CHM12-3

Lecture Unit 4
Reactions in Aqueous Solutions

1
Scope
1. Types of Reactions in Aqueous Solutions
 Precipitation reactions, Acid-Base, Redox
 Net Ionic Equation
 Dilution of Solution
2. Theories of Acids and Bases
3. Strengths of Acids
4. Acid- Base Reaction/ Titration
5. Redox reactions

2
A Review on Classification of Solute

 Electrolytes are soluble compounds that

conduct current when dissolved in water.
 Weak electrolytes dissociate partially into ions in
solution.
 Strong electrolytes dissociate completely into
ions in solution.
 Nonelectrolytes do not dissociate into ions
in solution.
 A Review on Classification of Solute

a) Sugar, a nonelectrolyte, does not conduct current when dissolved in water.

b) Acetic acid, a weak electrolyte, weakly conducts current when dissolved in
water.
c) Potassium chromate, a strong electrolyte, strongly conducts current when
dissolved in water.
A Review on Classification of Solute

 When a covalently bonded material

dissolves in water and the molecules
remain intact, they do not conduct current.
These compounds are nonelectrolytes.

C6 H12O6 (s) 
 C6 H12O6 (aq)
 The water molecules are not shown explicitly,
although their presence is indicated by the “(aq)”
on the product side.
A Review on Classification of Solute

 When an ionic solid dissolves in water, it

breaks into its constituent ions. This is
called a dissociation reaction. These
compounds conduct electric current and
are electrolytes.

NaCl(aq)  Na  (aq)  Cl  (aq)

A Review on Classification of Solute
 Not all compounds dissolve in water.
 Solubility varies from compound to compound.

Soluble ionic
compounds
dissociate. Most molecular
Ions are
compounds stay
solvated
associated in water.
Types of Reaction in Aqueous Solutions

 Precipitation Reactions
 Acid –Base
 Reduction –Oxidation (Redox)
Precipitation Reaction
 Precipitates are called insoluble – they do
not dissolve in solution
 Precipitation of an insoluble solid
 Mix a solution of nickel(II) chloride with one of
sodium hydroxide
 A solid forms: Ni(OH)2 (s)
Precipitation Reaction
 Precipitation Reaction
Soluble species
 All ammonium and group 1A (Na+, K+,…. and NH4+ salts)
 All nitrates (NO3-)
 Most chlorides, bromides and iodides
 (exceptions: AgX, Hg2X2, and PbX2 ; X = Cl-, Br-, I-).
 Most sulfates (SO42-)
 (exceptions: CaSO4, SrSO4, BaSO4, Ag2SO4, PbSO4, and Hg2SO4)
 All chlorates (ClO3-)
 All perchlorates (ClO4-)
 All acetates (CH3COO-)
Precipitation Reaction
(a) Nitrates (b) Hydroxides
(soluble) (insoluble)

AgNO3 Cu(NO3)2 Cu(OH)2 AgOH

(c) Sulfides

CdS Sb2S3 PbS (NH4)2S

soluble
insoluble
Precipitation Reaction

 precipitate
 an insoluble ionic compound
 AgNO3(aq) + KCl(aq) → KNO3(aq) + AgCl(s)
 Precipitation Reaction
When ionic solutions mix, a precipitate may
form:
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)

Not all ions react

KNO3(aq) + NaCl(aq) No reaction

A reaction occurs if a product is insoluble.

The solubility rules help predict reactions.

 Precipitation Reaction
Na2SO4(aq) and Ba(NO3)2(aq) are
mixed. Will they react?
Products? Na+ SO42-
Ba2+ NO3-

NaNO3 and BaSO4 . Insoluble?

Yes. BaSO4 – A reaction occurs:

Na2SO4(aq) + Ba(NO3)2(aq) BaSO4(s) + 2 NaNO3(aq)

 Precipitation Reaction
Soluble ionic compounds fully dissociate:
AgNO3(aq) Ag+(aq) + NO3-(aq)
KCl(aq) K+(aq) + Cl-(aq)
On mixing:
Ag+(aq) + NO3-(aq) + K+(aq) + Cl-(aq)
AgCl(s) + K+(aq) + NO3-(aq)
K+ and NO3- appear on both sides
 NO3- and K+ are spectator ions.
 They are not directly involved in the reaction.

