Complete Solutions Manual

to accompany

Chemical Principles
Sixth Edition
Steven S. Zumdahl

Thomas J. Hummel Steven S. Zumdahl University of Illinois at Urbana-Champaign

HOUGHTON MIFFLIN COMPANY

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New York

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TABLE OF CONTENTS

Page How to Use This Guide....................................................................................................................v Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter 11 Chapter 12 Chapter 13 Chapter 14 Chapter 15 Chapter 16 Chapter 17 Chapter 18 Chapter 19 Chapter 20 Chapter 21 Atoms, Molecules, and Ions.....................................................................................1 Stoichiometry.........................................................................................................16 Types of Chemical Reactions and Solution Stoichiometry ...................................51 Gases ......................................................................................................................96 Chemical Equilibrium..........................................................................................149 Acids and Bases ...................................................................................................192 Applications of Aqueous Equilibria.....................................................................254 Energy, Enthalpy, and Thermochemisty..............................................................341 Spontaneity, Entropy, and Free Energy ...............................................................369 Electrochemistry ..................................................................................................413 Quantum Mechanics and Atomic Theory ............................................................455 Bonding: General Concepts .................................................................................490 Covalent Bonding: Orbitals ................................................................................540 Chemical Kinetics................................................................................................576 Liquids and Solids................................................................................................624 Properties of Solutions.........................................................................................668 The Representative Elements...............................................................................707 Transition Metals and Coordination Chemistry...................................................730 The Nucleus: A Chemist’s View .........................................................................756 Organic Chemistry ...............................................................................................773 iii

HOW TO USE THIS GUIDE
Solutions to all of the end of chapter exercises are in this manual. This “Solutions Guide” can be very valuable if you use it properly. The way NOT to use it is to look at an exercise in the book and then immediately check the solution, often saying to yourself, “That’s easy, I can do it.” Developing problem solving skills takes practice. Don’t look up a solution to a problem until you have tried to work it on your own. If you are completely stuck, see if you can find a similar problem in the Sample Exercises in the chapter. Only look up the solution as a last resort. If you do this for a problem, look for a similar problem in the end of chapter exercises and try working it. The more problems you do, the easier chemistry becomes. It is also in your self interest to try to work as many problems as possible. Most exams that you will take in chemistry will involve a lot of problem solving. If you have worked several problems similar to the ones on an exam, you will do much better than if the exam is the first time you try to solve a particular type of problem. No matter how much you read and study the text, or how well you think you understand the material, you don’t really understand it until you have taken the information in the text and applied the principles to problem solving. You will make mistakes, but the good students learn from their mistakes. In this manual we have worked problems as in the textbook. We have shown intermediate answers to the correct number of significant figures and used the rounded answer in later calculations. Thus, some of your answers may differ slightly from ours. When we have not followed this convention, we have usually noted this in the solution. The most common exception is when working with the natural logarithm (ln) function, where we usually carried extra significant figures in order to reduce round-off error. In addition, we tried to use constants and conversion factors reported to at least one more significant figure as compared to numbers given in the problem. For some problems, this required the use of more precise atomic masses for H, C, N, and O as given in Chapter 3. This practice of carrying one extra significant figure in constants helps minimize round-off error. We are grateful to Claire Szoke for her outstanding effort in preparing the manuscript of this manual. We also thank Estelle Lebeau for her careful accuracy review and Jim Madru for his thorough copyediting of the Solutions Manual. We also are grateful to Don DeCoste for his assistance in creating solutions to some of the problems in this Solutions Guide. TJH SSZ

v

CHAPTER 2 ATOMS, MOLECULES, AND IONS
Development of the Atomic Theory
18. Law of conservation of mass: mass is neither created nor destroyed. The total mass before a chemical reaction always equals the total mass after a chemical reaction. Law of definite proportion: a given compound always contains exactly the same proportion of elements by mass. For example, water is always 1 g hydrogen for every 8 g oxygen. Law of multiple proportions: When two elements form a series of compounds, the ratios of the mass of the second element that combine with 1 g of the first element always can be reduced to small whole numbers. For CO2 and CO discussed in section 2.2, the mass ratios of oxygen that react with 1 g carbon in each compound are in a 2 : 1 ratio. 19. From Avogadro’s hypothesis (law), volume ratios are equal to molecule ratios at constant temperature and pressure. Therefore, we can write a balanced equation using the volume data, Cl2 + 3 F2 → 2 X. Two molecules of X contain 6 atoms of F and two atoms of Cl. The formula of X is ClF3 for a balanced reaction. a. The composition of a substance depends on the numbers of atoms of each element making up the compound (depends on the formula of the compound) and not on the composition of the mixture from which it was formed. b. Avogadro’s hypothesis (law) implies that volume ratios are equal to molecule ratios at constant temperature and pressure. H2 + Cl2 → 2 HCl. From the balanced equation, the volume of HCl produced will be twice the volume of H2 (or Cl2) reacted. 21. Hydrazine: 1.44 × 10 −1 g H/g N; Ammonia: 2.16 × 10 −1 g H/g N; Hydrogen azide: 2.40 × 10 −2 g H/g N; Let's try all of the ratios:
0.144 0.216 0.216 3 = 6.00; = 9.00; = 1.50 = 0.0240 0.0240 0.144 2

20.

All the masses of hydrogen in these three compounds can be expressed as simple wholenumber ratios. The g H/g N in hydrazine, ammonia, and hydrogen azide are in the ratios 6 : 9 : 1.

1

2
22.

CHAPTER 2 ATOMS, MOLECULES, AND IONS
The law of multiple proportions does not involve looking at the ratio of the mass of one element with the total mass of the compounds. To illustrate the law of multiple proportions, we compare the mass of carbon that combines with 1.0 g of oxygen in each compound: Compound 1: Compound 2: 27.2 g C and 72.8 g O (100.0 - 27.2 = mass O) 42.9 g C and 57.1 g O (100.0 - 42.9 = mass O)

The mass of carbon that combines with 1.0 g of oxygen is: Compound 1: Compound 2:
27.2 g C = 0.374 g C/g O 72.8 g O

42.9 g C = 0.751 g C/g O 57.1 g O

0.751 2 = ; this supports the law of multiple proportions as this carbon ratio is a whole 0.374 1 number. 23. To get the atomic mass of H to be 1.00, we divide the mass that reacts with 1.00 g of oxygen by 0.126, that is, 0.126/0.126 = 1.00. To get Na, Mg, and O on the same scale, we do the same division. Na: 2.875 1.500 1.00 = 22.8; Mg: = 11.9; O: = 7.94 0.126 0.126 0.126 H Relative value Accepted value 1.00 1.0079 O 7.94 15.999 Na 22.8 22.99 Mg 11.9 24.31

The atomic masses of O and Mg are incorrect. The atomic masses of H and Na are close. Something must be wrong about the assumed formulas of the compounds. It turns out that the correct formulas are H2O, Na2O, and MgO. The smaller discrepancies result from the error in the assumed atomic mass of H.

The Nature of the Atom
24. Deflection of cathode rays by magnetic and electrical fields led to the conclusion that they were negatively charged. The cathode ray was produced at the negative electrode and repelled by the negative pole of the applied electrical field. β particles are electrons. A cathode ray is a stream of electrons (β particles). Density of hydrogen nucleus (contains one proton only):

25.

CHAPTER 2

ATOMS, MOLECULES, AND IONS
4 3 4 π r = (3.14) (5 × 10 −14 cm) 3 = 5 × 10 − 40 cm 3 3 3

3

Vnucleus =

d = density =

1.67 × 10 −24 g = 3 × 1015 g/cm 3 − 40 3 5 × 10 cm

Density of H atom (contains one proton and one electron): Vatom = 4 (3.14) (1 × 10 −8 cm) 3 = 4 × 10 − 24 cm 3 3

d=
26.

1.67 × 10 −24 g + 9 × 10 −28 g = 0.4 g/cm 3 4 × 10 − 24 cm 3

From Fig. 2.13 of the text, the average diameter of the nucleus is ≈ 10 −13 cm, and the average diameter of the volume where the electrons roam about is ≈ 10 −8 cm.
10 −8 cm = 105; −13 10 cm
1 mile 5280 ft 63,360 in = = 1 grape 1 grape 1 grape

Because the grape needs to be 105 times smaller than a mile, the diameter of the grape would need to be 63,360/(1 × 105) ≈ 0.6 in. This is a reasonable size for a grape. 27. First, divide all charges by the smallest quantity, 6.40 × 10−13. 2.56 × 10 −12 = 4.00; 6.40 × 10 −13 7.68 = 12.00; 0.640 3.84 = 6.00 0.640

Because all charges are whole-number multiples of 6.40 × 10−13 zirkombs, the charge on one electron could be 6.40 × 10−13 zirkombs. However, 6.40 × 10−13 zirkombs could be the charge of two electrons (or three electrons, etc.). All one can conclude is that the charge of an electron is 6.40 × 10−13 zirkombs or an integer fraction of 6.40 × 10−13. 28. The proton and neutron have similar mass, with the mass of the neutron slightly larger than that of the proton. Each of these particles has a mass approximately 1800 times greater than that of an electron. The combination of the protons and the neutrons in the nucleus makes up the bulk of the mass of an atom, but the electrons make the greatest contribution to the chemical properties of the atom. If the plum pudding model were correct (a diffuse positive charge with electrons scattered throughout), then α particles should have traveled through the thin foil with very minor deflections in their path. This was not the case because a few of the α particles were deflected at very large angles. Rutherford reasoned that the large deflections of these α particles could be caused only by a center of concentrated positive charge that contains most of the atom’s mass (the nuclear model of the atom).

29.

4

CHAPTER 2 ATOMS, MOLECULES, AND IONS

Elements and the Periodic Table
30. a. A molecule has no overall charge (an equal number of electrons and protons are present). Ions, on the other hand, have electrons added to form anions (negatively charged ions) or electrons removed to form cations (positively charged ions). b. The sharing of electrons between atoms is a covalent bond. An ionic bond is the force of attraction between two oppositely charged ions. c. A molecule is a collection of atoms held together by covalent bonds. A compound is composed of two or more different elements having constant composition. Covalent and/or ionic bonds can hold the atoms together in a compound. Another difference is that molecules do not necessarily have to be compounds. H2 is two hydrogen atoms held together by a covalent bond. H2 is a molecule, but it is not a compound; H2 is a diatomic element. d. An anion is a negatively charged ion, for example, Cl−, O2−, and SO42− are all anions. A cation is a positively charged ion, for example, Na+, Fe3+, and NH4+ are all cations. 31. The atomic number of an element is equal to the number of protons in the nucleus of an atom of that element. The mass number is the sum of the number of protons plus neutrons in the nucleus. The atomic mass is the actual mass of a particular isotope (including electrons). As we will see in Chapter 3, the average mass of an atom is taken from a measurement made on a large number of atoms. The average atomic mass value is listed in the periodic table. a. Metals: Mg, Ti, Au, Bi, Ge, Eu, and Am. Nonmetals: Si, B, At, Rn, and Br. b. Si, Ge, B, and At. The elements at the boundary between the metals and the nonmetals are B, Si, Ge, As, Sb, Te, Po, and At. Aluminum has mostly properties of metals, so it is generally not classified as a metalloid. 33. a. The noble gases are He, Ne, Ar, Kr, Xe, and Rn (helium, neon, argon, krypton, xenon, and radon). Radon has only radioactive isotopes. In the periodic table, the whole number enclosed in parentheses is the mass number of the longest-lived isotope of the element. b. promethium (Pm) and technetium (Tc) 34. Carbon is a nonmetal. Silicon and germanium are called metalloids as they exhibit both metallic and nonmetallic properties. Tin and lead are metals. Thus metallic character increases as one goes down a family in the periodic table. The metallic character decreases from left to right across the periodic table. a. Five: F, Cl, Br, I, and At b. Six: Li, Na, K, Rb, Cs, and Fr (H is not considered an alkali metal.) c. 14: Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu d. 40: All elements in the block defined by Sc, Zn, Uub, and Ac are transition metals.

32.

35.

CHAPTER 2
36.

ATOMS, MOLECULES, AND IONS

5

a. Cobalt is element 27. A = mass number = 27 + 31 = 58; 58 Co
27

b. 37. a. b. d. f. h. 38. Symbol
238 92 U

10 B 5 24 Mg: 12

c.

23 Mg 12

d.

132 I 53

e.

19 F 9

f.

65 Cu 29

12 protons, 12 neutrons, 12 electrons 12 p, 12 n, 10 e 27 p, 32 n, 24 e c. e. g. i.
59 Co2+: 27 59 Co: 27

24 Mg2+: 12 59 Co3+: 27 79 Se: 34 63 Ni: 28

27 p, 32 n, 25 e

27 p, 32 n, 27 e 34 p, 45 n, 36 e 28 p, 31 n, 26 e

34 p, 45 n, 34 e 28 p, 35 n, 28 e

79 2− Se : 34 59 2+ Ni : 28

Number of Protons in Nucleus
92

Number of Neutrons in Nucleus
146

Number of Electrons
92

Net Charge
0

40 2+ Ca 20 51 3+ V 23 89 Y 39 79 − Br 35 31 3− P 15

20

20

18

2+

23

28

20

3+

39

50

39

0

35

44

36

1−

15

16

18

3−

39.

Atomic number = 63 (Eu); net charge = +63 − 60 = 3+; mass number = 63 + 88 = 151; symbol: 151 Eu3+ 63 Atomic number = 50 (Sn); mass number = 50 + 68 = 118; net charge = +50 − 48 = 2+; symbol: 118 Sn2+. 50

6
40.

CHAPTER 2 ATOMS, MOLECULES, AND IONS
Atomic number = 16 (S); net charge = +16 − 18 = 2−; mass number = 16 + 18 = 34; symbol: 34 S2−
16

Atomic number = 16 (S); net charge = +16 −18 = 2−; Mass number = 16 + 16 = 32; symbol: 32 S2−
16

41.

In ionic compounds, metals lose electrons to form cations, and nonmetals gain electrons to form anions. Group 1A, 2A and 3A metals form stable 1+, 2+ and 3+ charged cations, respectively. Group 5A, 6A, and 7A nonmetals form 3!, 2! and 1! charged anions, respectively. a. Lose 2 e − to form Ra2+. d. Gain 2 e − to form Te 2− . b. Lose 3 e − to form In3+. e. Gain 1 e − to form Br!. c. Gain 3 e − to form P 3− . f. Lose 1 e − to form Rb+.

42.

See Exercise 41 for a discussion of charges various elements form when in ionic compounds. a. Element 13 is Al. Al forms 3+ charged ions in ionic compounds. Al3+ b. Se2− c. Ba2+ d. N3− e. Fr+ f. Br−

Nomenclature
43. AlCl3, aluminum chloride; CrCl3, chromium(III) chloride; ICl3, iodine trichloride; AlCl3 and CrCl3 are ionic compounds following the rules for naming ionic compounds. The major difference is that CrCl3 contains a transition metal (Cr) that generally exhibits two or more stable charges when in ionic compounds. We need to indicate which charged ion we have in the compound. This is generally true whenever the metal in the ionic compound is a transition metal. ICl3 is made from only nonmetals and is a covalent compound. Predicting formulas for covalent compounds is extremely difficult. Because of this, we need to indicate the number of each nonmetal in the binary covalent compound. The exception is when there is only one of the first species present in the formula; when this is the case, mono- is not used (it is assumed). a. Dinitrogen monoxide is correct. N and O are both nonmetals resulting in a covalent compound. We need to use the covalent rules of nomenclature. The other two names are for ionic compounds. b. Copper(I) oxide is correct. With a metal in a compound, we have an ionic compound. Because copper, like most transition metals, forms at least a couple of different stable charged ions, we must indicate the charge on copper in the name. Copper oxide could be CuO or Cu2O, hence why we must give the charge of most transition metal compounds. Dicopper monoxide is the name if this were a covalent compound, which it is not. c. Lithium oxide is correct. Lithium forms 1+ charged ions in stable ionic compounds. Because lithium is assumed to form 1+ ions in compounds, we do not need to indicate the charge of the metal ion in the compound. Dilithium monoxide would be the name if Li2O were a covalent compound (a compound composed of only nonmetals).

44.

CHAPTER 2
45.

ATOMS, MOLECULES, AND IONS
b. dinitrogen tetroxide d. tetraphosphorus hexoxide b. magnesium phosphate d. sulfur difluoride f. j. l. sodium hydrogen phosphate magnesium hydroxide silver chromate c. cobalt(II) iodide h. sodium hypochlorite h. lithium nitride

7

a. sulfur difluoride c. iodine trichloride

46.

a. sodium perchlorate c. aluminum sulfate e. sulfur hexafluoride g. sodium dihydrogen phosphate i. sodium hydroxide k. aluminum hydroxide

47.

a. copper(I) iodide d. sodium carbonate f. i. tetrasulfur tetranitride barium chromate

b. copper(II) iodide g. sulfur hexafluoride j. ammonium nitrate

e. sodium hydrogen carbonate or sodium bicarbonate

48.

a. acetic acid d. iodine monochloride g. sulfuric acid j. tin(IV) oxide b. SO3 f.

b. ammonium nitrite e. lead(II) phosphate h. strontium nitride k. sodium chromate c. Na2SO3 g. Cr(C2H3O2)2 l. NaH

c. colbalt(III) sulfide f. i. l. potassium iodate aluminum sulfite hypochlorous acid

49.

a. SO2 e. Li3N i. j. (NH4)2HPO4

d. KHSO3 h. SnF4

Cr2(CO3)3

NH4HSO4: composed of NH4+ and HSO4− ions k. KClO4 n. HBr b. Na2O2 f. PbO k. ZnS n. P2O5 b. CuSO4; copper(II) sulfate d. MgSO4; magnesium sulfate f. CaSO4; calcium sulfate c. KCN g. PbO2
3+

m. HBrO 50. a. Na2O e. SiCl4 i. j. CdSe

d. Cu(NO3)2 h. CuCl

GaAs: We would predict the stable ions to be Ga and As3−. l. Hg2Cl2: Mercury(I) exists as Hg22+.

m. HNO2 51.

a. Pb(C2H3O2)2; lead(II) acetate c. CaO; calcium oxide e. Mg(OH)2; magnesium hydroxide

g. N2O; dinitrogen monoxide or nitrous oxide (common name)

8
52.

CHAPTER 2 ATOMS, MOLECULES, AND IONS
a. Iron forms 2+ and 3+ charged ions; we need to include a Roman numeral for iron. Iron(III) chloride is correct. b. This is a covalent compound so use the covalent rules. Nitrogen dioxide is correct. c. This is an ionic compound, so use the ionic rules. Calcium oxide is correct. Calcium only forms stable 2+ ions when in ionic compounds, so no Roman numeral is needed. d. This is an ionic compound, so use the ionic rules. Aluminum sulfide is correct. e. This is an ionic compound, so use the ionic rules. Mg is magnesium. Magnesium acetate is correct. f. Because phosphate has a 3− charge, the charge on iron is 3+. Iron(III) phosphate is correct.

g. This is a covalent compound, so use the covalent rules. Diphosphorus pentasulfide is correct. h. Because each sodium is 1+ charged, we have the O22− (peroxide) ion present. Sodium peroxide is correct. Note that sodium oxide would be Na2O. i. j. HNO3 is nitric acid, not nitrate acid. Nitrate acid does not exist. H2S is hydrosulfuric acid or dihydrogen sulfide or just hydrogen sulfide (common name). H2SO4 is sulfuric acid. b. perchloric acid, HClO4 e. phosphoric acid, H3PO4 c. acetic acid, HC2H3O2

53.

a. nitric acid, HNO3 d. sulfuric acid, H2SO4

Additional Exercises
54. a. The smaller parts are electrons and the nucleus. The nucleus is broken down into protons and neutrons, which can be broken down into quarks. For our purpose, electrons, neutrons, and protons are the key smaller parts of an atom. b. All atoms of hydrogen have 1 proton in the nucleus. Different isotopes of hydrogen have 0, 1, or 2 neutrons in the nucleus. Because we are talking about atoms, this implies a neutral charge, which dictates 1 electron present for all hydrogen atoms. If charged ions were included, then different ions/atoms of H could have different numbers of electrons. c. Hydrogen atoms always have 1 proton in the nucleus, and helium atoms always have 2 protons in the nucleus. The number of neutrons can be the same for a hydrogen atom and a helium atom. Tritium (3H) and 4He both have 2 neutrons. Assuming neutral atoms, then the number of electrons will be 1 for hydrogen and 2 for helium.

CHAPTER 2

ATOMS, MOLECULES, AND IONS

9

d. Water (H2O) is always 1 g hydrogen for every 8 g of O present, whereas H2O2 is always 1 g hydrogen for every 16 g of O present. These are distinctly different compounds, each with its own unique relative number and types of atoms present. e. A chemical equation involves a reorganization of the atoms. Bonds are broken between atoms in the reactants, and new bonds are formed in the products. The number and types of atoms between reactants and products do not change. Because atoms are conserved in a chemical reaction, mass is also conserved. 55. A compound will always have a constant composition by mass. From the initial data given, the mass ratio of H : S : O in sulfuric acid (H2SO4) is:
2.02 32.07 64.00 : : = 1 : 15.9 : 31.7 2.02 2.02 2.02

If we have 7.27 g H, then we will have 7.27 × 15.9 = 116 g S and 7.27 × 31.7 = 230. g O in the second sample of H2SO4. 56. Mass is conserved in a chemical reaction. Mass: Chromium(III) oxide + aluminum → chromium + aluminum oxide 34.0 g 12.1 g 23.3 ?

Mass aluminum oxide produced = (34.0 + 12.1) ! 23.3 = 22.8 g 57. From the Na2X formula, X has a 2! charge. Because 36 electrons are present, X has 34 protons, 79 ! 34 = 45 neutrons, and is selenium. a. True. Nonmetals bond together using covalent bonds and are called covalent compounds. b. False. The isotope has 34 protons. c. False. The isotope has 45 neutrons. d. False. The identity is selenium, Se. 58. a. Fe2+: 26 protons (Fe is element 26.); protons − electrons = charge, 26 − 2 = 24 electrons; FeO is the formula because the oxide ion has a 2− charge. b. Fe3+: 26 protons; 23 electrons; Fe2O3 d. Cs+: 55 protons; 54 electrons; Cs2O f. P3−: 15 protons; 18 electrons; AlP c. Ba2+: 56 protons; 54 electrons; BaO e. S2−: 16 protons; 18 electrons; Al2S3 g. Br−: 35 protons; 36 electrons; AlBr3

h. N3−: 7 protons; 10 electrons; AlN 59. From the XBr2 formula, the charge on element X is 2+. Therefore, the element has 88 protons, which identifies it as radium, Ra. 230 − 88 = 142 neutrons.

10
60. 61.

CHAPTER 2 ATOMS, MOLECULES, AND IONS
The solid residue must have come from the flask. In the case of sulfur, SO42− is sulfate, and SO32− is sulfite. By analogy: SeO42−: selenate; SeO32−: selenite; TeO42−: tellurate; TeO32−: tellurite

62.

The polyatomic ions and acids in this problem are not named in the text. However, they are all related to other ions and acids named in the text that contain a same group element. Because HClO4 is perchloric acid, HBrO4 would be perbromic acid. Because ClO3− is the chlorate ion, KIO3 would be potassium iodate. Since ClO2− is the chlorite ion, NaBrO2 would be sodium bromite. And finally, because HClO is hypochlorous acid, HIO would be hypoiodous acid. If the formula is InO, then one atomic mass of In would combine with one atomic mass of O, or: 4.784 g In A = , A = atomic mass of In = 76.54 16.00 1.000 g O If the formula is In2O3, then two times the atomic mass of In will combine with three times the atomic mass of O, or: 2A 4.784 g In = , A = atomic mass of In = 114.8 (3)16.00 1.000 g O The latter number is the atomic mass of In used in the modern periodic table.

63.

64.

a. Ca2+ and N3−: Ca3N2, calcium nitride c. Rb+ and F−: RbF, rubidium fluoride e. Ba2+ and I−: BaI2, barium iodide g. Cs+ and P3−: Cs3P, cesium phosphide

b. K+ and O2−: K2O, potassium oxide d. Mg2+ and S2−: MgS, magnesium sulfide f. Al3+ and Se2−: Al2Se3, aluminum selenide

h. In3+ and Br−: InBr3, indium(III) bromide; In also forms In+ ions, but you would predict In3+ ions from its position in the periodic table. 65. The cation has 51 protons and 48 electrons. The number of protons corresponds to the atomic number. Thus this is element 51, antimony. There are 3 fewer electrons than protons. Therefore, the charge on the cation is 3+. The anion has one-third the number of protons of the cation which corresponds to 17 protons; this is element 17, chlorine. The number of electrons in this anion of chlorine is 17 + 1 = 18 electrons. The anion must have a charge of 1−. The formula of the compound formed between Sb3+ and Cl– is SbCl3. The name of the compound is antimony(III) chloride. The Roman numeral is used to indicate the charge of Sb because the predicted charge is not obvious from the periodic table. 66. a. This is element 52, tellurium. Te forms stable 2− charged ions in ionic compounds (like other oxygen family members).

When wood burns. Of course. AND IONS 11 Rubidium. Let’s consider hydrogen and oxygen to be monatomic gases and that water has the simplest possible formula (HO). element 37. which escape. their mass percent composition will be identical. fits the data. Because this element forms anions. we can make oxygen a diatomic molecule: 2 H + O2 → 2 HO This does not require hydrogen to be diatomic. These compounds are called isomers of each other. Note that because the atomic mass of chlorine listed in the periodic table is closer to 35 than 37. Both compounds have C2H6O as the formula. 67. The heavier elements have significantly more neutrons than protons in their nuclei. most of the solid material in wood is converted to gases. Astatine. Rb. Because this is a relatively small number of neutrons. Because the gases are at the same temperature and pressure. c. However. we can assume that 35Cl is the more abundant isotope. the number of protons will be very close to the number of neutrons present. neutrons. b. electrons. This is discussed in Chapter 3. Challenge Problems 68. At is element 85. MOLECULES. From the halogens listed. a. c. the volumes are directly proportional to the number of molecules present. it is a nonmetal and will be a halogen because halogens form stable 1! charged ions in ionic compounds. we get: 2 H + O2 → 2 H2O The only way to balance this is to make hydrogen diatomic: 2 H2 + O2 → 2 H2O 69. with an average atomic mass of 35.CHAPTER 2 b. if we know water has the formula H2O. chlorine. for example.45. To correct this. these are different compounds with different properties because the atoms are bonded together differently. The two isotopes are 35Cl and 37Cl. this is not possible. ATOMS. and protons. Argon. The atom is not an indivisible particle but is instead composed of other smaller particles. which correspond to the coefficients in the equation: 2 H + O → 2 HO Because atoms cannot be created nor destroyed in a chemical reaction. d. Because they have the same formula. The gases produced are most likely CO2 and H2O. and the number of electrons in the 1! ion is 18. . We have the equation: H + O → HO But the volume ratios are also equal to the molecule ratios. forms stable 1+ charged ions. Ar is element 18.

0/1.56 The ratio of the masses of R that combines with 1. then: 21 g XY × 4. we get: experiment 1 experiment 2 experiment 3 X = 1.50 g Q 1.4) and a formula of X3Y for experiment 3 [three times as much X must be present in experiment 3 as compared to experiment 1 (10.00 g Q 4.2 g Y (and 1. if we assume the formula for experiment 2 is YZ and that of experiment 3 is XZ. there is no way of knowing an absolute answer here. Z = 5. Y = 7.5 Z = 1. The two hydride samples contain different isotopes of either hydrogen and/or lithium. If the compound in expt.56 g R = . of course. then: 21 g XY H 7 . Y = 21.0 g R 4.0.0) g XY Note that it could be that neither experiment 1 nor experiment 3 has XY as the formula. MOLECULES. 1 has formula XY.7 g X) (7. For each experiment. However. their properties are similar because different isotopes of the same element have similar properties (except.5 Our assumption about formulas dictates the rest of the solution.67 g R 7.12 CHAPTER 2 ATOMS.0 Y = 10.3 g Y (and 4.00 g Q 1.0 Y = 3. we get relative masses of: X = 2.67 = 2. then we get: X = 2.0 + 2.2 g Y = 19. 70. Therefore.00 g Q is .4 X = 1. Compound II: = 3. divide the larger number by the smaller. Although the compounds are composed of different isotopes.0.5/3.0 Y = 1.00 g Q 4. In doing so. Any answer that is consistent with your initial assumptions is correct. For example. Compound I: 14.99 ≈ 3.2 + 0.5 = 3)].00 g R 1.0. 71. Z = 15 (= 21/1. AND IONS d.4) and a formula of XY3 for experiment 1. 1.0 g Y = 16.4) g XY If the compound in experiment 3 has the XY formula. if we assume that the formula of the compound in experiment 1 is XY and that of experiment 2 is YZ.8 g X) (4.0 (= 7. their mass). The answer to part d depends on which (if any) of experiments 1 and 3 have a formula of XY in the compound.

