Reactions in Aqueous Solution

Chapter 4

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Describing Chemical Reactions

A chemical reaction is the process by which one or more

substances are changed into one or more different substances

reactan ts product s

(NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4H2O(g)

The reactant ammonium dichromate yields the products nitrogen, chromium (III) oxide and water

A CHEMICAL EQUATION represents, with symbols

and formulas, the identifies and relative amounts of the reactants and products in a chemical equation
2

Indications of a Chemical Reaction

1.

Evolution of heat and light is strong evidence that a chemical reaction has taken place! But, the evolution of
heat or light by itself is not necessarily a sign of a chemical change since many physical changes also release either heat or light.

2. 3.

Production of gas! (aka bubbles when two substances are

mixed)

Formation of precipitate! A solid that is produced as a result

of a chemical reaction in solution and that separates from the solution is known as a precipitate

4.

Color Change!

Characteristics of Chemical Equations

The equation must represent all reactants and products. 2. The equation must contain the correct formulas for the reactants and products 3. The law of conservation of mass MUST be satisfied!!
1.

Law of conservation of mass atoms are neither created nor destroyed in ordinary chemical reactions To equalized numbers of atoms, coefficients are added in front of the formulas where necessary
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Types of Chemical Reactions

A+BC CA+B A + BC AC + B AB + CD AD + CB
Synthesis (Combination)

Decomposition
Single Replacement Precipitation Reactions

(Double Replacement Acid + Base salt + water Reactions) Change of oxidation state Neutralization Reactions Hydrocarbon + O2 CO2 + (Acid/Base) H2O Redox Reactions Combustion
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PRECIPITATION REACTIONS
Double Replacement Reactions AB + CD AD + BC

A solution is a homogenous mixture of 2 or more substances The solute is(are) the substance(s) present in the smaller amount(s) The solvent is the substance present in the larger amount
Solution Soft drink (l) Air (g) Soft Solder (s)
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Solvent H2O N2 Pb

Solute Sugar, CO2 O2, Ar, CH4 Sn

aqueous solutions of KMnO4

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
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weak electrolyte

strong electrolyte

Conduct electricity in solution? Cations (+) and Anions (-)

Strong Electrolyte 100% dissociation NaCl (s)

H 2O

Na+ (aq) + Cl- (aq)

Weak Electrolyte not completely dissociated CH3COOH

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CH3COO- (aq) + H+ (aq)

Ionization of acetic acid

CH3COOH CH3COO- (aq) + H+ (aq)

A reversible reaction. The reaction can occur in both directions.

Acetic acid is a weak electrolyte because its ionization in water is incomplete.

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Hydration is the process in which an ion is surrounded by water molecules arranged in a specific manner.

d-

d+
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H2O

Nonelectrolyte does not conduct electricity? No cations (+) and anions (-) in solution C6H12O6 (s)
H 2O

C6H12O6 (aq)

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Precipitation Reactions
Precipitate insoluble solid that separates from solution
precipitate

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

PbI2 (s) + 2KNO3 (aq)

molecular equation
Pb2+ + 2NO3- + 2K+ + 2IPbI2 (s) + 2K+ + 2NO3-

ionic equation Pb2+ + 2IPbI2

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PbI2 (s)

net ionic equation K+ and NO3- are spectator ions

Precipitation of Lead Iodide

Pb2+ + 2I14

PbI2 (s)

PbI2

Solubility is the maximum amount of solute that will dissolve in a given quantity of solvent at a specific temperature.

15

Examples of Insoluble Compounds

CdS
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PbS

Ni(OH)2

Al(OH)3

Problem 4.20
Characterize the following compounds as (a) soluble or (b) insoluble in water: 1. CaCO3 2. ZnSO4 3. Hg(NO3)2 4. HgSO4 5. NH4ClO4

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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)

Ag+ (aq) + NO3- (aq) + Na+ (aq) + Cl- (aq)
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AgCl (s) + NaNO3 (aq)

AgCl (s) + Na+ (aq) + NO3- (aq)

Ag+ (aq) + Cl- (aq)

AgCl (s)

Predict what happens when a potassium hydroxide solution is mixed with a solution of sodium chloride. Write a net ionic equation for the reaction.