Net ionic equation: Ag+(aq) + Cl-(aq) → AgCl(s)

Net Ionic Equations
General rules:
1. Write a balanced equation.
2. Solubility?
3. Dissociate soluble compounds.
4. Write the complete ionic equation.
5. Cancel ions appearing on both sides
(spectators).
6. Check the charges are balanced.
 Net Ionic Equations
Example
Aqueous solutions of (NH4)2S and Hg(NO3)2 react to
give HgS and NH4NO3.
(a) Write the overall balanced equation
(b) Name each compound
(c) Write the net ionic equation
(d) What type of reaction is this?
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS + NH4NO3 not balanced
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS + 2 NH4NO3 balanced
 Net Ionic Equations
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS (s) + 2 NH4NO3(aq)
Product Solubility
HgS – insoluble
(All sulfides – except group 1A, 2A and NH4+ salts)
NH4NO3 – soluble
(All ammonium salts; all nitrates)
(b) name each compound
ammonium sulfide mercury(II) sulfide
mercury(II) nitrate ammonium nitrate
 Net Ionic Equations
(c) Write a net ionic equation
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS(s) + 2 NH4NO3(aq)

2 NH4+(aq) + S2-(aq) + Hg2+(aq) + 2 NO3-(aq)

→ HgS(s) + 2 NH4+(aq) + 2 NO3-(aq)

S2-(aq) + Hg2+(aq) → HgS(s)

(d) type of reaction?

Precipitation reaction
Net Ionic Equations
 Aqueous chemical reactions can be written
as a molecular equation. The complete
formula for each compound is shown.

 Note, all of the species may not be molecules.

HNO3 (aq) + NH 3 (g) 

 NH 4 NO3 (aq)
 Net Ionic Equations

 Dissociation of reactants and products is

emphasized by writing a total ionic equation
H+ (aq) + NO3 (aq) + NH3 (g) 
 NH+4 (aq) + NO3 (aq)

 Note: HNO3 is a strong acid and thus

dissociates completely, while NH3 does not
dissociate
 Net Ionic Equations
 Spectator ions are ions uninvolved in the
chemical reaction. When spectator ions
are removed, the result is the net ionic
equation.
 Total ionic equation
H+ (aq) + NO3 (aq) + NH3 (g) 
 NH+4 (aq) + NO3 (aq)
 Net ionic equation

H (aq) + NH 3 (g) 
+
 NH (aq)
+
4

Spectator ion = NO3

Precipitation Reaction
 A precipitation reaction is an aqueous
reaction that produces a solid, called a
precipitate.

Pb (aq)  2I (aq) 
2+
 PbI2 (s)
 Net ionic reaction for the precipitation of lead(II)
iodide.
 Precipitation Reaction

 Precipitation reaction between aqueous solutions of KI and Pb(NO3)2, which are

both colorless.
 The bright yellow solid, PbI2, is produced.
 PbI2 is insoluble as predicted by the solubility guidelines.
Precipitation Reaction
 When aqueous sodium carbonate and
barium chloride are combined, the solution
becomes cloudy white with solid barium
carbonate. Write the following equations:
a) molecular
b) total ionic

c) net ionic
Acid- Base Reactions

 Acids are substances that dissolve in water

to produce H+ (or H3O+) ions.
 Examples: HCl, HNO3, H3PO4, HCN

 Bases are substances that dissolve in

water to produce OH– ions.
 Examples: NaOH, Ca(OH)2, NH3
Acids and Bases
 Everyday life includes contact with many
acids and bases
Acid- Base Reactions
Acids
Increase the concentration of H+ ions in
water.
• Protons (H+) always combine with
water to form H3O+ (hydronium ion).
• Sour tasting.
• Change the color of pigments (indicators)
 Litmus, phenolphthalein…
Strong acids dissociate (>99%) in water (strong
electrolytes).
Weak acids partially dissociate (weak electrolytes).
 Acid- Base Reactions
Acids
Hydrochloric acid (HCl) ≈ 100% dissociated in
H2O
 Very few HCl molecules exist in solution.
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
 HCl is a strong acid
Acetic acid (CH3COOH) is 5% dissociated in H2O.
• 95% remain undissociated
CH3COOH(aq) + H2O(l) H3O+ + CH3COO-(aq)
• Acetic acid is a weak acid
 Acid- Base Reactions
Bases
Increase the concentration of OH- (hydroxide
ion) in water. Bases:
• Counteract an acid (neutralize an acid).
• Change an indicator’s color (phenolphthalein…).
• Have a bitter taste.
• Feel slippery.
Bases can be “strong” or “weak”.
H2O
NaOH(s) Na+(aq) + OH-(aq) strong

