Reactions in Aqueous Solution

Chapter 4

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Many chemical reactions and virtually all
biological precesses take place in water – the
so called universal solvent.
Three categories of ractions occur in aqueous
solutions:
1. precipitations reactions
2. acid-base reactions
3. redox reactions

We begin with general properties of

aqueous solutions.

2
 Solution, Solute & Solvent
A solution is a homogenous mixture of 2 or more
substances.
The solute is the substance present in the smaller
amount.
The solvent is the substance present in the larger
amount.

Solution Solvent Solute

Air (g) N2 O2, Ar, CH4
Soft drink (l) H 2O Sugar, CO2
aqueous solutions
Soft Solder (s) Pb Sn of KMnO4
3
 Solution, Solute & Solvent

So, a solution may be:

▪ gaseous (such as air)
▪ liquid (such as seawater)
▪ solid (such as an alloy)
Here we will discuss only aqueous solution
▪ in which the solute is a solid or liquid, and the
sovent is water
All solute that dissolve in water fit into two types:
▪ Electrolyte and Nonelectrolyte
Electrolytes are of two categories:
▪ Strong electrolyte and Weak electrolyte

4
 Electrolyte & Nonelectrolyte
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

5
 Electrolyte & Nonelectrolyte

Electrolyte conduct electricity in solution?

Cations (+) and Anions (-)

Strong Electrolyte – 100% dissociation

H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Weak Electrolyte – not completely dissociated

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

6
 Electrolyte & Nonelectrolyte

Ionization of acetic acid

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

A reversible reaction. The reaction can

occur in both directions.
Reaches an equilibrium.
Acetic acid is a weak electrolyte because its
ionization in water is incomplete.

7
 Electrolyte & Nonelectrolyte
Nonelectrolyte does not conduct electricity?

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

H2O
C6H12O6 (s) C6H12O6 (aq)

8
 Class Work - 4.9 & 4.10

Identify the following substnaces as a strong

electrolyte, weak electrolyte, or nonelectrolyte:
H2O Very weak electrolyte
KCl Strong electrolyte
HNO3 Strong electrolyte
CH3COOH Weak electrolyte
KOH Strong electrolyte
C12H22O11 Nonelectrolyte
NH4OH Weak electrolyte
9
 Solution Process
Hydration is the process in which an ion is
surrounded by water molecules arranged in a
specific manner.

δ−

δ+
H2O 10
 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
11
Precipitation of Lead Iodide

Pb2+ + 2I- PbI2 (s) PbI2

12
 Predicting Precipitation
How can we predict whether a precipitate will form?

It depends on the solubility of the solute.

Solubility is the maximum amount of solute that will dissolve

in a given quantity of solvent at a specific temperature.

Soluble

Substances Slightly All ionic compounds are

can be soluble strong electrolytes, but
not equally soluble.
Insoluble
13
Solubility Rules

14
Identify each of the following species as a
soluble or insoluble:

Siver sulfate, Ag2SO4 Insoluble

Calcium carbonate, CaCO3 Insoluble

Sodium phosphate, Na3PO4 Soluble

Copper sulfide, CuS Insoluble

Calcium hydroxide, Ca(OH)2 Insoluble

Zinc nitrate, Zn(NO3)2 Soluble

15
Examples of Insoluble Compounds

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

16
 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

Write the net ionic equation for the reaction of silver nitrate
with sodium chloride.
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
Ag+(aq) + NO3-(aq) + Na+(aq) + Cl-(aq) →
AgCl(s) + Na+(aq) + NO3-(aq)
Ag+(aq) + Cl-(aq) → AgCl(s) 17
Predict what happens when a potassium phosphate
K3PO4 solution is mixed with a strontium nitrate
Sr(NO3)2 solution. Write the ionic and net ionic
equation for the reaction.
2K3PO4(aq) + 3Sr(NO3)2(aq)
→ Sr3(PO4)2(s) + 6KNO3(aq)
Ionic:
6K+(aq) + 2PO43−(aq) + 3Sr2+(aq) + 6NO3−(aq)
→ Sr3(PO4)2(s) + 6K+(aq) + 6NO3−(aq)
Net ionic:
3Sr2+(aq) + 2PO43−(aq) → Sr3(PO4)2(s)

18
 Class Work – 4.21
Write ionic and net ionic equations:
2AgNO3(aq) + Na2SO4(aq)
→ Ag2SO4(s) + 2NaNO3(aq)

Ionic:
2Ag+(aq) + 2NO3−(aq) + 2Na+(aq) + SO42−(aq)
→ Ag2SO4(s) + 2Na+(aq) + 2NO3−(aq)