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What do we expect to see if we add copper (II) sulfate to sodium hydroxide? Write the molecular equation, ionic equation, and net ionic equation.

20

What do we expect to see if we add copper (II) sulfate to sodium hydroxide? Write the molecular equation, ionic equation, and net ionic equation.

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EXTRA PRACTICE Predict what happens when a potassium phosphate solution is mixed with a solution of calcium nitrate. Write a net ionic equation for the reaction.

22

Predict what happens when a silver nitrate solution is mixed with a solution of potassium hydroxide. Write a net ionic equation for the reaction.

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Types of Chemical Reactions

A+BC CA+B A + BC AC + B AB + CD AD + BC
Synthesis (Combination)

Decomposition
Single Replacement Precipitation Reactions

(Double Replacement Acid + Base salt + water Reactions) Change of oxidation state Neutralization Reactions Hydrocarbon + O2 CO2 + (Acid/Base) H2O Redox Reactions Combustion
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NEUTRALIZATION REACTIONS
Acid/Base Reactions Acid + Base Salt + Water

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Properties of Acids
Have a sour taste. Vinegar owes its taste to acetic acid. 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 2HCl (aq) + CaCO3 (s)
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CaCl2 (aq) + CO2 (g) + H2O (l)

Aqueous acid solutions conduct electricity.

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 is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

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Hydronium ion, hydrated proton, H3O+

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A Brnsted acid is a proton donor A Brnsted base is a proton acceptor

base

acid

acid

base

A Brnsted acid must contain at least one ionizable proton!

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Monoprotic acids
HCl H+ + ClStrong electrolyte, strong acid

HNO3
CH3COOH

H+ + NO3H+ + CH3COO-

Strong electrolyte, strong acid

Weak electrolyte, weak acid

Diprotic acids
H2SO4 HSO4H+ + HSO4H+ + SO42Strong electrolyte, strong acid Weak electrolyte, weak acid

Triprotic acids
H3PO4 H2PO4HPO4231

H+ + H2PO4H+ + HPO42H+ + PO43-

Weak electrolyte, weak acid

Weak electrolyte, weak acid Weak electrolyte, weak acid

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Identify each of the following species as a Brnsted acid, base, or both. (a) HI, (b) CH3COO-, (c) H2PO4-

HI (aq)

H+ (aq) + I- (aq)

Brnsted acid

CH3COO- (aq) + H+ (aq) H2PO4- (aq)

CH3COOH (aq)

Brnsted base

H+ (aq) + HPO42- (aq)

Brnsted acid

H2PO4- (aq) + H+ (aq)

H3PO4 (aq)

Brnsted base

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Problem 4.32
Identify each of the following as either a (a) Brnsted acid, (b) Brnsted base, or (c) both. 1. PO432. ClO23. NH4+ 4. HCO3-

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Neutralization Reaction
acid + base salt + water

HCl (aq) + NaOH (aq)

H+ + Cl- + Na+ + OH-

NaCl (aq) + H2O

Na+ + Cl- + H2O

H+ + OH-

H2O

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Neutralization Reaction Involving a Weak Electrolyte

weak acid + base salt + water

HCN (aq) + NaOH (aq)

HCN + Na+ + OH-

NaCN (aq) + H2O

Na+ + CN- + H2O

HCN + OH-

CN- + H2O

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Neutralization Reaction Producing a Gas

acid + base 2HCl (aq) + Na2CO3 (aq) 2H+ + 2Cl- + 2Na+ + CO32salt + water + CO2 2NaCl (aq) + H2O +CO2 2Na+ + 2Cl- + H2O + CO2

2H+ + CO32-

H2O + CO2

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Types of Chemical Reactions

A+BC CA+B A + BC AC + B AB + CD AD + BC
Synthesis (Combination)

Decomposition
Single Replacement Precipitation Reactions

(Double Replacement Acid + Base salt + water Reactions) Change of oxidation state Neutralization Reactions Hydrocarbon + O2 CO2 + (Acid/Base) H2O Redox Reactions Combustion
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OXIDATION REDUCTION REACTIONS