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) weak

Common Acids and Bases
Strong Acid Strong Base
HCl Hydrochloric acid LiOH Lithium hydroxide
HBr Hydrobromic acid NaOH Sodium hydroxide
HI Hydroiodic acid KOH Potassium hydroxide
HNO3 Nitric acid Ca(OH)2 Calcium hydroxide
H2SO4 Sulfuric acid Ba(OH)2 Barium hydroxide
HClO4 Perchloric acid Sr(OH)2 Strontium hydroxide

Weak Acid Weak Base

HF Hydrofluoric acid NH3 Ammonia
H3PO4 Phosphoric acid CH3NH2 Methylamine
CH3COOH Acetic acid
H2CO3 Carbonic acid
HCN Hydrocyanic acid
HCOOH Formic acid
C6H5COOH Benzoic acid
 Acid- Base Reactions

Neutralization Reactions
acid + base  salt + water.
salt = ionic compound made from an acid anion and
base cation.
HX(aq) + MOH(aq) MX(aq) + H2O(l)

HBr(aq) + KOH(aq) KBr(aq) + H2O(l)

H3PO4(aq) + 3 NaOH(aq) Na3PO4(aq) + 3 H2O(l)

Neutralizations are exchange reactions.

 Acid- Base Reactions
Net Ionic Equations for Acid-Base Reactions
Strong Acid + Strong Base
Overall: HX + MOH → MX + H2O

Full ionic:
H+(aq) + X-(aq) + M+(aq) + OH-(aq) →
M+(aq) + X-(aq) + H2O(l)

net ionic: H+(aq) + OH-(aq) → H2O(l)

 Acid- Base Reactions
Net Ionic Equations for Acid-Base Reactions
Weak Acid + Strong Base
Similar: HA + MOH → MA + H2O
but the weak-acid remains undissociated:
Full ionic
HA(aq) + M+(aq) + OH-(aq) →
M+(aq) + A-(aq) + H2O(l)

Net ionic: HA(aq) + OH-(aq) → A-(aq) + H2O(l)

 Acid- Base Reactions
Metal carbonate/acid exchange Carbonic acid
(unstable)
Overall:
CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + H2CO3(aq)
Tums®
H2CO3(aq) → H2O(l) + CO2(g)
often written:
CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)

Net ionic:
CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2O(l) + CO2(g)
 Acid- Base Reactions
Metal hydrogen carbonate/acid exchange
Overall:
NaHCO3(aq) + HCl(aq)→ NaCl(aq) + H2O(l) + CO2(g)

Alka-Seltzer ®

Net ionic
HCO3-(aq) + H+(aq) →
H2O(l) + CO2(g)
 Acid- Base Reactions
Metal sulfite/acid exchange Sulfurous acid
(unstable)
Similar. Overall:
Na2SO3(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2SO3(aq)
H2SO3(aq) → H2O(l) + SO2(g)
or
Na2SO3(aq) + 2 HCl(aq) →
2 NaCl(aq) + H2O(l) +SO2(g)

net ionic: SO32-(aq) + 2 H+(aq) → H2O(l) + SO2(g)

 Acid- Base Reactions

Metal sulfide/acid exchange

Overall:
Na2S(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2S(g)

net ionic: S2-(aq) + 2 H+(aq) → H2S(g)

Acid- Base Reactions

 Many metals will react with acids,

producing hydrogen gas
Acid- Base Reactions

 When aqueous solutions of acetic acid and

potassium hydroxide are combined, a
neutralization reaction will occur. Write the
following equations:

a) molecular
b) total ionic
c) net ionic
THEORIES OF ACIDS AND BASES

 Arrhenius Theory
 Brønsted-Lowry Concept
 Lewis Theory
Arrhenius Definition
Arrhenius: any substance which ionizes in
water to produce:
• Protons is an Acid
• Hydroxide ions is a Base

Better version of the Arrhenius definition:

Acid: Hydronium ions (H3O+) in water are acidic.
Base: Hydroxide ions (OH-) in water are basic.
So, why is NH3(aq) basic?
 Brønsted-Lowry Concept
An alternative definition:
Brønsted-Lowry Acid = Proton donor
Brønsted-Lowry Base = Proton acceptor
Works for non-aqueous solutions and explains why
NH3 is basic:
NH3(g) + H2O(l) NH4+(aq) + OH-(aq)
Base: Acid:
H+ acceptor H+ donor
 Brønsted-Lowry Concept
Strong acids and bases almost completely
ionize.
HNO (aq) + H O(l) H O+(aq) + NO -(aq)
3 2 3 3

Weak acids and bases do not fully ionize.

