Chapter 4

Three Major Classes of Chemical Reactions

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Three Major Classes of Chemical Reactions

4.1 The Role of Water as a Solvent

4.2 Writing Equations for Aqueous Ionic Reactions

4.3 Precipitation Reactions

4.4 Acid-Base Reactions

4.5 Oxidation-Reduction (Redox) Reactions 4.6 Elements in Redox Reactions

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Figure 4.1 Electron distribution in molecules of H2 and H2O.

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Figure 4.2

The dissolution of an ionic compound.

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Figure 4.3

The electrical conductivity of ionic solutions.

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Sample Problem 4.1 PROBLEM:

Determining Moles of Ions in Aqueous Ionic Solutions

How many moles of each ion are in the following solutions? (a) 5.0 mol of ammonium sulfate dissolved in water (b) 78.5 g of cesium bromide dissolved in water (c) 7.42 x 1022 formula units of copper(II) nitrate dissolved in water (d) 35 mL of 0.84 M zinc chloride

PLAN: We have to relate the information given and the number of moles of ions present when the substance dissolves in water.
H2O

SOLUTION: (a) (NH4)2SO4(s)

2NH4+(aq) + SO42-(aq)

5.0 mol (NH4)2SO4 x

2 mol NH4+ 1 mol (NH4)2SO4

= 10. mol NH4+

and 5.0 mol SO42-

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Sample Problem 4.1

continued (b) CsBr(s)

Determining Moles of Ions in Aqueous Ionic Solutions

Cs+(aq) + Br-(aq)

= 0.369 mol Cs+ = 0.369 mol CsBr and 0.369 mol Br-

78.5 g CsBr x
H2O

mol CsBr
212.8 g CsBr

(c) Cu(NO3)2(s)

Cu2+(aq) + 2NO3-(aq)

mol Cu(NO3)2 7.42 x 1022 formula units x 23 formula units = 0.123 mol Cu(NO3)2 6.022 x 10 Cu(NO3)2 = 0.246 mol NO3(d) ZnCl2(aq) 35 mL ZnCl2 x Zn2+(aq) + 2Cl-(aq) 1L 103 mL x 0.84 mol ZnCl2 L and 0.123 mol Cu2+ = 2.9 x 10-2 mol ZnCl2

= 2.9 x 10-2 mol Zn2+

and 5.8 x 10-2 mol Cl-

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2NaF(aq) + CaCl2(aq) CaF2(s) + 2NaCl(aq) Precipitation reaction

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Writing Equations for Aqueous Ionic Reactions

The molecular equation

shows all of the reactants and products as intact, undissociated compounds.

The total ionic equation

shows all of the soluble ionic substances dissociated into ions.

The net ionic equation

omits the spectator ions and shows the actual chemical change taking place.

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Figure 4.4

An aqueous ionic reaction and its equation.

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Figure 4.6

The reaction of Pb(NO3)2 and NaI.

NaI(aq) + Pb(NO3)2(aq) PbI2(s) + NaNO3(aq) 2NaI(aq) + Pb(NO3)2(aq) PbI2(s) + 2NaNO3(aq) 2Na+(aq) + 2I-(aq) + Pb2+(aq) + 2NO3-(aq) PbI2(s) + 2Na+(aq) + 2NO3-(aq) 2NaI(aq) + Pb(NO3)2(aq) PbI2(s) + 2NaNO3(aq) Double-displacement reaction (metathesis)

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Predicting Whether a Precipitate Will Form

1. Note the ions present in the reactants.

2. Consider the possible cation-anion combinations.

3. Decide whether any of the ion combinations is insoluble.

See Table 4.1 (next slide) for solubility rules.

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Sample Problem 4.2

PROBLEM:

Predicting Whether a Precipitation Reaction Occurs; Writing Ionic Equations

Predict whether a reaction occurs when each of the following pairs of solutions are mixed. If a reaction does occur, write balanced molecular, total ionic, and net ionic equations, and identify the spectator ions. (a) Potassium fluoride(aq) + strontium nitrate(aq) (b) Ammonium perchlorate(aq) + sodium bromide(aq) SOLUTION: (a) KF(aq) + Sr(NO3)2 (aq) 2KNO3(aq) + SrF2 (s)

PLAN: Write ions

2K+(aq) + 2F-(aq) + Sr2+(aq) + 2NO3-(aq) 2K+(aq) + 2NO3-(aq) + SrF2 (s) Combine anions & cations Check for insolubility Table 4.1 Eliminate spectator ions for net ionic equation 2F-(aq) + Sr2+(aq) SrF2 (s)

(b) NH4ClO4(aq) + NaBr (aq)

NH4Br (aq) + NaClO4(aq)

All reactants and products are soluble so no reaction occurs.