Redox Reactions Synthesis Reactions: A+BC Decomposition Reactions: C A + B Single Replacement Reactions: A + BC AC + B Combustion Reactions: hydrocarbon + O2 CO2 + H2O

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Oxidation-Reduction Reactions
(electron transfer reactions)

2Mg O2 + 4e40

2Mg2+ + 4e- Oxidation half-reaction (lose e-)

2O2Reduction half-reaction (gain e-) 2Mg + O2 + 4e2Mg2+ + 2O2- + 4e2Mg + O2 2MgO

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Zn (s) + CuSO4 (aq)

Zn Zn2+ + 2e- Zn is oxidized Cu2+ + 2e-

ZnSO4 (aq) + Cu (s)

Zn is the reducing agent

Cu Cu2+ is reduced Cu2+ is the oxidizing agent

Copper wire reacts with silver nitrate to form silver metal. What is the oxidizing agent in the reaction?

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Oxidation number
The charge the atom would have in a molecule (or an ionic compound) if electrons were completely transferred. 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.
4.4

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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 . -

HCO3

What are the oxidation numbers of all the elements in HCO3- ?

O = 2

H = +1

3x(2) + 1 + ? = 1
C = +4

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The Oxidation Numbers of Elements in their Compounds

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What are the oxidation numbers of all the elements in each of these compounds? NaIO3 IF7 K2Cr2O7

IF7 F = -1 7x(-1) + ? = 0

NaIO3

I = +7

Na = +1 O = -2
3x(-2) + 1 + ? = 0 I = +5 K2Cr2O7 O = -2 K = +1

7x(-2) + 2x(+1) + 2x(?) = 0 Cr = +6

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Problem 4.50
Give the oxidation number for the underlined atoms or in each of the following species: a) Mg3N2 b) CsO2 c) CaC2 d) CO32e) C2O42f) ZnO22g) NaBH4 h) WO42-

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Types of Oxidation-Reduction Reactions

Synthesis/Combination Reaction A+B
0 0

C
+3 -1

2Al + 3Br2 Decomposition Reaction C

+1 +5 -2

2AlBr3

A+B
+1 -1 0

2KClO3
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2KCl + 3O2

Types of Oxidation-Reduction Reactions

Combustion Reaction A + O2
0 0

B
+4 -2

S + O2

SO2

+2 -2

2Mg + O2
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2MgO

Types of Oxidation-Reduction Reactions

Displacement Reaction

A + BC
0 +1 +2 0

AC + B

Sr + 2H2O
+4 0

Sr(OH)2 + H2 Hydrogen Displacement

0 +2

TiCl4 + 2Mg
0
-1

Ti + 2MgCl2
-1
0

Metal Displacement Halogen Displacement

Cl2 + 2KBr
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2KCl + Br2

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
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Pb(OH)2 + H2

Problem 4.52
Which of the following metals can react with water to produce H2 (g)? a) Au b) Li c) Hg d) Ca e) Pt

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The Activity Series for Halogens

F2 > Cl2 > Br2 > I2

Halogen Displacement Reaction

0 -1 -1 0

Cl2 + 2KBr I2 + 2KBr

2KCl + Br2 2KI + Br2

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Types of Oxidation-Reduction Reactions

Disproportionation Reaction The same element is simultaneously oxidized and reduced. Example:
0

reduced
+1

-1

Cl2 + 2OHoxidized

ClO- + Cl- + H2O

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Classify each of the following reactions.

Ca2+ + CO32NH3 + H+ Zn + 2HCl Ca + F2

CaCO3 NH4+ ZnCl2 + H2 CaF2

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Problem 4.54
Predict the outcome of the reactions represented by the following equations by using the activity series, and balance the equations. Cu (s) + HCl (aq) I2 (g) + NaBr (aq) Mg (s) + CuSO4 (aq) Cl2 (g) + KBr (aq)

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Problem 4.56
Classify the following redox reactions by type: P4 + 10Cl2 4PCl5 2NO N2 + O2 Cl2 + 2KI I2 + 2KCl

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Solution Stoichiometry
Molarity Dilutions Gravimetric Analysis Titrations

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Solution Stoichiometry
The concentration of a solution is the amount of solute present in a given quantity of solvent or solution. M = molarity = moles of solute liters of solution

What mass of KI is required to make 5.00 x 102 mL of a 2.80 M KI solution?