HF(aq) + H2O(l) H3O+(aq) + F-(aq)
H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)
Acid: Base: Acid: Base:
H+ donor H+ acceptor H+ donor H+ acceptor

Note: the products are a new acid and base pair.

 Water’s Role as Acid or Base
Water acts as a base when an acid dissolves in
water:
HBr(aq) + H2O(l) H3O+(aq) + Br-(aq)
acid base acid base

But water acts as an acid for some bases:

H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)

acid base acid base
Water is amphiprotic - it can donate or accept a
proton (act as acid or base).
 Conjugate Acid-Base Pairs
Molecules or ions related by the loss/gain of one
H+. Conjugate Acid Conjugate Base
H3O+ H2O
CH3COOH CH3COO-
NH4+ donate H+ NH3
H2SO4 HSO4-
HSO4- accept H+ SO42-
HCl Cl-

NH4+ and NH2- are not conjugate

(conversion requires 2 H+)
Conjugate Acid-Base Pairs
Identify the base conjugate to HF(aq) and the acid
conjugate to HCO3-(aq)
HF H+ + F-
Acid: Conjugate
H+ donor Base

HCO3- + H+ H2CO3
Base: Conjugate
H+ acceptor Acid

( CO32- is the base conjugate to HCO3- )

 Relative Strength of Acids & Bases
Strong acids are better H+ donors than weak
acids
Strong bases are better H+ acceptors than weak
bases
 Strong acids have weak conjugate bases.
 Weak acids have strong conjugate bases.
Strong acid + H2O H3O+ + conjugate base
Fully ionized, reverse reaction essentially does not occur.
The conjugate base is weak.

Weak acid + H2O H3O+ + conjugate base

Weakly ionized, reverse reaction readily occurs.

The conjugate base is strong.
Relative Strength of Acids & Bases
Conjugate acid Conjugate base
H2SO4 HSO4-
HBr Br- extremely
stong acids
weak bases
HCl Cl-
HNO3 NO3-

Base strength increasing

H3O+ H2O
Acid strength increasing

H2SO3 HSO3-
HSO4- SO42-
H3PO4 H2PO4-
HF F-
CH3COOH CH3COO-
H2S HS-
H2PO4- HPO42-
NH4+ NH3
HCO3- CO32-
H2O OH-
OH- O2-
H2 extremely H- strong base
CH4 weak acids CH3 -
 Autoionization of Water
Two water molecules can react to form ions.
Autoionization occurs:
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Base Acid Acid Base

Heavily reactant favored.

Only a very small fraction is ionized:
Kw = [ H3O+ ] [ OH- ] [H2O]2 is
ionization omitted…
constant for
water
= (1.0 x 10-7)(1.0 x 10-7)
= 1.0 x 10-14 (at 25°C)
 Ionization Constant for Water
Kw, like all equilibrium constants, is T-
dependent.
T = 25°C (77°F) is usually used as the standard
T.
T (°C) Kw

10 0.29 x 10-14
15 0.45 x 10-14
20 0.68 x 10-14
25 1.01 x 10-14
30 1.47 x 10-14
50 5.48 x 10-14
 Autoionization of Water
H3O+ and OH- are present in all aqueous
solutions.
Neutral solution.
Pure water (@ 25°C): [H3O+] = 10-7 M = [OH-]
• [ H3O+ ] is increased, disturbing the equilibrium:
2 H2O H3O+ + OH-
Acidic solution
If acid is added to water:
• LeChatelier: equilibrium shifts to remove [H3O+] (and [OH-])
• Equilibrium is reestablished: [ H3O+ ] > 10-7 M > [OH-]

• [ H3O+ ][OH-] = Kw = 1.0 x 10-14 at 25°C

 Autoionization of Water
Basic solution.
If base is added to water.
 LeChatelier: equilibrium shifts to remove [ OH- ] (and [H3O+])
 New equilibrium: [H3O+] < 10-7 M < [OH-]
 [ H3O+ ][OH-] = Kw = 1.0 x 10-14 at 25°C
Example
Calculate the hydronium and hydroxide ion concentrations at 25°C in a 6.0 M
aqueous sodium hydroxide solution.
Kw = [H3O+][OH-] = 1.0 x 10-14
NaOH (aq) is strong (100% ionized) so [OH-] = 6.0 M.
[H3O+](6.0) = 1.0 x 10-14
[H3O+] = 1.7 x 10-15 M [ OH- ] = 6.0 M
Values of Acid and Base Ionization Constants

• Strong acid Ka are hard to measure

 They are very large, ≈100% ionized.
 Assume they are fully ionized.

