Chapter 4 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 4.7 Reaction Reversibilty and the Equilibrium State

Learn the material in Tables 4.1, 4.2 and 4.3.

Professor Geanangel, CHEM 1331 Chapter 4

The Role of Water as a Solvent

Pure water conducts very little electric current due to the lack of charged particles (ions).

Professor Geanangel, CHEM 1331 Chapter 4

 Professor Geanangel, CHEM 1331 Chapter 4

When an ionic compound dissolves in water, the light demonstrates that an electric current flows in the solution. As water dissolves ionic compounds, it dissociates them into ions.

NaCl(s)

H2O

Na+(aq) + Cl (aq)

Movement of + and ions in an electrolyte solution carries the electric current.

Professor Geanangel, CHEM 1331 Chapter 4

Solubility of Ionic Compounds

A substance, like KBr, that conducts a current when dissolved in water is an electrolyte. In dissolving, each ion in KBr becomes solvated, i.e., surrounded by solvent molecules.

KBr(s)

H2O

K+(aq) + Br (aq)
H2O

For KBr, one mole of compound dissociates into two moles of ions. Depends on the formula.

(NH4)2SO4(s) AlCl3(s)
H2O

! 2NH4+(aq) + SO42(aq)

Al3+(aq) + 3Cl (aq)

Soluble ionic compounds dissociate fully in solution

Professor Geanangel, CHEM 1331 Chapter 4

Skill: Using the formula to find the number of moles of ions in solution Problem: How many moles of each ion are in each solution?

Professor Geanangel, CHEM 1331 Chapter 4

35 mL of 0.84 M zinc chloride

Professor Geanangel, CHEM 1331 Chapter 4

Using Molecular Depictions to Understand Solution Reactions

Which compounds are present in each beaker? A: KCl, Na2SO4, MgBr2 or AgNO3?

B: NH4NO3, MgSO4, Ba(NO3)2 or KF?

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The Polar Nature of Water Water separates ions in ionic compounds by overcoming their electrostatic attractions. Its ionizing power is due to the distribution of its electrons and its shape. In covalent bonds between different atoms, the sharing of electrons is unequal. Polar covalent bonds, create partially charged poles (!) on a polar H2O molecule.

"
9

"

Professor Geanangel, CHEM 1331 Chapter 4

Each bonds polarity is indicated by a polar arrow, with the arrowhead pointing to the negative pole.
!+ !

Water molecule has a bent shape: O-H bonds at an angle. Combined effect of its shape and polar covalent bonds makes water polar and able to attract ions.

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Water molecules congregate over an ionic crystals surface. Electrostatic charges drive the separation of ions from the solid to the liquid.

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Covalent Compounds in Water Water dissolves many molecular substances NH3 sucrose ethanol (C2H6O) antifreeze (ethylene glycol, C2H6O2) Each has polar molecules that attract H2Os but do not dissociate into ions. Their solutions do not conduct electric current so the substances are nonelectrolytes. Some covalent substances like benzene (C6H6) and octane (C8H18) have nonpolar molecules that do not dissolve appreciably in water. Acids are covalent compounds that interact so strongly with H2O that they dissociate into ions.

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Workshop What volume (mL) of 0.625 M HCl(aq) can be prepared from 13.5 mL of 6.02 M HCl(aq)?

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Problem: In water, strong acids form H+(aq) ion. What is molarity of H+(aq) in 1.4 M sulfuric acid? Solution: 2 mol of H+(aq) formed per mol of H2SO4 H2SO4(aq) " 2H+(aq) + [SO4]2-(aq) Thus, 1.4 M H2SO4 contains 2.8 M H+(aq). H+ is simply a proton; positive charge in a tiny volume Concentrated + charge in H+ strongly attracts the ! pole of H2O giving a covalent H-O bond. H+(aq) is written as H3O +, the hydronium ion.

[H7O3]+

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Writing Equations for Ionic Reactions If solutions of two ionic compounds are mixed, a reaction occurs only if ions leave solution. Mixing aqueous solutions of CaCl2 and KNO3 just causes their ions to disperse within the solution.

