Reactions in Aqueous

Solution
Chapter 4

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 A Look Ahead…
• Solution, Solute & Solvent
• Electrolyte & Nonelectrolyte, Strong & Weak electrolyte
• Solution process & Solubility rule
• Precipitation reaction
• Writing molecular, ionic & net ionic reaction
• Acid & Bases, Acid-Base reactions
• Oxidation-Reduction reactions, Oxidation Numbers
• Solution Stoichiometry
• Titration, Acid-Base titration
2
 Introduction
 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.

3
 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) H2 O Sugar, CO2
Aqueous solutions
Soft Solder (s) Pb Sn of KMnO4

4
 Solution, Solute & Solvent
 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

Electrolyte Nonelectrolyte

Strong Weak
electrolyte electrolyte

5
 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

6
 Electrolyte & Nonelectrolyte

Electrolyte 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 (aq) CH3COO- (aq) + H+ (aq)

7
 Electrolyte & Nonelectrolyte
Nonelectrolyte does not conduct electricity?
No cations (+) and anions (-) in solution
H 2O
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)
Hydration is the process in which an ion is surrounded
by water molecules arranged in a specific manner.

-

+
H2O 10
Lets see an animation
on
Solution Process

11
 Precipitation Reactions
Precipitation reaction results in the formation of an insoluble
product, or precipitate.
Precipitate an insoluble solid that separates from the 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
PbI2 Na+ and NO3- are spectator ions
12
Precipitation of Lead Iodide

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

13
 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
sugar
Substances Slightly soluble All ionic compounds are
can be Ca(OH)2 strong electrolytes, but
Insoluble not equally soluble.
BaSO4
14
Solubility Rules

15
Identify each of the following species as
a soluble or insoluble:

Silver 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

16
Examples of Insoluble Compounds

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

17
 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) 

Ag+(aq) + Cl-(aq)  AgCl(s)

AgCl(s) + Na+(aq) + NO3-(aq) 18
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.
Molecular:
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: 19
 Class Work – 4.21
Write ionic and net ionic equations:
Molecular:
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:
20
2Ag+(aq) + SO 2−(aq)  Ag SO (s)
 Acids & Bases
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.
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 Acids & Bases
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.

23
Hydronium ion, hydrated proton, H3O+

24
 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!
25
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

26
 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

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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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12M (37%) HCl

5-6% Acetic acid

29
 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

30
 Class Work – 4.21
Write ionic and net ionic equations:
Molecular:
(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)
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 Acid-Base Neutralization
Neutralization reaction a reaction between an acid and a base.
acid + base  salt + water
Salt an ionic compound made up of cation other than H+ and an
anion other than OH- or O2-
a) Neutralization Reaction Involving Strong Electrolyte
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)
+

H2SO4(aq) + 2NaOH(aq)  Na2SO4(aq) + 2H2O(l)

32
b) 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)

Examples
HF(aq) + KOH(aq)  KF(aq) + H2O(l)
HNO3(aq) + NH4+(aq) + OH-(aq)  NH4NO3(aq) + H2O(l)

33
 c) Acid-Base Reactions Producing a Gas
CO32, HCO3
Salt + acid  salt + water + gas
SO42, S2

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

Na+(aq) + CO32-(aq) + 2H+(aq) + 2Cl-(aq) 
2Na+(aq) + 2Cl-(aq) + H2O(l) + CO2(g)
CO32-(aq) + 2H+(aq)  H2O(l) + CO2(g)
Examples
NaHCO3(aq) + HCl(aq)  NaCl(aq) + H2O(l) +CO2(g)
Na2SO4(aq) + 2HCl(aq)  2NaCl(aq) + H2O(l) + SO2(g)
K2S(aq) + 2HCl(aq)  2KCl(aq) + H2S(g)
34
 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 35
Oxidation-Reduction Reactions
(electron transfer reactions)

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

36
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) +2+Cu(s)-
Zn  Zn + 2e
Zn is oxidized
Zn is the reducing agent

Cu2+ + 2e-  Cu
Cu2+ is reduced
Cu2+ is the oxidizing agent

37
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(NO ) (aq)
2+ 3 2
+ 2Ag(s)
Cu  Cu + 2e -

Cu is oxidized
Cu is the reducing agent

Ag+ + e-  Ag
Ag+ is reduced
Ag+ is the oxidizing agent
38
 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:
Half Reactions Oxd. Agent
Red.agent
(a) Sr  Sr2+ + 2e− (Oxd.) O2
Sr
O2 + 4e−  2O2− (Red.)
(b) Li  Li+ + e− (Oxd.) H2
39
 Oxidation number
Definitions of oxidation & reduction in terms of loss & gain of
electron apply to
2Mg(s) + O2(g)  2MgO(s)
2Mg  2Mg2+ + 4e- (Oxid.) & O2 + 4e-  2O2- (Red.)
However, these definition do not accurately characterize the
formation of HCl and SO2
H2(g) + Cl2(g)  2HCl(g)
S(s) + O2(g)  SO2(g)
HCl and SO2 are not ionic compound but there is a partial transfer
of electrons.
To keep track of electrons in redox reactions, it is useful to assign
oxidation numbers to the reactants and products. 40
 Oxidation number
Oxidation number or Oxidation state number of charges the
atom would have in a molecule (or an ionic compound) if
electrons were transferred completely.

Assigning oxidation numbers

0 0 +1 -1
H2(g) + Cl2(g)  2HCl(g)
0 0 +4 -2
S(s) + O2(g)  SO2(g)

• The numbers reflect the number of electrons “transferred.”

• Increase in oxidation number, oxidation.
• Decrease in oxidation number, reduction.
• Sum of oxidation numbers is zero for neutral molecules.
41
 Oxidation number
Rules to assign oxidation numbers
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.

42
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 H = +1 O = –2
numbers of all the elements
in HCO3 ? 3x(–2) + 1 + C = –1
C = +4
43
The Oxidation Numbers of Elements in their Compounds

44
What are the oxidation IF7
numbers of 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
K = +1 O = -2
I = +5
7x(-2) + 2x(+1) + 2x(Cr) = 0
Cr = +6
45
 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

46
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

47
The Activity Series for Halogens
F2 > Cl2 > Br2 > I2

Halogen Displacement Reaction

0 -1 -1 0
Cl2 + 2KBr  2KCl + Br2

I2 + 2KBr  2KI + Br2

48
 Chemistry in Action: Breath Analyzer

+6
3CH3CH2OH + 2K2Cr2O7 + 8H2SO4 
+3
3CH3COOH + 2Cr2(SO4)3 + 2K2SO4 + 11H2O

50
 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
51
Preparing a Solution of Known Concentration

52
 Class Work – 4.60
Describe how would you prepare 250 mL of a 0.707 M
NaNO3 solution.
Ans: M NaNO3 M NaNO3
volume of solution moles grams

To make the solution, dissolve 15.0 g of NaNO3 in

enough water to make 250 mL of solution.

53
 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:

54
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
55
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
Mi 4.00 M
= 0.00300 L = 3.00 mL

Dilute 3.00 mL of acid with water to a total volume of

60.0 mL.
56
 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
57
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

58
 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.

59
 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:

60