) + H2O (l)

0 +1 +2 +1
+5 +4
+5
-2 -2 -2 -2

4-71
 Sample Problem 4.12

loses 2e-; oxidation

Cu(s) + HNO3(aq) → Cu(NO3)2(aq) + NO2(g) + H2O(l)

gains 1e-; reduction

Multiply to make e- lost = e- gained:

Cu (s) + 2HNO3 (aq) → Cu(NO3)2 (aq) + 2NO2 (g) + H2O (l)

Balance other atoms by inspection:

Cu (s) + 4HNO3 (aq) → Cu(NO3)2 (aq) + 2NO2 (g) + 2H2O (l)

4-72
 Sample Problem 4.12

(b) PbS (s) + O2 (g) → PbO (s) + SO2 (g)

SOLUTION:
Assign oxidation numbers and identify oxidized and reduced species:

(b) PbS (s) + O2 (g) → PbO (s) + SO2 (g)

+2 0 +2 +4
-2 +5 -2
-2

4-73
 Sample Problem 4.12

loses 6e-; oxidation

PbS (s) + O2 (g) → PbO (s) + SO2 (g)

gains 2e- per O; reduction

Multiply to make e- lost = e- gained:

PbS (s) + 3 O (g) → PbO (s) + SO2 (g)

2 2

Balance other atoms by inspection,

and multiply to give whole-number coefficients:

2PbS (s) + 3O2 (g) → 2PbO (s) + 2SO2 (g)

4-74
 Figure 4.14 The redox titration of C2O42- with MnO4-

4-75
 Sample Problem 4.13 Finding the Amount of Reducing Agent by
Titration

PROBLEM: To measure the Ca2+ concentration in human blood, 1.00 mL

of blood was treated with Na2C2O4 solution to precipitate the
Ca2+ as CaC2O4. The precipitate was filtered and dissolved in
dilute H2SO4 to release C2O42-, which was titrated with
KMnO4 solution. The solution required 2.05mL of 4.88x10-4 M
KMnO4 to reach the end point. The balanced equation is

2 KMnO4 (aq) + 5 CaC2O4 (s) + 8 H2SO4 (aq) →

2 MnSO4 (aq) + K2SO4 (aq) + 5 CaSO4 (s) + 10 CO2 (g) + 8 H2O (l)

Calculate the amount (mol) of Ca2+ in 1.00 mL of blood.

4-76
 Sample Problem 4.13

PLAN: Calculate the mol of KMnO4 from the volume and molarity of the
solution. Use this to calculate the mol of C2O42- and hence the
mol of Ca2+ ion in the blood sample.

volume of KMnO4 soln

convert mL to L and multiply by M
mol of KMnO4
molar ratio
mol of CaC2O4
ratio of elements in formula
mol of Ca2+

4-77
 Sample Problem 4.13

SOLUTION:

1L 4.88x10-4 mol KMnO

2.05 mL soln x x 4
= 1.00x10-6 mol KMnO4
103 mL 1L soln

1.00x10-6 mol KMnO4 x 5 mol CaC2O4

= 2.50x10-6 mol CaC2O4
2 mol KMnO4

2.50x10-6 mol CaC2O4 x 1 mol Ca2+ = 2.50x10-6 mol Ca+2

1 mol CaC2O4

4-78
 Elements in Redox Reactions
Types of Reaction
• Combination Reactions
– Two or more reactants combine to form a new compound:
– X+Y→Z
• Decomposition Reactions
– A single compound decomposes to form two or more products:
– Z→X+Y
• Displacement Reactions
– double diplacement: AB + CD → AC + BD
– single displacement: X + YZ → XZ + Y
• Combustion
– the process of combining with O2

4-79
 Figure 4.15 Combining elements to form an ionic compound.

4-80
 Figure 4.16 Decomposition of the compound mercury(II) oxide
to its elements.

4-81
 Figure 4.17 The active metal lithium displaces H2 from water.

4-82
 Figure 4.18 The displacement of H2 from acid by nickel.

O.N. increasing O.N. decreasing

oxidation reduction
occurring occurring
reducing agent oxidizing agent

0 +1 +2 0

Ni (s) + 2H+ (aq) → Ni2+ (aq) + H2 (g)

4-83
 Figure 4.19 A more reactive metal (Cu) displacing the ion of a
less reactive metal (Ag+) from solution.

4-84
 Figure 4.20 The activity series of the metals.

4-85
 Sample Problem 4.14 Identifying the Type of Redox Reaction

PROBLEM: Classify each of the following redox reactions as a

combination, decomposition, or displacement reaction.
Write a balanced molecular equation for each, as well as
total and net ionic equations for part (c), and identify the
oxidizing and reducing agents:

(a) magnesium (s) + nitrogen (g) → magnesium nitride (aq)

(b) hydrogen peroxide (l) → water (l) + oxygen gas

(c) aluminum (s) + lead(II) nitrate (aq) → aluminum nitrate (aq) + lead (s)

PLAN: Combination reactions combine reactants, decomposition

reactions involve more products than reactants and
displacement reactions have the same number of reactants
and products.

4-86
 Sample Problem 4.14

SOLUTION:

(a) This is a combination reaction, since Mg and N2 combine:

3Mg (s) + N2 (g) → Mg3N2 (s)

0 0 +2
-3

Mg is the reducing agent; N2 is the oxidizing agent.

4-87
 Sample Problem 4.14

(b) This is a decomposition reaction, since H2O2 breaks down:

2 H2O2 (l) → + 2H2O (l) + O2 (g)

+1 +1 0
-2 -2

H2O2 is both the reducing and the oxidizing agent.

4-88
 Sample Problem 4.14

(c) This is a displacement reaction, since Al displaces Pb2+ from

solution.
2Al (s) + 3Pb(NO3)2 (aq) → 2Al(NO3)3 (aq) + 3Pb (s)

0 +2 +3 0
+5 +5
-2 -2
Al is the reducing agent; Pb(NO3)2 is the oxidizing agent.

The total ionic equation is:

2Al (s) + 3Pb2+ (aq) + 2NO3- (aq) → 2Al3+ (aq) + 3NO3- (aq) + 3Pb (s)

The net ionic equation is:

2Al (s) + 3Pb2+ (aq) → 2Al3+ (aq) + 3Pb (s)

4-89
 Figure 4.21 The equilibrium state.

4-90