CaCl2(s)
KNO3(s)

H2O
2

! HO !

Ca2+(aq) + 2Cl (aq)

K+(aq) + NO3(aq)

No reaction occurs since all possible combinations, CaCl2, KNO3, Ca(NO3)2, and KCl, are water soluble.

Three major types of aqueous ionic reactions:

(1) precipitation reactions (2) neutralization reactions (3) reactions that form a gaseous product.
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Precipitation Reactions
Solutions of ionic compounds may react to form an insoluble product, a precipitate. Mixing AgNO3 and Na2CrO4 solutions gives a reddish precipitate of Ag2CrO4. Molecular equation shows reactants and products as undissociated compounds: 2AgNO3(aq)+ Na2CrO4(aq) ! Ag2CrO4(s) + 2NaNO3(aq) Total ionic equation shows all the soluble ionic substances dissociated into ions. 2Ag+(aq) +2NO3-(aq) + 2Na+ (aq) + CrO42-(aq) ! Ag2CrO4(s)+ 2Na+ (aq) + 2NO3-(aq)

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What Really Happens?

"
Note: equal numbers of Na+ and NO3 present on both sides. Spectator ions; not involved in the chemical change. Net ionic equation: spectator ions are eliminated, leaving the actual chemical change that occurs: 2Ag+(aq) +2NO3-(aq) + 2Na+ (aq) + CrO42-(aq) ! Ag2CrO4(s)+ 2Na+ (aq) + 2NO3-(aq)

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Table 4.1 Solubility Rules For Ionic Compounds in Water

Soluble Ionic Compounds

Insoluble Ionic Compounds

1. All common metal hydroxides are insoluble, except those of Group !!! 1A(1) and the larger members of Group 2A(2)(beginning with Ca2+). 2. All common carbonates (CO32-) and phosphates (PO43-) are insoluble, except those of Group 1A(1) and NH4+. 3. All common sulfides are insoluble except those of Group 1A(1), Group 2A(2) and NH4+.

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Memorize
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1. All common compounds of Group 1A(1) ions (Li+, Na+, K+, etc.) and ammonium ion (NH4+) are soluble. 2. All common nitrates (NO3-), acetates (CH3COO- or C2H3O2-) and most perchlorates (ClO4-) are soluble. 3. All common chlorides (Cl-), bromides (Br-) and iodides (I-) are soluble, except those of Ag+, Pb2+, Cu+, and Hg22+. All common fluorides (F-) are soluble except those of Pb2+ and Group 2A(2). 4. All common sulfates (SO22-) are soluble, except those of Ca2+, Sr2+, Ba2+, Ag+, and Pb2+.

Predicting formula of precipitate and writing ionic equations for precipitation and acid-base reactions Problem: Predict whether a reaction occurs when solutions below are mixed. If so, show molecular, total ionic, net ionic equations and spectator ions, if any. (a) sodium sulfate (aq) + lead(II) nitrate(aq) " ?
Na2SO4(aq) + Pb(NO3)2 (aq) " 2 NaNO3 + PbSO4

(b) ammonium perchlorate (aq) + sodium bromide(aq)

NH4ClO4(aq) + NaBr (aq) " NH4Br + NaClO4

Plan: In each case, write cation-anion combinations and determine if any are insoluble.

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(a) Beside Na2SO4 and Pb(NO3)2, PbSO4 and NaNO3. PbSO4 is insoluble so a precipitation reaction occurs. Molecular equation: Total ionic equation:
Na2SO4(aq) + Pb(NO3)2 (aq) # 2 NaNO3(aq) + PbSO4(s)

2 Na+(aq) + SO42-(aq) + Pb2+(aq) + 2 NO3-(aq) # 2 Na+(aq) + 2 NO3-(aq) + PbSO4(s)

Na + and NO3 are spectator ions. Net ionic equation: (b) Possible product ion combinations are ammonium bromide and sodium perchlorate.
NH4+(aq) + ClO4-(aq) + Na+ (aq) + Br-(aq) # NH4+ (aq) + Br-(aq) + Na+ (aq) + ClO4- (aq)