• Larger Ka = stronger acid

• Strong base Kb are hard to measure…

• Larger Kb = stronger base
 Ka Values for Polyprotic Acids
Phosphoric acid (H3PO4) is weak. It has three acidic
protons:

H+ is harder to remove
Ka decreasing
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4- (aq)

Ka = 7.5 x 10-3

H2PO4-(aq) + H2O(l) H3O+(aq) + HPO42- (aq)

Ka = 6.2 x 10-8

HPO42-(aq) + H2O(l) H3O+(aq) + PO43- (aq)

Ka = 3.6 x 10-13
 Molecular Structure and Acid Strength
What makes a strong acid?
 A weak H–A bond, so H+ can be easily removed!
Consider the binary acids HF, HCl, HBr, HI.

larger acid strength

HX Bond Energy (kJ) Ka

smaller bond energy

HF weak acid 566 7 x 10-4
HCl 431 1 x 107
strong acids

HBr 366 1 x 108

HI 299 1 x 1010
 Lewis Acids and Bases
A more general acid-base definition:
A Lewis acid accepts a pair of e- to form a bond.
A Lewis base donates a pair of e- to form a bond.

A + A B
..
B

Acid Base Coordinate

e- pair acceptor e- pair donor covalent bond

Coordinate covalent bond: a shared e- pair, with both e- donated by the same atom.
 Lewis Acids and Bases
H H
Examples:
H + O H O H
Lewis acid Lewis base H
H+ + H2O H3O+

F H F H
F B + N H F B N H

F H F H
Lewis acid Lewis base
 Positive Metal Ions as Lewis Acids
Metal ions can act as Lewis acids. They have:
 Missing e-
 Empty valence orbitals
 Metal atom + Lewis base → complex ion
Ag+ (aq) + 2 :NH3 (aq) [H3N:Ag:NH3]+ (aq)

Hydroxide ions are Lewis bases δ- δ+

 O is e- rich (has large electronegativity) -

:
:O–H
 Can easily donate an e- pair to a bond

:
 Positive Metal Ions as Lewis Acids
Many metal hydroxides are amphoteric – they react
with acids and bases.

Aluminum hydroxide can act as a Lewis acid:

Al(OH)3(s) + OH-(aq) [Al(OH)4]-(aq)

or as a Brønsted-Lowry base:
Al(OH)3(s) + 3 H3O+(aq) Al3+(aq) + 6 H2O(l)
 Lewis Acids and Bases
Predict if the following are Lewis acids or Lewis bases.
PH3 BCl3 Cr3+ CO
base acid acid base

(base = e--pair donor; acid = e--pair acceptor)

H Cl
P H Cl B
C O
H Cl
Acid-Base Titrations
 Commonly used to determine the
concentration of a dissolved species or its
percentage in a mixture
 Titration
 Measuring the volume of a standard solution
(known concentration) needed to react with a
measured quantity of a sample
Titrations
 Titrant (in the buret)
 Know concentration
 Know volume
 Analyte (in the Erlenmeyer flask)
 Know volume or mass
 Determine concentration or mass percent by
reacting with the titrant
Analyzing for Acetic Acid
 HC2H3O2 (aq) + OH- (aq) ⇌ C2H3O2- (aq) + H2O
 The objective is to determine when the reaction is
complete
 When the number of moles of acid equals the
number of moles of OH-, the equivalence point has
been reached
 Equivalence point is where the number of moles of
acid equals the number of moles of base
 The endpoint is indicated by a color change in the
acid-base indicator
An Acid- Base Titration
 An Acid- Base Titration
Titrant: Base
of known
concentration
Buret = volumetric glassware used for
titrations.
Slowly add standard solution.

End point: indicator changes

color.

Determine Vtitrant added.