. In terms of balanced equations. assume that c = f = 1. CxHy + n O2 → 8 CO2 + 9 H2O. AND IONS 13 As expected from the law of multiple proportions. 72. Avogadro proposed that equal volumes of gases (at constant temperature and pressure) contain equal numbers of molecules. 2 Xa + Yb → 2 XeYf From the balanced equations. this ratio is a small whole number.31 × 10 −23 g = 43. 73.14. The ratio of the mass of the molecule to the mass of a nuclear particle will give a good approximation of the number of nuclear particles (protons and neutrons) present. Most of the mass of the atom is due to the protons and the neutrons in the nucleus. Yb be the formula for the atom/molecule Y. so one molecule of octane must contain 9 × 2 = 18 atoms of H.67 × 10−24 g). Thus: X2 + 2 Y2 → 2 XY2 and 2 X2 + Y2 → 2 X2Y Compound I = XY2: If X has relative mass of 1. Let Xa be the formula for the atom/molecule X. all hydrogen in octane ends up as hydrogen in H2O. Xa + 2 Yb → 2 XcYd.8 ≈ 44 nuclear particles 1. and protons and neutrons have about the same mass (1. 7. the following would be the balanced equations for the production of the two compounds. Substituting into the balanced equations: X2c + 2 Y2f → 2 XcY2f 2 X2c + Y2f → 2 X2cYf For simplest formulas. 1. Similarly. Because compound I contains three times the mass of R per gram of Q as compared with compound II (RQ).00 + 2 y 74. Octane formula = C8H18 and the ratio of C:H = 8:18 or 4:9.67 × 10 −24 g Thus there are 44 protons and neutrons present. the formula of compound I should be R3Q.00. and XeYf be the formula of compound II between X and Y. Assuming one molecule of octane reacting. If the number of protons equals the number of neutrons. a = 2c = e and b = d = 2f. then 1 molecule of CxHy produces 8 molecules of CO2 and 9 molecules of H2O. Avogadro’s hypothesis (law) implies that volume ratios will be identical to molecule ratios. Because all the carbon in octane ends up as carbon in CO2. XcYd be the formula of compound I between X and Y. octane must contain 8 atoms of C. 1. MOLECULES. One possibility would be the molecule CO2 [6 + 2(8) = 22 protons]. we have 22 protons in the molecule.00 = 0.CHAPTER 2 ATOMS. y = 1. Using the volume data.3043.

0 Assuming 6. Data set 1: A = 6.401 = 2. the new table of relative masses would be: 6 ( mass A 2 ) 0. One such solution that fits the gas volume data is: 6 A2 + B4 → 4 A3B B4 + 4 C3 → 4 BC3 3 A2 + 2 C3 → 6 AC In any correct set of reactions.14 times that of X.0. b.602 = .602 = 2.33 when B = 1.583(mass B4) mass B 4 0. AND IONS Compound II = X2Y: If X has relative mass of 1. Marathon Problem 75.14.0 for the relative mass of A.374 = . then Y will have an atomic mass of 114. MOLECULES. mass A2 = 0.04 when B = 1. Gas volumes are proportional to the number of molecules present.295 4 ( mass C 3 ) 0. C = 1. B = 3. 0. mass C3 = 0. Thus if X has an atomic mass of 100. mass A2 = 0.172 2 (mass C 3 ) 0. Here. divide the larger number by the smaller number to determine relative masses.6364. a.0 and A = 6.00 0.33.0 Data set 3: C = 3.0 or C = 7.00 = 0.00 0.00 + y The relative mass of Y is 1.570(mass C3) 3 (mass A 2 ) 0.1 and B = 3.17.00 0. the relative masses would be A = 6. 2. 2.0.0 (if simplest formulas are assumed). There are many possible correct answers for the balanced equations.14 CHAPTER 2 ATOMS. C = 2.17 when A = 1.320 .5 and A = 3.04. multiply the results by 3.00. For each set of data.0 Data set 2: C = 7.320 To have whole numbers.401 = .295 0.374 = 1.172 0. the calculated mass data must match the mass data given initially in the problem.0 and B = 3. and C = 7. y = 1.340(mass B4) mass B 4 0. A = 2.

583(12) = 7. This is just one possibility.0.0 and C = 7. MOLECULES.0. AND IONS 15 Assume some relative mass number for any of the masses. Mass C3 = 0.CHAPTER 2 ATOMS.0) = 12.0. .0. and C = 7. B = 9. so mass B4 = 4(3.570(7. mass C = 7. mass A = 4.0. The relative masses having all whole numbers would be A = 6. Note that any set of balanced reactions that confirms the initial mass data is correct.0/3.0) = 4.0 When we assume a relative mass for B = 3. We will assume that mass B = 3.0.0/2 = 2.0.0/3 Mass A2 = 0. then A = 2.

0140(203.6260(186.0 = 0.74 + 109.3740 A = 0. A = 0.207 = 0.2 amu.32% 81Br. 186.0013)x x = 48%.0730(46. 79Br81Br. 186.956) + 0.9209) 100 15196 = (150.9196)x + 15292.947841) + 0.84/2 = 80. 27.3740(A).0540(49.86 + 49.09 − (152.9196) + (100 − x)(152. each 2 mass units apart.0 = 207.0800(45.9759) + 0.5240(207. or 78.2210(206.7380(47.92.207 .944792) = 47.3740(A) A= 26.9766) A = 2. The peak at 157.951764) + 0. The peaks in the mass spectrum correspond to 79Br2.973) + 0. the element is Pb.CHAPTER 3 STOICHIOMETRY Atomic Masses and the Mass Spectrometer 23. This isotope has mass equal to 157.68% 79Br and 49.84 corresponds to a Br2 molecule composed of two atoms of the lighter isotope. −96 = −(2.64 + 45.0550(48.95269) + 0.2410(205.2 = 185 amu (A = 184. differing in mass by two mass units. 151. 24. There are three peaks in the mass spectrum.92.84/2.947947) + 0. 16 . The second isotope is 81Br with mass equal to 161.96 = x(150. 48% 151Eu and 100 − 48 = 52% 153Eu 25. This corresponds to 79Br. and 81Br2 in order of increasing mass. The actual abundance is 50.9209)x. 69. then x + y = 100 and y = 100 − x.95 amu without rounding to proper significant figures) 0.88 amu This is element Ti (titanium). This is consistent with two isotopes. from the periodic table. The intensities of the highest and lowest masses tell us the two isotopes are present at about equal abundance.9745) + 0. Let x = % of 151Eu and y = % of 153Eu.117.

We get this ratio from the following probability table: .3 7.2 100.92 126.92 129.87 4.92 131. 144 146 Ga2As2 can be 69Ga2As2.5 13.92 124.79 34. The mass spectrum will have three peaks at 288.0 50 0 122 124 126 128 130 132 134 29.46 0.09 2.3 92.71 31.92 127.61 6. 290. or 71Ga2As2.1 2.99 18.CHAPTER 3 28.4 20.93 0. and 292 with intensities in the ratio of 36 : 48 : 16 or 9 : 12 : 4.92 125.92 123. 69Ga71GaAs2. GaAs can be either 69GaAs or 71GaAs.3 54. The mass spectrum for GaAs will have two peaks at 144 (= 69 + 75) and 146 (= 71 + 75) with intensities in the ratio of 60 : 40 or 3 : 2.48 0. STOICHIOMETRY 17 Scaled Intensity Compound Mass Intensity Largest Peak = 100 __________________________________________________________________ H2120Te H2122Te H2123Te H2124Te H2125Te H2126Te H2128Te H2130Te 100 121.

50 × 10 −2 mol CO2 6.04 g H2O mol 6.224 mol H2O × 12 atoms total = 3.60) 0.40) 288 290 292 Moles and Molar Masses 30.16 Ga (0.58 × 1021 molecules CH3OH 6 atoms total .224 mol H2O × 0.71 × 1022 molecules CO2 × 4.35 × 1023 molecules H2O × 2.022 × 10 23 molecules = 3.02 g = 4.92 × 1023 atoms total molecule 18.35 × 1022 atoms total × 1 molecule = 5.50 × 10 −2 mol CO2 × 44.022 × 10 23 molecules = 1.022 × 10 23 molecules 1.27 × 1022 molecules C6H6 × 0.24 71 STOICHIOMETRY Ga (0.13 × 1022 atoms total molecule CO 2 2.43 × 10 −2 mol C6H6 78.98 g CO2 mol 3 atoms total = 8.35 × 1023 molecules H2O mol 3 atoms total = 4.18 69 69 71 CHAPTER 3 Ga (0.27 × 1022 molecules C6H6 mol Each molecule of C6H6 contains 6 atoms C + 6 atoms H = 12 total atoms.36 0.11 g 5.01 g = 1. 4.24 0. 3.60) Ga (0.24 g C6H6 × 1 mol = 5.40) 0.05 × 1023 atoms total molecule 1 mol = 4.43 × 10 −2 mol C6H6 × 6.71 × 1022 molecules CO2 × 3.

01) = 100.95 g/mol 5.58 × 1021 molecules CH3OH × 9.01 × 1022 atoms N molecule C 2 H 5 O 2 N b.07 g/mol 5.67 × 1022 atoms N mol N . 1. 20.00) = 164.00 g Mg3N2 × 1 mol Mg 3 N 2 6.10 g Ca ( NO 3 ) 2 × × 2 mol N mol Ca ( NO 3 ) 2 6.008) + 2(16.022 × 10 23 molecules C 2 H 5 O 2 N × 75.72 × 1021 molecules C2H5OH × c. A chemical formula gives atom ratios as well as mole ratios.08 + 2(14.022 × 10 23 formula units Mg 3 N 2 × 100.297 g CH3OH mol 31.04 g = 0.50 g CO2 × 1 mol = 3.27 × 10 −3 mol CH3OH × 32.03 × 10 −4 mol C8H10N4O2 1000 mg 194. a. Molar mass of Mg3N2 = 3(24.41 × 10 −2 mol CO2 44.CHAPTER 3 STOICHIOMETRY 1 mol = 9.022 × 10 23 atoms N = 3.022 × 10 23 molecules 19 5.01) + 5(1.27 × 10 −3 mol CH3OH 6.00 g C2H5O2N × 1 mol C 2 H 5 O 2 N 6.0 mg C8H10N4O2 × 1g 1 mol × = 1.00 g Ca(NO3)2 × 1 mol Ca ( NO 3 ) 2 164.31) + 2(14.01 g 32.95 g Mg 3 N 2 mol Mg 3 N 2 × 2 atoms = 5.52 × 10 −3 mol C2H5OH 23 6. We will use both ideas to show how these conversion factors can be used.10 g/mol 5. 2.00) + 14. Molar mass of Ca(NO3)2 = 40.01) + 6(16.20 g 1 mol = 4.07 g C 2 H 5 O 2 N mol C 2 H 5 O 2 N H 1 atom N = 4.0l = 75. a. Molar mass of C2H5O2N = 2(12.022 × 10 molecules b.97 × 1022 atoms N mol Mg 3 N 2 c.

00 g N2O4 × STOICHIOMETRY 6.2 × 1024 atoms 1 mol F2 1 mol F 1 mol CO 2 3 mol atoms (1 C + 2 O) 6.21 × 1024 atoms 146.0 g He < 1.0 × 1023 atoms 4.9 × 1021 atoms N e.0 mol F2 < 44.0 g H2 < 146 g SF6 34. 10.02 g N 2 O 4 mol N 2 O 4 = 6. 1.02 × 10 23 atoms N × × 294.0 × 1019 molecules C14H18N2O5 1000 mg 294.022 × 10 23 atoms H × × = 2.3 g = 459 g C14H18N2O5 mol d.07 g SF6 1 mol SF6 1 mol atoms The order is: 4.81 × 1024 atoms 4.022 × 10 23 atoms F × = 1.007 g + 18 mol H × + 2 mol N × mol C mol H mol N + 5 mol O × b.3 g mol 1 mol C14 H18 N 2 O 5 2 mol N 6. a.01) + 4(16. 5. 1.0 g He × 1.022 × 10 23 atoms N 1 mol N 2 O 4 2 mol N × × mol N 92.0 g H2 × 1 mol H 2 2 mol H 6.016 g H 2 1 mol H 2 1 mol H 1 mol He 6.003 g He 1 mol He 2 mol F 6.999 g = 294.305 g/mol mol O 1 mol C14 H18 N 2 O 5 = 3.3 g C14 H18 N 2 O 5 c.01 g CO 2 1 mol CO 2 1 mol atoms = 1.0 g CO2 < 4.0 g C14H18N2O5 × 15.02 g/mol 5.3 g C14 H18 N 2 O 5 mol C14 H18 N 2 O 5 mol N = 4.54 × 1022 atoms N 33.0079 g 14. Molar mass of N2O4 = 2(14.56 mol × 294.011 g 1.4 × 1024 atoms 2.40 × 10−2 mol C14H18N2O5 294.022 × 10 23 atoms He × = 6.20 CHAPTER 3 d.02 × 10 23 molecles × × = 1.0 g CO2 × 146 g SF6 × 1 mol SF6 7 mol atoms (1 S + 6 F) 6. 14 mol C H 12.0 mg × 1g 1 mol 6.022 ×10 23 atoms × × = 4.2 g C14H18N2O5 × .022 × 10 23 atoms × × 44. 4.0 mol F2 H 44.00) = 92.

Molar mass = 20(12.0 g × c.4 × 1016 molecules C2H4Br2 mol C 2 H 4 Br2 Percent Composition 37.0 lb flour × 454 g flour 30.373 × 10−19 g 23 mol 6.0 × 10 −9 g C 2 H 4 Br2 1 mol C 2 H 4 Br2 × × lb flour g flour 187.023 mol C2H3Cl3O2 165. 500 molecules × 1 mol 165.3 g × = 4. 5.022 × 10 atoms 35.008) + 3(35. 1.3 g C2H3Cl3O2 mol b.01) g C × 100 = 71.689% H 336.43 g compound 29(1.0 × 10-2 mol × d.6 g chloral hydrate × × 35.00) = 165.0 × 109 molecules × g. STOICHIOMETRY 1 mol 294. 1. 2(12.305 g × = 4.02 × 10 23 molecules 3 atoms Cl × × 165.39 g/mol 1 mol = 3.39 g × = 1.01) + 3(1.00) = 336.5 × 1022 atoms of chlorine e. 2.39 g = 3. 1 molecule × 1 mol 294. 500.43 g compound Mass % H = .00 + 3(16.008) g H × 100 = 8.02 × 10 23 molecules = 4.01) + 29(1.45 g 3 mol Cl mol C 2 H 3Cl 3O 2 f.9 × 10−13 g 23 mol 6.39 g C 2 H 3Cl 3O 2 = 1.9 g C 2 H 4 Br2 × 6.887 × 10−22 g C14H18N2O5 23 mol 6.45) + 2(16. a.CHAPTER 3 f.43 g/mol Mass % C = 20(12.39 g mol molecule = 5.40% C 336.0 g C2H3Cl3O2 × 1 mol 6.008) + 19.0 g Cl × 1 mol Cl 1 mol C 2 H 3Cl 3O 2 165.02 × 10 atoms 21 1.022 × 10 molecules 36.39 g 165.

00) g O × 100 = 14.93 g Co mol Co = 7.689 + 5.008) + 4(14.34 g Co × 1 mol Co 1 mol cyanocobalamin × 58.014 g N × 100 = 63.40 + 8. determine the mass of 1 mole of compound.008) + 1(16.20 g C8 H10 N 4 O 2 194.01) g C × 100 = 52.07 g C 2 H 5 OH The order from lowest to highest mass percentage of carbon is: sucrose (C12H22O11) < caffeine (C8H10N4O2) < ethanol (C2H5OH) 39. N2O: % N = 40.30 g C12 H 22 O11 C2H5OH: Molar mass = 2(12.447% N 46.648% F 336.43 g compound C8H10N4O2: Molar mass = 8(12.10% C 342.014 g N × 100 = 30.26% O or: Mass % O = 38. 3(16.00) = 46.00 g F × 100 = 5.08 × 100 = × 100 = 49. 28.22 Mass % F = 19.008) + 11(16.005 g NO 2 28. a.07 g/mol Mass % C = 2(12.01) + 6(1.01) + 22(1.00 g cyanocobalamin: mol cyanocobalamin = 4.006 g NO 14. 12(12.0l) + 2(16.007 g N × 100 = 30.00 ! (71. For each compound.30 g/mol Mass % C = c. NO2: % N = c.007 g N × 100 = 46.00) = 194. a.47% C 194.013 g N 2 O Assuming 100. NO: % N = b.20 b.20 g/mol Mass % C = 8(12.27% O 336.681% N 30.14% C 46. and then calculate the mass percentage of N in 1 mole of that compound. C12 H22O11: Molar mass = 12(12. N2O4: % N = 14.01) g C 96.649% N 44.648) = 14.36 × 10−2 mol cyanocobalamin .00) = 342.447% N 92.01) g C × 100 = 42.43 g compound CHAPTER 3 STOICHIOMETRY Mass % O = 100.01) + 10(1.010 g N 2 O 4 d.

6 g Ca 242.16 g Ca = 12 g Ca 172. 12 g Ca3Al2O6. Mass percent Ca: 50. x = molar mass = 1360 g/mol = 1 mol cyanocobalamin 7. Mol fungal laccase = 0.000 g fungal laccase.CHAPTER 3 STOICHIOMETRY 23 x g cyanocobalamin 100.81 = 47 g Ca % Ca = 47 g Ca × 100 = 47% Ca 100.96 g Al = 2.08 g Ca × × = 26 g Ca 228.0 g Ca2AlFeO5.0 g Ca2AlFeO5 × 3.0 g of Portland cement. 8.08 g Ca = 0. There are 0. g Ca3SiO5.390 g Cu × 1 mol Cu 1 mol fungal laccase × = 1. we have 50. If we have 100.16 g Ca = 2.5 g CaSO4•2H2O. and 3.390 g Cu for every 100. g Ca3SiO5 × 1 mol Ca 3SiO 5 3 mol Ca 40.53 × 10 −3 mol 42.6 + 0.33 g Ca 3SiO 5 1 mol Ca 3SiO 5 1 mol Ca 25 g Ca2SiO4 × 80.3 g Ca 270.24 g Ca = 5.4 g Al 270.00 g .0 g Ca2AlFeO5 × 26.54 × 104 g/mol 1 mol fungal laccase 1.5 g CaSO4•2H2O × 40.000 g of fungal laccase.0 g cement Mass percent Al: 12 g Ca3 Al2O6 × 53.98 g Al = 0. Let’s assume 100.25 g Ca 2SiO 4 120.99 g Ca 2 AlFeO5 12 g Ca3Al2O6 × 8. x = molar mass = 6. 25 g Ca2SiO4.36 × 10 − 2 mol 41.18 g CaSO 4 • 2 H 2 O Mass of Ca = 26 + 12 + 5.20 g Ca 3 Al2 O 6 80.55 g Cu 4 mol Cu x g fungal laccase 100.000 g = .53 × 10−3 mol 63.20 g Ca 3 Al 2 O 6 8.81 g Ca 172.99 g Ca 2 AlFeO5 .3 + 2.89 g Al 242.

002%. The smallest whole number ratio of the atoms (the empirical formula) is NO2.89 g × 100 = 3.7135) 30. a. elemental analysis will give us only the empirical formula.00 − (40. 44.7135% 60.999) = 60.026 g/mol ⎟ ⎝ ⎠ %C= 12.011) + 4(1.0158 g H × 100 = 40.000 − (40.7136% 180.052 g/mol %C= 24.999 g ⎞ + 1 mol O ⎜ ⎜ mol O ⎟ = 30.284% c.0079 g ⎞ a.155 g C 6 H12 O 6 %H= 12(1.022 g × 100 = 40.000 − (40.002 + 6.026 g CH 2 O %O= 15.026 g CH 2 O 30. Molar Mass of HC2H3O2 = 2(12. The composition of all three in mass percent is also the same (within rounding differences).285% All three compounds have the same empirical formula.155 g % O = 100.3% Al 100.026 g CH 2 O = 53.7135) = 53. ⎛ 12.0079) + 2(15.284% O or % O = 100.999) = 180.0079) + 6(15.052 g % O = 100. Therefore.7135% H 30.999 g O × 100 = 53.002% C. and different molecular formulas.24 % Al = 2.011 g ⎞ ⎛ 1.8 g 55. % Fe = × 100 = 1.011) + 12(1. CH2O.011 g C 2.285% b.85 g Fe = 1.002%.4 g + 0.0079) g × 100 = 6. .052 g %H= 4.0 g Ca2AlFeO5 × 1.0316 g × 100 = 6.0 g CHAPTER 3 STOICHIOMETRY Mass percent Fe: 8. Molar mass of C6H12O6 = 6(12. 60.002 + 6.0 g Empirical and Molecular Formulas 43.7136) = 53.155 g/mol %C= 72.8 g Fe.99 g Ca 2 AlFeO5 100.002 + 6. The molecular formula is N2O4.8% Fe 242. 180.066 g C × 100 = 40. % H = × 100 = 6. Molar mass of CH2O = 1 mol C ⎜ ⎜ mol C ⎟ + 2 mol H ⎜ mol H ⎟ ⎜ ⎟ ⎟ ⎝ ⎝ ⎠ ⎠ ⎛ 15.

0581 g C.00 g of adrenaline.401 g Hg × 1 mol Hg 1 mol O = 2.4172 g HgxOy − 0.591 0.591 = 8. = 1.0581 g C = 0. 46.00 g O The mole ratio between Hg and O is 2 : 1. we will determine composition in mass percent.591 mol N 15. 8. 47.000 × 10−3 mol Hg 200. so the empirical formula is Hg2O.6 g Hg 16.6498 g HgxOy − 0.51 1. Out of 100.016 g O = 0.01 g C 0. First. We assume that all the carbon in the 0.CHAPTER 3 STOICHIOMETRY 25 b.51 mol H 12.00 × 10−3 mol O 16.00 × 10−3 mol Hg.00.0.6018 g Hg = 0. Compound I: mass O = 0.999 g O 14.0% C 44.591 0.157 g compound .401 g Hg 0. Molecular formula: C3H6.773 mol O. 0.157 g of the compound. 0.728 6.00 g O The mole ratio between Hg and O is 1 : 1.0480 g O 0.0480 g O × 1 mol O = 3. there are: 56.6018 g Hg × 1 mol Hg = 3. Molecular formula: C6H12O6. empirical formula: P2O5 d.37 g O H Dividing each mole value by the smallest number: 4. Molecular formula: P4O10. 6.0 × 10−3 mol O 200. so the empirical formula of compound I is HgO.00.00 0.0310 g H2O came from the 0. % C = × 100 = 37.591 This gives adrenaline an empirical formula of C8H11O3N. empirical formula: CH2 c. empirical formula: CH2O 45. Compound II: mass Hg = 0.213 g CO2 came from the 0.01 g N 28.773 0.157 g of the compound and that all the hydrogen in the 0. = 11.56 g H × = 6.011 g C 1.591 0.008 g H 1 mol O 1 mol N = 1. = 3.79 g C × 1 mol C 1 mol H = 4.6 g Hg 0.01 g CO 2 0.213 g CO2 × 12.28 g N H = 0.016 g O × = 1.728 mol C.

Divide all mole values by the smallest number: 3.47 g H = 55.5% O So. 42.0310 g H2O × CHAPTER 3 STOICHIOMETRY 2.00.39 g C × 55. 2. there are: 37.01 + 1.157 g We get the mass percent of N from the second experiment: 0.14 g O × 1 mol C 1 mol H = 3. we need to find simple whole number ratios.47 × 10 −3 g = 3.31 Multiplying all these ratios by 3 gives an empirical formula of C7H5N3O6.44 mol H 12. The empirical formula mass is 12.011 g C 1. 48.016 g H 3.66 = 2.31 2.446 mol O 15.21 g H × = 2. % H = × 100 = 2.67.02 g/mol. so the empirical formula is CHO.39 g C − 3.008 g H 1 mol N 1 mol O = 1.21% H 18.008 g H 1 mol O = 3.3) = 42.00 g O 18.21 + 18.35.999 g O All are the same mole values.08 2.0 g C × 1 mol C 1 mol H = 3. Molar mass = 15. Assuming 100.0230 g NH3 H 14.31 1.00 g of compound (mass oxygen = 100.3% N 0.14 g O): 41.31 mol N.3 g N × Lastly. 3.02 g H 2 O 0.01 g N = 1.00 = 29. = 2.00 g of compound.103 g The mass percent of oxygen is obtained by difference: % O = 100.00 g − 41. out of 100.19 mol H 12.89 × 10−2 g N 17.5 g O × = 2.19 1.89 × 10 −2 g × 100 = 18.008 + 16.31 1.01 g N 16.0 + 2. = 1.31 1.00 − (37.47 g H × = 3.0 g = 116 g/mol 0.03 1.26 0.08 mol C.446 mol C.47 × 10−3 g H. and often the hardest part.01 g C 1.66 mol O 14.03 g NH 3 %N= 1.129 mol . = 1.

737 2. 3.98 mg CO2 × 12.81 mg % O = 100. % C = × 100 = 57.105 mol C.00.105 6.81 mg 6. the empirical formula is C3H5O2.64% H 18.737 mol O 15.85 + 3. molecular formula = (C3H5O2)2 = C6H10O4 Empirical formula mass 73.000 2.50.00 g terephthalic acid.0) + 5(1.31 g C − 43.46 mg C.85% C 44. molecular formula = (CHO)4 = C4H4O4 29.51% O Out of 100.CHAPTER 3 STOICHIOMETRY 27 Molar mass 116 = = 4. = 1.5 : 1 or 4 : 3 : 2.011 g C 1.407 2.1 = = 2.011 mg C 11.009 mg CO 2 19.737 2.500. = 2.407 38.737 = 1.722 mg H. there are: 57.816 mol C.51 g O × 4.31 g C × 1 mol C 1 mol H = 4.85 g C × 1 mol C 1 mol H = 4. Empirical formula mass ≈ 3(12. The empirical formula is C4H3O2.407 mol O 15. % H = × 100 = 3.0 50.407 = 1.45 mg H2O × 2.00.816 = 2.02 Empirical mass 49.0) +2(16.407 The C : H : O mole ratio is 2 : 1. = 1. Assuming 100.722 mg = 0.85 mol H 12.79 g O × Dividing all mole values by 2.64 g H × = 3.64) = 38.00 − (57.90 g H): 49.011 g C 1.008 g H 1 mol O = 2.000 2.008 g H 1 mol O = 2. 2.79 g O = 6.00 g − 49.50.61 mol H 12.85 2.999 g O 3. 41.0 g/mol Molar mass 146.90 g H × = 6.46 mg = 11.001.999 g O 43.61 2. .0) = 73. 6.02 mg H 2 O 19.00 g of compound (mass hydrogen = 100.016 mg H 0.737 gives: 4.737 Because a whole number ratio is required.

(40. Only acrylonitrile contains nitrogen. 88 a.37 mg H2O × %H= 0.605 g Br2 × 1 mol C 4 H 6 54.3% C3H3N 100.00 g of the compound.250 mol 83 First.406 3 The empirical formula mass of C3H4O3 is ≈ 3(12) + 4(1) + 3(16) = 88 g. the empirical formula is C3H4O3.406 mol C.54 4 Dividing by the smallest number: = 1. Because 52.33 .369 mg C 44.011 g C 1000 mg × = 4.58% H.016 g H 1000 mg × = 0.58) = 54.51% O 10. 3. 0. the molecular formula is C8H6O4.489 mg × 100 = 4.3 g C3H3N 14.008 g H 1 mol O = 3.00 g of polymer: 8. 176. we have: 40.01 mg CO2 × 1g 1000 mg × 12. .91% C 10.205 g C4H6 159.011 g C 1.00 .00 g polymer % C3H3N = Only butadiene in the polymer reacts with Br2: 0.0.58 g H × = 4. the molecular formula is C6H8O6.999 g O 4.54 mol H 12.68 mg So.3 g C 3 H 3 N = 33.489 mg H 18.0.28 Mass of C4H3O2 ≈ 4(12) + 3(1) + 2(16) = 83 Molar mass = 51. = 2.5 g 166 = 166 g/mol.91 g C × 54.02 g H 2 O g 4.09 g C 4 H 6 1 mol Br2 × × = 0. % O = 100.80 g N × 1 mol C 3 H 3 N 53. in 100.8 g Br2 mol Br2 mol C 4 H 6 .51 g O × 1 mol H 1 mol C = 3. CHAPTER 3 STOICHIOMETRY 41. If we have 100.91 + 4.009 g CO 2 g %C= 4.369 mg C × 100 = 40. 4.1 = 2.68 mg compound 1g 1000 mg × 2.01 g N 1 mol C 3 H 3 N 33.407 mol O 15.06 g C 3 H 3 N × = 33. we will determine composition by mass percent: 16.