Net ionic:
2Ag+(aq) + SO42−(aq) → Ag2SO4(s)

19
 Acid-Base Reactions
Properties of Acids
▪ Have a sour taste. Vinegar owes its taste to acetic acid.
Lemons & 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
Litmus
2HCl(aq) + CaCO3(s) → CaCl2(aq) + CO2(g) + H2O(l)
▪Aqueous acid solutions conduct electricity.
20
 Acid-Base Reactions
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 & Base
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
 Brønsted Acid & Base
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
 Identify each of the following as a Brønsted acid, base, or
both. (a) HI, (b) CH3COO−, (c) H2PO4−, (d) HSO4−

HI (aq) H+ (aq) + I- (aq) Brønsted acid

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

H2PO4- (aq) H+ (aq) + HPO42- (aq) Brønsted acid

H2PO4- (aq) + H+ (aq) H3PO4 (aq) Brønsted base

HSO4- (aq) H+ (aq) + SO42- (aq) Brønsted acid

HSO4- (aq) + H+ (aq) H2SO4 (aq) Brønsted base

25
 Class Work – 4.32
Identify the following substnaces as a Brønsted
acid, base, or both:

PO43− Base HBr Acid

ClO2− Base NO2− Base
NH4+ Acid H3O+ Acid
HCO3− Both H2O Both

26
 Mono-, Di- & Triprotic Acids
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
27
12M (37%) HCl

5-6% Acetic acid

28
 Class Work – 4.30
Identify the following species as a weak or strong
acid or base:
NH3 Weak base
H3PO4 Weak acid
LiOH Strong base
HCOOH Weak acid
H2SO4 Strong acid
HF Weak acid
Ba(OH)2 Strong base

29
 Class Work – 4.21
Write ionic and net ionic equations:
(NH4)2CO3(aq) + CaCl2(aq)
→ CaCO3(s) + 2NH4Cl(aq)
Ionic:
2NH4+(aq) + CO32−(aq) + Ca2+(aq) + 2Cl−(aq)
→ CaCO3(s) + 2NH4+(aq) + 2Cl−(aq)

Net ionic:
Ca2+(aq) + CO32−(aq) → CaCO3(s)

30
 Neutralization Reaction

acid + base → salt + water

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

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) →

Na+(aq) + Cl-(aq) + H2O(l)

H+(aq) + OH-(aq) → H2O(l)

31
Neutralization Reaction Involving a
Weak Electrolyte

weak acid + base → salt + water

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

HCN(aq) + Na+(aq) + OH-(aq) →

Na+(aq) + CN-(aq) + H2O(l)

HCN(aq) + OH-(aq) → CN-(aq) + H2O(l)

32
 Neutralization Reaction Producing a Gas

acid + base → salt + water + CO2

2HCl(aq) + Na2CO3(aq) →
2NaCl(aq) + H2O(l) +CO2(g)

2H+(aq) + 2Cl-(aq) + 2Na+(aq) + CO32-(aq) →

2Na+(aq) + 2Cl-(aq) + H2O(l) + CO2(g)

2H+(aq) + CO32-(aq) → H2O(l) + CO2(g)

33
 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 34
Oxidation-Reduction Reactions
(electron transfer reactions)

Oxidation
Is
Loss of e−
Reduction
Is
OILRIG Gain of e−

35
Zinc bar reacts with copper(II)
sulfate to form copper metal.
Write the redox reaction,
half-reactions & identify the
oxidizing agent, reducing agent.
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
36
Copper wire reacts with silver
nitrate to form silver metal. Write
the redox reaction,
half-reactions & identify the
oxidizing agent, reducing agent.

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

Cu → Cu2+ + 2e-
Cu is oxidized
Cu is the reducing agent

Ag+ + e- → Ag
Ag+ is reduced
Ag+ is the oxidizing agent
37
 Class Work – 4.43
For the complete redox reaction given here,
(i) break down each reaction into its half-reactions;
(ii) identify the oxidizing agent and the reduding agent.
(a) 2Sr + O2 → 2SrO
(b) 2Li + H2 → 2LiH
Ans:
(i) Half Reactions (ii) Oxidizing Agent (iii) Reducing Agent
(a) Sr → Sr2+ + 2e− O2 Sr
O2 + 4e− → 2O2−
(b) Li → Li+ + e− H2 Li
H2 + 2e− → 2H−
38
 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.
39
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.
Oxidation number of oxygen in the superoxide ion,
O2 −, is –½. −
HCO3
What are the oxidation numbers O = –2 H = +1
of all the elements in HCO3− ? 3x(–2) + 1 + C = –1
C = +4
40
The Oxidation Numbers of Elements in their Compounds