Unknown acid + phenolphthalein
(colorless in acid)… …turns pink
in base
 Solution Preparation
Solutions are prepared either by:

1. Diluting a more concentrated solution.

or…
2. Dissolving a measured amount of solute
and diluting to a fixed volume.
Dilution of Solution
 Dilution is the process in which solvent is
added to a solution to decrease the
concentration of the solution.
 The number of moles of solute is the same
before and after dilution.
 Since the number of moles of solute equals the
product of molarity and volume (M  V), we can

M V = M V
write the following equation, where the subscripts
denote initiali and final
i values.
f f
 Dilution of Solution
MconcVconc = MdilVdil
Example
Commercial concentrated sulfuric acid is 17.8 M.
If 75.0 mL of this acid is diluted to 1.00 L, what is the
final concentration of the acid?
Mconc = 17.8 M Vconc = 75.0 mL
Mdil = ? Vdil = 1000. mL
Mdil = MconcVconc = 17.8 M x 75.0 mL = 1.34 M
Vdil 1000. mL
Dilution of Solution
 A chemist requires 1.5 M hydrochloric acid,
HCl, for a series of reactions. The only
solution available is 6.0 M HCl. What
volume of 6.0 M HCl must be diluted to
obtain 5.0 L of 1.5 M HCl?
Solution Preparation from Pure Solute

Prepare a 0.5000 M solution of potassium

permanganate in a 250.0 mL volumetric flask.
Mass of KMnO4 required
nKMnO4 = [KMnO4] x V
= 0.5000 M x 0.2500 L (M ≡ mol/L)
= 0.1250 mol KMnO4
Mass of KMnO4 = 0.1250 mol x 158.03 g/mol
= 19.75 g
Solution Preparation from Pure Solute
Weigh exactly 19.75 g of pure
KMnO4
Transfer it to a volumetric flask.

• Rinse all the solid from the weighing

dish into the flask.
• Fill the flask ≈ ⅓ full.
• Swirl to dissolve the solid.

• Fill the flask to the mark on the neck.

• Shake to thoroughly mix.
Molarity and Reactions in Aqueous Solution

nA = [ A ] x V

[product] = nproduct / (total volume).

Calculations Involving Molarity
 Example 11-1: If 100.0 mL of 1.00 M NaOH
and 100.0 mL of 0.500 M H2SO4 solutions
are mixed, what will the concentration of
the resulting solution be?
 What is the balanced reaction?
 It is very important that we always use a
balanced chemical reaction when doing
stoichiometric calculations.

75
Calculations Involving Molarity

2 NaOH + H2SO4  Na 2SO4  2 H2O

Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol
Before
Reaction: 100 mmol 50 mmol 0 mmol 0 mmol
After
Reaction: 0 mmol 0 mmol 50 mmol 100 mmol
Calculations Involving Molarity
 What is the total volume of solution?
100.0 mL + 100.0 mL = 200.0 mL
 What is the sodium sulfate amount, in
mmol?
50.0 mmol
 What is the molarity of the solution?
M = 50 mmol/200 mL = 0.250 M Na2SO4

77
Calculations Involving Molarity
 Example 11-2: If 130.0 mL of 1.00 M KOH
and 100.0 mL of 0.500 M H2SO4 solutions
are mixed, what will be the concentration of
KOH and K2SO4 in the resulting solution?
 What is the balanced reaction?

78
Calculations Involving Molarity
2 KOH + H 2SO 4  K 2SO 4 + 2 H 2 O
Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol

Before
Reaction: 130 mmol 50 mmol 0 mmol 0 mmol
After
Reaction: 30 mmol 0 mmol 50 mmol 100 mmol

79
Calculations Involving Molarity
 What is the total volume of solution?
130.0 mL + 100.0 mL = 230.0 mL
 What are the potassium hydroxide and
potassium sulfate amounts?
30.0 mmol & 50.0 mmol
 What is the molarity of the solution?
M = 30.0 mmol/230.0 mL = 0.130 M KOH
M = 50.0 mmol/230.0 mL = 0.217 M K2SO4
80
Calculations Involving Molarity
 Example 11-3: What volume of 0.750 M
NaOH solution would be required to
completely neutralize 100 mL of 0.250 M
H3PO4?
You do it!

