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Chapter 4:

Reactions in Aqueous Solution

CHM 165 - Spring 2014

Looking ahead.
Different forms of reactions Precipitation Reactions Acid Base Reactions Oxidation Reduction Reactions Electrolytes & nonelectrolytes Redox (Oxidation Reduction) Reactions Redox titrations

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Some Ways That Chemical Reactions Occur

Precipitation Reactions: Processes in which soluble reactants yield an insoluble solid product

Pb(NO3)2(aq) + 2KI(aq)

2KNO3(aq) + PbI2(s)

Acid-Base Neutralization Reactions: acid reacts with a base to yield water plus an ionic compound called a salt

HCl(aq) + NaOH(aq)

H2O(l) + NaCl(aq)

Oxidation-Reduction (Redox) Reactions: Processes in which one or more electrons are transferred between reaction partners (atoms, molecules, or ions) Mg(s) + 2HCl(aq)

MgCl2(aq) + H2(g)

Electrolytes in Aqueous Solution

Electrolytes: Substances which dissolve in water to produce conducting solutions of ions
H2O

NaCl(s)

Na+(aq) + Cl-(aq)

Nonelectrolytes: Substances which do not produce ions in aqueous solutions

H2O

C12H22O11(s)

C12H22O11(aq)

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Electrolytes in Aqueous Solution

Strong Electrolytes: Compounds that dissociate to a large extent into ions when dissolved in water KCl(aq) K+(aq) + Cl-(aq)

Weak Electrolytes: Compounds that dissociate to a small extent into ions when dissolved in water CH3CO2H(aq) H+(aq) + CH3CO2-(aq)

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Electrolytes in Aqueous Solution

Strong Acids:

Molecular Compounds

Ionic Compounds

Weak acids

Aqueous Reactions and Net Ionic Equations

Molecular Equation: All substances in the chemical equation are written using their complete formulas as if they were molecules. Pb(NO3)2(aq) + 2KI(aq) 2KNO3(aq) + PbI2(s)

strong electrolytes

precipitate

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Ionic Equation: All of the strong electrolytes are written as ions.

Pb(NO3)2(aq)
Pb2+(aq) + 2NO3-(aq) +

2KI(aq)
2K+(aq) + 2I-(aq)

2K+(aq) + 2NO3-(aq) + PbI2(s) 2KNO3(aq) Spectator Ions: Ions that undergo no change during the reaction and appear on both sides of the reaction arrow. Pb2+(aq) + 2NO3-(aq) + 2K+(aq) + 2I-(aq) 2K+(aq) + 2NO3-(aq) + PbI2(s)

Net Ionic Equation: Only the ions undergoing change are shown. Pb2+(aq) + 2I-(aq) PbI2(s)

Precipitation Reactions and Solubility Guidelines

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Write the molecular, ionic, and net ionic equations for the reaction that occurs when aqueous solutions of AgNO3 and Na2CO3 are mixed. 2Ag+(aq) + 2NO3- (aq) + 2Na+(aq) + CO32-(aq) Ag2CO3(s) + 2Na+(aq) + 2NO3-(aq)

2Ag+(aq) + CO32-(aq)

Ag2CO3(s)

Acids, Bases, and Neutralization Reactions

Acid (Arrhenius): A substance that dissociates in water to produce hydrogen ions, H+: HA(aq) HCl(aq) H+(aq) + A-(aq) H+(aq) + Cl-(aq)

In water, acids produce hydronium ions, H3O+: HCl(aq) + H2O(aq) H3O+(aq) + Cl-(aq)

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Acids, Bases, and Neutralization Reactions

Base (Arrhenius): A substance that dissociates in water to produce hydroxide ions, OH-: MOH(aq) NaOH(aq) M+(aq) + OH-(aq) Na+(aq) + OH-(aq)

Ammonia is weakly basic because it reacts to a small extent with water to yield ammonium and hydroxide ions: NH3(aq) + H2O(aq) NH4+(aq) + OH-(aq)

Acids, Bases, and Neutralization Reactions

Strong acids and strong bases are strong electrolytes. Weak acids and weak bases are weak electrolytes.

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Acids, Bases, and Neutralization Reactions

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ite ate

Acids, Bases, and Neutralization Reactions

These acid-base neutralization reactions are doublereplacement reactions just like the precipitation reactions: HA(aq) + MOH(aq) Acid Base E.g.s 1. Write the molecular, ionic, and net ionic equations for the reaction of aqueous HBr and aqueous Ba(OH)2. 2. Write the molecular, ionic, and net ionic equations for the reaction of aqueous NaOH and aqueous HF. MA(aq) + H2O(l) Salt Water

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Oxidation-Reduction (Redox) Reactions

Oxidation: The loss of one or more electrons by a substance whether element, compound or ion Reduction: The gain of one or more electrons by a substance Oxidation-Reduction (Redox) Reaction: Any process in which electrons are transferred from one substance to another

MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l) 2Mg(s) + O2(g) 2MgO(s)

Oxidation Number (State): A value which indicates whether an atom is neutral, electron-rich, or electron-poor Rules for Assigning Oxidation Numbers
1. An atom in its elemental state has an oxidation number of 0.