41
What are the oxidation numbers of IF7
all the elements in each of these
compounds? F = -1
NaIO3 IF7 K2Cr2O7
7x(-1) + I = 0
NaIO3 I = +7

Na = +1 O = -2
K2Cr2O7
3x(-2) + 1 + I = 0
O = -2 K = +1
I = +5
7x(-2) + 2x(+1) + 2x(Cr) = 0
Cr = +6
42
 Class Work – 4.47 & 4.49
Find the oxidation number of the underlined atoms:
(a) K2CrO4, (b) NaHCO3, (c) KO2, (d) PF6−, (e) PtCl62−
Ans:
(a) K2CrO4: K +1, O −2, Cr +6
(b) NaHCO3: Na +1, H +1, O −2, C +4
(c) KO2: K +1, O −1/2
(d) PF6−: F −1, P +5
(e) PtCl62−: Pt +4

43
 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
44
 Types of Oxidation-Reduction Reactions

Combustion Reaction

A + O2 → B
0 0 +4 -2
S + O2 → SO2

0 0 +2 -2
2Mg + O2 → 2MgO

45
 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

46
 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

47
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

48
The Activity Series for Halogens
F2 > Cl2 > Br2 > I2

Halogen Displacement Reaction

0 -1 -1 0
Cl2 + 2KBr → 2KCl + Br2

I2 + 2KBr → 2KI + Br2

49
 Classify each of the following reactions.

Ca2+ + CO32- → CaCO3 Precipitation

NH3 + H+ → NH4+ Acid-Base

Zn + 2HCl → ZnCl2 + H2 Redox (H2 Displacement)

Ca + F2 → CaF2 Redox (Combination)

50
 Chemistry in Action: Breath Analyzer
+6
3CH3CH2OH + 2K2Cr2O7 + 8H2SO4 →

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

51
 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

What mass of KI is required to make 500.0 mL of a

2.80 M KI solution?
M KI M KI
volume of KI solution moles KI grams KI

1L 2.80 mol KI 166 g KI

500.0 mL x x x = 232 g KI
1000 mL 1 L soln 1 mol KI
52
Preparing a Solution of Known Concentration

53
 Class Work – 4.60
Describe how would you prepare 250 mL of a 0.707 M
NaNO3 solution.
Ans:
volume of solution moles grams

To make the solution, dissolve 15.0 g of NaNO3

in enough water to make 250 mL of solution.

54
 Class Work – 4.64
Calculate the molarity of the solution where
6.57 g of methanol (CH3OH) is present in 1.50
× 102 mL of solution.
Ans:

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)

=
Mi V i = Mf V f
56
 How would you prepare 60.0 mL of 0.200 M HNO3
from a stock solution of 4.00 M HNO3?
MiVi = MfVf

Mi = 4.00 M Mf = 0.200 M
Vi = ? L Vf = 0.0600 L

MfVf
Vi = = 0.200 M x 0.0600 L = 0.00300 L = 3.00 mL
Mi 4.00 M

Dilute 3.00 mL of acid with water to a total volume

of 60.0 mL.
57
 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.

58
 Titrations
In a titration a solution of accurately known concentration is
added gradually 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
59
Titrations can be used in the analysis of

Acid-base reactions

H2SO4 + 2NaOH → 2H2O + Na2SO4

Redox reactions

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

60
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 reqd 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
61
16.42 mL of 0.1327 M KMnO4 solution is needed to
oxidize 25.00 mL of an acidic FeSO4 solution. What is
the molarity of the iron solution?
WRITE THE CHEMICAL EQUATION!
5Fe2+ + MnO4- + 8H+ Mn2+ + 5Fe3+ + 4H2O

M rxn V
volume red moles red moles oxid M oxid
red coef. oxid

16.42 mL = 0.01642 L 25.00 mL = 0.02500 L

0.1327 mol KMnO4 5 mol Fe2+ 1

0.01642 L x x x = 0.4358 M
2+
1L 1 mol KMnO4 0.02500 L Fe
62
 Class Work – 4.69
Describe how to prepare 1.00 L of 0.646 M HCl
solution, starting with a 2.00 M HCl solution.
Ans:

To prepare the 0.646 M solution, you would dilute

323 mL of the 2.00 M HCl solution to a final volume
of 1.00 L.

63
 Class Work – 4.86
Calculate the concentration (in molarity) of a NaOH
solution if 25.0 mL of the solution are needed to
neutralize 17.4 mL of a 0.312 M HCl solution.
Ans:

64