Ammonium and sodium salts are soluble so no reaction occurs. All are spectator ions!
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Neutralization (AcidBase) Reactions Acids produce H+ ions when dissolved in H2O. Bases produce water. OH in

Table 4.2 Selected Acids and Bases Acids Strong hydrochloric acid, HCl hydriodic acid, HI nitric acid, HNO3 sulfuric acid, H2SO4 perchloric acid, HClO4 Weak hydrofluoric acid, HF phosphoric acid, H3PO4 acetic acid, CH3COOH or HC2H3O2) hydrobromic acid, HBr

Acids and bases are electrolytes - grouped by strength- how extensively they dissociate into ions in solution.

Professor Geanangel, CHEM 1331 Chapter 4

Strong sodium hydroxide, NaOH potassium hydroxide, KOH calcium hydroxide, Ca(OH)2 barium hydroxide, Ba(OH)2 Weak ammonia, NH3

Weak acids and bases dissociate less; most molecules remain intact. Strong bases contain either the OH or O 2 ions.

strontium hydroxide, Sr(OH)2

Weak base ammonia does not contain O2 or OH, but produces some OH ions in reaction with water

Professor Geanangel, CHEM 1331 Chapter 4

Memorize
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Strong acids and bases dissociate fully into ions when dissolved in water.

Bases

Memorize
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Consider the molecular equation for reaction of strong acid HCl with strong base Ba(OH)2 : The cation of the salt (Ba2+) is contributed by the base and the anion (Cl) by the acid. Both HCl and Ba(OH)2 dissociate completely to ions, so the total ionic equation is:

The net ionic equation is:

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Acid-Base Titrations: Neutralization reactions done quantitatively Acid-base titration, a standardized base solution is slowly added to an acid solution of unknown concentration. Known volume of acid is placed in a flask with some indicator soln. Base solution is added slowly from a buret clamped above the flask.

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Near the end point, indicator changes color as a drop of base is added. Titration end point occurs when a tiny excess of OH changes indicator to its basic color permanently. At equivalence point: mol H+ (acid) = mol of OH (buret) 2HCl(aq) + Ba(OH)2(aq) " BaCl2(aq) + 2H2O(l)

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Skill: Calculating an unknown concentration from an acid-base or redox titration Problem: 50.00 mL HCl(aq) is placed in a flask. A buret holds 0.1524 M NaOH; vol. = 0.55 mL. At end point, vol. = 33.87 mL. What is HCl concentration?

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Find moles of NaOH added:

Find moles of HCl originally present:

Calculate molarity of HCl:

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Redox Reactions: the importance of the net movement of electrons in the redox process Consider the flashbulb reaction, in which an ionic compound, MgO, forms from its elements:

2 Mg + O2 " 2 MgO
Each Mg atom loses two electrons and each O atom gains them, forming Mg 2+ and O 2 ions.

2+ 2-

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Some Essential Redox Terminology oil rig

Oxidation is loss of electrons; reduction is gain of e In the formation of MgO, Mg undergoes oxidation (e loss) and O2 undergoes reduction (e gain). Oxidation half rxn: Mg $ Mg2+ + 2e Reduction half rxn: 1/2 O2 + 2e- $ O2 O2 gains electrons, so O2 is oxidizing agent. Mg loses electrons, so Mg is reducing agent. Remember: Oxidizing agent gets reduced, accepting electrons. Reducing agent gets oxidized as it loses electrons.

The no. of e moving is given by oxidation numbers

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Table 4.3 Rules for Assigning an Oxidation Number (O.N.)

General rules
1. For an atom in its elemental form (Na, O2, Cl2, etc.): O.N. = 0 "(ON) = 0 2. For a monoatomic ion: O.N. = ion charge 3. Sum of O.N. values for the atoms in a compound equals zero. The sum of O.N. values for atoms in a polyatomic ion equals ions charge.

Rules for specific atoms or periodic table groups

"(ON) = ion chg.