Na

H2

Br2

Ne

Oxidation number 0 2. An atom in a monatomic ion has an oxidation number identical to its charge. Na+ +1 Ca2+ +2 Al3+ +3 Cl-1 O2-2

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3. An atom in a polyatomic ion or in a molecular compound usually has the same oxidation number it would have if it were a monatomic ion. a) Hydrogen can be either +1 or -1.
1-

H +1

O -2 -1

Ca +2

H -1

b) Oxygen usually has an oxidation number of -2. H +1 O -2 H +1 +1 H O -1 O -1 H +1

c) Halogens usually have an oxidation number of -1. +1 -1

Cl

4. The sum of the oxidation numbers is 0 for a neutral compound and is equal to the net charge for a polyatomic ion.

H2SO4 +1 ? -2

2(+1) + (?) + 4(-2) = 0 (net charge)

? = +6

Cr2O72? -2

2(?) + 7(-2) = -2 (net charge) ? = +6

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Identifying Redox Reactions

Oxidizing Agent
Causes oxidation Gains one or more electrons Undergoes reduction Oxidation number of atom decreases

Reducing Agent
Causes reduction Loses one or more electrons Undergoes oxidation Oxidation number of atom increases

Oxidizing Agent
0

reduction -2 2Fe2 O3 (s) +3 oxidation 4Fe(s) + 3O2(g)

Reducing Agent

The Activity Series of the Elements

Elements that are higher up in the table are more likely to be oxidized.

Thus, any element higher in the activity series will reduce the ion of any element lower in the activity series.

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The Activity Series of the Elements

Reaction of an aqueous cation (metal ion) with a free element

Fe(s)

Cu2+(aq)

Fe2+(aq)

Cu(s)

Balancing Redox Reactions: The Half-Reaction Method

Balance the following net ionic equation in acidic solution: Cr2O72-(aq) + Cl-(aq) Cr3+(aq) + Cl2(aq)

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Write the two unbalanced half-reactions. Cr2O72-(aq) Cl-(aq) Cr3+(aq) Cl2(aq)

Balance both half-reactions for all atoms except O and H. Cr2O72-(aq) 2Cl-(aq) 2Cr3+(aq) Cl2(aq)

Balance each half-reaction for O by adding H2O, and then balance for H by adding H+. 14H+(aq) + Cr2O72-(aq) 2Cl-(aq) 2Cr3+(aq) + 7H2O(l) Cl2(aq)

Balance each half-reaction for charge by adding electrons to the side with greater positive charge. reduction: oxidation: 6e- + 14H+(aq) + Cr2O72-(aq) 2Cl-(aq) 2Cr3+(aq) + 7H2O(l) Cl2(aq) + 2e-

reduction:
oxidation:

6e- + 14H+(aq) + Cr2O72-(aq)

3 2Cl-(aq)

2Cr3+(aq) + 7H2O(l)
Cl2(aq) + 2e-

14H+(aq) + Cr2O72-(aq) + 6Cl-(aq) 2Cr3+(aq) + 7H2O(l) + 3Cl2(aq)

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Redox Titrations

Redox titration (also called oxidation-reduction titration) is a type of titration based on a redox reaction between the analyte and titrant

5H2C2O4(aq) + 2MnO4-(aq) + 6H+(aq) 10CO2(g) + 2Mn2+(aq) + 8H2O(l)

Redox Titrations
A solution is prepared with 0.2585 g of oxalic acid, H2C2O4. 22.35 mL of an unknown solution of potassium permanganate are needed to titrate the solution. What is the concentration (molarity) of the potassium permanganate solution? 5H2C2O4(aq) + 2MnO4-(aq) + 6H+(aq) 10CO2(g) + 2Mn2+(aq) + 8H2O(l)
Mass of H2C2O4 Moles of H2C2O4 Moles of KMnO4 Molarity of KMnO4

Molar Mass of H2C2O4

Mole Ratio
2012 Pearson Education, Inc.

Molarity of KMnO4
Chapter 4/28

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5H2C2O4(aq) + 2MnO4-(aq) + 6H+(aq) 10CO2(g) + 2Mn2+(aq) + 8H2O(l) Moles of H2C2O4 available: 0.2585 g H2C2O4 x 1 mol 90.04 g = 0.002871 mol H2C2O4

Moles of KMnO4 reacted: 0.002871 mol H2C2O4 2 mol KMnO4 x = 0.001148 mol KMnO4 5 mol H2C2O4
Concentration of KMnO4 solution: 0.001148 mol KMnO4 22.35 mL x 1000 mL 1L = 0.05136 M KMnO4

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