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Sample Problem 4.4

Determining the Molarity of H+ Ions in an

Aqueous Solution of an Acid PROBLEM: Nitric acid is a major chemical in the fertilizer and explosives industries. In aqueous solution, each molecule dissociates and the H becomes a solvated H+ ion. What is the molarity of H+(aq) in 1.4 M nitric acid? PLAN: Use the formula to find the molarity of H+.

+ SOLUTION: One mole of H (aq) is released per mole of nitric acid (HNO3)

HNO3(l)

H2O

H+(aq) + NO3-(aq)

1.4 M HNO3(aq) has 1.4 M H+(aq).

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Sample Problem 4.5 PROBLEM:

Writing Ionic Equations for Acid-Base Reactions

Write balanced molecular, total ionic, and net ionic equations for each of the following acid-base reactions and identify the spectator ions.

(a) Strontium hydroxide(aq) + perchloric acid(aq)

(b) Barium hydroxide(aq) + sulfuric acid(aq) PLAN: Reactants are strong acids and bases and therefore completely ionize in water Product is Water Spectator ions

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Sample Problem 4.5 continued

Writing Ionic Equations for Acid-Base Reactions

SOLUTION: (a) Sr(OH)2(aq) + 2HClO4(aq) Sr(ClO4)2(aq) + 2H2O(l) Sr2+(aq) + 2ClO4-(aq) + 2H2O(l)

Sr2+(aq) + 2OH-(aq) + 2H+(aq) + 2ClO4-(aq)

2OH-(aq)+ 2H+(aq)

2H2O(l)
BaSO4(s) + 2H2O(l) BaSO4(s) + 2H2O(l) BaSO4(s) + 2H2O(l)

(b) Ba(OH)2(aq) + H2SO4(aq)

Ba2+(aq) + 2OH-(aq) + 2H+(aq) + SO42-(aq) Ba2+(aq) + 2OH-(aq) + 2H+(aq) + SO42-(aq)

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Figure 4.7

An acid-base titration.

Start of titration Excess of acid

Point of neutralization

Slight excess of base

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Sample Problem 4.6

PROBLEM:

Finding the Concentration of Acid from an

Acid-Base Titration You perform an acid-base titration to standardize an HCl solution by placing 50.00 mL of HCl in a flask with a few drops of indicator solution. You put 0.1524 M NaOH into the buret, and the initial reading is 0.55 mL. At the end point, the buret reading is 33.87 mL. What is the concentration of the HCl solution?

PLAN:

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Sample Problem 4.6

continued

Finding the Concentration of Acid from an Acid-Base Titration

SOLUTION:

NaOH(aq) + HCl(aq)
1L 103 mL

NaCl(aq) + H2O(l)

(33.87 mL - 0.55 mL) x

= 0.03332 L NaOH

0.03332 L x 0.1524 M

= 5.078 x 10-3 mol NaOH

From the stoichiometric ratio in the balanced equation, 5.078 x 10-3 mol NaOH = 5.078 x 10-3 mol HCl

5.078 x 10-3 mol HCl 0.05000 L

= 0.1016 M HCl

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Figure 4.8

An aqueous strong acid-strong base reaction on the atomic scale.

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Figure 4.9

The redox process in compound formation.

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Sample Problem 4.7 PROBLEM:

Determining the Oxidation Number of an Element

Determine the oxidation number (O.N.) of each element in these compounds: (a) Zinc chloride (b) Sulfur trioxide (c) Nitric acid

PLAN:

The O.N.s of the ions in a polyatomic ion add up to the charge of the ion and the O.N.s of the atoms or ions in a compound add up to zero.

SOLUTION: (a) ZnCl2. The O.N. for zinc is +2 and that for chloride is -1. (b) SO3. Each oxygen is an oxide with an O.N. of -2. Therefore, the O.N. of sulfur must be +6. (c) HNO3. H has an O.N. of +1 and each oxygen is -2. Therefore, the N must have an O.N. of +5.