1. For Group 1A(1): O.N. = +1 in all compounds 2. For Group 2A(2): O.N. = +2 in all compounds 3. For hydrogen: O.N. = +1 in combination with nonmetals O.N. = -1 in combination with metals and boron 4. For fluorine: O.N. = -1 in all compounds 5. For oxygen: O.N. = -1 in peroxides O.N. = -2 in all other compounds(except with F) 6. For Group 7A(17): O.N. = -1 in combination with metals, nonmetals (except O), and other halogens lower in the group

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Skill: Determining the oxidation number (O.N.) of any atom in a compound. Problem: Determine O.N. of each in: L48593_ch04_140-185 3:12:07the 11:30pm Page element 161 4.5 Oxidation-Red (a) zinc chloride (b) sulfur trioxide (c) nitric acid Solution: (a) ZnCl a Zn2+ Page and two Cl 48593_ch04_140-185 3:12:07 11:30pm 161 2 Contains ON of Zn2+ is +2. ON of each Cl is -1. As Sample Problem 4.8 shows, a redox reaction can be (b) SO3 The ON of each oxygen is -2. the oxidation numbers of the species The !(ONs) in a compound = 0 change. (In the re red type ind Section 4.6, blue type indicates oxidation, 4.5and Oxidation-Reduct

4.5 Oxidation-Re (c) HNO ON of H= +1; NO group sums to -1 As Sample Problem 4.8 shows, a redox reaction be de 3 3 SAMPLE PROBLEM 4.8 Identifying Redox can Reaction

Professor Geanangel, CHEM 1331 Chapter 4

type indicates oxidation, and red typecan indica Section 4.6, As Sample shows, a redox reaction be (a) CaO( s ) blue COProblem 4.8 CaCO 2(g) 3(s) the oxidation numbers of the species change. (In the r 2K2O(s) 2N2(g) 5O2(g) (b) 4KNO3(s) blue type4.8 indicates and H red type in Section 4.6, SAMPLE PROBLEM (c) NaHSO (aq ) NaOH( aq) Identifying oxidation, Na2SORedox 4 4(aq) Reactions 2O(l) PLAN To determine whether a reaction is an oxidation-reduction PROBLEM Use oxidation numbers to decide which of the following Skill: Identifying Redox Reactions Prob. 4.8) to assign atom O.N. and if it changes as the reactan (a) CaO( seach ) CO CaCO s)(Samp. 2(g) an 3(see SAMPLE PROBLEM 4.8 Identifying Redox Reaction
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the oxidation numbers numbers of the species change. the follow rest PROBLEM Use oxidation to decide which (In of the

There is a change in oxidation number in all redox SOLUTION ( s ) ) redox 2N2(g ) 5O2(g) (b) 4KNO 3 2O(s reactions. Which of 2K these are reactions? PROBLEM Use oxidation numbers to decide which of the follow 2 4 4 (c) NaHSO ( aq ) NaOH( aq ) Na SO ( aq ) H2O(l) 4 2 4 (a) CaO( s ) CO ( g ) CaCO ( s ) 2 3 2 determine 2 2 2 PLAN To whether a reaction is an oxidation-reduction pro

an 2K 2N (g) 5O2(g)as the reactants (b) 4KNO 3(s) 2O(s) to assign each atom O.N. and see2if it changes (a) CaO(s) CO2( g) CaCO ) SO (aq) H O(l) 3( sNa (c) NaHSO SOLUTION 4(aq) NaOH(aq) 2 4 2 Because each atom in the product has the same O.N. that it had PLAN whether a is an oxidation-reduction 2 To determine 4 reaction 4 clude that this is a redox reaction. 2 each 2 notan 2 and 2 see if it changes as the reacta to assign atom O.N.
decreased: reduction SOLUTION (a) CaO(sO.N. ) CO2( g) CaCO3( s) 2 4 4 5 each atom Because in the product has the same O.N. that it had in 22 2 1 2 2 1 02 0 clude that this is not a redox reaction.