CS2(l) + NH3(g) → H2S(g) + NH4SCN(s) C and S are balanced.205 g × 100 = 17.99.1 g C4H6 × 1 mol C 4 H 6 = 0. a.316 0. so balance with 6 HCl on left: Fe2S3(s) + 6 HCl(g) → 2 FeCl3(s) + 3 H2S(g) c.00. and then go on to balance the remaining elements. If we have 100. start with elements that appear in only one of the reactants and one of the products. Balancing Chemical Equations 53. C6H12O6(s) + O2(g) → CO2(g) + H2O(g) Balance C atoms: C6H12O6 + O2 → 6 CO2 + H2O Balance H atoms: C6H12O6 + O2 → 6 CO2 + 6 H2O Lastly.1% C4H6 1. Fe2S3(s) + HCl(g) → FeCl3(s) + H2S(g) Balance Fe atoms: Fe2S3 + HCl → 2 FeCl3 + H2S Balance S atoms: Fe2S3 + HCl → 2 FeCl3 + 3 H2S There are 6 H and 6 Cl on right.316 0.20 g 29 b. = 1.CHAPTER 3 STOICHIOMETRY % C4H6 = 0.628 0.316 0. balance O atoms: C6H12O6(s) + 6 O2(g) → 6 CO2(g) + 6 H2O(g) b.06 g 17.09 g C 4 H 6 49.476 mol C8H8 104.628 mol C3H3N 53.14 g C8 H 8 0.6 g C8H8 × 1 mol C8 H 8 = 0. balance N: .3 g C3H3N × 1 mol C 3 H 3 N = 0.0 g of polymer: 33. or (A4B2S3)n. = 1.316: This is close to a mole ratio of 4 : 2 : 3. Thus there are 4 acrylonitrile to 2 butadiene to 3 styrene molecules in the polymer.316 mol C4H6 54. When balancing reactions.476 = 1.316 Dividing by 0.51 0.

a. We have to use all three equations: . 16 Cr(s) + 3 S8(s) → 8 Cr2S3(s) b. C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(g) b.000 kg Al × 3 mol NH 4 ClO 4 117. FeCO3(s) + H2CO3(aq) → Fe(HCO3)2(aq) Reaction Stoichiometry 57. 54. 2 NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g) c. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g) d. 2 C6H6(l) + 15 O2(g) → 12 CO2(g) + 6 H2O(g) 56. 1.6 × 107 mol HNO3 kg HNO 3 63. then the balanced reaction is incorrect.0 × 106 kg HNO3 × 1000 g HNO 3 1 mol HNO 3 × = 1.98 g Al 3 mol Al mol NH 4 ClO 4 = 4355 g NH4ClO4 58. 1. PCl5(l) + 4 H2O(l) → H3PO4(aq) + 5 HCl(g) e. CS2(l) + 2 NH3(g) → H2S(g) + NH4SCN(s).49 g NH 4 ClO 4 1000 g Al 1 mol Al × × × kg Al 26. 2 KClO3(s) → 2 KCl(s) + 3 O2(g) d. An important part to this problem is writing out correct formulas. Fe2O3(s) + 6 HNO3(aq) → 2 Fe(NO3)3(aq) + 3 H2O(l) c. 2 MoS2(s) + 7 O2(g) → 2 MoO3(s) + 4 SO2(g) g. If the formulas are incorrect.0 g HNO 3 We need to get the relationship between moles of HNO3 and moles of NH3. 3 Pb(NO3)2(aq) + 2 Na3PO4(aq) → Pb3(PO4)2(s) + 6 NaNO3(aq) 55. a. a. 2 Eu(s) + 6 HF(g) → 2 EuF3(s) + 3 H2(g) e. 2 KO2(s) + 2 H2O(l) → 2 KOH(aq) + O2(g) + H2O2(aq) or 4 KO2(s) + 6 H2O(l) → 4 KOH(aq) + O2(g) + 4 H2O2(aq) b.30 CS2 + 2 NH3 → H2S + NH4SCN CHAPTER 3 STOICHIOMETRY H is also balanced. 2 CaO(s) + 5 C(s) → 2 CaC2(s) + CO2(g) f.

0 g CO 2 1 mL air 1L 1 min 1h × × × = 68 h = 2.98 g Al = 0.CHAPTER 3 STOICHIOMETRY 31 2 mol HNO 3 16 mol HNO 3 2 mol NO 2 4 mol NO × × = 3 mol NO 2 2 mol NO 4 mol NH 3 24 mol NH 3 Thus we can produce 16 mol HNO3 for every 24 mol NH3 that we begin with: 1.95 g LiOH 2 mol LiOH mol CO 2 4. Fe2O3(s) + 2 Al(s) → 2 Fe(l) + Al2O3(s) 15.7 × 105 kg NH3 reacted. 59. 0. = 140 L/min. then the conversion factor between mol NH3 and mol HNO3 turns out to be 1 : 1.269 mol Fe.269 mol Fe × 0.26 g Al 55.5 g Fe2O3 2 mol Fe mol Fe 2 O 3 0.0 kg NH 4 1 mol NH 4 1000 g × × × × + + 100 kg waste kg 18.6 × 107 mol HNO3 × 24 mol NH 3 17.0010 g air 1000 mL 140 L air 60 min 62.70 g Fe 2 O 3 × = 21.04 g NH 4 55 mol NH 4 113. that is.0 g Fe × 1 mol Fe 2 mol Al 26. the NO produced in the third step is recycled back continuously into the process in the second step.269 mol Fe × × = 7. 1 mol Al 2 O 3 101. 1 mol of NH3 produces 1 mol of HNO3. In practice.01 g CO 2 100 g air × × × × 23. If this is taken into consideration.0 × 104 kg waste × + + 1 mol C 5 H 7 O 2 N 3.8 g P4O10 122.000 g LiOH × 1 mol LiOH 1 mol CO 2 44.4 × 104 g tissue if all NH4+ converted mol C 5 H 7 O 2 N . 1.9 g KClO3 × 1 mol KClO3 3 mol P4 O10 283.1 × 105 kg NH3 16 mol HNO 3 mol NH 3 This is an oversimplified answer.7 g Al2O3 2 mol Fe mol Al2 O 3 10 KClO3(s) + 3 P4(s) → 3 P4O10(s) + 10 KCl(s) 52.55 g KClO3 10 mol KClO3 mol P4 O10 61. 2 LiOH(s) + CO2(g) → Li2CO3(aq) + H2O(l) The total volume of air exhaled each minute for the 7 astronauts is 7 × 20.96 g Al2 O 3 × = 13.1 g C 5 H 7 O 2 N = 3.269 mol Fe × 60.8 days 0.88 g P4 O10 × × = 36.0 g NH 3 × = 4.1 × 108 g or 4. Taking into consideration that NO is recycled back gives an answer of 2. 25.85 g Fe 2 mol Fe mol Al 1 mol Fe 2 O 3 159.

In the following table we have listed three rows of information.060 cm) 8.18 g Ca 3 (PO 4 ) 2 1 mol P4 2 mol Ca 3 (PO 4 ) 2 64. the other species present in the product representtation is excess O2.4 × 104 g) = 3.55 g Cu mol Cu mol NH 3 Limiting Reactants and Percent Yield 65.000 boards × × 123.95)(3. 6 NO(g) + 3 O2(g) → 6 NO2(g) For smallest whole numbers. 1.6 g Cu ( NH 3 ) 4 Cl 2 1 mol Cu × × 63. Therefore.03 g NH 3 1 mol Cu × × = 5.88 g P4 = 150 g P4 mol P4 (8.5 × 105 g Cu × 1 mol Cu ( NH 3 ) 4 Cl 2 202. The “Initial” row is the number of molecules present initially. 6 NO molecules react with 3 O2 molecules to form 6 NO2 molecules. the “Change” row is the number of molecules that react to reach completion. The product formed in the reaction is NO2.9 × 105 g Cu 3 board cm Amount of Cu to be recovered = 0.80 × (6.0 cm × 0.0 cm × 16. In the pictures.5 × 105 g Cu 5.0 × 103 g phosphorite × 75 g Ca 3 (PO 4 ) 2 1 mol Ca 3 (PO 4 ) 2 × × 100 g phosphorite 310. To determine the limiting reactant. the balanced reaction is: 2 NO(g) + O2(g) → 2 NO2(g) 66.8 × 106 g Cu(NH3)4Cl2 5. and the “Final” row is the number of molecules present at completion.9 × 105 g NH3 63.5 × 105 g Cu × 4 mol NH 3 17. let’s calculate how much of one reactant is necessary to react with the other.32 Because only 95% of the NH4+ ions react: CHAPTER 3 STOICHIOMETRY mass of tissue = (0.55 g Cu mol Cu mol Cu ( NH 3 ) 4 Cl 2 = 1.9 × 105 g) = 5. Total mass of copper used: 10.96 g × = 6. NO is the limiting reactant. 10 molecules O2 × 4 molecules NH 3 = 8 molecules NH3 to react with all the O2 5 molecules O 2 .2 × 104 g or 32 kg bacterial tissue 63.

77 × 10−2 mol HCl mol BaO 2 Excess mol HCl = 1.0 mL × 0.0 g Ag2O × 1 mol = 0. the denominator (BaO2) is the limiting reagent.77 × 10−2 mol = 1.02 g H 2 O 2 × = 0.11 8.86 × 10−3 mol BaO2 × 2 mol HCl = 1.86 × 10−3 mol BaO2 169.0 × 10−3 mol HCl Mass of excess HCl = 1.6 × 10−2 g HCl mol HCl 50.0272 g HCl 1 mol HCl × = 1.86 × 10 −3 mol BaO 2 Because the actual mole ratio is larger than the required mole ratio.3 g BaO 2 25.8 g 1 mol = 0.87 × 10−2 mol HCl mL 36. 25. 67.46 g HCl The required mole ratio from the balanced reaction is 2 mol HCl to 1 mol BaO2.29 g 36.108 mol Ag2O 231.301 g H2O2 mol BaO 2 mol H 2 O 2 The amount of HCl reacted is: 8.0 g C10H10N4SO2 × .46 g HCl = 3. Initial Change Final 4 NH3(g) 10 molecules !8 molecules 2 molecules + 5 O2(g) → 4 NO(g) 10 molecules 0 !10 molecules +8 molecules 0 8 molecules + 6 H2O(g) 0 +12 molecules 12 molecules The total number of molecules present after completion = 2 molecules NH3 + 0 molecules O2 + 8 molecules NO + 12 molecules H2O = 22 molecules.87 × 10 −2 mol HCl = 2. 8. The actual mole ratio is: 1.50 g BaO2 × 1 mol BaO 2 = 8.87 × 10−2 mol − 1.CHAPTER 3 STOICHIOMETRY 33 Because we have 10 molecules of NH3 and only 8 molecules of NH3 are necessary to react with all the O2.86 × 10−3 mol BaO2 H 1 mol H 2 O 2 34.200 mol C10H10N4SO2 250.0 × 10−3 mol HCl × 68. O2 is limiting. 1.

1142 g C6H5Cl × 485 g C2HOCl3 × 1 mol C 2 HOCl3 = 3.55 g C 6 H 5 Cl 0.20 × 103 kg Cu 1.29 mol C2HOCl3 × 1 mol C14 H 9 Cl 5 354. 2.50 metric tons Cu3FeS3 × 1 mol Cu 3 FeS3 1000 kg 1000 g 3 mol Cu × × × × metric ton kg 342.20 metric tons Cu (actual) 1 mol C 6 H 5 Cl = 10.55 g = 1.29 mol C2HOCl3 × 2 mol C 6 H 5 Cl 112. 3. so C10H10N4SO2 is limiting. so the denominator of the actual mole ratio (C2HOCl3) is limiting.200 = 1. The actual mole ratio is greater than 3. and C6H5Cl is in excess.29 mol C 2 HOCl3 the required mole ratio.38 g C 2 HOCl3 2 mol C 6 H 5 Cl From the balanced equation.15 mol C6H5Cl 112. 2 mol AgC10 H 9 N 4SO 2 357.4 g AgC10H9N4SO2 produced 69. c. the required mole ratio is = 2.200 mol C10H10N4SO2 × 70.0 g DDT × 100 = 17.18 g × 2 mol C10 H10 N 4SO 2 mol AgC10 H 9 N 4SO 2 = 71.1% 1170 g DDT .15 mol C 6 H 5 Cl = 3.29 mol C2HOCl3 147.20 × 106 g Cu = 1. C2HOCl3 is limiting.09. The actual 1 mol C 2 HOCl 3 mole ratio present is 10. 3.39 × 106 g Cu (theoretical) mol Cu 86.46 g C14 H 9 Cl 5 × = 1170 g C14H9Cl5 (DDT) mol C 2 HOCl3 mol C14 H 9 Cl 5 b.108 CHAPTER 3 STOICHIOMETRY The actual mole ratio is less than the required mole ratio (2). a.3 g Cu (actual) = 1.71 g 1 mol Cu 3 FeS3 63.85 (actual) = Mol Ag 2 O 0. Percent yield = 200.34 Mol C10 H10 N 4SO 2 0.55 g C 6 H 5 Cl × = 741 g C6H5Cl reacted mol C 2 HOCl3 mol C 6 H 5 Cl 1142 g ! 741 g = 401 g C6H5Cl in excess d. g Cu ( theoretical) = 1.39 × 106 g Cu (theoretical) × 100.

00 g O 2 3 mol O 2 5.7 mol C3H3N 32.00 × 106 g CH4 × 1 mol CH 4 2 mol HCN × = 3.04 × 105 mol HCN. We will solve this limiting reagent problem using the same method as described in Exercise 3.04 g CH 4 2 mol CH 4 O2 is limiting because it produces the smallest amount of HCN.50 × 103 g NH3 × 1 mol NH 3 2 mol C 3 H 3 N × = 88.00 × 106 g O2 × 72.02 g H 2 O × × = 5.12 × 105 mol HCN 16.00 × 103 g C3H6 × 1 mol C 3 H 6 42. Although more product could be produced from NH3 and CH4.03 g NH 3 2 mol NH 3 2.04 × 105 mol HCN 32.00 g O 2 3 mol O 2 1 mol H 2 O 2 C3H6(g) + 2 NH3(g) + 3 O2(g) → 2 C3H3N(g) + 6 H2O(g) a. and the mass of acrylonitrile that can be produced is: 23.04 × 105 mol HCN × 27. STOICHIOMETRY 35 An alternative method to solve limiting-reagent problems is to assume that each reactant is limiting and then calculate how much product could be produced from each reactant.03 g HCN = 2.26 × 103 g C3H3N mol . The mass of HCN that can be produced is: 1.71. The reactant that produces the smallest amount of product will run out first and is the limiting reagent. 5. only enough O2 is present to produce 1. 1 mol O 2 6 mol H 2 O 18.00 × 106 g O2 × 1 mol O 2 2 mol HCN × = 1.00 × 103 g O2 × 2 mol C 3 H 3 N 1 mol O 2 × = 41.8 mol × 53.81 × 106 g HCN mol HCN 5.1 mol C3H3N 17. 1.00 × 106 g NH3 × 1 mol NH 3 2 mol HCN × = 2.CHAPTER 3 71.94 × 105 mol HCN 17.63 × 106 g H2O 32.03 g NH 3 2 mol NH 3 5.08 g C 3 H 6 × 2 mol C 3 H 3 N = 23.8 mol C3H3N 2 mol C 3 H 6 1.00 g O 2 3 mol O 2 C3H6 is limiting because it produces the smallest amount of product.06 g C 3 H 3 N = 1.

97 g PF3 4 mol PF3 mol F2 99.10 × 103 g NH3 and 860 g O2 are in excess. From the reaction stoichiometry we would expect to produce 4 mol of acetaminophen for every 4 mol of C6H5O3N reacted. x = 0. g PF3 (actual) × 100. the theoretical yield of PF3 is: 120. Solving for percent yield by mass (where M = molar mass acetaminophen): percent yield = 3 mol × M × 100 = 75% 4 mol × M b.10 × 103 g NH3 Amount O2 needed: 23.00 g O 2 × = 1.29 × 103 g H2O 2 mol C 3 H 3 N mol H 2 O Amount NH3 needed: 23.14 × 103 g = 860 g O2 1. g of PF3 if the percent yield is 78.1%.8 mol C3H3N × 2 mol NH 3 17.75. (0. 74.0 g PF3 ( theoretical) = 154 g PF3 (theoretical) 78.8 g F2 87.88.1 g PF3 (actual) 154 g PF3 × 1 mol PF3 6 mol F2 38. The actual yield is 3 mol of acetaminophen compared with a theoretical yield of 4 mol of acetaminophen.8 g F2 are needed to actually produce 120.98)(x) = 0.50 × 103 g − 405 g = 1.00 g F2 × × = 99. a.8 mol C3H3N × 3 mol O 2 32. 73.14 × 103 g O2 2 mol C 3 H 3 N mol O 2 Amount O2 in excess = 2.8 mol C3H3N × CHAPTER 3 STOICHIOMETRY 6 mol H 2 O 18. 23.36 b.87)(0.03 g NH 3 × = 405 g NH3 2 mol C 3 H 3 N mol NH 3 Amount NH3 in excess = 1. P4(s) + 6 F2(g) → 4 PF3(g). step III has a percent yield of 88%.02 g H 2 O × = 1. 75%. The product of the percent yields of the individual steps must equal the overall yield. .00 × 103 g − 1.

50.50 g C4H10 mol C 4 H10 77. Assuming Cl2 is limiting: .2 = 2.2 mol H.9 g/mol) = 35.022 × 10 23 molecules The mass of X = 1/2(70.01 g C 17.25 mol E 0. atomic mass of E = 28.CHAPTER 3 STOICHIOMETRY 37 Additional Exercises 75. Assuming 100.25 mol E 1.1 g/mol.008 g H 8 mol H 58.87 g/mol M 0.30 × 10−2 mol C4H10 × 76.73 g H × 1 mol H 3 mol E × = 3.53 g M = 88.008 g H 12.7 g C × = 6. 82.89 mol C 1. and the name of YCl3 is yttrium(III) chloride. x = molar mass of E = 28.105 g = 70.537 mol Cl 35. 6.27 g E = .45 g 1 mol M = 0.00 g of MX3 compound: 54.47 g Cl × 1 mol = 1.022 × 10 23 molecules = 4.9 g/mol Molar mass X2 = 1 mol 20 8.92 × 10 molecules × 6. The balanced equation is 2 Y + 3 Cl2 → 2 YCl3.30 × 10−2 mol C4H10 4. xgE 91.1 amu 1 mol E 3.5 g/mol. the empirical formula is C2H5.537 mol Cl × Molar mass of M = M is the element yttrium (Y). 17.5123 mol M 1.59 × 1023 atoms H × 1 molecule C 4 H10 1 mol C 4 H10 × 10 atoms H 6. Molecular formula = (C2H5)2 = C4H10 2.12 g = 2.5123 mol M 3 mol Cl 45.00 g E3H8: Mol E = 8. This is the element chlorine. so two times the empirical formula would put the compound in the correct range of the molar mass.3 g H H 1 mol H 1 mol C = 17.89 The empirical formula mass is ~29 g. Assuming 100.

because 104.44 g of the unknown element. Aluminum forms Al3+ ions. 18.00303 mol CuSO 4 1 mol CuSO 4 80. The simplest compound of the two elements is Al2O3.00 g Y × Because Cl2. we would expect the formula of a Group 6A element with Al to be Al2X3. In 1 hour. compound formula = CuSO4•5H2O. Let’s use this information to determine the molar mass of X.032 mol of X.02 g H 2 O 0.032 mol X × 26. Cl2 is the limiting reagent.0151 mol H 2 O 4.022 × 10 23 atoms × × = 9. produces the smaller amount of product. the molecular formula for styrene is (CH)8 = C8H8.38 1. Empirical formula mass = 12.62 g CuSO 4 0.56 g Al and 81.00 g of compound.01 + 1.008 = 13.26 g YCl3 1 mol Cl 2 × × = 1. X.00 g Cl2 × CHAPTER 3 STOICHIOMETRY 2 mol YCl3 195.20 g YCl3 88. 1 mol C8 H 8 8 mol H 6.00 g C8H8 × 79.272 g H2O × 1 mol H 2 O = 0.272 g H2O 0. x = 0.84 g YCl3 70.% H2O. there are 18.20)x. which will allow us to identify X from the periodic table.14/13.56 g Al × 1 mol Al 3 mol X = 1. kg of wet cereal contains 580 kg H2O and 420 kg of cereal.14 g C8 H 8 mol C8 H 8 mol H Mass of H2O = 0.755 g CuSO4•xH2O − 0. x = 84 + (0.98 mol H 2 O = . out of 100. Consider the case of aluminum plus oxygen. Assuming this. x = 105 ≈ 110 kg H2O 420 + x The amount of water to be removed is 580 − 110 = 470 kg/h.90 g Cl 2 3 mol Cl 2 1 mol YCl3 2 mol YCl3 195.44 g of X must contain 1. 78. Let x = mass of H2O in final product. oxygen forms O2− anions.998 ≈ 8.02 = 7.25 × 1022 atoms H 104. x = 5 0. and the theoretical yield is 1.02 g/mol. 2.84 g YCl3. . We want the final product to contain 20. Similarly. 81.483 g CuSO4 = 0.483 g CuSO4 × 1 mol CuSO 4 = 0.91 g Y 2 mol Y 1 mol YCl3 Assuming Y is limiting: 1. when it all reacts.0151 mol H2O 18.20.98 g Al 2 mol Al 81.26 g YCl3 1 mol Y × × = 2.00303 mol CuSO4 159. the 1000.

1% 233. 3.1 g Ba and 53.91 g/mol 1.2 mol Ca 3 (PO 4 ) 2 This is larger than the required mole ratio. 83.20 g CO2 × 1 mol C 24 H 30 N 3O 1 mol CO 2 1 mol C 376.672 mol 46. 0. 82.124 g BaSO4 × 137.2 g CaSO 4 × = 1300 g CaSO4 produced mol Ca 3 (PO 4 ) 2 mol CaSO 4 .1 g Ba × This molar mass is close to that of bromine.0 × 103 g Ca3(PO4)2 × 1 mol Ca 3 (PO 4 ) 2 = 3. the molar mass of the halogen is = 80. There must also be: 1 mol Ba 2 mol X = 0.158 g BaX 2 The formula is BaX2 (from positions of the elements in the periodic table). 0.51 g × × × 44. The 10.032 mol X 39 Molar mass of X = From the periodic table.2 mol Ca3(PO4)2 × 3 mol CaSO 4 136. and the formula is Al2Se3.3 g Ba mol Ba 53.0 g of compound contains 46.0 × 103 g conc.0729 g Ba = 0.428 g C 24 H 30 N 3O × 100 = 42. % Ba = × 100 = 46.44 g X = 78.1 g H 2SO 4 The required mole ratio from the balanced equation is 3 mol H2SO4 to 1 mol Ca3(PO4)2.2 g Ca 3 (PO 4 ) 2 1.9 g Therefore.9 g of halogen × 137. Ca3(PO4)2(s) + 3 H2SO4(aq) → 3 CaSO4(s) + 2 H3PO4(aq) 1. 3. and 100. Thus the formula of the compound is BaBr2.01 g mol CO 2 24 mol C mol C 24 H 30 N 3O = 0. 1. the unknown element is selenium.9 g of the unknown halogen.00 g sample 84. The reaction is BaX2(aq) + H2SO4(aq) → BaSO4(s) + 2 HX(aq).0729 g Ba.4 g BaSO 4 0.2 g/mol. mol H 2SO 4 actual ratio is = 3. so Ca3(PO4)2 is the limiting reagent. H2SO4 × 98 g H 2SO 4 1 mol H 2SO 4 = 10.8% C24H30N3O (LSD) 1.672 mol of the halogen in 53.2 mol Ca3(PO4)2 310.CHAPTER 3 STOICHIOMETRY 81. mol H2SO4 × 100 g conc.1.3 g Ba 0. H 2SO 4 98.428 g C24H30N3O 0.

000000) + 2(1.70 g Fe 2 O 3 1 mol Fe × × = 648 g Fe2O3 55.445 5.85 g Fe 2 mol Fe mol Fe 2 O 3 648 g Fe 2 O 3 × 100 = 86.046950 amu C1H216O: 1(12. 13.9117) + 0. Rb atoms If we had exactly 100 atoms.2785(A) = 85.4678 − 61.506 = 3.7215(84. 453 g Fe × 1 mol Fe 2 O 3 159.667)3 = C11H17N3O8.994915) = 29.1 − (2.007825) + 1(15.506 mol O 1.9395 To get whole numbers for each element.26 = 86.92 amu 0.15.9395 0.591.445 mol C.667 0.591)x.1 = 2.007825) = 30.999 g O Divide by the smallest number: 3. = 5.667H5. 72. 40. 12 C21H6: 2(12. .67NO2. multiply through by 3.011 g C 14.9395 mol N 12.667.007 g N 5.67.9395 0.000000) + 6(1. 85 87.40 3.16 g N × = 0. x = = 72. = 2.2 mol Ca3(PO4)2 × CHAPTER 3 STOICHIOMETRY 2 mol H 3 PO 4 98.591 100 − x 0. x = 259.0 g H 3 PO 4 = 630 g H3PO4 produced × mol Ca 3 (PO 4 ) 2 mol H 3 PO 4 85.00 g of tetrodotoxin: 41. x 259.2785 1 mol C 1 mol N = 3.003074) + 1(15.4678. Assuming 100.33 2. the mass of the empirical formula is 319.37 g H × 1 mol H 1 mol O = 5. x = number of 85Rb atoms and 100 − x = number of 87Rb atoms.15% 85Rb 3.3 g/mol.008 g H 15.2% 752 g ore Mass % Fe2O3 = 86.38 g C × 85.09 g O × = 2.994915) = 30.33 mol H.591.010565 amu N16O: 1(14. 87 Rb atoms = 2. A = 88. Empirical formula: (C3.997989 amu 12 14 The peak results from 12C1H216O.

PaO2 + O2 → PaxOy (unbalanced) 0.025 × 10 −3 mol O Mol O 2 8 mol O = 2.2081 g PaxOy − 0. XI2 contains 0.634 g N gH II: 6.008) 1 For example. C11H17N3O8. Thus the formulas are: I: NH3 The mass ratios are: I: 4.01 3(1. for compound I: 90.8 g AgI 126. empirical formula: Pa3O8 = −4 Mol Pa 3 3 mol Pa 7.01 II: 14.200 g PaO2 × 231 g Pa = 0.0 A 4.) 263 g PaO 2 1 mol O = 2.7 g N gH II: N2H4 III: HN3 If we set the atomic mass of H equal to 1.66 .025 × 10−3 mol O 16.257 g X.7431 g I.022 × 10 23 molecules 41 Molar mass tetrodotoxin = Because the empirical mass and molar mass are the same. The volume of a gas is proportional to the number of molecules of gas. μg 1 × 10 −6 g 1 mol 6. 0.4 × 1018 molecules tetrodotoxin is the LD50 dosage 89.7431 g I and 0.1757 g Pa H 1 mol Pa = 7. 234.3 g 1 mol = 1. 2 = . 14.634 = . the molecular formula is the same as the empirical formula.1757 g Pa (We will carry an extra significant figure. A = 14.0324 g O H 0.61 × 10−4 mol Pa 231 g Pa 2.856 × 10−3 mol I 234.9 g I = 0. 1.59 × 10 −21 g = 319 g/mol 1 mol 3 molecules × 6. 165 lb × 1 kg 10.1757 g Pa = 0.0324 g O.022 × 10 23 molecules × × × × 2. then the atomic mass for nitrogen is: I: 14.949 g N gH III: 41.375 g AgI × 1 mol AgI = 5.01 III.856 × 10−3 mol AgI = 5.8 g AgI .CHAPTER 3 STOICHIOMETRY 1.2046 lb kg μg 319.375 g AgI × 1.00 g O 0.008.61 × 10 mol Pa 91.

0/A z (60.8 amu (X is Sr. lets calculate the molar mass of E: 286. 121. the molecular formula of vitamin A is C20H30E. Challenge Problems 95. 16O18O+ (mass = 34).1056 g H 1 mol H × = 30. The only combination of these individual ions that can explain the mass data at low discharge is 16O16O+ (mass = 32).0% Z by mass. E = oxygen.0)A x where A = molar mass For XZ2. Therefore.008) + molar mass E. % Z = 100.0 g/mol From the periodic table. 11B35Cl3 (116).4 g vitamin A): mol C = 286. 40. 118. the gas mixture contains 16O16O. 119. B37Cl3 (121). To determine the .0079 g H Because 1 mole of vitamin A contains 20 mol C and 30 mol H.3% X. and the molecular formula of vitamin A is C20H30O.928 × 10 mol X 92.0% X and 60.00 mol C g vitamin A 12. 10B35Cl37Cl2 (119).0/A x (40.4 g vitamin A × 0.3 = 85.011 g C mol H = 286. molar mass E = 16.257 g X 87. 11B37Cl3 (122) We would see a total of eight peaks at approximate masses of 115. 116. and 40Ar. When the discharge voltage is increased. O .928 × 10−3 mol X 2 mol I CHAPTER 3 STOICHIOMETRY Molar mass = 0.0)A z mol X =2= = or Az = 3Ax X2Z: 40. Assuming 1 mole of vitamin A (286. the bonds in the molecules are broken.4 g = 20(12. 10B35Cl237Cl (117). 117.8396 g C 1 mol C × = 20. 16O18O. and the ions present are in the form of individual atoms. We would see the peaks corresponding to: 10 10 B35Cl3 [mass ≈ 10 + 3(35) = 115 amu].42 5.0 − 14. and 40Ar+ (mass = 40). and 40Ar+ are present. 120.01 mol H g vitamin A 1. and 122. Mass % X = Ax × 100 = 14. 11B35Cl237Cl (118). 11B35Cl37Cl2 (120).7% Z 7A x 93. mol Z 60. the high discharge data indicate that the ions 16 + 18 + O . When the discharge voltage is low.01) + 30(1. molar mass = Ax + 2Az = Ax + 2(3Ax) = 7Ax.8 g = . To determine E. Therefore.856 × 10−3 mol I × 1 mol X = 2.4 g vitamin A × 0. atomic mass = 87. the ions present are in the form of molecules.) −3 mol 2. 94.