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Figure 4.10

Highest and lowest oxidation numbers of reactive main-group elements.

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Figure 4.11

A summary of terminology for oxidation-reduction (redox) reactions.

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Sample Problem 4.8

Recognizing Oxidizing and Reducing Agents

PROBLEM: Identify the oxidizing agent and reducing agent in each of the following: (a) 2Al(s) + 3H2SO4(aq) Al2(SO4)3(aq) + 3H2(g)

(b) PbO(s) + CO(g)

Pb(s) + CO2(g)

(c) 2H2(g) + O2(g)

2H2O(g)

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Sample Problem 4.8

Recognizing Oxidizing and Reducing Agents

PROBLEM: Identify the oxidizing agent and reducing agent in each of the following: (a) 2Al(s) + 3H2SO4(aq) (b) PbO(s) + CO(g) (c) 2H2(g) + O2(g) Al2(SO4)3(aq) + 3H2(g) Pb(s) + CO2(g) 2H2O(g)

PLAN: Assign an O.N. for each atom and see which atom gained and which atom lost electrons in going from reactants to products.

An increase in O.N. means the species was oxidized (and is the reducing agent) and a decrease in O.N. means the species was reduced (is the oxidizing agent).
SOLUTION: 0 +1 +6 -2 +3 +6 -2 0

(a) 2Al(s) + 3H2SO4(aq)

Al2(SO4)3(aq) + 3H2(g)

The O.N. of Al increases; Al is oxidized; it is the reducing agent. The O.N. of H decreases; H is reduced; H2SO4 is the oxidizing agent.

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Sample Problem 4.8 continued +2 -2

Recognizing Oxidizing and Reducing Agents +2 -2 0 +4 -2

(b) PbO(s) + CO(g)

Pb(s) + CO2(g)

The O.N. of C increases; C is oxidized; CO is the reducing agent. The O.N. of Pb decreases; Pb is reduced; PbO is the oxidizing agent. 0 0 +1 -2

(c) 2H2(g) + O2(g)

2H2O(g)

The O.N. of H increases; it is oxidized; H2 is the reducing agent. The O.N. of O decreases; it is reduced; O2 is the oxidizing agent.

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Three Classifications of Redox Reactions

1. Combination

2Ca(s) + O2(g) 2CaO(s)

2. Decomposition

2KClO3(s) 2KCl(s) + 3O2(g)

3. Single Displacement (Single Replacement)

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Figure 4.12

An active metal displacing hydrogen from water.

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Figure 4.13

Displacing one metal by another.

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Figure 4.14

The activity series of the metals.

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Sample Problem 4.9 PROBLEM:

Identifying the Type of Redox Reaction

Classify each of the following redox reactions as a combination, decomposition, or displacement reaction, write a balanced molecular equation for each, as well as total and net ionic equations for part (c), and identify the oxidizing and reducing agents: magnesium nitride (aq) water(l) + oxygen gas aluminum nitrate(aq) + lead(s)

(a) Magnesium(s) + nitrogen(g) (b) Hydrogen peroxide(l)

(c) Aluminum(s) + lead(II) nitrate(aq)

PLAN: Combination reactions produce fewer products than reactants. Decomposition reactions produce more products than reactants.

Displacement reactions have the same number of products and reactants.

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Sample Problem 4.9 continued

Identifying the Type of Redox Reaction 0 3Mg(s) + 0 N2(g) +2 -3 Mg3N2(aq)

(a) Combination

Mg is the reducing agent; N2 is the oxidizing agent. (b) Decomposition +1 -1 H2O2(l) 2H2O2(l) H2O2 is the oxidizing and reducing agent. (c) Displacement 0 +2 +5 -2 +3 +5 -2 0 +1 -2 H2O(l) + 0 or

1 O (g) 2 2 2H2O(l) + O2(g)

Al(s) + Pb(NO3)2(aq) 2Al(s) + 3Pb(NO3)2(aq)

Al(NO3)3(aq) + Pb(s) 2Al(NO3)3(aq) + 3Pb(s)

Pb(NO3)2 is the oxidizing agent; Al is the reducing agent.

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