Professor Geanangel, CHEM 1331 Chapter 4

2( g) (a) 4KNO O.N. decreased: reduction CaO(s )(s CO CaCO3( s) ) 2K (b) 3 2O(s) 2N2( g) 5O2( g) Because 5 each atom in the product has the same O.N. that it had increased: oxidation clude that is not reaction. 1 2 this O.N. 1a redox 2 0 0 O.N. of O.N. decreased: reduction In this case, the N 5 to 0, and the O.N 4KNO 2K2O( s) changes 2N2( g)from 5O (b) 3(s) 2( g)
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simultaneously. In other words, a complete reaction cannot be or a reduction; it must be an oxidation-reduction. Figur Oxidation: increase in oxidation number. redox terminology.

Reduction, gain of electrons, is represented by a decrease in O.N. Skill: Selecting oxidizing4.9 and reducing agents. SAMPLE PROBLEM Recognizing Oxidizing and Re Problem: and reducing agentsagent in: in each o PROBLEMIdentify Identifythe theoxidizing oxidizing agent and reducing

nt

minolox)

(a) 2Al(s) 3H2SO4(aq) Al2(SO4)3(aq) 3H2(g) (b) PbO(s) CO(g) Pb(s) CO2(g) O2(g)to 2H(or g) based on rules. (c) 2H 2(g) O.N. 2O(ion) Plan: Assign atoms PLAN We = rst assign an (O.N.) to each atom (or io reactant red. agent if oxidation it has an number atom that is oxidized in Table 4.3. The reactant is the reducing agent if it contains an a reactant = ox. agent if it has an atom that is reduced (O.N. increased from left side to right side of the equation). The rea agent if it contains an atom that is reduced (O.N. decreased). SOLUTION (a) Assigning oxidation numbers:
6 1 2 6 2
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Professor Geanangel, CHEM 1331 Chapter 4

2Al(s) 3H2SO4(aq) Al2(SO4)3(aq) 3H2 Solution: (a) Assign oxidation numbers: The O.N. of Al increased from 0 to 3 (Al lost electrons), so Al was o +3 +6-2 +1 +6 -2 0 0 Al is the reducing agent. (a) +H 3H $ Al + 3H The2Al(s) O.N. of decreased 1 to 04) (H gained electrons), so H w 2SO4(aq) from 2(SO 3(aq) 2(g) ON +3,oxidizing Al is oxidized SO0 is the agent.so Al is reducing agent H2Al 4 to ON H +1 to 0, oxidation H reduced so H2SO4 is oxidizing agent (b) Assigning numbers: +2 -2 (b) Assigning +2 -2 +4 -2 2 2 0 2 ONs: 2 0
(b) PbO(s) + CO(g) " Pb(s) + CO2(g) PbO(s) CO( g) Pb(s) CO2( g) Pb is reduced; ON from +2 to 0; PbO = ox. agent Pb O.N. from 2 to 0, = so PbO was reduced; PbO is C isdecreased oxidized, its ON from +2 to +4; CO red. agent

Professor Geanangel, CHEM 1331 Chapter 4

C increased its O.N. from 2 to 4, so CO was oxidized; CO is t In general, when a substance (such as CO) becomes one with mo CO2), it is oxidized; and when a substance (such as PbO) becom atoms (such as Pb), it is reduced. (c) Assigning oxidation numbers:
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Balancing Redox Reactions by Oxidation No. Method

No. of e lost by the oxidized reactant must equal the number of e gained by the reduced reactant. Changes in oxidation numbers give the number of e transferred; can be used to balance redox reactions.

Five steps in the method listed on text page 163.

+2 -2 -3 +1 0 0 +1 -2

PbO(s) +2NH3(aq) $ Pb(s) + N2(g) + H2O(l) PbO(s) + 2NH3(aq) $ Pb(s) + N2(g) + H2O(l)
3PbO(s) + 2NH3(aq) $ 3Pb(s) + N2(g) + 3H2O(l)

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Skill: Balancing redox equations Problem: Use oxidation no. method to balance:
Cu(s) + HNO3(aq) $ Cu(NO3)2(aq) + NO2(g) + H2O(l)

Assign ONs to all atoms:

ON of Cu: 0 in Cu to +2 in Cu2+; Cu oxidized ON of N: +5 in HNO3 to +4 in NO2; N reduced

loses 2eCu(s) + 2HNO3(aq) $ Cu(NO3)2(aq) + 2NO2(g) + H2O(l)

gains 1e- x2 to balance e Professor Geanangel, CHEM 1331 Chapter 4

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Multiply by factors to make e lost equal e gained, and use the factors as coefficients.
Cu(s) + HNO3(aq) $ Cu(NO3)2(aq) + NO2(g) + H2O(l)

Complete the balancing by inspection.