81
Calculations Involving Molarity

3 NaOH + H 3PO 4  Na 3PO 4 + 3 H 2O

0.250 mol H 3PO 4
? L NaOH = 0.100 L H 3PO 4  
1 L H 3PO 4
3 mol NaOH 1 L NaOH
  0.100 L NaOH
1 mol H 3PO 4 0.750 mol NaOH

82
 Oxidation-Reduction Reactions
Oxidation
Originally: add oxygen.
2 Cu(s) + O2(g) 2 CuO(s)
2 CO(g) + O2(g) 2 CO2(g)
Cu and CO are oxidized. O2 is the oxidizing agent for both.
Reduction
Originally: reduce ore to metal; reverse of oxidation.
CuO(s) + H2(g) Cu(s) + H2O
SnO2(s) + 2 C(s) Sn(s) + 2 CO(g)
CuO and SnO2 are reduced. H2 and C are the reducing agents

(note: H2 is oxidized, so CuO is an oxidizing agent)

 Oxidation-Reduction Reactions
In all cases:
 If something is oxidized, something must be reduced.

• Oxidation-reduction = redox.
• Redox reactions move e-.
+2 e-
2 Ag+(aq) + Cu(s) 2 Ag(s) + Cu2+(aq)
-2 e-
Here:
• Cu changes to Cu2+.
• Cu loses 2 e-; each Ag+ gains one e-
• Ag+ is reduced (ore turned to metal)
• Gain of e- = reduction (so, loss of e- = oxidation)
 Redox Reactions and Electron Transfer
Loss of electrons is oxidation
Gain of electrons is reduction
Leo says ger

Oxidation is loss
Reduction is gain
Oil rig
 Redox Reactions and Electron Transfer
e-

M X
M loses electron(s) X gains electron(s)
M is oxidized X is reduced
M is a reducing agent X is an oxidizing agent
Common Oxidizing and Reducing Agents
Oxidizing Agent Reaction Product
O2 (oxygen) O2- (oxide ion)
H2O2 (hydrogen peroxide) H2O(l)
F2, Cl2, Br2, I2 (halogen) F-, Cl-, Br-, I- (halide ion)
HNO3 (nitric acid) nitrogen oxides (NO, NO2..)
Cr2O7- (dichromate ion) Cr3+ (chromium(III) ion)
MnO4- (permanganate ion) Mn2+ (manganese(II) ion)
Reducing Agent Reaction Product
H2 (hydrogen) H+ or H2O
C CO and CO2
M (metal: Na, K, Fe…..) Mn+ (Na+, K+, Fe3+…..)
Oxidation Numbers & Redox Reactions
Oxidation number
Compares the charge of an uncombined atom
with its actual or relative charge in a
compound.
General rules:
 Pure element = 0.

 Monatomic ion = charge of ion.

 Some elements have the same oxidation number in
almost all their compounds…
 The sum of the oxidation numbers of all atoms in any
species = the charge of the species.
Oxidation Numbers & Redox Reactions

Element Ox. No. Exceptions?

F −1 None
Cl, Br, I −1 Interhalogens (various values)
H +1 Metal hydrides = -1
(e.g. NaH, MgH2)
O −2 Metal peroxides = -1
(MO2)
Halogen oxides (various values)
(OXn)
Oxidation Numbers & Redox Reactions

Find the oxidation number for all elements in

SO32-
O = -2 ( not a peroxide, not bonded to halogen)
Sulfur?
Sum of the oxidation numbers = charge = -2
(ox. no. for S) + 3(ox. no. for O) = -2
(ox. no. for S) + 3(-2) = -2
(ox. no. for S) – 6 = -2
Sulfur = +4
Oxidation Numbers
Assign oxidation numbers to each element in the
following compounds:
 NaNO3
 Na = +1
 O = -2
 N = +5
 Calculate
 +1 + 3(-2) + x = 0
 x = +5

91
 Oxidation Numbers
 K2Sn(OH)6
 K = +1
 O = -2
 H = +1
 Sn = +5
 Calculate
 2(+1) + 6(-2) + 6(+1) + x = 0
 x = +5

92
 Oxidation Numbers
 H3PO4
You do it!
 H = +1
 O = -2
 P = +5

93
 Oxidation Numbers
 HCO3-
 O = -2
 H = +1
 C = +4
 Calculate
 +1 + 3(-2) + x = -1
 x = +4

94
 Oxidation Numbers
 Cr2O72-
You do it!
 O = -2
 Cr = +6

95
Oxidation Numbers & Redox Reactions
Compound Known Unknown
SO2 O = -2 S = +4
SO42- O = -2 S = +6
NH4+ H = +1 N = -3
NO2- O = -2 N = +3
NO3- O = -2 N = +5
OF2 F = -1 O = +2
ClF5 F = -1 Cl = +5
KMnO4 K = +1 O = -2 Mn = +7
H2O2 H = +1 O = -1
Oxidation Numbers & Redox Reactions
Ox. numbers always change during redox
reactions
Increase ox. number = Oxidation
Decrease ox. number = Reduction
If an element reacts to form a compound, it is a redox
reaction.