From mole ratios. so that 0.0015 + 1.3581 − x) = 0. Fe(s) + 1 2 O 2 (g) → FeO(s) .7515 Note: 18F instead of 18O could also explain the data. XCl4 contains 2.079 mol FeO 0.00 g Assuming x mol of FeO is produced from x mol of Fe.3581 − 0.2488 mol O 2 .2488 mol O2 consumed (1 extra sig. 2 Fe(s) + 1 mol Fe = 0.CHAPTER 3 STOICHIOMETRY 43 percent composition of each isotope.) 32.3581 − x) mol Fe + ⎜ ⎟ mol O 2 → ⎜ ⎟ mol Fe 2 O 3 2 ⎝ 2 2 ⎠ ⎝ ⎠ Setting up an equation for total moles of O2 consumed: 1 2 x + 3 4 (0.7500 + 0. For 40Ar: 1. 2. fig.4 g Fe2O3 produced mol 10.0000 1. 96.3581 − x ⎞ (0.0791 = 0.140 mol Fe2O3 × 97.55 g XCl4.7500 0. x = 0.140 mol Fe2O3 2 0. 159.20 − 3. we use the relative intensity data from the high discharge data to determine the percentage that each isotope contributes to the total relative intensity.00 g Fe × (11. for 18O: × 100 = 8.079 = 0.3581 – x mol of Fe reacts to form Fe2O3: x Fe + 1 x O 2 → x FeO 2 3 ⎛ 0. However.24) g O 2 × 1 mol O 2 = 0.55 g Cl reacted with XCl2 to form XCl4.55 g Cl and 10.3581 − x ⎞ ⎛ 0.70 g Fe 2 O 3 = 22. This is why 18O is the best choice because O2(g) does form.82% 16O.079 mol FeO × 71.0000 × 100 = × 100 = 57. mass X in XCl2 = 10.45 g X.85 g FeO = 5.3581 mol 55. .6 × 10−2% 18O 1. 10.7515 0.55 g Cl. OF(g) is not a stable compound.00 g XCl2 must also contain 2.85 g 3 2 O 2 (g ) → Fe 2 O 3 (s) 20.55 = 7.0000 For 16O: 0.00 g XCl2.00 ! 2.00 g XCl2 + excess Cl2 → 12.094% 40Ar 1.7515 1.7 g FeO produced mol Mol Fe2O3 produced = 0.0015 × 100 = 42.

38 4.008 g × 100 = 40.008 g Mg.5171 g H2 × 0.0158 g H 2 Mol H2 = 0.60 × 10 −2 mol X 35.44 2.96 g Sc 1 mol H 2 = 0. The balanced equation is 2 Sc(s) + 2x HCl(aq) → 2 ScClx(aq)+ x H2(g).25 g Sc × 2 . For a gas.00 − x + .55 g Cl × CHAPTER 3 STOICHIOMETRY 1 mol XCl 2 1 mol Cl 1 mol X × × = 3. 100. Mol H2 = 0. so X is Pb. so 10. density and molar mass are directly proportional to each other. The mol ratio of Sc to H2 = Mol Sc = 2.45 g X = 207 g/mol X. the element is Ge.008 g) = 72. The two relevant equations are: Zn(s) + 2 HCl(aq) → ZnCl2(aq) + H2(g) and Mg(s) + 2 HCl(aq) → MgCl2(aq) + H2(g) Let x = mass Mg. The molar mass of X is: 7.58 − 4(1.45 g X. the formula is ScCl3.00) = 8.0158 g H 2 x 10. Molar mass XHn = 2. 24. moles H2 = moles 1 mol H 2 = 0. x 0. 3.2565 mol H2 2.08% Mg 10.31 65.58 g .07451 .45 g Cl 2 mol Cl mol XCl 2 So. x 2 mol H 76.23 × 10 mol XH n Molar mass X = 76.0500 = .803 g H2O × mol 18.1502 g H2 × 2 0.393(32.55 g/mol.60 × 10 − 2 mol X 98. x = 4. 0. Zn + moles Mg.0500 mol Sc 44.91 × 10−2 mol H 1 mol Sc = 0. solving.91 × 10 −2 mol H 4 mol H = −2 mol XH n 2.00 ! x = mass Zn.60 × 10 −2 mol X has a mass equal to 7.07451 mol H2 2. atomic mass = 207 amu.02 g H 2 O = 8.00 g 99.2565 = From the balanced equations. 3. x = 3.

b 1.723 g 8.CHAPTER 3 101.0/2 (from CO) + 12. The initial moles of C equals 72.000)A + 256.000 3.00 ⎟ ⎝ ⎠ (8. b = 6.0 mol O2.008).0 mol C and the initial moles of O2 equals 72. The initial reaction mixture contained: 92.21 = A + 32. The balanced equations are: C(s) + 1/2 O2(g) → CO(g) and C(s) + O2(g) → CO2(g) If we have 100. 16.21 g = 0. XaH6 has a molar mass of 62. CxHyOz + oxygen → x CO2 + y/2 H2O 2.0224 = .0 (from CO2) + 16. atomic mass = 184 amu 102.04 Some possible identities for X could be Fe (a = 1).0 (unreacted O2) = 92.09 g/mol. 103. so one of the elements in the compound is hydrogen.723 g MO2 There must be twice as many moles of MO2 as moles of M2S3 in order to balance M in the reaction.0 mol O2.0671 mol 62.09 = a(molar mass of X) + 6(1.000 g 3.0 = (7.2.0 mol O 2 = 1. and 12.0 (from CO2) + 16.05 mol O2/mol C 88.0671 62. Setting up an equation for 2(mol M2S3) = mol MO2 where A = molar mass M: ⎛ ⎞ 4. and Li (a = 8).02 g / mol 2 0.2. a(molar mass of X ) = 56. b 0. then we have 72.0 mol of products. mol H2O = = 0.00 (from CO) = 88.07) ⎟ = A + 2(16. the mole ratio between XaHb and H2O = Mol compound = 2 .01 g C × × 44.0% C 1.20 g CO 2 × 1 mol C 1 mol CO 2 12. A = 184 g/mol. XaHb + O2 → H2O + ? To balance the H atoms.39 g 1.0 mol CO2. STOICHIOMETRY 45 4.0 mol C 104.00 g aspirin Mass % C in aspirin = .0 mol CO. We know that water is a product.554)A = 102.446)A + 358.723 2⎜ ⎜ 2A + 3(32. (0.00) .01 g CO 2 mol CO 2 mol C = 60.0224 mol. 2A + 96. Si (a = 2). N (a = 4).09 g / mol 18. N fits the data best so N4H6 is the most likely formula.000 g M2S3 → 3.

LaH2.90 and x = 0.00 g aspirin Mass % O = 100.0 g C × 1 mol C 1 mol H = 5.400 g H 2 O × CHAPTER 3 STOICHIOMETRY Mass % H in aspirin = 1 mol H 2 O 2 mol H 1.% La3+. LaH2 would be the formula.44 mol H 12.5 g O × Empirical formula: (C2.48% H 1.25.90 is the formula. = 2.% La2+.00 ! (60. x 7 9.01 g C 1. Empirical mass ≈ 9(12) + 8(1) + 4(16) = 180 g/mol.48) = 35. CaHbOc = salicylic acid = C7H6O3 105.120 mol O2 30.0 + 4.07 2 44.008 g H × × 18.00 g O 5. or 90. Use the balanced reaction to set up an equation for the moles of O2 required. If only La3+ is present.25 H2.22 2. so the molecular formula is also C9H8O4. LaH3 would be the formula. If only La2+ is present. 4.00 2. CaHbOc + C4H6O3 → C9H8O4 + C2H4O2.22 mol O 16.07 g/mol 44.00 g aspirin: 60.09 g/mol Let x = mass C2H6. or 10.00 and 2x + 3y = 2.44 Dividing by the smallest number: = 2. Let x = mol La2+ and y = mol La3+: (La2+)x(La3+)yH(2x + 3y) where x + y = 1. Balance the aspirin synthesis reaction to determine the formula for salicylic acid.48 g H × = 4. 1 9 La2+.00 y = 0. and La3+.00 mol C.46 0.780 ! x = mass C3H8.5% O Assuming 100. so 9.02 g H 2 O mol H 2 O mol H = 4.90 contains 106.008 g H 1 mol O = 2.90 −2x − 2y = −2.00O)4 = C9H8O4.09 1 . 10 10 2 C2H6(g) + 7 O2(g) → 4 CO2(g) + 6 H2O(l).90 Solving by simultaneous equations: 2x + 3y = 2. this is in the 170–190 g/mol range.780 − x 5 × + × = 1. C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) 30.00 4.10 LaH2.22 35.

708 100. MO3.11 g/mol Mol KCl = x y . 2.00 – 56.11 Knowing that the mixture is 43.01 g M = 40. We must have fewer moles of M than moles O present in the formula.9 g KCl.0 g.999 g O If MO is the formula of the oxide.5245)x + (0. then in the 100. molar mass KNO3 = 101. 32.0 g of mixture.750 mol M This is too low for the molar mass.55 101. .9% KCl 100. Then the molar mass of M is: 56. Some possibilities are MO2.11 ⎠ We have two equations and two unknowns: (0. but calcium forms an oxide having the CaO formula. Assuming 100.7 g × 100 = 38% C2H6 by mass 9.00 g compound: 43. not CaO2. x + y = 100. It is a guessing game as to which to try. mol KNO3 = 74.2% K.01 = 43.10 ⎜ + ⎟ = 43.3867)y = 43.7 g C2H6. then M has a molar mass of 56.2 x + y = 100.0 g mixture: y ⎞ ⎛ x 39.077 × 100 = × 100 = 56.55 101.9 g × 100 = 32.750 mol O 15. Let’s assume an MO2 formula. Molar mass KCl = 74. etc. 107 .99 g O × 1 mol O = 2.780 g 47 Solving: x = 3. 108. Let x = mass KCl and y = mass KNO3.01% M total mass compound 3. x = 32.73 g/mol 1 mol M 2.0 g Let M = unknown element Mass % M = mass M 2.2 ⎝ 74.CHAPTER 3 STOICHIOMETRY 3.99% O Assuming 100.0 Solving.750 mol O × 2 mol O This is close to calcium.55 g/mol.37 g/mol.01 g M = 20. M2O3.

4x + 4 × 0.92 g/mol 1 mol M 2. x = 0.0.12 Mol NO = 4x = 4 × 0.00 − 6.48 CHAPTER 3 STOICHIOMETRY If MO3 is assumed to be the formula. Some reasonable possibilities are 2. Trying a mol O to mol M ratio of 2.12 = 0.25.05) + b(17.00.25 mol O2 reacted.0 −20x − 20y = −10. The other choices for the O : M mole ratios between 2 and 3 do not give as reasonable results.25. then the molar mass of M calculates to be 61.00 (N mol balance) (O mol balance) (H mol balance) (mass balance) Solving the simultaneous equations gives a = 1.5 mol O This is the molar mass of vanadium and V2O5 is a reasonable formula for an oxide of vanadium. and the formula is V2O5. and let 4y = number of moles of NO2 formed.062) 4 a + 3b = 2d a(32.01 g M = 50. M is vanadium. 2.062) O2 → c NO2 + d H2O Setting up four equations to solve for the four unknowns: 2a + b = c 2c + d = 2(10.75 (these are reasonable because they will lead to whole number formulas).48 mol NO formed 110.5 to 1 gives a molar mass of: 56. 2. so 5x + 7y = 3. a N2H4 + b NH3 + (10.1 mol N 2 H 4 × 32. Then: 4x NH3 + 5x O2 → 4x NO + 6x H2O and 4y NH3 + 7y O2 → 4y NO2 + 6y H2O All the NH3 reacted. Therefore.05 g / mol N 2 H 4 × 100 = 58% N2H4 61.00 g . the mol O to mol M ratio must be between 2 and 3.0 8y = 3.00 − 4. and 2. Solving by the method of simultaneous equations: 20x + 28y = 13.00.5. so 4x + 4y = 2. Therefore.67.03) = 61. 109.75 = 3. 10.10 g/mol which is too large.38 = 2.38.33.00 − 4.1 mol N2H4. 2. y = 0. 1. The balanced equations are: 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g) and 4 NH3(g) + 7 O2(g) → 4 NO2(g) + 6 H2O(g) Let 4x = number of moles of NO formed.750 mol O × 2.12 = 1.

Determining the empirical formula of B: 5.01 g CO 2 mol CO 2 mol C 6. 5.00 1.66 = 2. the molecular formula of substance B could be H2O. Determining the empirical formula for substance C: .99 g.0 g A The remainder of the molar mass (64.66 42.) 4.00 2.000 × 1019 (assuming 4 sig.32 mol H.66 16. substance C must contain carbon and hydrogen and may contain oxygen.CHAPTER 3 STOICHIOMETRY 49 Marathon Problems 111.000 × 1019 molecules A × 1 mol A = 6.8 g CO2 × 1 mol CO 2 1 mol C 12.36 g H + 42.008 g H 2.022 × 10 molecules A Molar mass of A = 4.08 g/mol. etc.642 × 10 −5 mol A Mass of carbon in 1 mol of A is: 64.1 g) is due to the alkaline earth metal.0 g carbon = 2 mol carbon in substance A 100.1 g A × 37.0 g.00 g O Empirical formula: H2O.26 × 10 −3 g A = 64.008 g H × × = 0.5 g O = 47.02 g H 2 O mol H 2 O mol H 9.22 g carbon + 0.0 g = 40.1 g/mol 6. Substance C + O2 → CO2 + H2O.24.92 g H2O × 1 mol H 2 O 2 mol H 1. To solve the limiting-reagent problem.36 g H × 1 mol H 5.774 g hydrogen 18. H4O2. there is no oxygen present in substance C.32 = 5. H6O3. because substance C initially weighed 10. figs.01 g C × × = 9.22 g carbon 44. = 2.66 mol O.1 g . 40 million trillion = (40 × 106) × 1012 = 4. we must determine the formulas of all the compounds so that we can get a balanced reaction.9 g. From the periodic table.5 g O × 1 mol O 2. The most reasonable choice is water (H2O) for substance B. a.642 × 10-5 mol A 23 6. calcium has a molar mass of 40. substance B only contains H and O. = 1. The formula of substance A is CaC2. Determining the mass of carbon and hydrogen in substance C: 33. c.774 g hydrogen = 9. b.5 g C = 24.

1 mol C 2 H 2 26.01 + 5(B) = 3(44. i.10 g CaC 2 1 mol H 2 O mol H 2 O 1.28 mol H2O × 112. The balanced equation is: CaC2(s) + 2 H2O(l) → C2H2(g) + Ca(OH)2(aq) 45. c.22 g × 1 mol C = 0. Because the mass spectrum data indicate a molar mass of 26 g/mol. We can solve this without mass percent data simply by balancing the equation: A + 5 O2 → 3 CO2 + 4 H2O A must be C3H8 (which has a similar molar mass to CO2).774 g H × 1 mol H = 0. the molecular formula for substance C is C2H2.01) + 8(1.01) + 4(18. So this checks. Substance D is Ca(OH)2. then we cannot determine the limiting reactant because. If the molar mass of B is greater than the molar mass of A.008 g H Mol C/mol H = 1.28 mol H2O. Note: 3(12.02).02 g H 2 O mol CaC 2 0.01 g C CHAPTER 3 STOICHIOMETRY 0. the empirical formula is CH which has an empirical formula mass ≈ 13.0 g H2O × Because the actual mole ratio present is smaller than the required 2 : 1 mole ratio from the balanced equation.7 g C2H2 = mass of product C 2 mol H 2 O mol C 2 H 2 If the molar mass of A is greater than the molar mass of B. H2O is limiting.008) . This is also the empirical formula. 1. ii.702 mol CaC2 64. solving: B = 32. we also need fewer moles of A (from the balanced reaction). a. = 1.28 = = 1. while we have a fewer number of moles of A.0 g/mol Because B is diatomic.768 mol carbon 12.768 mol hydrogen 1. b.01) × 100 = 81. then B is the limiting reactant because we have a fewer number of moles of B and we need more B (from the balanced reaction).702 23.71% C.50 9. Now we can answer the question. the best choice for B is O2. 3(12.00.04 g C 2 H 2 × = 16. d.82 18. A + 5 B → 3 CO2 + 4 H2O To conserve mass: 44.0 g CaC2 × 1 mol CaC 2 = 0.

c. so it is a strong electrolyte. b. 13. MgSO4(s) → Mg2+(aq) + SO42−(aq). This process is called hydration. picture iv represents the Ba2+ and NO3− ions present in Ba(NO3)2(aq). A concentrated solution can also contain a nonelectrolyte dissolved in water. These are not full charges as in ionic compounds but are charges much smaller in magnitude. AgCl is an insoluble ionic compound so the ions stay together in solution and fall to the bottom of the container as a precipitate. HNO3 is a strong acid and exists as separate hydrated H+ ions and hydrated NO3− ions in solution. Polar molecules have a partial negative end and a partial positive end. b.CHAPTER 4 TYPES OF CHEMICAL REACTIONS AND SOLUTION STOICHIOMETRY Aqueous Solutions: Strong and Weak Electrolytes 10. NH4NO3(s) → NH4+(aq) + NO3−(aq) a. The oxygen end of water (the partial negative end of the polar water molecule) aligns with the partial positive end of the polar solute. CO is a polar covalent molecule and is hydrated as explained in part a. 12. 51 . C6H12O6 is hydrated as described in part a. picture ii represents NaCl(aq). Nonpolar solutes do not have permanent partial negative and partial positive ends. Polarity is a term applied to covalent compounds. 11. whereas the hydrogens of water (the partial positive end of the polar water molecule) align with the partial negative end of the solute. Some ionic compounds are not soluble in water. Acids are either strong or weak electrolytes. Polar covalent compounds have an unequal sharing of electrons in bonds that results in unequal charge distribution in the overall molecule. Ba(NO3)2(aq) → Ba2+(aq) + 2 NO3−(aq). Water is a polar molecule and dissolves other polar solutes readily. RbCl is a soluble ionic compound. These opposite charge attractions stabilize polar solutes in water. KF(aq) actually exists as separate hydrated K+ ions and hydrated F− ions in solution. so it exists as separate hydrated Rb+ ions and hydrated Cl− ions in solution. a. Only statement b is true. for example. concentrated sugar water. nonpolar solutes are not stabilized in water and do not dissolve. KF is a soluble ionic compound. C6H12O6 is a polar covalent molecule that is a nonelectrolyte. d. NaCl(aq) → Na+(aq) + Cl−(aq). so they are not labeled as a specific type of electrolyte.

250 L 0.250 mol NaOH 40.0) = 4. M Ca ( NO3 ) 2 = 0. K2CO3(aq) → 2 K+(aq) + CO32−(aq).00) = 2. molarity = mL 46. mixing several times along the way. d.0 M 1. M Ca 2 + = 1. instead using 114 mL of the 1. instead using 38.79 g 1 mol 1.250 mol NaOH 1 L stock = 0. M SO c.00 mol NaOH Add 500. mL of 1. 75. M NO − = 2(1.75 mol K 2 CrO 4 Similar to the solution made in part b.00 L × 0.25 L 4 2− Na2SO4(s) → 2 Na+(aq) + SO42−(aq).00 L × Place 20. a.52 CHAPTER 4 SOLUTION STOICHIOMETRY c. add water to dissolve the NaOH. M Na + = 2(2. 16. a. 5.0 mL × 0.0 M .500 L × L 1. M Na 2SO 4 = 2.3 mol × = 5.0935 mol NH4Cl 53.2 M C2H5OH = 1.8 g K2CrO4.0 g NaOH in a 2-L volumetric flask.0 M. 2. mixing several times along the way. 2.0 g NaOH L mol 15.49 g NH 4 Cl = 2.100 L 3 Ca(NO3)2(s) → Ca2+(aq) + 2 NO3−(aq).3 mol C2H5OH. d. Solution Concentration: Molarity 14. and fill to the mark with water.00 M b.100 mol K 2 CrO 4 194.00 M.00 M 0.114 L L 1.1 g 0.00 L × 0. picture i represents MgSO4(aq). fill to the mark with water.00 L × 0. picture iii represents K2CO3(aq).00 M NaOH stock solution to a 2-L volumetric flask.00 g NH4Cl × 1 mol NH 4 Cl = 0. c. 2.75 M K2CrO4 stock solution.100 mol Ca ( NO3 ) 2 = 1. MgSO4(aq) → Mg2+(aq) + SO42−(aq).20 g K 2 CrO 4 × = 38. 2. b.8 g K2CrO4 L mol K 2 CrO 4 Similar to the solution made in part a.100 mol K 2 CrO 4 1 L stock × = 0.5 mol Na 2SO 4 = 2.00 g NaOH × = 20.

315 M 10.0188) = 0.0 mL mL .0 × 10 −3 g 2. M SO 4 2− = 0.89 × 10 −1 mol 1000 mL × = 1. Mol Na2CO3 = 0.00 + 50.187 M 0.21 mol Na2CO3 L Na2CO3(s) → 2 Na+(aq) + CO32−(aq).89 × 10 −2 mol 1000 mL × = 0. 25. M K + = 3(0.0700 L + 0. mol Na+ = 0.89 mol L = 1.0 mL 500.71 × 10−3 mol K3PO4 212.030 mol 0.89 × 10−1 mol (NH4)2SO4 132.5 M Na+ 0. M NH d.5000 L 4 + 53 M NH 4Cl = NH4Cl(s) → NH4+(aq) + Cl−(aq).630 M.187 M 1 mol K 3 PO 4 = 4.0 mol Na 2 CO 3 = 0.0564 M.0935 mol NH 4 Cl = 0.42 mol 1.00) mL L + (NH4)2SO4(s) → 2 NH4+(aq) + SO42−(aq).1000 L 18.0 g (NH4)2SO4 × 1 mol = 1.15 g Molarity = 1.71 × 10 −3 mol = 0.21) = 0.2500 L 4 3− K3PO4(s) → 3 K+(aq) + PO43−(aq).0 mg 10. M NH 19.0700 L × 3. M PO 17.42 mol + 0.89 M (NH4)2SO4 100.0300 L × M Na + = total mol Na + total volume = 0.030 mol = 0.45 mol = = 4.00 × 10 −5 g steroid = = 500. Stock solution = 4 = 2(0.89 × 10−2 mol (NH4)2SO4 Moles of (NH4)2SO4 in final solution = 10.00 g K3PO4 × = M Cl − = 0.CHAPTER 4 SOLUTION STOICHIOMETRY 0.0 mL L 1.0188 M 0.315) = 0.0 mol NaHCO 3 = 0.0188 M Mol NaHCO3 = 0.315 M (NH4)2SO4 (10. 1.0300 L 0. mol Na+ = 2(0.030 mol NaHCO3 L NaHCO3(s) → Na+(aq) + HCO3−(aq).27 g M K 3PO 4 = 4.00 × 10−3 L × Molarity of final solution = 1.

94 g Mn 2 + = 2.0 ppb Hg in water = 5. a.00 × 10 −5 g steroid × = 2.0 ng Hg 5.0 × 10 −9 g Hg = mL H 2 O mL H 2 O 21.584 g Mn2+ × 1 mol Mn 2 + 2.442 × 10−3 mol Mn2+ 1000 mL L 1.768 × 10−7 mol Mn2+ L Molarity = 5. M = 1.00 × 10 −6 g steroid 1000 mL 1 mol steroid × × = 5.5 × 10−8 M Hg mL 200.768 × 10−5 M Mn2+ 0.95 × 10−8 M steroid 100.4 g steroid 20.883 × 10−2 mol Mn2+.00 mL × 1L 1.883 × 10 −2 mol × = 1.768 × 10 −5 mol = 5.54 100.442 × 10-3 M Mn2+ 1000.00 × 10−3 L × 5. Stock solution: 1.154 × 10−6 M Mn2+ 0.442 × 10 −5 mol = 5.768 × 10 −7 mol = 1.5000 L 5. 5. 2.442 × 10 −3 mol 1000 mL × = 1.442 × 10 −3 mol × = 1.0 × 10 −9 g Hg 1 mol Hg 1000 mL × × = 2.6 g Hg L .0 mL L Molarity = Solution B contains: 10.0 × 10-6 L stock × CHAPTER 4 SOLUTION STOICHIOMETRY 1000 mL 2.00 × 10−6 g steroid L mL This is diluted to a final volume of 100.883 × 10−2 M Mn2+ Solution A contains: 50.000 L 54.0 mL L 336.2500 L Molarity = Solution C contains: 10.442 × 10−5 mol Mn2+ 1000 mL L 1.00 mL × 1L 2.0 mL.883 × 10 −2 mol = 2.

dilute 5. ppm standard: 100.0 mL.0 mL of stock solution 1000. dilute 7. 22.8 × 10−7 M DDT mL 354. Precipitation Reactions 23. ppm solution.50 mL of the 1000.0 ppm stock to 100. and BaSO4. 50. Hydroxides: NaOH. and Hg2Br2. Similarly: 75.4 g CHCl 3 L 10. and Cu(OH)2 (and others) would be insoluble. K2SO4.0 ppm standard.0 × 10 −9 g CHCl 3 1 mol CHCl 3 1000 mL × × = 8.0 ppm stock solution to a 100-mL volumetric flask. SOLUTION STOICHIOMETRY 55 1. To make the 100. KBr.0 ppm standard. transfer 10.0 ppm As = 10. Some soluble bromides by Rule 2 would be NaBr. Ca(OH)2 (and others) would be soluble.0 ppm standard. and PbSO4 (or Hg2SO4) would be insoluble. and dilute to the mark.0 mL of 100. and (NH4)2SO4 (and others) would be soluble.0 ppm standard.0 mL.10 × 10 −6 g DDT 1 mol DDT 1000 mL × × = 2. KOH. Sulfates: Na2SO4.33 × 10−4 M As mL 74. 0. to make 100.00 × 104 µg Cu needed mL 1.CHAPTER 4 b. . dilute 1.92 g As L d.0 mL of the 1000. 25.5 g DDT L We want 100.0 × 10 −6 g As = mL mL c. 10. The insoluble bromides by Rule 3 would be AgBr.00 mL of the 1000. PbBr2. Similar reasoning is used for the other parts to this problem.0 mL solution = 1.00 × 104 µg Cu × 1 mL stock = 10. 10.0 × 10 −6 g As 1 mol As 1000 mL × × = 1.0 μg As 10. and NH4Br (there are others).0 ppm stock to 100. μg Cu × 100. Use the solubility rules in Table 4.0 mL of each standard.0 ppm stock to 100.0 mL.00 mL of the 1000. CaSO4.0 μg Cu Therefore.0 mL.1. Fe(OH)3. dilute 2.4 × 10−9 M CHCl3 mL 119. and Al(OH)3.50 mL of the 1000.0 ppm stock to 100.

followed by the complete ionic equation. the spectator ions K+ and NO3− are still present. Pb(NO3)2 would be a soluble Pb2+ salt. and PbS (and others) would be insoluble.0 mol of the PbI2 precipitate. and FePO4 (and others) would be insoluble. (NH4)2SO4(aq) + Ba(NO3)2(aq) → 2 NH4NO3(aq) + BaSO4(s) 2 NH4+(aq) + SO42−(aq) + Ba2+(aq) + 2 NO3−(aq) → 2 NH4+(aq) + 2 NO3−(aq) + BaSO4(s) Ba2+(aq) + SO42−(aq) → BaSO4(s) is the net ionic equation (spectator ions omitted).0 mol of Pb2+ ions would react with the 2. PbI2. the balanced molecular equation is first. No reaction occurs because all possible products are soluble. are both soluble in water. PbBr2. 25. CuCl2(aq) + 2 NaOH(aq) → Cu(OH)2(s) + 2 NaCl(aq) Cu2+(aq) + 2 Cl−(aq) + 2 Na+(aq) + 2 OH−(aq) → Cu(OH)2(s) + 2 Na+(aq) + 2 Cl−(aq) Cu2+(aq) + 2 OH−(aq) → Cu(OH)2(s) 26. K3PO4. The possible products. Pb(NO3)2(aq) + 2 KI(aq) → PbI2(s) + 2 KNO3(aq) (molecular equation) Pb2+(aq) + 2 NO3−(aq) + 2 K+(aq) + 2 I−(aq) → PbI2(s) + 2 K+(aq) + 2 NO3−(aq) (complete ionic equation) The 1. Pb(NO3)2(aq) + 2 NaCl(aq) → PbCl2(s) + 2 NaNO3(aq) Pb2+(aq) + 2 NO3−(aq) + 2 Na+(aq) + 2 Cl−(aq) → PbCl2(s) + 2 Na+(aq) + 2 NO3−(aq) Pb2+(aq) + 2 Cl−(aq) → PbCl2(s) c. . PbSO4.0 mol of I− ions to form 1. b. d. In each scheme. a. Lead: PbCl2. Therefore. Ca3(PO4)2. no reaction occurs. potassium phosphate and sodium nitrate. (NH4)3PO4 (and others) would be soluble. 24. e. For the following answers. The following schemes show reagents to add in order to precipitate one ion at a time. Even though the Pb2+ and I− ions are removed. Pb(OH)2. and Ag3PO4. The solution above the precipitate will conduct electricity because there are plenty of charge carriers present in solution.56 CHAPTER 4 SOLUTION STOICHIOMETRY Phosphates: Na3PO4. and then the net ionic equation. NaOH can be added to precipitate the last remaining ion.