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1. Assign ONs:

PbS(s) + O2(g) $ PbO(s) + SO2(g)

2. S ( 2 in PbS) is oxidized (+4 in SO2) O (0 in O2 ) is reduced (2 in PbO and in SO2 )

loses 6e-

3.

PbS(s) + 3/2O2(g)

PbO(s) +

SO2(g)

gains 2e- per O; need 3/2 O2 to make 3O2-

4. Multiply all by 2 to have whole number coefficients. 2PbS(s) + 3O2(g) $ 2PbO(s) + 2SO2(g)

total of 6e- transferred

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Workshop: Use ON change to balance this equation

+7 +2 +2 +3

MnO4(aq) + Fe2+(aq) " Mn2+(aq) + Fe3+(aq) (acidic)

gains 5eloses 1e-

MnO4(aq) + 5Fe2+(aq) " Mn2+(aq) + 5Fe3+(aq) MnO4(aq) + 5Fe2+(aq) " Mn2+(aq) + 5Fe3+(aq) + 4H2O

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Using ON change to balance in acidic solution

Cr2O72- + 2I " 2 Cr3+ + I2 (acidic aqueous soln, H+/H2O)
+6 -2 -1 +3 0

Cr2O72- + 2I = 2Cr3+ + I2 Cr2O72- + 6I- = 2Cr3+ + 3I2 (electrons balanced!) Cr2O72- + 6I- = 2Cr3+ + 3I2 + 7H2O Cr2O72- + 6I- + 14H+ = 2Cr3+ + 3I2 + 7H2O

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4.6 Summary of General Reaction Types

Combination (synthesis) X + Y " Z Decompositon Z " X + Y Single displacement Double displacement (metathesis) X + YZ " XZ + Y WX + YZ " WZ + YX

Combustion 2C4H10 + 13O2 " 8CO2 + 10H2O S8 + 8O2 " 8SO2

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Combination: Two nonmetals form a binary covalent compound. Industrial production of ammonia (Haber): Some nonmetal oxides react with O2 to form higher oxides. Metal oxide and nonmetal oxide react to form an ionic compound with an oxoanion. Note: its not a redox reaction.

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Thermal decomposition: Z " X + Y Heating ionic compounds with oxoanions may form a metal oxide and a non-metal oxide. Hydroxides, hydrates and some oxoacids release water on heating Some metal oxides, chlorates, and perchlorates release O2 on heating

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Displacement Reactions: Number of Reactants Equals The Number of Products

An atom or ion in a compound is displaced by an atom or ion of another element.

Single-displacement reactions 1. Some metals can displace hydrogen from either water or an acid.
Ni(s)+2HCl(aq) $ NiCl2(aq) + H2(g)

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A metal may displace another metal from solution. 2AgNO3(aq) + Cu(s) " Cu(NO3)2(aq) + 2Ag(s)

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Skill: Identifying combination, decomposition, and displacement reactions

Problem: Classify each of the following reactions and write a balanced equation for each: ammonium dichromate(s) " nitrogen(g) +chromium(III) oxide(s) +water(g)

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b) magnesium(s) + nitrogen(g) $ magnesium nitride(s)

Combination: two substances form one.

Mg(s) +

N2(g)

Mg3N2 (s)

(c) hydrogen peroxide(l) $ water(l) + oxygen (g) Decomposition: one substance forms two. H2O2 is sold in brown bottles because it decomposes in light

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(d) aluminum(s) + lead(II) nitrate(aq) $ aluminum nitrate(aq) + lead(s)

Section 4.7. Reversible Reactions is omitted END OF CHAPTER 4

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