Oxidation and reduction must both occur.

S8(s) + 8 O2(g) 8 SO2(g)
S : 0 → +4 (oxidized: added O; lost e-; increased ox. no.)
O : 0 → -2 (reduced: lost O; gained e-; decreased ox. no.)
Oxidation Numbers & Redox Reactions
A more complex example:
0 +1 +5 −2
Cu(s) + 4 H+(aq) + 2 NO3-(aq)
Cu2+ (aq) + 2 NO2 (g) + 2 H2O(l)
+2 +4 −2 +1 −2

Cu is oxidized (ox. no. ↑; loss of e-).

H is unchanged.

O is unchanged.
N is reduced (ox. no. ↓; gain of e-).
Oxidation Numbers & Redox Reactions

Exchange reactions are not redox

– no change in oxidation state occurs.
e.g.
+1 +1 −1 +1 +1 −1
AgNO3(aq) + KCl(aq)  KNO3(aq) + AgCl (s)

NO3-: N is in a +5, and O is in a -2 ox. state.

 Oxidation-Reduction Reactions
Write and balance the formula unit, total ionic, and net
ionic equations for the oxidation of sulfurous acid to
sulfuric acid by oxygen in acidic aqueous solution.
 Formula unit equation

2 H 2SO 3aq   O2g   2 H 2SO 4aq 

 Total ionic equation
You do it!

 2
2 H 2SO 3aq   O2g   4 H (aq)  2 SO 4(aq)100
Oxidation-Reduction Reactions
 Net ionic equation
You do it!
 2
2 H 2SO 3aq   O2g   4 H (aq)  2 SO 4(aq)

 Which species are oxidized and reduced?

 Identify the oxidizing and reducing agents.
You do it!

101
Oxidation-Reduction Reactions
 H2SO3 is oxidized.
 The oxidation state of S in H2SO3 is +4.
 In SO42-, S has an oxidation state of +6.
 O2 is reduced.
 Oxidation state of O in O2 is 0
 In SO42-, O has an oxidation state of –2.
 H2SO3 is reducing agent.
 O2 is oxidizing agent.

102
Redox Titrations
 Redox reactions can be used to analyze an unknown in
the same way as is done with acid-base reactions
Stoichiometry of Redox Reactions
 Just as we have done stoichiometry
with acid-base reactions, it can also
be done with redox reactions.
 Example : What volume of 0.200 M
KMnO4 is required to oxidize 35.0
mL of 0.150 M HCl? The balanced
reaction is:
2 KMnO 4  16 HCl  2 KCl + 2 MnCl 2  5 Cl2  8 H2O
You do it!
104
Stoichiometry of Redox Reactions

35 mL HCl0150
. M HCl  5.25 mmol HCl
 2 mmol KMnO 4 
5.25 mmol HCl   0.656 mmol KMnO 4
16 mmol HCl 
 1 mL 
0.656 mmol KMnO 4    3.28 mL
 0.200 mmol KMnO 4 

105
Stoichiometry of Redox Reactions
 Example : A volume of 40.0 mL of iron
(II) sulfate is oxidized to iron (III) by
20.0 mL of 0.100 M potassium
dichromate solution. What is the
concentration of the iron (II) sulfate
solution? The balanced equation is:
2
6 Fe  Cr2O7  14 H +  6 Fe3+  2 Cr3+  7 H2O
2+

You do it!
106
Stoichiometry of Redox Reactions

20.0 mL 0.100 M Cr2O7 2

  2.00 mmol Cr O
2 7
2

  
2+
6 mmol Fe
2.00 mmol Cr2 O 7  
2
2 
 12.0 mmol Fe 2+

 1 mmol Cr2 O 7 
12.0 mmol Fe2+
 0.300 M Fe 2+
40.0 mL

107
End of Lecture Unit 4
 Many medicines are
deliberately made as
conjugate acids or
bases so that they
become active
ingredients after
passage through the
stomach.

108
Scope
1. Types of Reactions in Aqueous Solutions
 Precipitation reactions, Acid-Base, Redox
 Net Ionic Equation
 Dilution of Solution
2. Theories of Acids and Bases
3. Strengths of Acids
4. Acid- Base Reaction/ Titration
5. Redox reactions

109
 CHM12-3
Lecture Unit 4
Reactions in Aqueous Solutions

110