Ag . CoCl2(aq) + 2 NaOH(aq) → Co(OH)2(s) + 2 NaCl(aq) Co2+(aq) + 2 OH−(aq) → Co(OH)2(s) c. Cu2+(aq) + S2−(aq) → CuS(s) b. Cr3 Na2SO4 + + + Ag . When AgNO3(aq) is added to KI(aq). Therefore. CuSO4(aq) + Na2S(aq) → CuS(s) + Na2SO4(aq). Cr3+ NaCl Cr3+ + BaSO4(s) AgCl(s) b. AgNO3(aq) + KI(aq) → AgI(s) + KNO3(aq). Cu2+ NaCl Cu2 27. Therefore. Na+ (the gray spheres) and SO42− (the bluish green spheres) are the spectator ions.CHAPTER 4 SOLUTION STOICHIOMETRY 57 a. Ba2 . Hg22 . + PbSO4(s) Hg2Cl2(s) AgCl(s) a. Therefore. the precipitate that forms is CuS(s). Ag . Ag+(aq) + I−(aq) → AgI(s) . Pb . the precipitate that forms is AgI(s). the precipitate that forms is Co(OH)2(s). Cu + 2+ 2+ c. When CuSO4(aq) is added to Na2S(aq). Ni2 + + Na2SO4 Ni2 + NaCl Ag+. When CoCl2(aq) is added to NaOH(aq). Na+ (the gray spheres) and Cl. K+ (the red spheres) and NO3− (the blue spheres) are the spectator ions.(the green spheres) are the spectator ions.

20 mol AgNO3 = 0.15 mol CaCl 2 = 0.020 mol AgNO3 dissolves to form 0.015 mol CaCl2 dissolves to form 0. Because no precipitate formed with KCl.020 mol NO3−. both these cations could be present. the possible cations are Ba2+. We will generally choose Na+ and NO3− as the spectator ions because sodium salts and nitrate salts are usually soluble in water.020/0. Pb(NO3)2(aq) + Na2SO4(aq) → PbSO4(s) + 2 NaNO3(aq) d.250 mol Pb( NO 3 ) 2 2 mol Na 3 PO 4 1 L Na 3 PO 4 × × = 0. Hg2(NO3)2(aq) + 2 NaCl(aq) → Hg2Cl2(s) + 2 NaNO3(aq) c. whereas the chloride and hydroxide salts of strontium are soluble). For students who do a more rigorous study of solubility. mL Na3PO4 30. Pb2+ and Hg22+ cannot be present.1500 L × 0.9 g AgCl 1 mol AgNO3 mol AgCl The net ionic equation is Ag+(aq) + Cl−(aq) → AgCl(s). 0.100 mol Na 3 PO 4 = 250. Pb2+.1). Mass AgCl = 0.030 mol Cl−.1000 L × 0.3 : 1).015 = 1. and Ca2+ (from the solubility rules).3 (1.020 mol Cl− reacted . The actual mole ratio present is 0.58 28.1000 L × 0. BaCl2(aq) + Na2CrO4(aq) → BaCrO4(s) + 2 NaCl(aq) 29. NO3− and Ca2+ (all Ag+ is used up in forming AgCl). Hg22+. The moles of each ion present initially (before reaction) can be easily determined from the moles of each reactant. Mol unreacted Cl− = 0.015 mol CaCl2 L The required mol AgNO3 to mol CaCl2 ratio is 2 : 1 (from the balanced equation). Because a precipitate formed with Na2SO4. AgNO3 is the limiting reagent.020 mol AgNO3 × 1 mol AgCl 143.020 mol AgNO3 L Mol CaCl2 = 0. the cations could be Ba2+ and Ca2+ (by the solubility rules in Table 4. Sr2+ could also be a possible cation (it forms an insoluble sulfate salt. Therefore. The ions remaining in solution are the unreacted Cl− ions and the spectator ions. Therefore.030 mol Cl− initially − 0.015) = 0.4 g AgCl × = 2. Because both Ba2+ and Ca2+ form soluble chlorides and soluble hydroxides.015 mol Ca2+ and 2(0.020 mol Ag+ and 0. Fe(NO3)3(aq) + 3 NaOH(aq) → Fe(OH)3(s) + 3 NaNO3(aq) b. 0. a.250 L L 3 mol Pb( NO 3 ) 2 0. 2 Na3PO4(aq) + 3 Pb(NO3)2(aq) → Pb3(PO4)2(s) + 6 NaNO3(aq) 0. CHAPTER 4 SOLUTION STOICHIOMETRY There are many acceptable choices for spectator ions. 31. 2 AgNO3(aq) + CaCl2(aq) → 2 AgCl(s) + Ca(NO3)2(aq) Mol AgNO3 = 0.

00 L 4.2000 L 32.50 M and M NO − = = 2.010 mol Cl− unreacted M Cl− = 0. M Ca + = 2 0. the number of Cu2+ ions will decrease by a factor of four as the precipitate forms.00 mol Cu(NO3)2. V2 NO 3 + K NO3 - - K 2+ + NO 3 - - V1 K + Cu NO 3 - NO3 NO 3 - K + - NO 3 K + K + NO 3 Cu(OH)2 Cu(OH)2 Cu(OH)2 b.00 M.075 M Ca2+ 0.00 L × 2.020 mol NO 3 0.00 mol KOH.00 L OH− ions will be zero because OH− is the limiting reagent.00 mol/L = 6. a.050 M Cl− total volume 0.250 M ⎝8⎠ − .00 L × 3. The following drawing summarizes the ions that remain in solution and the relative amount of precipitate that forms.00 mol K + = 1. Because the volume of solution doubled.1000 L + 0. Or using moles.1000 L The molarity of the spectator ions are: M NO − = 3 0. then OH− is limiting.015 mol Ca 2 + = 0.00 mol NO 3 6.CHAPTER 4 SOLUTION STOICHIOMETRY 59 Mol unreacted Cl− = 0. The drawing exaggerates the amount of precipitate that would actually form. the concentration of Cu2+ ions will decrease by a factor of eight after the two beakers are mixed: ⎛1⎞ M Cu + = 2. V1 is the volume of solution A or B and V2 is the volume of the combined solutions with V2 = 2V1.00 ⎜ ⎟ = 0. The spectator ion concentrations will be one-half the original spectator ion concentrations in the individual beakers because the volume was doubled. The concentration of 3 4.010 mol Cl − 0. M K + = 8.010 mol Cl − = = 0. In the drawing.00 mol/L = 4. Cu(NO3)2(aq) + 2 KOH(aq) → Cu(OH)2(s) + 2 KNO3(aq) Solution A contains 2. From the drawing. Note that K+ and NO3− ions are spectator ions.10 M NO3−. One Cu2+ ion remains as 3 Cu(OH)2(s) formula units form as precipitate. and solution B contains 2.2000 L − = 0. Let’s assume in our picture that we have 4 formula units of Cu(NO3)2 (4 Cu2+ ions and 8 NO3− ions) and 6 formula units of KOH (6 K+ ions and 6 OH− ions). With 4 Cu2+ ions and 6 OH− ions present.

2% 1.45 g All the Tl in TlI came from Tl in Tl2SO4.235 g Al2(SO4)3 mol Al2 (SO 4 ) 3 Mass % Al2(SO4)3 = 36. 35.1824 g TlI × 204. 2 AgNO3(aq) + Na2CrO4(aq) → Ag2CrO4(s) + 2 NaNO3(aq) 0.00 L × 3. XCl2(aq) + 2 AgNO3(aq) → 2 AgCl(s) + X(NO3)2(aq) 1.17 g Al2 (SO 4 ) 3 = 0.607 g Na2CrO4 L 2 mol AgNO 3 mol Na 2 CrO 4 34.107 g Al(OH)3 × × × × 78.00 mol Cu2+ reacted − L 2 mol OH 2.9 g Tl 2SO 4 × = 0.00 g XCl 2 = 208 g/mol.235 g × 100 = 16.00 mol OH − 1 mol Cu 2 + × = 3.60 CHAPTER 4 SOLUTION STOICHIOMETRY Alternately. The conversion from TlI to Tl2SO4 uses the molar masses and formulas of each compound.00 mol Cu2+ present initially L Mol Cu2+ present initially = 2.00 mol Cu 2 + = 0.00 L × Excess Cu2+ present after reaction = 4.00 mol − 3.1390 g Tl2SO4 331. one could certainly use moles to solve for M Cu 2+ : Mol Cu2+ reacted = 2. 0.00 mol = 1.00 mol KOH × Mass of precipitate = 293 g Cu(OH)2 33.4 g Tl 504. x = 137 g/mol Use aluminum in the formulas to convert from mass of Al(OH)3 to mass of Al2(SO4)3 in the mixture. 0.250 M 2. 4.57 g Cu (OH) 2 × 2 mol KOH mol Cu (OH) 2 Mass of precipitate = 6. 1 mol Al(OH) 3 1 mol Al 2 (SO 4 ) 3 1 mol Al3+ 0.00 mol Cu 2+ = 4.100 mol AgNO 3 1 mol Na 2 CrO 4 161.0750 L × 0.00 g mol Al(OH) 3 2 mol Al3+ 342.3 g TlI 408. x + 2(35.98 g Na 2 CrO 4 × × = 0.00 L 1 mol Cu (OH) 2 97.38 g AgCl × 1 mol AgCl 1 mol XCl 2 × = 4.4 g 2 mol AgCl 1.00 mol Cu2+ excess M Cu 2+ = 1.91 × 10 −3 mol XCl 2 The metal X is barium (Ba).8 g Tl .45) = 208.00 L + 2.81 × 10 −3 mol XCl2 143.

Average mass % = 38. The net ionic reaction is Ag+ + Cl− → AgCl(s). (molecular equation) NH3(aq) + H+(aq) + NO3−(aq) → NH4+(aq) + NO3−(aq) (complete ionic equation) (net ionic equation) Ba(OH)2(aq) + 2 HCl(aq) → 2 H2O(l) + BaCl2(aq) Ba2+(aq) + 2 OH−(aq) + 2 H+(aq) + 2 Cl−(aq) → Ba2+(aq) + 2 Cl−(aq) + 2 H2O(l) OH−(aq) + H+(aq) → H2O(l) .9 g saccharin × = 0. so: molar mass = 1.42 g M 2SO 4 = 142 g/mol 9.07 g S Average mass 0.3949 g saccharin × 100 = 67.486 g pesticide 61 Mass % Tl2SO4 = 37. atomic mass M = 23 amu From periodic table.36 g CaSO4 × 1 mol CaSO 4 1 mol M 2SO 4 = 9.03720 L × 0.00% saccharin by mass 0.88 g douglasite × × × L mol mol Ag + 4 mol Cl − = 0.42 g M2SO4 was reacted.2900 g douglasite 0.3949 g saccharin 233. 0.07 g S 183. a. M is Na(sodium). then use the formula of douglasite to convert from Cl− to douglasite.15 g CaSO 4 mol CaSO 4 From the problem.3949 g 3.1390 g Tl 2SO 4 × 100 = 1.4 g BaSO 4 32.99 × 10 −3 mol M 2SO 4 142 amu = 2(atomic mass M) + 32.1000 mol Ag + 1 mol Cl − 1 mol douglasite 311. Acid-Base Reactions 40.74% 0.949 × 10 −2 g 39.CHAPTER 4 SOLUTION STOICHIOMETRY 0. The conversion from BaSO4 to saccharin uses the molar masses and formulas of each compound.99 × 10−3 mol M2SO4 × 136.07 + 4(16.465% Tl2SO4 9. NH3(aq) + HNO3(aq) → NH4NO3(aq) NH3(aq) + H+(aq) → NH4+(aq) b. 1.5894 g Use the silver nitrate data to calculate the mol Cl− present.2900 g × 100 = 63. M2SO4(aq) + CaCl2(aq) → CaSO4(s) + 2 MCl(aq) 1.00).4550 g Mass % douglasite = 39. 0.49 mg = = = Tablet 10 tablets tablet tablet 0. All the sulfur in BaSO4 came from the saccharin.5032 g BaSO4 × 32.

66 g C × 42.468 4.406 0.406 10 Therefore.06 = 0. HNO3(aq) + CsOH(aq) → H2O(l) + CsNO3(aq) c. We get the empirical formula from the elemental analysis.999 g O Dividing the moles by the smallest number gives: 4.0.692.62 c. CHAPTER 4 SOLUTION STOICHIOMETRY 3 HClO4(aq) + Fe(OH)3(s) → 3 H2O(l) + Fe(ClO4)3(aq) 3 H+(aq) + 3 ClO4-(aq) + Fe(OH)3(s) → 3 H2O(l) + Fe3+(aq) + 3 ClO4−(aq) 3 H+(aq) + Fe(OH)3(s) → 3 H2O(l) + Fe3+(aq) d. Perchloric acid reacted with potassium hydroxide is a possibility. = 10.0.406 as a common factor: = 11.468 mol C.00 g carminic acid there are: 53.641 These numbers don’t give obvious mole ratios.06 = 1.09 g H H = 4.011 g C 1. AgOH(s) + HBr(aq) → AgBr(s) + H2O(l) AgOH(s) + H+(aq) + Br−(aq) → AgBr(s) + H2O(l) AgOH(s) + H+(aq) + Br−(aq) → AgBr(s) + H2O(l) 41. The balanced reaction is HA(aq) + OH−(aq) → H2O(l) + A−(aq) where HA is an abbreviation for carminic acid.54 2. .25 g O × 1 mol C 1 mol H = 4. Hydroiodic acid reacted with calcium hydroxide is a possibility. an acid with one acidic proton (H+). We can get molar mass from the titration data. = 6.50 0.641 4. Nitric acid reacted with cesium hydroxide is a possibility.06 2. 4.468 = 1.641 4. C22H20O13 is the empirical formula.641 mol O 15.008 g H 1 mol O = 2.10 = 4.468 11 = 1. 2 HI(aq) + Ca(OH)2(aq) → 2 H2O(l) + CaI2(aq) 42.06 10 So let's try 4. a. Out of 100.06 mol H 12. HClO4(aq) + KOH(aq) → H2O(l) + KClO4(aq) b. Let’s determine the mol C to mol H ratio: 4.406 0. 2.

00 × 10−3 mol NaOH to be neutralized. 3 NaOH(aq) + H3PO4(aq) → Na3PO4(aq) + 3 H2O(l) 5.00 mL of 0. HC2H3O2(aq) + NaOH(aq) → H2O(l) + NaC2H3O2(aq) 5.00 × 10−3 mol NaOH × 1 mol H 3 PO 4 1 L soln × = 8.300 mol H 2SO 4 .100 M NaOH.33 × 10−3 L or 8. then: 50.00 × 10−3 L × 0.50 × 10−2 L mol NaOH 0.0406 mol NaOH 1 mol carminic acid × L soln mol NaOH = 7.0 mL f. L a.00 × 10−3 mol NaOH × 1 mol H 2SO 4 1 L soln × = 8.150 mol HNO 3 e.32 × 10 mol The empirical formula mass of C22H20O13 ≈ 22(12) + 20(1) + 13(16) = 492 g.3602 g 492 g = −4 mol 7. 43.100 mol H 2SO 3 c.00 × 10−3 mol NaOH × 1 mol H 2SO 3 1 L soln × = 2.200 mol H 3 PO 4 d.3 mL mol NaOH 0.00 × 10−3 mol NaOH × 1 mol HNO 3 1 L soln × = 3. Therefore. 2 NaOH(aq) + H2SO3(aq) → 2 H2O(l) + Na2SO3(aq) 5. NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l) 5. the molecular formula of carminic acid is also C22H20O13.33 × 10−2 L or 33.02 × 10−3 L soln × Molar mass = 0. HNO3(aq) + NaOH(aq) → H2O(l) + NaNO3(aq) 5. If we begin with 50.CHAPTER 4 SOLUTION STOICHIOMETRY 0. H2SO4(aq) + 2 NaOH(aq) → 2 H2O(l) + Na2SO4(aq) 5.100 mol b.100 mol = 5.0 mL mol NaOH 0.00 × 10−3 mol NaOH × 1 mol HC 2 H 3O 2 1 L soln × = 2.00 × 10−2 L or 50.32 × 10−4 mol carminic acid 63 18.0 mL 2 mol NaOH 0.200 mol HC 2 H 3O 2 or 25.33 mL 3 mol NaOH 0.50 × 10−2 L or 25.33 mL 2 mol NaOH 0.33 × 10−3 L or 8.00 × 10−3 mol NaOH × 1 mol HCl 1 L soln × = 5.

so the base must contain 2 OH− in each formula unit. Because KHP is a monoprotic acid. A possible reaction would be 2 HCl(aq) + Ca(OH)2(aq) → 2 H2O(l) + CaCl2(aq). For the HCl reaction.0 mL of the unknown strong base contains 1. the reaction is (KHP is an abbreviation for potassium hydrogen phthalate): NaOH(aq) + KHP(aq) → NaKP(aq) + H2O(l) 0.80 × 10 −3 mol OH− L mol H + The 30. Sr(OH)2.07 × 10−2 mol NaOH L .0600 M OH− 0.67 × 10 L 47.528 × 10−2 M NaOH −3 34.22 g KHP mol KHP There is 5. The acid is a diprotic acid (H2A) meaning that it has two H+ ions in the formula to donate to a base. The most common examples are Ca(OH)2. the concentration of sodium hydroxide is: 5.150 mol H + 1 mol OH − × = 1. 0.1082 g KHP × 1 mol KHP 1 mol NaOH × = 5.298 × 10−4 mol NaOH 204. the base has the ability to accept two protons.298 × 10 −4 mol = 1.213 mol = 1.0500 L × Amount of NaOH neutralized by HCl: 0.8 × 10 −3 mol OH − = 0. These are all possible identities for the strong base. CHAPTER 4 SOLUTION STOICHIOMETRY Strong bases contain the hydroxide ion.103 mol HCl 1 mol NaOH × = 1.80 × 10 −3 mol OH− . and Ba(OH)2.0120 L × 0. where A2− is what is left over from the acid formula when the two protons (H+ ions) are reacted. 1.67 mL of solution.36 × 10−3 mol NaOH L HCl mol HCl 0.0300 L The unknown base concentration is one-half the concentration of OH− ions produced from the base. 46. The reaction is H2A(aq) + 2 NaOH(aq) → 2 H2O(l) + Na2A(aq). The three soluble strong bases that have 2 OH− ions in the formula are Ca(OH)2.01321 L HCl H 0. and Ba(OH)2.298 × 10−4 mol of sodium hydroxide in 34. 45.64 44. The pertinent reactions are: 2 NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2 H2O(l) HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) Amount of NaOH added = 0. OH−. Therefore. Sr(OH)2. The reaction that occurs is H+ + OH− → H2O.

6 mL Ba(OH)2 49.CHAPTER 4 SOLUTION STOICHIOMETRY 65 The difference. Ca(OH)2 and RbOH are strong bases.052 g = 50.200 mol HNO 3 1 mol H + × = 0.7 × 10−3 mol H2SO4 2 mol NaOH 4.100 mol HCl 1 mol H + × + L mol HCl 0.0500 L × 0. the reaction is: NaOH(aq) + KHP(aq) → H2O(l) + NaKP(aq) Mass KHP = 0.40 g HC2H3O2 Mass of HC2H3O2 = 0.8393 M HC2H3O2 Concentration of acetic acid = 0.22 g KHP × × L NaOH mol NaOH mol KHP = 0.0576 L L 2 mol H 3 PO 4 0.4178 g KHP 51. 2 H3PO4(aq) + 3 Ba(OH)2(aq) → 6 H2O(l) + Ba3(PO4)2(s) 0.00500 + 0. is the amount of NaOH neutralized by the sulfuric acid.010% 1006 g 50.1000 L × .0521 mol Ba (OH) 2 = 57.5062 mol NaOH 1 mol acetic acid × L so ln mol NaOH = 8.000 L of solution: total mass = 1000.7 × 10 −3 mol = 4. The net ionic equation that occurs is H+(aq) + OH−(aq) → H2O(l). If we have 1.1000 L Concentration of H2SO4 = 48. HCl and HNO3 are strong acids. Because KHP is a monoprotic acid.01000 L 1. Mol H+ = 0.8393 mol × mol a.141 mol H 3 PO 4 3 mol Ba (OH) 2 1 L Ba (OH) 2 × × = 0.0250 mol H+ L mol HNO 3 0.1000 mol NaOH 1 mol KHP 204.7 × 10−2 M H2SO4 0. mL × = 1006 g solution mL 60. 9.58 × 10−3 L soln H Mass % acetic acid = 50.393 × 10−3 mol acetic acid 8. 16.3 × 10−3 mol NaOH × 1 mol H 2SO 4 = 4.0200 = 0.393 × 10 −3 mol = 0. HC2H3O2(aq) + NaOH(aq) → H2O(l) + NaC2H3O2(aq) 0.006 g b.40 g × 100 = 5. 9.01420 L × 0.3 × 10−3 mol.02046 L NaOH × 0.

0 × 10 −3 mol OH − = = 2. M OH − = mol OH − excess 6.88 × 10−2 mol HCl = 1.0050 mol OH− excess.66 Mol OH− = 0. x = molar mass of HA = 176 g/mol = mol HA 0.0250 L × 0.88 × 10−2 mol Cl− 0. we have (2.0300 mol OH− L mol RbOH We have an excess of OH−.0776 M NH3 50.0125 mol HA L 1 mol NaOH 2.48 − 1. H+(aq) + OH−(aq) → H2O(l) 75.2250 L 54. Let HA = unknown acid. M OH − = 0. HA(aq) + NaOH(aq) → NaA(aq) + H2O(l) Mol HA present = 0.2000) L 0.0050 mol OH − 0.0300 mol OH− initially − 0. The actual mol OH− to mol H+ ratio is greater than 1 : 1.24 × 10−2 mol Ba2+ + L 2.0 × 10−3 L × The net ionic equation requires a 1 : 1 mol ratio between OH− and H+.0550 mol Ba (OH) 2 = 1.2000 L × 0.8500 L 0. 3.0250 mol OH− reacted (with H+) = 0. Because 1.88 × 10 −3 mol = 0.0.60 × 10−2 mol OH− in excess.88 × 10−3 mol NH3 L mol HCl 52.500 mol NaOH 1 mol HA × = 0.0100 + 0.48 × 10−2 mol OH− 225. .5000 L × CHAPTER 4 SOLUTION STOICHIOMETRY 0.47 × 10−3 L HCl H Molarity of NH3 = 53.24 × 10−2 mol Ba(OH)2 = 1.05000 + 0.0050 mol = = 5.0984 mol HCl 1 mol NH 3 × = 3.1000 + 0.88 × 10−2 mol H+ + L 1.0750 L + 0.9 × 10 −3 M (0.88) × 10−2 = 0.0 × 10−3 L × 0.00 × 10 −3 L Ba(OH)2(aq) + 2 HCl(aq) → BaCl2(aq) + 2 H2O(l). so the solution is basic (not neutral).100 mol RbOH 1 mol OH − × = 0. Because 176/88 = 2.0200 = 0.0125 mol HA Empirical formula mass ≈ 3(12) + 4(1) + 3(16) = 88 g/mol. the molecular formula is (C3H4O3)2 = C6H8O6.20 g HA x g HA .88 × 10−2 mol OH− will be neutralized by the H+.5000 + 0.0100 mol Ca (OH) 2 2 mol OH − × + L mol Ca (OH) 2 0. 39. The moles of excess OH− = 0.0 × 10−2 M OH− total volume 0. so OH− is in excess.250 mol HCl = 1.

+1. +1. −1 i. +1. which gives nickel a +4 oxidation state. C. −2. +5 g. O. O. O. i. Na. +2. O. +2. +5 a. +1. −2. Mn. !2. +2. H. 0 e. O. 2x + 7(!2) = !2. −2. S.ions. 0 d. for Bi: +1 + x + 3(−2) = 0. For P in HPO42−: +1 + y + 4(−2) = -2. HAsO2: Assign H = +1 and O = -2. x = +3 O. −2. x = −3 = oxidation state of N. S. O. UO22+: O. Pb. Mg.CHAPTER 4 SOLUTION STOICHIOMETRY 67 Oxidation-Reduction Reactions 55. C. +6 i. O. +3 g. for As: +1 + x + 2(−2) = 0. Pb. O. +7. H. Mg2P2O7: Composed of Mg2+ ions and P2O74− ions. As4: As. P. O. which gives manganese a +7 oxidation state because the sum of oxidation states for all atoms in MnO4− must equal the 1− charge on MnO4−. Ni. Mg2+ and CO32− ions present. y = +5 = oxidation state of P. +4. O. −2. (NH4)2HPO4 is made of NH4+ cations and HPO42− anions. −2. +2 f. Xe. O. O. Cl. For N in NH4+: x + 4(+1) = +1. P. −2. Hg2Cl2: Hg. -2. c. −2. Sr. g. NaBiO3: Na. !2. F. for As: 2(x) + 3(−2) = 0. Pb2+ and SO32− ions present. +4. +4. 0 a. +4 j. Assign oxygen an oxidation state value of −2. K4Fe(CN)6 is composed of K+ cations and Fe(CN)64− anions. !2. KMnO4 is composed of K+ and MnO4− ions. +2. For an overall anion charge of 4−. O. !2. 2x + 4(!2) = !2. Ca(NO3)2: Composed of Ca2+ ions and NO3− ions. O. h. −1. +4 . +2. x = +6 b. Cr. !1 c. C. −2. b. O. Fe(CN)64− is composed of iron and CN− anions. −2. Mg. +1. −2. −2. Apply rules in Table 4. +4 Na+ and C2O42− ions present. Cl. for U: x + 2(−2) = +2. Na2S2O3: Composed of Na+ ions and S2O32. SrCr2O7: Composed of Sr2+ and Cr2O72− ions. As2O3: O. S. d. Assign +1 as oxidation state of H and −2 as the oxidation state of O. C. x = +3 c. C. j. +2 h. O. x = +3 f. Assign O a −2 oxidation state. +1. K. −2. !1 f. O. 56. Ca. a. F. 57. 0 e. N. −2. Na. +1. x = +6 b. Fe. +2.3. + 8/3 h. O. x = +5 d. Cu. iron must have a +2 oxidation state. −1. Ag. e.

+6 l. If the oxidation states do not change. H. Cr. g. Balance C and H first. d. h. We need 2 mol of silver on each side to balance the charge. and carbon is oxidized (−8/3 → +4). and copper is oxidized (0 → +2). −3. no oxidation states change from reactants to products. Redox? a. and aluminum Al is oxidized (0 → +3). c. Balancing S is most complicated because sulfur is in both products. . +1. Ammonium ion has a 1+ charge (NH4+). assign oxidation states. N. −2. Balance C and H first. it is not charge balanced. c. −2. b. O. and carbon is oxidized (!4 → +4). then balance O. d. +3 To determine if the reaction is an oxidation-reduction reaction. Yes Yes No Yes Yes Yes No No Yes Oxidizing Agent O2 HCl − O3 H2O2 CuCl − − SiCl4 Reducing Agent CH4 Zn − NO H2O2 CuCl − − Mg Substance Oxidized Substance Reduced __________________________________________________________________________________________ CH4 (C) Zn − NO (N) H2O2 (O) CuCl (Cu) − − Mg O2 (O) HCl (H) − O3 (O) H2O2 (O) CuCl (Cu) − − SiCl4 (Si) In c. O. Although this reaction is mass balanced. C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) Oxygen is reduced (0 → −2). i. If the oxidation states change for some elements. a. the oxidation state of cerium must be +4 (Ce4+). e.68 CHAPTER 4 SOLUTION STOICHIOMETRY k. then worry about S. the species oxidized (called the reducing agent) shows an increase in the oxidation states. then the reaction is a redox reaction. b. and sulfate ion has a 2− charge (SO42−). In redox reactions. g. f. Therefore. and the species reduced (called the oxidizing agent) shows a decrease in oxidation states. S. Al(s) + 3 HCl(aq) → AlCl3(aq) + 3/2 H2(g) or 2 Al(s) + 6 HCl(aq) → 2 AlCl3(aq) + 3 H2(g) Hydrogen is reduced (goes from the +1 oxidation state to the 0 oxidation state). CH4(g) + 4 S(s) → CS2(l) + 2 H2S(g) Sulfur is reduced (0 → !2). 58. then the reaction is not a redox reaction. 59. Cu(s) + 2 Ag+(aq) → 2 Ag(s) + Cu2+(aq) Silver is reduced (+1 → 0). and h.

an increase of 2. We need 2 Ag atoms for every Cu atom. a decrease of 2. We need 7/2 O atoms for every C atom.11 of the text for rules on balancing by the half-reaction method. an increase of seven. We need 2 H atoms for every Mg atom. The oxidation state of magnesium changes from 0 to +2. a decrease of 1. The oxidation state of copper increases by 2 (0 to +2) and the oxidation state of silver decreases by 1 (+1 to 0). The balanced equation is: Mg(s) + 2 HCl(aq) → Mg2+(aq) + 2 Cl−(aq) + H2(g) c. The first step is to separate the reaction into two half-reactions. The balanced equation is: Cu(s) + 2 Ag+(aq) → Cu2+(aq) + 2 Ag(s) d. Each oxygen atom changes from 0 to −2. The oxidation state of hydrogen changes from +1 to 0. a. Review Section 4. and then balance each halfreaction separately. SOLUTION STOICHIOMETRY 69 a. We need 2 H atoms for every Zn atom. The first step is to assign oxidation states to all atoms (see numbers above the atoms). C2H6 + 7/2 O2 → CO2 + H2O Balancing the remainder of the equation by inspection: or C2H6(g) + 7/2 O2(g) → 2 CO2(g) + 3 H2O(g) 2 C2H6(g) + 7 O2(g) → 4 CO2(g) + 6 H2O(g) b. Each hydrogen atom gains one electron (+1 → 0). and each zinc atom loses two electrons (0 → +2). The equation is balanced. (2 Cl− → Cl2 + 2 e−) × 3 Cr2O72− → 2 Cr3+ + 7 H2O 6 e + 14 H + Cr2O72− → 2 Cr3+ + 7 H2O − + . −3 +1 0 +4 −2 +1 −2 C2H6 + O2 → CO2 + H2O Each carbon atom changes from −3 to +4.CHAPTER 4 60. (Cu → Cu2+ + 2 e−) × 3 NO3− → NO + 2 H2O (3 e + 4 H + NO3− → NO + 2 H2O) × 2 − + Adding the two balanced half-reactions so electrons cancel: 3 Cu → 3 Cu2+ + 6 e− 6 e + 8 H + 2 NO3− → 2 NO + 4 H2O ___________________________________________________________________ − + 3 Cu(s) + 8 H+(aq) + 2 NO3−(aq) → 3 Cu2+(aq) + 2 NO(g) + 4 H2O(l) b. This is the ratio in the given equation: Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(g) 61.