M KI

volume of KI solution
5.00x102
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moles KI
x 2.80 mol KI 1 L soln x

M KI

grams KI
= 232 g KI

mL x

1L 1000 mL

166 g KI 1 mol KI

Problem 4.60
Calculate the mass in grams of sodium nitrate required to prepare 2.50 x 102 mL of a 0.707 M solution.

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Preparing a Solution of Known Concentration

61

Dilution is the procedure for preparing a less concentrated solution from a more concentrated solution.

Dilution
Add Solvent

Moles of solute before dilution (i)

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=
=

Moles of solute after dilution (f)

MiVi

MfVf

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 Vf = 0.0600 L Vi = MfVf Vi = ? L

Mi

= 0.200 M x 0.0600 L = 0.00300 L = 3.00 mL 4.00 M

Dilute 3.00 mL of acid with water to a total volume of 60.0 mL.

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Problem 4.70
Water is added to 25.0 mL of a 0.866 M KNO3 solution until the volume of the solution is exactly 500 mL. What is the concentration of the final solution?

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Problem 4.72
You have 505 mL of a 0.125 M HCl solution and you want to dilute it to exactly 0.100 M. How much water should you add? (assume that the volumes are additive.)

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Gravimetric Analysis
1. Dissolve unknown substance in water 2. React unknown with known substance to form a precipitate 3. Filter and dry precipitate 4. Weigh precipitate 5. Use chemical formula and mass of precipitate to determine amount of unknown ion

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A 0.5662 g sample of an ionic compound containing chloride ions and an unknown metal is dissolved in water, and treated with excess AgNO3. If 1.0882 g of AgCl precipitate forms, what is the percent by mass of Cl in the original compound?
35.45 g Cl %Cl 100 % 24 .72 % 143.4 g AgCl

mass of Cl 0.24721.0882 g 0.2690 g

This is the amount of Cl in the original sample, so 0.2690 g %Cl 100 % 47 .51 % 0.5662 g
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Problem 4.78
A sample of 0.6760 g of an unknown compound containing barium ions (Ba2+) is dissolved in water and treated with an excess of Na2SO4. If the mass of the BaSO4 precipitate formed is 0.4105 g, what is the percent by mass of Ba in the original unknown compound?

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Titrations
In a titration a solution of accurately known concentration is added gradually added 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
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Titrations can be used in the analysis of Acid-base reactions

H2SO4 + 2NaOH
Redox reactions

2H2O + Na2SO4

5Fe2+ + MnO4- + 8H+

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Mn2+ + 5Fe3+ + 4H2O

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
M rxn

2H2O + Na2SO4
M

volume acid

acid

moles red

coef.

moles base

base

volume base

25.00 mL x
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4.50 mol H2SO4 1000 mL soln

2 mol NaOH 1 mol H2SO4

1000 ml soln 1.420 mol NaOH

= 158 mL

Problem 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.

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16.42 mL of 0.1327 M KMnO4 solution is needed to oxidize 25.00 mL of an acidic FeSO4 solution. What is the molarity of the iron solution? WRITE THE CHEMICAL EQUATION! 5Fe2+ + MnO4- + 8H+
M rxn

Mn2+ + 5Fe3+ + 4H2O

V

volume red

red

moles red

coef.

moles oxid

oxid

M oxid

16.42 mL = 0.01642 L 0.1327 mol KMnO4 1L

25.00 mL = 0.02500 L 5 mol Fe2+ 1 mol KMnO4 1 0.02500 L Fe2+

0.01642 L x
73

= 0.4358 M

Problem 4.92
The SO2 present in air is mainly responsible for the acid rain phenomenon. Its concentration can be determined by titrating against a standard permanganate solution as follows: 5SO2 + 2MnO4- + 2H2O 5SO42- + 2Mn2+ + 4H+

Calculate the number of grams of SO2 in a sample of air if 7.37 mL of 0.00800 M KMnO4 solution are required for the titration.
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