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:
 precipitations reactions
 acid-base reactions
 redox reactions

 We begin with general properties of

aqueous solutions.

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 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) H2O Sugar, CO2
aqueous solutions
Soft Solder (s) Pb Sn of KMnO4
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 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

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 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

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 Electrolyte & Nonelectrolyte

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)

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 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.

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 Electrolyte & Nonelectrolyte
Nonelectrolyte does not conduct electricity?

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

H2 O
C6H12O6 (s) C6H12O6 (aq)

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




H2O 9
 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
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Precipitation of Lead Iodide

Pb2+ + 2I- PbI2 (s) PbI2

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

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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

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Examples of Insoluble Compounds

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

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 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+ + NO3- + Na+ + Cl- AgCl(s) + Na+ + NO3-

Ag+ + Cl- AgCl(s)
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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)

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 Acid-Base Reactions
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.
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 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:

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 Arrhenius Acid & Base
Arrhenius acid is a substance that produces H+ (H3O+) in water.

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

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Hydronium ion, hydrated proton, H3O+

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 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!
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 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
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23
 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

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 Neutralization Reaction

acid + base salt + water

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

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

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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

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 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

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 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 28
29
 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

 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
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 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. 31
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.
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 + ? = –1
C = +4
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The Oxidation Numbers of Elements in their Compounds

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

Na = +1 O = -2
K2Cr2O7
3x(-2) + 1 + ? = 0
O = -2 K = +1
I = +5
7x(-2) + 2x(+1) + 2x(?) = 0
Cr = +6
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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
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Types of Oxidation-Reduction Reactions

Combustion Reaction

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

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

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 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

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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

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

Halogen Displacement Reaction

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

I2 + 2KBr 2KI + Br2

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 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

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 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)

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 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
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Preparing a Solution of Known Concentration

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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 44
 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 Vf = 0.0600 L Vi = ? 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.
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 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
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Titrations can be used in the analysis of

Acid-base reactions

H2SO4 + 2NaOH 2H2O + Na2SO4

Redox reactions

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

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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
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