Pb → PbSO4 Pb + H2SO4 → PbSO4 + 2 H+ Pb + H2SO4 → PbSO4 + 2 H+ + 2 e− PbO2 → PbSO4 PbO2 + H2SO4 → PbSO4 + 2 H2O 2 e− + 2 H+ + PbO2 + H2SO4 → PbSO4 + 2 H2O Add the two half-reactions with two electrons transferred: 2 e− + 2 H+ + PbO2 + H2SO4 → PbSO4 + 2 H2O Pb + H2SO4 → PbSO4 + 2 H+ + 2 e− _____________________________________________ Pb(s) + 2 H2SO4(aq) + PbO2(s) → 2 PbSO4(s) + 2 H2O(l) This is the reaction that occurs in an automobile lead storage battery. Mn2+ → MnO4− (4 H2O + Mn2+ → MnO4− + 8 H+ + 5 e−) × 2 NaBiO3 → Bi3+ + Na+ 6 H + NaBiO3 → Bi3+ + Na+ + 3 H2O − (2 e + 6 H+ + NaBiO3 → Bi3+ + Na+ + 3 H2O) × 5 + 8 H2O + 2 Mn2+ → 2 MnO4− + 16 H+ + 10 e− 10 e + 30 H+ + 5 NaBiO3 → 5 Bi3+ + 5 Na+ + 15 H2O ___________________________________________________________________ 8 H2O + 30 H+ + 2 Mn2+ + 5 NaBiO3 → 2 MnO4− + 5 Bi3+ + 5 Na+ + 15 H2O + 16 H+ − Simplifying: 14 H+(aq) + 2 Mn2+(aq) + 5 NaBiO3(s) → 2 MnO4-(aq) + 5 Bi3+(aq) + 5 Na+(aq) + 7 H2O(l) e. d. H3AsO4 → AsH3 H3AsO4 → AsH3 + 4 H2O 8 e− + 8 H+ + H3AsO4 → AsH3 + 4 H2O (Zn → Zn2+ + 2 e−) × 4 8 e− + 8 H+ + H3AsO4 → AsH3 + 4 H2O 4 Zn → 4 Zn2+ + 8 e− _______________________________________________________ 8 H+(aq) + H3AsO4(aq) + 4 Zn(s) → 4 Zn2+(aq) + AsH3(g) + 4 H2O(l) f. As2O3 → H3AsO4 As2O3 → 2 H3AsO4 (5 H2O + As2O3 → 2 H3AsO4 + 4 H+ + 4 e−) × 3 .70 CHAPTER 4 SOLUTION STOICHIOMETRY Add the two balanced half-reactions with six electrons transferred: 6 Cl− → 3 Cl2 + 6 e− 6 e + 14 H + Cr2O72− → 2 Cr3+ + 7 H2O ___________________________________________________________ 14 H+(aq) + Cr2O72−(aq) + 6 Cl−(aq) → 3 Cl2(g) + 2 Cr3+(aq) + 7 H2O(l) − + c.

b. (2 Br. This converts the reaction to a basic solution while keeping it balanced.CHAPTER 4 SOLUTION STOICHIOMETRY NO3− → NO + 2 H2O 4 H + NO3− → NO + 2 H2O (3 e− + 4 H+ + NO3− → NO + 2 H2O) × 4 + 71 12 e− + 16 H+ + 4 NO3− → 4 NO + 8 H2O 15 H2O + 3 As2O3 → 6 H3AsO4 + 12 H+ + 12 e− ______________________________________________________________ 7 H2O(l) + 4 H+(aq) + 3 As2O3(s) + 4 NO3−(aq) → 4 NO(g) + 6 H3AsO4(aq) g. convert H+ to OH− as described in section 4. we are done.→ Br2 + 2 e−) × 5 MnO4− → Mn2+ + 4 H2O (5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O) × 2 10 Br− → 5 Br2 + 10 e− 10 e− + 16 H+ + 2 MnO4− → 2 Mn2+ + 8 H2O ____________________________________________________________ 16 H+(aq) + 2 MnO4−(aq) + 10 Br−(aq) → 5 Br2(l) + 2 Mn2+(aq) + 8 H2O(l) h. Al → Al(OH)4− 4 H2O + Al → Al(OH)4− + 4 H+ 4 H2O + Al → Al(OH)4− + 4 H+ + 3 e− MnO4− → MnO2 3 e + 4 H + MnO4− → MnO2 + 2 H2O − + 4 H2O + Al → Al(OH)4− + 4 H+ + 3 e− 3 e + 4 H+ + MnO4− → MnO2 + 2 H2O ______________________________________________ 2 H2O(l) + Al(s) + MnO4−(aq) → Al(OH)4−(aq) + MnO2(s) Because H+ doesn’t appear in the final balanced reaction.11 of the text. After the final balanced equation. CH3OH → CH2O (CH3OH → CH2O + 2 H+ + 2 e−) × 3 Cr2O72− → Cr3+ 14 H + Cr2O72− → 2 Cr3+ + 7 H2O 6 e− + 14 H+ + Cr2O72− → 2 Cr3+ + 7 H2O + 3 CH3OH → 3 CH2O + 6 H+ + 6 e− 6 e + 14 H + Cr2O72− → 2 Cr3+ + 7 H2O _______________________________________________________________ 8 H+(aq) + 3 CH3OH(aq) + Cr2O72−(aq) → 2 Cr3+(aq) + 3 CH2O(aq) + 7 H2O(l) − + 62. Use the same method as with acidic solutions. The extra step involves converting H+ into H2O by adding equal moles of OH− to each side of the reaction. Cl2 → Cl− 2 e− + Cl2 → 2 Cl− Cl2− → ClO− 2 H2O + Cl2− → 2 ClO− + 4 H+ + 2 e− 2 e− + Cl2 → 2 Cl− 2 H2O + Cl2 → 2 ClO− + 4 H+ + 2 e− ________________________________ 2 H2O + 2 Cl2 → 2 Cl− + 2 ClO− + 4 H+ . a.

5 S2− → 5 S + 10 e− + 2 S2− → 2 MnS + 8 H2O 10 e + 16 H + 2 ________________________________________________________ 16 OH− + 16 H+ + 7 S2− + 2 MnO4− → 5 S + 2 MnS + 8 H2O + 16 OH− − + MnO4− 16 H2O + 7 S2− + 2 MnO4− → 5 S + 2 MnS + 8 H2O + 16 OH− Reducing gives: 8 H2O(l) + 7 S2−(aq) + 2 MnO4−(aq) → 5 S(s) + 2 MnS(s) + 16 OH−(aq) e. Applying these steps gives 4 OH− + 2 Cl2 → 2 Cl− + 2 ClO− + 2 H2O. After this step.+ 6 H+ + 6 e− 6 e + 8 H+ + 2 MnO4− → 2 MnO2 + 4 H2O ___________________________________________________________ 2 OH− + 2 H+ + 3 CN− + 2 MnO4− → 3 CNO− + 2 MnO2 + H2O + 2 OH− − Reducing gives: H2O(l) + 3 CN−(aq) + 2 MnO4−(aq) → 3 CNO−(aq) + 2 MnO2(s) + 2 OH−(aq) . − + 3 H2O + 3 CN− → 3 CNO. S2− → S (S2− → S + 2 e−) × 5 MnO4− →MnS MnO4− + S2− → MnS − + ( 5 e + 8 H + MnO4− + S2− → MnS + 4 H2O) × 2 Common factor is a transfer of 10 e−. cancel identical species on both sides (2 H2O). The 4 OH− will react with the 4 H+ on the product side to give 4 H2O. NO2− → NH3 6 e + 7 H + NO2− → NH3 + 2 H2O − + Al → AlO2− (2 H2O + Al → AlO2− + 4 H+ + 3 e−) × 2 Common factor is a transfer of 6 e−. which can be further simplified to: 2 OH− (aq) + Cl2(g) → Cl−(aq) + ClO−(aq) + H2O(l) c. CN− → CNO− (H2O + CN− → CNO− + 2 H+ + 2 e−) × 3 MnO4− → MnO2 (3 e + 4 H + MnO4− → MnO2 + 2 H2O) × 2 Common factor is a transfer of 6 electrons.72 CHAPTER 4 SOLUTION STOICHIOMETRY Now convert to a basic solution. 6e− + 7 H+ + NO2− → NH3 + 2 H2O 4 H2O + 2 Al → 2 AlO2− + 8 H+ + 6 e− _______________________________________________ OH− + 2 H2O + NO2− + 2 Al → NH3 + 2 AlO2− + H+ + OH− Reducing gives: OH−(aq) + H2O(l) + NO2−(aq) + 2 Al(s) → NH3(g) + 2 AlO2−(aq) d. Add 4 OH− to both sides of the equation.

d. Add 97 e− to the product side. (Ce4+ + e− → Ce3+) × 97 Cr(NCS)64− → Cr3+ + NO3− + CO2 + SO42− 54 H2O + Cr(NCS)64− → Cr3+ + 6 NO3− + 6 CO2 + 6 SO42− + 108 H+ I− → I3− (3 I− → I3− + 2 e−) × 8 Charge on left = −4. Left: charge = 97(+4) −4 = +384. SOLUTION STOICHIOMETRY 73 a. Charge on right = +3 + 6(−1) + 6(−2) + 108(+1) = +93. For simplicity. Cl2 → Cl− (2 e− + Cl2 → 2 Cl−) × 27 . H+ → H2 (2 H+ + 2 e− → H2) × 3 Fe → HFeCl4 (H+ + 4 Cl− + Fe → HFeCl4 + 3 e−) × 2 6 H+ + 6 e− → 3 H2 2 H+ + 8 Cl− + 2 Fe → 2 HFeCl4 + 6 e− _________________________________ 8 H+ + 8 Cl− + 2 Fe → 2 HFeCl4 + 3 H2 or b. and then add the two balanced half-reactions with a common factor of 97 e− transferred. Right: charge = 97(+3) + 3 + 6(−1) + 6(−2) + 108(+1) = +384. 54 H2O + Cr(NCS)64− → Cr3+ + 6 NO3− + 6 CO2 + 6 SO42− + 108 H+ + 97 e− 97 e− + 97 Ce4+ → 97 Ce3+ ___________________________________________________________________________ 97 Ce4+(aq) + 54 H2O(l) + Cr(NCS)64−(aq) → 97 Ce3+(aq) + Cr3+(aq) + 6 NO3−(aq) + 6 CO2(g) + 6 SO42−(aq) + 108 H+(aq) This is very complicated. CrI3 → CrO42− + IO4− (16 H2O + CrI3 → CrO42− + 3 IO4− + 32 H+ + 27 e−) × 2 Common factor is a transfer of 54 e−.CHAPTER 4 63. 8 HCl(aq) + 2 Fe(s) → 2 HFeCl4(aq) + 3 H2(g) IO3− → I3− 3 IO3− → I3− 3 IO3− → I3− + 9 H2O 16 e− + 18 H+ + 3 IO3− → I3− + 9 H2O 16 e− + 18 H+ + 3 IO3− → I3− + 9 H2O 24 I− → 8 I3− + 16 e− _______________________________ 18 H+ + 24 I− + 3 IO3− → 9 I3− + 9 H2O Reducing: 6 H+(aq) + 8 I−(aq) + IO3−(aq) → 3 I3−(aq) + 3 H2O(l) c. A check of the net charge is a good check to see if the equation is balanced. HCl(aq) dissociates to H+(aq) + Cl−(aq). let's use H+ and Cl− separately.

64 OH− + 32 H2O + 2 CrI3 + 27 Cl2 → 54 Cl− + 2 CrO42− + 6 IO4− + 64 H2O Reducing gives: 64 OH−(aq) + 2 CrI3(s) + 27 Cl2(g) → 54 Cl−(aq) + 2 CrO42− (aq) + 6 IO4−(aq) + 32 H2O(l) e. then add 75 H+ to right to balance H+. Add 39 H2O to left. and then add the two balanced half-reactions with a common factor of 61 e− transferred. 39 H2O + Fe(CN)64− → Fe(OH)3 + 6 CO32− + 6 NO3− + 75 H+ net charge = 4− net charge = 57+ Add 61 e− to the product side. 39 H2O + Fe(CN)64− → Fe(OH)3 + 6 CO3− + 6 NO3− + 75 H+ + 61 e− 61 e− + 183 H2O + 61 Ce4+ → 61 Ce(OH)3 + 183 H+ _______________________________________________________________________ 222 H2O + Fe(CN)64− + 61 Ce4+ → 61 Ce(OH)3 + Fe(OH)3 + 6 CO32− + 6 NO3− + 258 H+ Adding 258 OH− to each side.74 CHAPTER 4 SOLUTION STOICHIOMETRY 54 e− + 27 Cl2 → 54 Cl− 32 H2O + 2 CrI3 → 2 CrO42− + 6 IO4− + 64 H+ + 54 e− ___________________________________________________ 32 H2O + 2 CrI3 + 27 Cl2 → 54 Cl− + 2 CrO42− + 6 IO4− + 64 H+ Add 64 OH− to both sides and convert 64 H+ into 64 H2O. Ce4+ → Ce(OH)3 (e + 3 H2O + Ce4+ → Ce(OH)3 + 3 H+) × 61 − Fe(CN)64− → Fe(OH)3 + CO32− + NO3− Fe(CN)64− → Fe(OH)3 + 6 CO32− + 6 NO3− There are 39 extra O atoms on right.) . and then reducing gives: 258 OH−(aq) + Fe(CN)64−(aq) + 61 Ce4+(aq) → 61 Ce(OH)3(s) + Fe(OH)3(s) + 6 CO32−(aq) + 6 NO3−(aq) + 36 H2O(l) 64. Mn → Mn2+ + 2 e− HNO3 → NO2 HNO3 → NO2 + H2O (e− + H+ + HNO3 → NO2 + H2O) × 2 + Mn → Mn2+ + 2 e− 2 e + 2 H + 2 HNO3 → 2 NO2 + 2 H2O ________________________________________________________ 2 H+(aq) + Mn(s) + 2 HNO3(aq) → Mn2+(aq) + 2 NO2(g) + 2 H2O(l) or − 4 H+(aq) + Mn(s) + 2 NO3−(aq) → Mn2+(aq) + 2 NO2(g) + 2 H2O(l) (HNO3 is a strong acid.

034 g 5 mol H 2 C 2 O 4 − − Molarity = 66.97 mL L 5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O a.00 × 10 −3 L 6 e− + 14 H+ + Cr2O72− → 2 Cr3+ + 7 H2O b.62 × 10−3 L soln × 0.8 mL .700 × 10 −4 mol MnO 4 1000 mL × = 1.48 × 10−2 L or 24. (H2C2O4 → 2 CO2 + 2 H+ + 2 e−) × 5 − + (5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O) × 2 5 H2C2O4 → 10 CO2 + 10 H+ + 10 e− 10 e + 16 H + 2 MnO4− → 2 Mn2+ + 8 H2O ________________________________________________________________ 6 H+(aq) + 5 H2C2O4(aq) + 2 MnO4−(aq) → 10 CO2(g) + 2 Mn2+(aq) + 8 H2O(l) 0. (Fe2+ → Fe3+ + e−) × 5 The balanced equation is: 8 H+(aq) + MnO4−(aq) + 5 Fe2+(aq) → 5 Fe3+(aq) + Mn2+(aq) + 4 H2O(l) 20.700 × 10−4 mol MnO4− 90.CHAPTER 4 SOLUTION STOICHIOMETRY 75 (2 e− + 2 H+ + IO4− → IO3− + H2O) × 5 (4 H2O + Mn2+ → MnO4− + 8 H+ + 5 e−) × 2 − 8 H2O + 2 Mn2+ → 2 MnO4− + 16 H+ + 10 e− 10 e + 10 H+ + 5 IO4− → 5 IO3− + 5 H2O _____________________________________________________________ 3 H2O(l) + 2 Mn2+(aq) + 5 IO4−(aq) → 2 MnO4−(aq) + 5 IO3−(aq) + 6 H+(aq) 65.46 × 10 −2 mol Fe 2+ 1 mol Cr2 O 7 × L 6 mol Fe 2+ 2− × 1L 0.0150 mol Cr2 O 7 2− = 2. 4.00 × 10−3 L × 4.1058 g H2C2O4 × 1 mol H 2 C 2 O 4 2 mol MnO 4 × = 4.0216 mol MnO 4 5 mol Fe 2+ = 2.23 × 10 −3 mol Fe 2+ = 4.23 × 10−3 mol Fe2+ × − L so ln mol MnO 4 − Molarity = 2. (Fe2+ → Fe3+ + e−) × 6 The balanced equation is: 14 H+(aq) + Cr2O72−(aq) + 6 Fe2+(aq) → 6 Fe3+(aq) + 2 Cr3+(aq) + 7 H2O(l) 50.622 × 10−2 M MnO4− 28.46 × 10−2 M Fe2+ 50.

581 = 0. 0. 16 e− + 18 H+ + 3 IO3− → I3− + 9 H2O 24 I− → 8 I3− + 16 e− 16 e− + 18 H+ + 3 IO3− → I3− + 9 H2O ______________________________ 18 H+ + 24 I− + 3 IO3− → 9 I3− + 9 H2O (3 I− → I3− + 2 e−) × 8 Reducing: 6 H+(aq) + 8 I−(aq) + IO3−(aq) → 3 I3−(aq) + 3 H2O(l) .1516/0. a. We then convert this to a mass of iron and calculate the mass percent of iron in the sample.6% Fe 0.80 × 10−3 mol Fe present − 3.94 g V × × × = 0.1516 g V − 2+ L mol V mol VO mol MnO 4 − 0.37 × 10−3 L MnO4− × 0.80 × 10−3 mol Fe2+ × − L mol MnO 4 = 3. 38.212 g × 100 = 34.80 × 10−3 mol Fe × Mass % Fe = 68.02250 mol MnO 4 5 mol VO 2+ 1 mol V 50.0198 mol MnO 4 5 mol Fe 2 + = 3.0494 L = 49.02645 L × 0.4 mL HCl 24.76 67.31 g Mg mol Mg 5. 55. The two halfreactions to balance are: VO2+ → V(OH)4+ and MnO4− → Mn2+ Balancing by the half-reaction method gives: MnO4−(aq) + 5 VO2+(aq) + 11 H2O(l) → 5 V(OH)4+(aq) + Mn2+(aq) + 2 H+(aq) 0.212 g Fe mol Fe 0.1516 g V .581 = 0.85 g Fe = 0.6128 g The unbalanced reaction is: VO2+ + MnO4− → V(OH)4+ + Mn2+ This is a redox reaction in acidic solution and must be balanced accordingly. Mg(s) + 2 HCl(aq) → MgCl2(aq) + H2(g) 3.261 g ore sample mass of ore sample 69. CHAPTER 4 SOLUTION STOICHIOMETRY (Fe2+ → Fe3+ + e−) × 5 5 e + 8 H + MnO4− → Mn2+ + 4 H2O __________________________________________________________ 8 H+(aq) + MnO4−(aq) + 5 Fe2+(aq) → 5 Fe3+(aq) + Mn2+(aq) + 4 H2O(l) − + From the titration data we can get the number of moles of Fe2+.00 g Mg × 1 mol Mg 2 mol HCl 1 L HCl × × = 0.0 mol HCl 70.

275 mol CaCl 2 = 6.07 g KIO3 in a 500-mL volumetric flask.75 × 10−2 L = 57.0100 mol KIO3 3 mol I 3 2 mol Na 2S2 O 3 × × = − L mol KIO3 mol I 3 1.50 × 10−3 mol Na2S2O3 − M Na 2S2O3 = e. Additional Exercises 71. 0. Pb(NO3)2. 0.00-mL mark.00 mol HCl 2 S2O32− → S4O62− + 2 e− Adding the balanced half-reactions gives: 2 S2O32−(aq) + I3−(aq) → 3 I−(aq) + S4O62−(aq) d.10 mol CaCl 2 Volume H2O evaporated = 230.5000 L H 1.810 × 10−3 mol KIO3 × 2. There are other possible correct choices for the following answers.810 × 10−3 mol KIO3 214.33 × 10−2 mol CaCl2 L CaCl 2 The volume of CaCl2 solution after evaporation is: 6.6013 g KIO3 H 2. continue adding water to the 500.0 g KI × = 3.5 mL = 173 mL H2O evaporated 72.07 g KIO3 × L mol KIO3 Place 1. Ag+(aq) + Cl−(aq) → AgCl(s). and Hg2(NO3)2 would form precipitates with the Cl− ion. Mol CaCl2 present = 0.810 × 10−3 mol KIO3 × c.62 × 10−3 L = 5. mL − 57.230 L CaCl2 × 0.62 mL HCl mol KIO3 3. We have listed only three possible reactants in each case.5 mL CaCl2 1. with mixing along the way.0100 mol KIO3 214.0 g KIO3 = 1.732 g KI mol KIO3 mol KI 77 b.0 g KIO3 8 mol KI 166. a. I3− + 2 e− → 3 I− 6 mol HCl 1L × = 5. Pb2+(aq) + 2 Cl-(aq) → PbCl2(s) Hg22+(aq) + 2 Cl−(aq) → Hg2Cl2(s) .CHAPTER 4 SOLUTION STOICHIOMETRY 1 mol KIO3 = 2. 25.33 × 10−2 mol CaCl2 × 1 L CaCl 2 = 5.04 × 10 −3 L 0. AgNO3.50 × 10 −3 mol = 0.0468 M Na2S2O3 32. add water to dissolve the KIO3.00 × 10−3 L KIO3 × 0.

213 g MgCl 2 × 100 = 14.500 mol AgNO3 1L = 8.100 mol KOH = 0.50 g mixture b. Na2SO4.21 g = 0. Hg22+(aq) + 2 Cl−(aq) → Hg2Cl2(s) Hg22+ (aq) + 2 I−(aq) → Hg2I2(s) f. Ca2+(aq) + SO42−(aq) → CaSO4(s). Al(NO3)3(aq) + 3 KOH(aq) → Al(OH)3(s) + 3 KNO3(aq) 0.21 g mol MgCl 2 0.0200/0. and Ca(NO3)2 would form precipitates with the SO42− ion.200 mol Al( NO 3 ) 3 = 0. Fe3+(aq) + 3 OH−(aq) → Fe(OH)3(s). Na2SO4. and Na2CO3 would form precipitates with the Fe3+ ion. NaOH.641 g AgCl × 1 mol MgCl 2 1 mol AgCl 95. 0. Pb2+(aq) + SO42−(aq) → PbSO4(s) Ca2+(aq) + SO42−(aq) → CaSO4(s) e. and NaI would form precipitates with the Hg22+ ion. Na2S.0100 = 2 (2 : 1). Ag+(aq) + Br−(aq) → AgBr(s). Hg22+ (aq) + SO42−(aq) → Hg2SO4(s).213 g MgCl2 × × 143. a.0100 mol Al(NO3)3 L 0. NaCl.2000 L × 0. 3 moles of KOH are required to react with 1 mole of Al(NO3)3 (3 : 1 mole ratio). MgCl2(aq) + 2 AgNO3(aq) → 2 AgCl(s) + Mg(NO3)2(aq) 0. Ba2+(aq) + SO42−(aq) → BaSO4(s). Ca2+(aq) + CO32−(aq) → CaCO3(s) 3 Ca2+(aq) + 2 PO43−(aq) → Ca3(PO4)2(s) c. and Na3PO4 would form precipitates with the Ag+ ion.95 mL AgNO3 74. and Na3PO4 would form precipitates with the Ca2+ ion.213 g MgCl2 × 2 mol AgNO3 1 mol MgCl 2 1L 1000 mL × × × 95. 2 Ag+(aq) + CrO42−(aq) → Ag2CrO4(s) 3 Ag+(aq) + PO43−(aq) → Ag3PO4(s) 73.4 g AgCl 2 mol AgCl mol MgCl 2 0. Na2CO3. The actual KOH to Al(NO3)3 mole ratio present is 0. Pb(NO3)2. 2 Fe3+(aq) + 3 S2−(aq) → Fe2S3(s) 2 Fe3+(aq) + 3 CO32−(aq) → Fe2(CO3)3(s) d.2% MgCl2 1. .0200 mol KOH L From the balanced equation. BaCl2.78 CHAPTER 4 SOLUTION STOICHIOMETRY b. NaBr.0500 L × 0. Na2CrO4.

016 g H 5. 29.8% Co.0761 g = 0.09% H.02 g H 2 O 100. 4 Co(OH)2(s) + O2(g) → 2 Co2O3(s) + 4 H2O(l) . % O = × 100 = 40.4 g O = 40.0 g compound 45.45 g Cl 5. Assuming 100.09% H 18. % H = × 100 = 5.5 g H2O × 2.0 g compound The mass percent composition is 24.09 g H. CoCl2•6H2O(aq) + 2 AgNO3(aq) → 2 AgCl(s) + Co(NO3)2(aq) + 6 H2O(l) CoCl2•6H2O(aq) + 2 NaOH(aq) → Co(OH)2(s) + 2 NaCl(aq) + 6 H2O(l) Co(OH)2 → Co2O3 This is an oxidation-reduction reaction.5%. Out of 100.8) = 45.4% O.00 g Al(OH) 3 × = 0.7 + 24. 29.86 g Co 0. KOH is the limiting reagent.93 g Co 35.0761 g Cl. which is also the molecular formula.45 g Cl 0. 5.93) + 3(16. 40.00) = 165.7% Cl 143.(29. % Cl = × 100 = 29.02 g H 2 O 100.145 g Co2O3 × 117.308 g AgCl × 35.8% Co 165.4 g O × = 2.09 g H × 1 mol 1 mol = 5.008 g H 16.4 g AgCl 0. c. is water.53 mol O 1.7% Cl.00 g O Dividing all results by 0.5 g H2O × 16.103 g = 0.0 g of compound.416 g The remainder.7 g Cl × = 0.CHAPTER 4 SOLUTION STOICHIOMETRY 79 Because the actual mole ratio present is less than the required mole ratio. Co2O3: 2(58.520 g Al(OH)3 3 mol KOH mol Al(OH) 3 75. and 40. % Co = × 100 = 24.838 mol Cl 58. The obvious choice is O2. 0. we get CoCl2•6H2O for the empirical formula.0 .0 g of compound: 45.4% O 18. 0.8 g Co H 1 mol 1 mol = 0. there are: 24.421 mol Co.05 mol H.09 g H = 5.00 g O 40. a. 100. Thus we also need to include an oxidizing agent.103 g Co.86 g/mol 0.0200 mol KOH × 1 mol Al(OH ) 3 78. b.4 g O.86 g Co 2 O 3 0.256 g Cobalt(III) oxide.421.

b.44(2. CHAPTER 4 a.008) = 106.195 2.0.11)y = 0. Fe(NO3)3: 55. 42.1586.290 × 10−3 − y Because the molar mass of NaCl is 58.00 g of material.1586 g 58.1000 mol/L = 2.23 g C × 1 mol C 1 mol F = 3.107 g Fe(OH)3 × 55.456 g Ag+(aq) + Cl−(aq) → AgCl(s).0559 g Fe × 241. 0. 0.290 × 10−3 mol Cl−.00) + 3(1.55 g / mol × 100 = 72.86 g/mol 0.85 g Fe = 0. let x = mol NaCl and y = mol KCl.55)y = 0.44)x + (74. Fe3+(aq) + 3 OH−(aq) → Fe(OH)3(s) SOLUTION STOICHIOMETRY Fe(OH)3: 55.3470 L × 0.4% KCl 0. = 15.54 × 10 −3 mol × 74.81 g B 3.80 76.290 × 10−3 mol Ag+ = 2. (22.00 g F 1 mol B = 0.242 g Fe(NO3)3 55.01267 mol = 4.54 × 10−3 mol KCl Mass % KCl = 1.9 g Fe( NO 3 ) 3 = 0.44 g/mol and the molar mass of KCl is 74.0248. (16.90 × 10−3 L) × 0.85 g Fe c.0 Dividing by the smallest number: 0.87 g/mol 0.9 g Fe(OH) 3 b. y = 1. 55.929 = 18. Mass % Fe(NO3)3 = 77.11 g B × The empirical formula is C18F15B.195 0.1586 g % NaCl = 100.6% NaCl 78.290 × 10−3 mol Cl− total x + y = 2.516 mol C.516 2.55)y = 0.242 g × 100 = 53.55 g/mol: (58.85 + 3(16.0 − 72.290 × 10−3 − y) + (74. a.1% 0.929 mol F 12.0559 g Fe 106.195 mol B 10.85 + 3(14.396 × 10 −3 mol BARF L .66 g F × = 2. Assume 100.011 g C 19. x = 2.00) = 241.4 = 27.01) + 9(16.

79.CHAPTER 4 SOLUTION STOICHIOMETRY 2.400 mol HCl 1 mol NaOH = 4.307 mol = 6. so Cr(NO2)3 (the denominator) is limiting. actual yield = (8. 1 mol Cr2 (CrO 4 ) 3 452.00 × 10−2 mol × L mol HCl MNaOH = 80.99 g.69 (actual).22 g The amount of KHP used = 0.137 L × 0.396 × 10 −3 mol 81 Molar mass of BARF = The empirical formula mass of BARF is 511.967 × 10−3 mol NaOH.880) = 7. .69 × 10 −2 mol Cr(NO2)3 L 0. C18F15B.1000 L × to react with HCl 0.06 g Cr(OH)3 × to form precipitate 1 mol Cr (OH) 3 3 mol NaOH = 6.00 × 10 −2 mol + 4.00 M NaOH volume 0. Cr(NO3)3(aq) + 3 NaOH(aq) → Cr(OH)3(s) + 3 NaNO3(aq) Mol NaOH used = 2. 6.34 g)(0. Therefore. 204.0623 mol = 1. 3.02 g mol Cr (OH) 3 NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l) Mol NaOH used = 0. Actual > required.880 = 81.1 g/mol 4.4016 g × Because 1 mole of NaOH reacts completely with 1 mole of KHP.34 g Cr2(CrO4)3 2 mol Cr ( NO 2 ) 3 mol Cr2 (CrO 4 ) 3 actual yield . the molecular formula is the same as the empirical formula.0500 L 3 (NH4)2CrO4(aq) + 2 Cr(NO2)3(aq) → 6 NH4NO2(aq) + Cr2(CrO4)3(s) 0. the balanced reaction requires a 3/2 = 1.34 g 1 mol = 1.34 g Cr2(CrO4)3 isolated 8.967 × 10−3 mol KHP.00 × 10−2 mol × 103.69 × 10 −2 mol Cr(NO2)3 × 0.0369 mol between (NH4)2CrO4 and Cr(NO2)3.269 mol = 3.00 g Cr2 (CrO 4 ) 3 × = 8. the NaOH solution contains 1.203 L × 0.00 × 10 −2 mol total mol NaOH = = 2.251 g = 512.5 to 1 mole ratio 0.23 × 10 −2 mol (NH4)2CrO4 L 0.

91 × 10 −3 mol = = 3.323 g (carrying extra sig.1%. Dissolve the KIO3 in water.834 × 10 −2 mol NaOH = L 25. We should use a 1L volumetric flask to make the solution.30 × 10−3 mol C6H8O7 192.967 × 10 −3 mol 7. . The advantage of the first method is that it shows that we made all our individual measurements to four significant figures.0 g 214. meaning that citric acid has three acidic hydrogens per citric acid molecule (citric acid is a triprotic acid).237 g.01 mol citric acid 1.0198 mol × 214.00) = 214.) mol mol We should weigh out between 4.30 × 10 −3 mol Therefore.00016 M.0202 mol × = 4.1 g C 6 H 8 O 7 Let HxA represent citric acid.0 g = 4.0202 M.9 + 3(16.967 × 10 −3 mol 7. An alternate way is to express the molarity as 0.06 × 10 −3 L 1.1 mg.0200 ± 0.24 and 4.91 × 10−3 mol OH− L x= mol OH − 3. figs.07849 ±0. 83. where x is the number of acidic hydrogens.865 × 10 −2 mol NaOH = L 25.0785 ±0. The balanced neutralization reaction is: HxA(aq) + x OH−(aq) → x H2O(l) + Ax−(aq) Mol OH− reacted = 0.0198 and 0.0 g/mol 0.32 g of KIO3.82 Molarity of NaOH = CHAPTER 4 SOLUTION STOICHIOMETRY 1.11 × 10 −3 L Maximum molarity = Minimum molarity = We can express this as 0.10 + 126.01 × 10 −3 L 1.0198 mol and 0.0002 M. Desired uncertainty is 1% of 0. This will produce a solution whose concentration is within the limits and is known to at least the fourth decimal place. and dilute to the mark in a 1-liter volumetric flask. 82.849 × 10 −2 mol NaOH = L 25. We want to weigh out between 0. They are good to ±0.967 × 10 −3 mol 7. So we want the solution to be 0. or the concentration should be between 0. 0.0202 mol of KIO3.250 g C6H8O7 × 1 mol C 6 H 8 O 7 = 1.105 mol OH − = 3. the general acid formula for citric acid is H3A. This second way shows the actual number of significant figures in the molarity. or ±0.0002.0372 L × 0. We should weigh it to the nearest milligram or 0.02. Mol C6H8O7 = 0. Molar mass of KIO3 = 39.0002 M.

13 g Mg × 100 = 31.8 (carrying 1 extra sig.00 mol Ag + 1 mol Cl − × = 0.31 65.31 g Mg mol Mg 65. and let y = mass K2SO4.03105 L ⎜ ⎜ L ⎝ ⎞ ⎛ 1 mol C 2 H 5 OH ⎞ ⎛ 46.27 g/mol Molar mass of PbCl2 = 278.1 g/mol.44 g/mol.00.0429 g C2H5OH ⎟ ⎜ 2 mol Cr O 2 − ⎟ ⎜ mol C 2 H 5 OH ⎟ ⎠ 2 7 ⎠⎝ ⎠⎝ 0.6.468 ⎟ + 24. b. one can setup an equation relating mol Cl− present to mol Ag+ added.00 M HCl 0. molar mass of K2SO4 = 174.31 (130.2 ! (48. Because mol Ag+ = mol Cl− present. So x + y = 10.156 L × MHCl = % Mg = 3. fig. 2(6 e− + 14 H+ + Cr2O72− → 2 Cr3+ + 7 H2O) 3 H2O + C2H5OH → 2 CO2 + 12 H+ + 12 e− ___________________________________________________________________________ 16 H+ + 2 Cr2O72− + C2H5OH → 4 Cr3+ + 2 CO2 + 11 H2O ⎛ 0.00 − 2 x 2x 2(10.38 ⎜ = 0.62)x = 743. so 10.468 mol = 6.38 65.38 ⎠ ⎝ 24. a. Let x = mass of NaCl.468 mol Cl− L mol Ag + 20.8)x + 486.2)x = 257.31 × 65.468.468 mol HCl added L mol Ag + 0.38 g Zn mol Zn = 0.156 L × 3.00 − x) g Zn × × 24.0 g blood 85.) (82.13 g Mg.468 mol Cl− = 0. Let x = mass of Mg.3% Mg 10. The same is true for Zn.0429 g C 2 H 5 OH × 100 = 0.00 − x) ⎞ ⎛ 2x + = 0. there is a 2 : 1 mole ratio between mol Mg and mol Cl−. x = 3.00 − x = mass of Zn.0780 L 86.00 g mixture 3. x g Mg × 1 mol Mg 2 mol Cl − 1 mol Zn 2 mol Cl − × + (10.3 g/mol . Two reactions occur: Pb2+(aq) + 2 Cl−(aq) → PbCl2(s) and Pb2+(aq) + SO42−(aq) → PbSO4(s) Molar mass of NaCl = 58.00 mol Ag + 1 mol Cl − × = 0. molar mass of PbSO4 = 303. 24.CHAPTER 4 SOLUTION STOICHIOMETRY 83 Challenge Problems 84.07 g ⎞ ⎟⎜ ⎟⎜ ⎟ = 0. 0.143% C2H5OH 30. From the given balanced equations.0600 mol Cr2 O 7 2− 0. Ag+(aq) + Cl−(aq) → AgCl(s).

z = 0. 6.27 mass of PbCl2 + mass PbSO4 SOLUTION STOICHIOMETRY = total mass of solid x y (1/2)(278.6 g Zn are present. let y = volume (L) delivered by Y and z = volume (L) delivered by Z.150 mol/L) + z(0.9 g Ag 65.0825 mol H+.44 174.6 g Zn 14. (2.269 − (9.84 CHAPTER 4 x y = moles NaCl.380.740)y = 21.255 L .6 = 14.250) = 0.0 g.379)x + (1. 87.0 − y) = 9.2750 L × 0.1) + (303.268 × 10−3)x Substituting x = 29.81 g NaCl × 100 = 68.059 × 10−2)y = 0. 0.38 g Zn 1 mol Zn 88. Then x + y = 29.312.75 and x + y = 10. Solving: x = 6. y = 14.300 mol/L = 0.268 × 10−3(29.059 × 10−2(19.3) = 21.4 g Ag are also present after the reaction is stopped.75 58.0825 mol H+ 0. y + z = 0.380 ! y)(0.2750 L + y + z = 0. solving: y = 0.0825.125 L.00. and 29.655 L.0 − y) = (9.150) + (0.27 We have two equations: (2.0 − y) g Zn × Simplifying: 3.380 ! y y(0.0 − y) Solving: 0. H+(aq) + OH−(aq) → H2O(l).268 × 10−3)y.44 174.059 × 10−2(19.00 g mixture Zn(s) + 2 AgNO2(aq) → 2 Ag(s) + Zn(NO2)2(aq) Let x = mass of Ag and y = mass of Zn after the reaction has stopped.132 × 10−2)y = 0. Because the moles of Ag produced will equal two times the moles of Zn reacted: (19.1% NaCl 10. = moles K2SO4 58.581 − (3. y(0. 1 mol Ag 1 mol Zn 2 mol Ag × = x g Ag × 107. z = 0.0 − 14.0 − y into the equation gives: 3.81 g NaCl.250 mol/L) mol OH− = 0.

0.20 + (34.20 + (34.45 = 143.7)x − (187.45 = 74. 0.90 = 119. 125 mL 255 mL = 2.1 g PbCl 2 1 mol PbCl 2 0. so.1889 g = (143.8)y x = 1. C12H10-nCln + n Ag+ → n AgCl.0800 L × 6.1 = 22.01225 mol Pb2+ 278.01225 mol = 6.8 g/mol Let x = number of moles of KCl in mixture and y = number of moles of KBr in mixture. KBr.9% 0.100 L a. x = moles AgCl and y = moles AgBr.008) + n(35. .7)x.407 g PbCl2 × 1 mol PbCl 2 1 mol Pb 2+ × = 0. molar mass of AgCl = 143.13 M Pb2+ (evaporated concentration) 2. 39.0 0.55 g/mol.1024 g Pb2+(aq) + 2 Cl−(aq) → PbCl2(s) 3. 107.0790 g × 100 = 77.9 + 35.4)x + (187.90 = 187.06 × 10−3 mol KCl × 74.8)y Multiply the first equation by 187.06 mL/min.65 min 60. and then subtract from the second.55)x + (119. % KBr = 100.00 g/mol AgCl.1024 g = (74.0273 = (25.01) + (10 − n)(1.CHAPTER 4 SOLUTION STOICHIOMETRY 85 Flow rate for Y = 89.0 − 77. flow rate for Z = = 4.10 + 79.0)y and 0.20 mL/min 60.8)y −0.8 . Setting up two equations from the given information: 0.13 mol / L = 4.0790 g KCl mol KCl Mass % KCl = 90. 119.90 M 0. 107. AgBr.1889 = (143.10 + 35.55 KCl = 0.65 min Molar masses: KCl.4 g/mol Molar mass of PCB = 12(12.4) g of AgCl will be produced for every [154.4 g/mol.45) = 154. Ag+ + Cl− → AgCl and Ag+ + Br− → AgBr. 1.00 × 10 −3 L Original concentration = 91.1616 = −(117.44)n] g of PCB reacted.9 + 79.44)n Because n mol AgCl are produced for every 1 mol PCB reacted. n(143. 39.1%.06 × 10−3 mol KCl 0.4)x + (187.407 g 3.

4)n Mass of PCB 154.25 mg HCl 1g × × × × = 2.85 g The two possible reactions are: I.097 92.00 g × 1 mol Fe = 0.00 h × 60 min 60 s 1. and we can produce: 0. n = 7. Flow rate = 5. reaction I occurs because it fits the data best.80)n.44)n] = 0.20 + (34.44)n] = massPCB(143.80 × 10 4 L 4. CHCl = 3. CuSO4 is limiting.4)n = or massAgCl[154.86 CHAPTER 4 SOLUTION STOICHIOMETRY Mass of AgCl (143.46 g HCl 2 mol HCl mol CaO 2.0439 mol CuSO4 × 3 mol Cu 63. 76.12)n = (27.20 + (34. 1 ppm = 1 mg/kg H2O = 1 mg/L (assuming density = 1.0358 mol Fe × 1 mol Cu 63.50 × 103 L/s = 5.79 g Cu 3 mol CuSO 4 mol Cu Assuming 100% yield. Mol CuSO4 = 87.6 mL × 1L 0. and we can produce: 0.69 × 106 g CaO 36.35 × 104 L/s b.1947(143.35 × 10 4 c.50 × 103 (65. 3 CuSO4(aq) + 2 Fe(s) → 3 Cu(s) + Fe2(SO4)3(aq) If reaction I occurs. Fe is limiting.25 ppm HCl 5. CuSO4(aq) + Fe(s) → Cu(s) + FeSO4(aq) II.44)n b.0358 mol 55.20 + (34.65 + (17.00 × 104 L/s + 3. 93. a.500 mol × = 0.4)n.65 = (10.00 g/mL) 8.4971[154.55 g Cu × = 2. The concentration of Ca2+ going into the second plant was: . 0.0) = 4.92)n 76.20 × 106 g HCl h min s L 1000 mg 1 mol HCl 1 mol CaO 56.0439 mol 1000 mL L Mol Fe = 2.20 × 106 g HCl × d.28 g Cu 1 mol Fe mol Cu If reaction II occurs.08 g Ca × × = 1.55 g Cu × = 2.

80 × 104 L/s × (8. (1.+ S2O82.66 × 10−3 mol Cr 1.0% of this water is returned. C Ca 2+ (final) = 94.00 × 60 × 60) s = 5.80 × 104) × 0.00 g Cr = 8.66 × 10−3 mol Cr3+ × 2+ 2− 6 mol Fe mol Cr2 O 7 = 1.900 = 1.66 × 10−3 mol Cr × 52.68 × 10−3 = 4.21 × 106 g Ca2+ was added to this water. a.87 ppm Ca2+ is mixed with (5. (1.53 ppm) = 10.58 × 10−3 L × 2 0.18 × 108 L Because 90.87 ppm) + (3. 56.0520 mol Cr2 O 7 − 6 mol Fe 2+ = 2.34 = 11.55 × 10 4 L / s)(9.80) × 104 = 3.69 × 106 g CaO × 40.08 g Ca 2 + = 1.62 × 104 L/s of water with 11.08 g CaO C Ca 2+ (plant water) = 9.000 g Fe(NH4)2(SO4)2•6H2O × 1 mol = 7.17 g 7. 1.1. 8.53 ppm Ca2+.21 × 109 mg = 9.00 × 10 4 (10.CHAPTER 4 SOLUTION STOICHIOMETRY 5.97 × 10−3 mol Fe2+ reacted with Cr2O72− generated from the Cr plating.62 × 10 4 L / s)(11.650 × 10−3 mol Fe2+ 392.→ 2 SO42−) × 3 ________________________________________________________________ 7 H2O(l) + 2 Cr3+(aq) + 3 S2O82−(aq) → Cr2O72−(aq) + 14 H+(aq) + 6 SO42−(aq) (Fe2+ → Fe3+ + e−) × 6 6 e + 14 H + Cr2O72− → 2 Cr3+ + 7 H2O ____________________________________________________________ 14 H+(aq) + 6 Fe2+(aq) + Cr2O72−(aq) → 2 Cr3+(aq) + 6 Fe3+(aq) + 7 H2O(l) − + b.35 .97 × 10−3 mol Fe2+ × 2 1 mol Cr2 O 7 − 2 mol Cr 3+ = 1.53 + 2.55 × 10 4 L / s 7 H2O + 2 Cr3+ → Cr2O72− + 14 H+ + 6 e− (2 e. The Cr plating contained: 4.68 × 10−3 mol of excess Fe2+ × 2− L mol Cr2 O 7 Fe2+ (total) = 3.63 × 10−2 g Cr mol Cr .62 × 10 4 L / s + 3.55 × 104 L/s of water containing 9.53 + 1.87 ppm 5.3 ppm 1.35 × 10 4 87 The second plant used: 1.53 ppm 5.650 × 10−3 − 2.2) = 9.18 × 108 L of water.

2 = 88.2 = 554. (e− + Cu2+ + I− → CuI) × 2 3I− → I3− + 2 e− 2 Cu2+(aq) + 5 I−(aq) → 2 CuI(s) + I3−(aq) 2 e− + Cu3+ + I− → CuI 3I− → I3− + 2 e− ______________________________ Cu3+(aq) + 4 I−(aq) → CuI(s) + I3−(aq) Only Cu2+ present. formula is YBa2Cu3O7.57 × 10−3 L × 2 0. b. µm 2 40.1000 mol S2 O 3 − 1 mol I 3 2 mol Cu 2 + × × − 2 L 2 mol S2 O 3 − mol I 3 = 2.2 g/mol 7.5402 g Molar mass of YBa2Cu3Ox = = 670.63 × 10−2 g × SOLUTION STOICHIOMETRY 1 cm 3 = 1.257 × 10−3 mol Cu2+ − 2.523 × 10−4 mol "123" 3 mol Cu 0. Check with Step I data: Both Cu2+ and Cu3+ present.00 × 10−4 cm = 300.523 × 10 − 4 mol 670. .00). 3x = 6.2 + x(16. x = +3. x = +2 1/3 or 2.0 cm +3 + 2(+2) + 3x + 6.25." 22.33 This corresponds to two Cu2+ and one Cu3+ present.3) + 3(63. a. Only Cu3+ present.88 CHAPTER 4 Volume of Cr plating = 8.55) + x(16. YBa2Cu3O8: +3 + 2(+2) + 3x + 8(−2) = 0. Step II data: All Cu is converted to Cu2+. x = +2 YBa2Cu3O7: +3 + 2(+2) + 3x + 7(−2) = 0.250.257 × 10−3 mol Cu × 1 mol "123" = 7. 670.20 × 10 −2 cm 3 = 3. 2 S2O32− → S4O62− + 2 e− 2 e− + I3− → 3 I− ____________________________________ 2 S2O32−(aq) + I3−(aq) → 3 I−(aq) + S4O62−(aq) c.20 × 10−2 cm3 = area × thickness 7.00) x = 7. Note: Superconductor abbreviated as "123.5: 1.91 + 2(137.19 g Thickness of Cr plating = 95. YBa2Cu3O6.5(−2) = 0 7 + 3x − 13 = 0.

nCu 3+ = 2.123 g SO 4 = 0.518 × 10−3 − 1.205 g 2− 2− = 60.518 × 10−3 − nCu 3+ − nCu 2+ 2 = −1. Average oxidation state of Cu: +3 + 2(+2) + 3(x) + 7.07 g SO 4 0.889 × 10−3 mol I3− × 2− L 2 mol S2 O 3 − 89 37.77 × 10−3 L × We get 1 mol I3− per mol Cu3+ and 1 mol I3− per 2 mol Cu2+. x = 7. this superconductor sample contains equal moles of Cu2+ and Cu3+. There are: . 3x = 7.518 × 10−3 mol Cu total = nCu 3+ + nCu 2+ Solving by simultaneous equations: nCu 3+ + nCu 2+ = 2. x = +2. 14. 96.26 × 10−3 mol Cu2+.393 × 10−4 mol "123" 670.50 mol Cu3+.2 g / mol This amount of "123" contains: 3(8.889 × 10−3 ___________________________________________ nCu 2+ 2 = 6.889 × 10−3 mol 0. x = 7.1000 mol S2 O 3 − 1 mol I 3 = 1.123 g SO42−.26 × 10−3 mol Cu3+ This sample of superconductor contains equal moles of Cu2+ and Cu3+.25 The two experiments give the same result.29 × 10−4 nCu 2+ = 1.CHAPTER 4 SOLUTION STOICHIOMETRY 2 0.0 g of the mixture of Na2SO4 and K2SO4.50. Solving for x using oxidation states: +3 + 2(+2) + 1. % sulfate = 233.50. then: nCu 3+ + In addition: nCu 2+ 2 = 1.50 = 2x.25. Let nCu 3+ = mol Cu3+ and nCu 2+ = mol Cu2+. 1 mole of YBa2Cu3Ox contains 1. Therefore.50(+3) + x(−2) = 0.50(+2) + 1.50 mol Cu2+ and 1.5625 g = 8. giving an average oxidation state of +2.0% Assume we have 100.4 g BaSO 4 0.25 with formula YBa2Cu3O7.50 As determined from Step I data.298 g BaSO4 × 96.25(-2) = 0.393 × 10−4) = 2.26 × 10−3 = 1. 0.

0 g of mixture.45) g Cl = (0. 0. Mass of Ag in AgNO3 = x g AgNO3 × 107.55 = 0.6557)z Similarly.25 ! y.25 ! 0.10)y + (22.35 g AgCl 2(35.9 ! (39.0 48.91 g AgNO3 .10)x + (22.4404 g Cl 143.35 mol K2SO4 × 174. then x + y = 1. let’s calculate the mass of metals in each salt.99)y = 40. There are three unknowns so we need three equations to solve for the unknowns. The Cl− in CuCl2 and FeCl3 will react with the excess AgNO3 to form the precipitate AgCl(s).0.0 g. y = mass CuCl2.99)y = 40.90: Mass of Cl in mixture = 1. Setting up an equation: 39.0000 g.25 ! y) + (22. The total mass of Na+ and K+ must be 40.0 g mol mol So.25 mol of 1+ cations to balance the 2! charge of SO42−.27 g mol = 61 g K2SO4 We assumed 100. we have two equations with two unknowns: x + y = 1.55 mol Na+ and x = 1.0 g in the assumed 100.5273)y + (0. the mixture is 61% K2SO4 and 39% Na2SO4. therefore. !(16. Let x = mass AgNO3.70 mol K+ × 1 mol K 2 SO 4 2 mol K + = 0.45) g Cl = (0. Assuming silver has an atomic mass of 107.25. and z = mass FeCl3.5273)y 134.25 and (39.4404 g Cl = (0.45 g Cl = 0.625 mol SO42− 96.11)y = !8.35 mol K2SO4.9 g Ag = (0. Let x = number of moles of K+ and y = number of moles of Na+.70 mol K+ Therefore: 0. so 39.625 = 1.45 g CuCl 2 Mass of Cl from FeCl3 = z g FeCl3 × 3(35.07 g There must be 2 × 0.99)y = 40.20 g FeCl3 The second equation is: 0.6557)z 162.9 y = 0.0 g SO42− × CHAPTER 4 SOLUTION STOICHIOMETRY 1 mol = 0.0 x = 1.10 g 22. Then x + y + z = 1.7809 g AgCl × Mass of Cl from CuCl2 = y g CuCl2 × 35.99 g x mol K+ × + y mol Na+ × = 40.6350)x 169.10(1.90 60. 97.

1009 = −(0.2907)z] 0.07% CuCl2.6350)x + (0.5273)y + (0. the remainder must be the mass of metal in each salt.3443)z The third equation is: 0. The general equation is: Mx(SO4)y(aq) + y Ba2+(aq) → y BaSO4(s) + x Mz+ Depending on the value of y.4727)y + (0.0000 g 1 mol = 9.3443)z _____________________________________________ −0. Solving: x + y + z) −0.4684 = (0.2907)z 0.6350)x + (0.2327 g × The moles of the sulfate salt depends on the formula of the salt.99% AgNO3 1.94% 1.5273)y = (0. y = 0.4684 g metals = (0.6557)z −0.1623)y − (0.1009 = 0.3494 g FeCl3 0.4404 = (0.4007 − 0.CHAPTER 4 SOLUTION STOICHIOMETRY 91 For CuCl2 and FeCl3. mass % FeCl3 = 34.2499 g AgNO3 Mass % AgNO3 = 0.2499 g × 100 = 24.2888)z.5273)y + 0.6557(0.0000 g Mass % CuCl2 = 0.1623)y − (0. Mass of Cu in CuCl2 = y − (0.4007 g × 100 = 40. z= 0.4727)y + (0.4007 g CuCl2 x = 1.1666 = −(0.0000 − 0. the equation becomes: TiSO4(aq) + Ba2+(aq) → BaSO4(s) + Ti2+(aq) .1666 = −(0.0000 − y − z = 1. Mol BaSO4 = 0.3443)z We now have three equations with three unknowns. we already calculated the amount of Cl in each initial amount of salt.3494).4 g 98.6350 (1.970 × 10 −4 mol BaSO4 233.2888 0. For example.1623 ____________________________________________________________ 0.0000 = 0. if Pat thinks the formula is TiSO4. the mole ratio between the unknown sulfate salt and BaSO4 varies.6557)z = (0.4727)y Mass of Fe in FeCl3 = z − (0.5273 [−0.4404 = (0.3494 = 0.

Thus Na2SO4 is also reasonable. that the salt is titanium sulfate. the molar mass of Ga2(SO4)3 is 427.970 × 10 −4 mol = 147.1472 g/9. but its formula is Ti2(SO4)3. which would have the formula Na2SO4.95 g/mol. Thus Ga2(SO4)3 is also reasonable. there is a 1:1 mole ratio between mol BaSO4 and mol Na2SO4. one could dissolve the sulfate salt in water and add NaOH.970 × 10 mol BaSO 4 Using atomic masses. Ga3+ would form a precipitate with the hydroxide. sodium sulfate (Na2SO4) exists as a white solid with orthorhombic crystals. For sodium sulfate to be a reasonable choice.9 g/mol × −4 mol Ga 2 (SO 4 ) 3 9. the calculated molar mass should be around 443 g/mol. To distinguish between Na2SO4 and Ga2(SO4)3. whereas Na2SO4 would not. it must have a molar mass of about 147. the compound would have a molar mass of (assuming the TiSO4 formula): 0. However. the molar mass of Na2SO4 is 142. Looking in references. The equation is: Na2SO4(aq) + Ba2+(aq) → BaSO4(s) + 2 Na+(aq) As with TiSO4.65 g/mol. Chris thinks the salt is sodium sulfate. M(CHO2)2(aq) + Na2SO4(aq) → MSO4(s) + 2 NaCHO2(aq) From the balanced molecular equation.970 × 10 −4 mol of TiSO4.97 g/mol.92 CHAPTER 4 SOLUTION STOICHIOMETRY Because there is a 1 : 1 mole ratio between mol BaSO4 and mol TiSO4.1472 g of salt was used. the moles of M(CHO2)2 present initially must equal the moles of MSO4(s) formed. From just these data. Because this has the same formula as gallium sulfate. Titanium sulfate exists as a green powder. you need 9. Marathon Problems 99.1472 g Ga 2 (SO 4 ) 3 3 mol BaSO 4 = 442. TiSO4 seems reasonable. Because moles = mass/molar mass and letting AM = the atomic mass of M: . The equation would be: Ga2(SO4)3(aq) + 3 Ba2+(aq) → 3 BaSO4(s) + 2 Ga3+(aq) The calculated molar mass of Ga2(SO4)3 would be: 0. who chose gallium. References confirm that gallium hydroxide is insoluble in water. the molar mass of TiSO4 is 143. deduces that gallium should have a 3+ charge (because it is in column 3A). the molar mass of Ti2(SO4)3 is 383.6 g/mol. Because 0. Randy. and the formula of the sulfate would be Ga2(SO4)3. whereas gallium sulfate Ga2(SO4)3 is a white powder.6 g/mol From atomic masses in the periodic table. Using atomic masses. It is unlikely. then.05 g/mol.

from the periodic table. The moles of CHO2− ions present initially are: mol Pb(CHO 2 ) 2 2 mol CHO 2 9. We must determine the moles of CHO2− ions present in order to determine volume of KMnO4 solution.00 mL of diluted solution are: 0. 0.00 g 1 mol Na 2 C 2 O 4 5 mol C 2 O 2− 4 − − = 2. the balanced reaction between MnO4.7416 g Pb(CHO2)2 × × = 6. the unknown element M is Pb.7416 g = molar mass of M (CHO 2 ) 2 A M + 90.2 g 1 mol Pb(CHO 2 ) 2 The moles of CHO2− present in 10.2500 L − − Using the half-reaction method in basic solution.756 × 10 −3 mol = 0.9392 g = molar mass of MSO 4 A M + 96. Using the half-reaction method.01855 L From the third paragraph.01000 L × 6.622 × 10−3 mol CHO2− 0.1976 From the information in the second paragraph.9 = (9.CHAPTER 4 SOLUTION STOICHIOMETRY mass MSO 4 9.is: 5 C2O42−(aq) + 2 MnO4−(aq) + 16 H+(aq) → 10 CO2(g) + 2 Mn2+(aq) + 8 H2O(l) 1 mol Na 2 C 2 O 4 1 mol C 2 O 2 − 2 mol MnO 4 4 Mol MnO4 = 0.556 × 10 −2 mol CHO 2 = 2.9234 g Na2C2O4 × × × 134.and C2O42. the standard KMnO4 solution reacts with formate ions from the filtrate.9392 9.04 AM = 41. we can determine the concentration of the KMnO4 solution.07 mass M (CHO 2 ) 2 9.7416)AM + 935.556 × 10−2 mol CHO2− 297. (9.04 93 mol MSO4 = mol M(CHO2)2 = Because mol MSO4 = mol M(CHO2)2: 9.07 A M + 90.0 = 207.7416 = .9 A M + 96. the balanced reaction between CHO2.756 × 10−3 mol MnO4− M KMnO 4 = M MnO − = 4 mol MnO 4 volume − = 2.1486 mol/L 0.and MnO4− is: 3 CHO2−(aq) + 2 MnO4−(aq) + OH−(aq) → 3 CO32−(aq) + 2 MnO2(s) + 2 H2O(l) .9392)AM + 894.

2 g K2CrO4 mol .622 × 10 mol CHO2 × −3 SOLUTION STOICHIOMETRY − 2 mol MnO 4 3 mol CHO 2 − − × 1L 0.50) = 27.00 g Mol M = ½ mol N = 0. 331.50 g = 107.01 g N Thus the mass of nitrate in the compound = 8.246 g = 0. b. this is equal to the molar mass of Ag2CrO4. The reaction is: 2 AgNO3(aq) + K2CrO4(aq) → Ag2CrO4(s) + 2 KNO3(aq) The blood red precipitate is Ag2CrO4(s). but Zr does not form stable 2+ ions in solution.176 × 10−2 L = 11. Compound A = M(NO3)x.246 + 28. 2. From the balanced reaction.00 ! 2(36.000 mol K2CrO4 × 169.2943 mol 2 27. 6 + x(!2) = !2.25 g = 36.5886 mol 14. If x = 1: mass of M = 100.00 ! 36.94 CHAPTER 4 Determining the volume of MnO4− solution: 2. Ag. in 100.00 g).74 g/mol Molar mass of metal M = 0.8 g) of Ag2CrO4. Using oxidation states. 100.8 g AgNO3 mol 194. x = 4.: 8.76 mL The titration requires 11. Compound B is K2CrO4 (potassium chromate).00 g of compd.01 g / mol 63.000 mol AgNO3 × 1. This salt is composed of K+ and CrOx2− ions. we need 2 mol AgNO3 to react with 1 mol K2CrO4 to produce 1 mol (331.5886 mol = 0.25 g O 14.76 mL of the standard KMnO4 solution. c. Because we cannot have x = 3 or more nitrates (three nitrates would have a mass greater than 100. compound A must be AgNO3.2943 mol This is close to Zr. Compound B: K2CrOx is the formula.00 g = 91.2 g = 194. so 1 mole of precipitate formed.00 g O = 28.50 g Mol M = mol N = 8.9 g/mol (This is silver.1486 mol MnO 4 − = 1.246 g N × 48.5886 mol Molar mass of metal M = If x = 2: mass of M = 100.9 g = 339.50 g (if x = 1). it forms stable 4+ ions.50 g = 63. a.) 0.8 g Ag2CrO4 formed.

000 M NO3− 3 1.000 mol !2. M Ag + = 0 M (the limiting reagent) 1. its concentration will be 0 M after precipitation is complete.2 g quantities are correct. Because Ag+ is limiting. We only have 194.000 M Ag+ .000 mol M K+ = M CrO 2− 2 × 1.500 M CrO42− d. M NO − = = 2. Solution A: 2.2 g K2CrO4 (1 mol) reacts.8 g AgNO3 + 339. moles of K+ and moles of NO3− remain unchanged because they are spectator ions. After the reaction.5000 L 0.0 mol) must be present to react with all the K2CrO4. AgNO3 must be limiting.000 M K+. 339.500 M K+.000 mol = 3.5000 L 0.750 mol 0 +1.CHAPTER 4 SOLUTION STOICHIOMETRY 95 The problem says that we have equal masses of reactants. 0.5000 L = 3.8 g K2CrO4.750 mol = 0.2 g 2− − = 4.8 g K2CrO4 or 194.000 mol 0 + CrO42−(aq) → Ag2CrO4(s) 1. 2 Ag+(aq) Initial Change After rxn 2.000 mol 0. 0.750 mol K2CrO4 194. and we have reacted 339.0000 L 1. Instead of K2CrO4 limiting.750 M CrO42−.8 g K2CrO4 × 1.750 mol CrO 4 2 × 1. then when 194.5000 L 1 mol = 1.0000 L 4 = 0.000 M NO3− Solution B: 339.000 mol Ag + = 4.2 g AgNO3 + 194.750 mol 2.2 g K2CrO4. If we assume the 194.8 g AgNO3 and 339. this cannot be correct.2 g AgNO3 present. Our two choices are 339.000 mol 1.750 mol !1.8 g AgNO3 (2.0000 L .000 mol NO 3 2.750 mol K + = 7.

845 atm 760 torr 0.56 × 104 Pa atm b.5 torr × = 6. If the levels of mercury in each arm of the manometer are equal. When they are unequal. torr 96 . then the pressure in the flask is equal to atmospheric pressure.013 × 105 Pa = 8.28 atm × c. a. Pflask = 760.5 torr. − 118 = 642 torr 642 torr × 1 atm = 0. 47.25 × 10−2 atm × 1. Pflask = 635 − 118 = 517 torr.013 × 105 Pa = 6. Pflask < Patm. Pflask > Patm. the difference in height in millimeters will be equal to the difference in pressure in millimeters of mercury between the flask and the atmosphere.28 atm 760 torr 1.013 × 105 Pa = 1. torr + 215 torr = 975 torr 975 torr × 1 atm = 1.5 mm Hg or 47.30 × 105 Pa atm 1. Pflask = 760.845 atm × 1. Pflask = 635 + 215 = 850.75 cm × 10 mm 1 atm = 47. 4. Which level is higher will tell us whether the pressure in the flask is less than or greater than atmospheric.CHAPTER 5 GASES Pressure 21.33 × 103 Pa atm 22.25 × 10−2 atm cm 760 torr 6.

The pressure is proportional to the mass of the fluid.986 atm. a.03 atm. 0.59 = 1. Pflask = 760.3 = 749 torr 749 torr × 1.6 = 781 torr 781 torr × 1.0956)PHg ⎜ ⎟ ⎟ ⎝ 13.CHAPTER 5 23. assuming the area of the column of fluid is constant).) To exert the same pressure.1 kg m/s2 = 10.00 cm × 76.01 × 105 Pa.0 cm3: mass = 76.1 N Force 10.01 × 10 2 2 Area m ⎠ cm m ⎝ (Note: 76.0956) torr = 760.03 kg 1000 g F = mg = 1. − 11.03 atm × = 1. moil = Hg oil .0cm column of mercury.0 cm = V = 76. d = density = mass .6 ⎠ ⎠ This conversion applies only to the column of silicon oil.013 × 105 Pa 1 atm = 0.1 N ⎛ 100 cm ⎞ 5 N × ⎜ = or 1. d d Hg d oil d Hg Because P is proportional to the mass of liquid: ⎛d Poil = PHg ⎜ oil ⎜ d Hg ⎝ ⎞ ⎟ = PHg ⎛ 1. 2 V= m Hg m d m m = oil . 24. a.04 × 105 Pa atm 760 torr .30 ⎞ = (0.99 × 104 Pa 760 torr atm b.0 cm × 13. VHg = Voil.01 × 105 Pa ⎟ = 1.013 × 105 Pa 1 atm = 1.03 kg × 9.0 cm Hg = 1 atm = 1.986 atm × = 9.3 m. the volume of silicon oil is the same as the volume of mercury in volume Exercise 22.03 × 103 g × 1 kg = 1. a column of water will have to contain the same mass as the 76. torr + (215 × 0. GASES 97 Suppose we have a column of mercury 1. + 20.0 cm3 × 13.81 m/s2 = 10.0956) torr = 760. The mass is proportional to the volume of the column of fluid (or to the height of the column.03 × 103 cm = 10.59 times taller or 76. Thus the column of water will have to be 13. 1.00 cm × 1. Pflask = 760. torr − (118 × 0.59 g/cm3 = 1.

a. P = nR constant = V V 1 V f.6/1.7 psi = 4. PV = nRT PV = nR = constant T PV = constant P = constant × P P PV T 1/V P V . The advantage of using a less dense fluid than mercury is in measuring small pressures. PV = nRT PV = constant b. 4. d. PV = nRT e. 4. 4.8 atm × = 71 psi atm atm Gas Laws 26.6 × 103 mm Hg × atm mm Hg = 3. PV = nRT ⎛ P ⎞ T= ⎜ ⎟ × V = const × V ⎝ nR ⎠ PV P T V T V d. 25. the height of the silicon oil column would be 13. PV = nRT ⎛ nR ⎞ P= ⎜ ⎟ × T = const × T ⎝ V ⎠ c. If we are measuring the same pressure.30 = 10. 3. a.6 × 103 torr c.6 × 103 mm Hg. b.9 × 105 Pa.98 CHAPTER 5 GASES b. Thus the measurement will be more precise.5 times the height of a mercury column.8 atm × 1.8 atm × 760 mm Hg 1 torr = 3. The height difference measured will be larger for the less dense fluid.013 × 105 Pa 14.

00 L × 760.0667 atm × = 50. PV = nRT. 27. moles × molar mass = mass P R P1 P2 n1 (molar mass)T1 n ( molar mass)T2 mass1 × T1 mass 2 × T2 . Plots b.0 g × ⎟× × 300. 1 1 = 2 2 .82 L.08 atm V 4. torr = 80. and use the relationship P1V1 = P2V2 (n and T are constant).00 × 103 g × 291 K × 650.00 = 1. For H2: P2 = P1V1 2. Treat each gas separately. 1 1 = 2 2 .00 L = 80.7 torr atm 3.08206 L atm ⎜ 22. n is constant. psi = = 309 g T2 P1 299 K × 2050. torr × = 240.200 atm × Ptotal = PH 2 + PN 2 = 317 + 50. torr × = 240 torr V1 1.00 L . torr (273 + 23) K 31. c.00 L 29. torr V2 3. torr For N2: P1 = P2 V2 3.0667 atm. V2 = 1 1 2 T T1 T2 P2 T1 30. Any equation that has this form will produce a straight line with slope equal to m and a y intercept equal to b.82 L × 220.00 L 760 torr 1. = 2 = P1 P2 P1 P2 mass2 = mass1 × T1P2 1. PV = nRT.00 L = 475 torr × = 317 torr V2 3.00 L = 360.00 L Ptotal = PH 2 + PN 2 . P = PCO 2 ⎛ 1 mol ⎞ 0.7 = 368 torr 28. and e have this straight-line form.01 g ⎟ K mol ⎝ ⎠ = = = 3. PN 2 = Ptotal − PH 2 = 320.82 − 1. torr (273 − 31) K = 2. K ⎜ n CO 2 RT 44.CHAPTER 5 GASES 99 Note: The equation for a straight line is y = mx + b where y is the y axis and x is the x axis. ΔV = 2. nT V nT n T = = constant. psi PV PV PV VPT = nR = constant. V2 = 1. For H2: P2 = P1V1 2.00 L For N2: P2 = 0. torr − 240. 0.00 L = 0.

08 atm + ⎜ 740. 4/3 π (r2 ) 3 = T1 280.05 atm Ptotal = PCO 2 + Pair = 3.100 CHAPTER 5 GASES With air present.016 g H 2 = 2.09 cm = radius of sphere after heating 280.11 × 103 mol × For H2: 1.0 × 10 2 mL (273 + 820) K = 710 torr × × = 5. PV PV PV = nR = constant. for a gas at two conditions: nT P1V1 PV P P = 2 2 . Vsphere = 4/3 πr3 T2 n1T1 n 2 T2 T1 V2 = 3 r2 = V1T2 4/3 π (1.0 × 102EC P1 758 torr P1V1 PV = 2 2 n1T1 n 2 T2 36. 1 1 = 2 2 T T1 T2 P2 = P1V1T2 5.44 × 103 g He mol 2. r2 = (1. Because the container is flexible. K 35. n= For He: 1. For a gas at two conditions: .29.974 = 4.08 + 0. torr × ⎜ 760 torr ⎟ ⎝ ⎠ 32. K 361 K = 1.11 × 103 mol × 34.003 g He = 4. because n and V are constant: 1 = 2 n1T1 n 2 T2 T1 T2 T2 = P2 T1 2500 torr × 294.00 cm) 3 × 361 K .29)1/3 = 1.) K PV 135 atm × 200.0 L = = 1.2 K = = 970 K = 7. P is assumed constant. PV = R. V P1V1 PV V = 2 2 . The moles of gas present are also constant.08 atm. The total pressure will be the sum of the partial pressures. 1 = 2 .08206 L atm RT × (273 + 24) K K mol 4.24 × 103 g H2 mol 33.11 × 103 mol 0. the partial pressure of CO2 will still be 3. ⎛ 1 atm ⎞ ⎟ = 3.1 × 104 torr V2 T1 25 mL (273 + 30.

0 mL × = 12. 1 1 = 2 2 T T1 T2 38.000 = V2 1. n O 2 = 1. 37. The unit conversions from other P or V units would cancel when applied to both conditions.50 mol × 800.00 × 103 m 3 40.50 = 1.20 × 103 m 3 × = 1 2 = = 0.77 – 1. nT n T nT P = = constant.5 mL 2 n1 n1 n2 N2O4(g) will occupy one-half the original volume of NO2(g). n2 = 1 2 1 n1T1 n 2 T2 P1T2 101 Because V is constant: n2 = 1. Using Avogadro’s law: 1 n V1 V = 2 . the moles of gas present will decrease by a factor of one-half (from the 2 : 1 mol ratio in the balanced equation).000 (273 + 58) K = 75 psi × × = 82 psi V2 T1 1.00 g O 2 . However.040 (273 + 19) K 39. torr × 298 K = 2.921 n1 T2 V1 335 K 4. P2 = V1 1. P is constant. V2 = V1 × 2 = 25. V2 = (1.CHAPTER 5 GASES P1 P nPT = 2 .80 × 102 mg O2 × 1 mol O 2 1g × = 5. There will be less math if we calculate the total pressure from the ideal gas law.63 × 10−3 mol O2 1000 mg 32. As NO2 is converted completely into N2O4. torr × 323 K Moles of gas added = n2 – n1 = 2. not necessarily atm and L. units for P and V just need to be the same units for both conditions. PV = nRT. PV PV PV = nR = constant. temperature always must be converted to the Kelvin scale. We can use the ideal gas law to calculate the partial pressure of each gas or to calculate the total pressure. PV = nRT.040 P1V1T2 1.040)V1.27 mol For two-condition problems.77 mol 400. n is constant. The temperature conversions between other units and Kelvin will not cancel each other. 1 1 = 2 2 V R V1 V2 n2 TV 294 K 4.

50 × 10 2 mL × ) 760 torr 1000 mL 0.022 × 10 23 molecules NO = 1.146 mol He 4.08206 L atm × 293 K K mol = 1.02 × 10−2 mol N2 × 43. PNO = × 0.05 × 10 − 2 mol total PO 2 = 41.05 × 10 − 2 At constant T and P.00 atm = 760.49 × 10−2 = 4. X must have the formula BrF3. For O2.49 × 10−2 mol NO ntotal = n N 2 + n O 2 + n NO = 2.00 × 10−2 + 5. χ N 2 = mole fraction of N2 4.586 g × 1 mol = 0.05 × 10 − 2 4.00 L × CHAPTER 5 GASES 1000 cm 3 9. Ptotal = 1. n N2 = = 1.126 atm.02 × 10−2 mol N2 42. In terms of balanced equations.8 torr.907 atm = 0. that is. 28.05 × 10 − 2 mol × 0. two moles of X must contain 2 moles of Br and 6 moles of F.907 atm 1. torr = PHe + 23.102 nNO = 1. . PHe = 736 torr nHe = 0.00 L Ptotal = PN 2 = χ N 2 Ptotal = 2.286 g N2 mol N 2 PHe + PH 2O = 1.02 g N 2 = 0. so P1V1 = P2V2. 5.907 atm = 0. n and T are constant.63 × 10 −3 1.5 torr.907 atm = 0.08206 L atm × 298 K K mol = 3. Br2 + 3 F2 → 2 X.08206 L atm × 273 K K mol = 0. Avogadro’s law applies.69 L 1 atm 736 torr × 760 torr V= n He RT = PHe 44. PN 2 = 743 torr PN 2 × V RT (743 torr × 1 atm 1L ) × (2.00 atm = 760. equal volumes contain equal moles of molecules.003 g 0.334 atm 4.00 × 10 −2 mol N 2 × 0.05 × 10−2 mol n total RT = V 4.49 × 10 −2 × 0.00 × 1018 molecules NO 1 mol NO × × 3 L cm 6.146 mol × 0. we can say that mole ratios and volume ratios between the various reactants and products will be equal to each other. torr = PN 2 + PH 2O = PN 2 + 17.448 atm.63 × 10−3 + 1.

If we had 100.175 atm + 0.915 = 0.412 = 0.076 mol ethane .32 atm.CHAPTER 5 P1 = GASES 103 P2 V2 1. PXe = 600.822 = 0.161 mol = 9. ntotal = Ptotal × V 0.822 mol methane nethane = 0. PH 2 O = 785 ! 761 = 24 torr 45. χ CH 4 = n CH 4 n total . − 582 = 18 torr 47.588 × 0.5 mol He + 0.0 g Xe.161 mol 0.0 g 50.03 g O2 46.588 b. 50.47 × 10−2 mol O2 × = 3.44 – 1.94 L = 785 torr × = 761 torr = PO 2 V1 2.898 ! 0.412 × 0.0 g 12.0 g of the gas.04 g CH 4 = 1. n CH 4 = χ CH 4 × n total = 0. torr = 582 torr.412 0.381 mol Xe + 4.32 = 0.970 50.44 atm × 15. Mole fraction CH4 = χ CH 4 = χ O 2 = 1. PV = nRT.06 g CH4 mol CH 4 32.250 atm c.000 – 0.898 mol natural gas 0.47 × 10−2 mol O2.898 mol × 0.08206 L atm RT × 293 K K mol nmethane = nnatural gas × χmethane = 0.175 atm = 0. Pmethane = Ptotal × χmethane = 1. The partial pressures can be determined by using the mole fractions. a.161 mol = 6.00 L = = 0.00 g O 2 mol O 2 6.425 atm × 10. 9. we would have 50.3 g/mol χ He = n He n He + n Xe PHe = χHePtotal = 0.003 g/mol = = = 0.0 g He and 50.12 atm Determining the number of moles of natural gas combusted: nnatural gas = PV 1.44 atm × 0. Pethane = 1.970 × 600.003 g/mol 131.0 g 12.5 L = = 0.5 mol He 4.63 × 10−2 mol CH4 16.00 L Ptotal = PO 2 + PH 2 O .63 × 10−2 mol CH4 × n O 2 = 0.08206 L atm RT × 338 K K mol PCH 4 Ptotal = 0.915 = 1.

02 g H 2 O × = 29. there are: 87. = 2.01 g N 1 mol H 12.104 CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l).93/2 = 35.08206 L atm × 273.977 g 0. and Reaction Stoichiometry 48. = 1.5 mol H. Gas Density. where d = density.47. Molar mass = dRT where d = density of gas in units of g/L.822 mol CH4 × CHAPTER 5 GASES 2 C2H6 + 7 O2(g) → 4 CO2(g) + 6 H2O(l) 2 mol H 2 O 18.1 g H2O 2 mol C 2 H 6 mol H 2 O 0.4 g N × 1 mol N 6. Therefore.0 g/mol 1 atm P 710. 49.0 g of compound.24 = 6. P × (molar mass) = dRT. Molar Mass.08206 L atm × × 373 K dRT L K mol Molar mass = = = 32.6 g H2O 1 mol CH 4 mol H 2 O 6 mol H 2 O 18. so the atomic mass = 70.02 g H 2 O × = 4. Out of 100. 50. P × (molar mass) = × RT volume V . the molecular formula is N2H4. and the identity of the gas is Cl2. 0. P × (molar mass) = dRT.24 12.008 g H 6.164 g/L × Molar mass = 0.0 g.7 g H2O. torr × 760 torr Empirical formula mass of NH2 = 16.076 mol C2H6 × The total mass of H2O produced = 29.6 g + 4.2 K K mol = 70.00 1.98 g/mol 1.24 mol N.1 g = 33.00 6. This is chlorine.6 g H × Empirical formula is NH2.5 = 12.24 14. 0. d = mass mass . P 3.000 atm The gas is diatomic.

08206 L atm × 373 K mass × RT K mol Molar mass = = = 96. The value of 28.0 + 35.00 2815 = (28.00 − x = the number of moles that are Ar atoms. x = 98.2 torr × ) × (22.01) + (100. If Be2+.6 × 10 L) 760 torr Data set II: 0.9 g/mol 1 atm PV (750. K mass × RT K mol molar mass = = = 202 g/mol 1 atm PV (764. (11.00 mol of total gas present.17% Ar Ratio of moles of Ar to moles of N2 = 1.17 = 1.5 = 48. the formula is Be(C5H7O2)3 and molar mass ≈ 13. the formula is Be(C5H7O2)2 and molar mass ≈ 9.5 + 15(12) + 21(1) + 6(16) = 311 g/mol.01 g/mol is the true value for the molar mass of N2.2224 g × These results are close to the expected value of 207 g/mol for Be(C5H7O2)2.00 − x = 1.15 = x(28.00 − x)(39. Thus we conclude from these data that beryllium is a divalent element with an atomic weight (mass) of 9.6 torr × ) × (26. Then 100.256 L 760 torr Mass of CHCl ≈ 12. Solving: 28.15 g/mol is the average molar mass of the amount of N2 and Ar in air.CHAPTER 5 GASES 0.0 × 10 −3 L) 760 torr 0.08206 L atm 0. torr × ) × 0. Assume 100.9 = 2.94)x = 1180.95) 100. 48.95)x.08206 L atm × 290.0 + 10(12) + 14(1) + 4(16) = 207 g/mol.01)x + 3995 − (39. % Ar = 100.2022 g × × 286 K mass × RT K mol = = 209 g/mol molar mass = 1 atm PV −3 (765. molecular formula is C2H2Cl2. 98.00. We assume that 28. 51.5. 96.800 g × 105 0.5 If Be3+.0 + 1. 52. Data set I (molar mass = dRT/P and d = mass/V): 0.18 × 10−2. and let x = the number of moles that are N2 molecules.83% N2.83 .0 g/mol.

00 − x = 1.1 × 105.84% CH4 by volume.08206 L atm × 290.12 × 10 4 mol × VH 2 = 0.64 × 10 4 mol × = 8.00 atm 55.1 × 106 L air 21 L O 2 3 mol H 2 = 3.66 × 105 L O2 × 100 L air = 4.3 − (4.66 × 105 L of O2 1.0 atm × ⎢4800 m 3 × ⎜ ⎟ × 3⎥ ⎝ m ⎠ 1000 cm ⎥ ⎢ PV ⎣ ⎦ = = 0.04)x + 400. Assume 100.08206 L atm × 290.90 g/mol P 1. 15.04 × 104 mol Mo × 1 mol MoO 3 7/2 mol O 2 × = 3. x = 98. = (12. K K mol = 7.90 = x(16.16% He by volume 54.00 mol of total gas present.04 × 104 mol Mo kg 95.04 × 104 mol Mo × 3.04)x.94 g Mo 1. K K mol = 8.00 1190.64 × 104 mol O2 mol Mo mol MoO 3 0. 1590.1 × 105 mol 2.106 CHAPTER 5 0. n H2 3 ⎡ 1L ⎤ ⎛ 100 cm ⎞ 1.42 × 105 L of H2 1.% of the total amount of H2 that had to be generated: 0. This is 80. 15.6 × 105 mol H2 .04) + (100.08206 L atm × × 273.00 L of mixture because T and P are constant.00 atm VO 2 = n O 2 RT P 3. 1. This value of x is also equal to the volume percentage of CH4 in 100.000 atm GASES 53.00 − x)(4.00 mol mixture. and let x = mol of CH4 in the 100. % He = 100.12 × 104 mol H2 mol Mo 1.1 × 105 mol H2 are in the balloon.003)x 100.90 g/mol is the average molar mass of the mixture of methane and helium.2 K dRT L K mol Molar mass = = = 15.00 × 103 kg Mo × 1000 g 1 mol Mo × = 1.08206 L atm RT × 273 K K mol = 2.003) .70902 g 0. = (16. total mol H2 = 2.80(total mol H2) = 2.

16.5 × 107 g Fe mol H 2 mol Fe 107 2.1 × 103 mol NH3 0.640 : 1).1 × 103 mol/min. In 1 minute. Because the actual volume ratio present is smaller than the required volume ratio.0 L/2 = 8.09 g H 2SO 4 100 g reagent × × = 2.00 L CH3OH are produced (theoretical yield).3 × 104 g urea/min min 2 mol NH 3 mol urea 57. we need: 1.5 × 102 mol CO2/min min 2 mol NH 3 Because 660 mol CO2/min are present. L = 1.0 L/25.6 × 105 mol H2 × 2.85 g Fe × = 1.1 × 103 mol NH 3 1 mol urea 60. 1 mol H 2SO 4 98.08206 L atm RT × 273 K K mol . Because P and T are constant. 1.6 × 102 mol/min.00 L = 0.1 × 103 mol NH 3 1 mol CO 2 × = 5. The volume of CH3OH produced at STP will be one-half the volume of H2 reacted due to the 1 : 2 mole ratio in the balanced equation. L = 6.6 × 102 mol CO2 0.08206 L atm × 496 K K mol NH3 flows into the reactor at a rate of 1.6 × 105 mol H2 × 56. To react completely with 1.6 × 107 g of 98% mol H 2 mol H 2SO 4 98 g H 2SO 4 sulfuric acid For ammonia (in 1 minute): n NH 3 = PNH 3 × VNH 3 RT = 90.06 g urea × × = 3. V and n are directly proportional. For CO2 (in 1 minute): n CO 2 = PCO 2 × VCO 2 RT = 45 atm × 600.00 atm × 8.0 L = 0.1 × 103 mol NH3/min. atm × 500. ammonia is the limiting reagent.CHAPTER 5 GASES 1 mol Fe 55.640 (0. The balanced equation requires 2 L of H2 to react with 1 L of CO (2 : 1 volume ratio due to 2 : 1 mole ratio in the balanced equation). H2 is the limiting reactant. n CH 3OH = PV 1.357 mol CH3OH in 1 minute = 0.08206 L atm × 496 K K mol CO2 flows into the reactor at 6. The actual volume ratio present in 1 minute is 16.

850 g 1 mol × = 1.00 atm × 70. K K mol = 0.85 mol O2 available = 0.02 g NaN 3 × = 135 g NaN3 3 mol N 2 mol NaN 3 Mass NaN3 reacted = 3.08206 L atm RT × 273 K K mol 2 mol NaN 3 65.74 atm = 2.00 mol O2 are required to react completely with all the CH3OH available.5 mol N2 produced 60.00 mol O2 2 mol CH 3OH 1. 1.108 0.0 mL × 0.2 atm. This is three times the moles of N2 produced.33 mol CH3OH(l) available mL 32. 60.5% yield theoretical yield 11.357 mol CH3OH × Percent yield = 58.85 mol O2.10 g mol (CH 3 ) 2 N 2 H 2 150 g (CH3)2N2H2 × PN 2 = nRT = V 7. Ptotal will be three times larger than PN 2 . 2 NaN3(s) → 2 Na(s) + 3 N2(g) n N2 = PV 1.85 mol O2 × 59.04 g CH 3OH = 11. 0.04 g n O2 = PV 2. CHAPTER 5 GASES 32.4 g CH3OH (theoretical yield per minute) mol CH 3OH 5.8 L = 1. We only have 1. K K mol 3 mol O 2 = 2.00 atm × 22.74 atm 250 L We could do a similar calculation for PH 2O and PCO 2 and then calculate Ptotal (= PN 2 + PH 2O + PCO 2 ) . so O2 is limiting.12 mol N2 are needed to fill the air bag. Therefore.08206 L atm × 300.30 g actual yield × 100 = × 100 = 46. 4 mol H 2 O = 2.4 g CH3OH + 3/2 O2 → CO2 + 2 H2O or 2 CH3OH(l) + 3 O2(g) → 2 CO2(g) + 4 H2O(g) 50. Ptotal = 3 × PN 2 = 3 × 0. Or we can recognize that 9 total moles of gaseous products form for every mole of (CH3)2N2H2 reacted.5 mol × 0.08206 L atm RT × 300.33 mol CH3OH × 2.0 L = = 3.47 mol H2O 3 mol O 2 1 mol (CH 3 ) 2 N 2 H 2 3 mol N 2 × = 7.12 mol N2 × .

549 × 10 −2 g 12.1023 g 44.253 g 64.3% N 0.44 g NaClO3 × 3 mol O 2 mol NaClO3 = 0.48 atm = = 2.08206 L atm × (273 + 22) K K mol 2 mol NaClO3 106.79% C 0. GASES 109 2 NaClO3(s) → 2 NaCl(s) + 3 O2(g) Ptotal = PO 2 + PH 2O .1023 g 18.22 × 10−3 mol O2 × 62.20 × 10−3 mol N2 H Mass % N = 3. PO 2 = Ptotal − PH 2O = 734 torr – 19.549 × 10−2 g C.11 × 10−2 g H.08206 L atm × 298 K K mol 28.CHAPTER 5 61.8765 g n O2 = PO 2 × V RT Mass NaClO3 decomposed = 2.0572 L ⎜ 714 torr × ⎜ 760 torr ⎟ ⎠ ⎝ = = 2. 0.9% H 0.158 g × 100 = 18.924 atm × 31.00.8 torr = 702 torr H PN 2 × V RT 1 atm = 0.48 atm is the pressure of the amount of F2 reacted. Ptotal = PN 2 + PH 2O .22 × 10−3 mol O2 0.36 × 10 −2 g × 100 = 13.011 g C = 7.24 atm 63. V and T are constant.158 g NaClO3 0. 10. P = constant. % H = × 100 = 10.8 × 10 −3 L = 1.009 g CO 2 1.02 g N 2 = 3. PN 2 = 726 torr – 23.10 atm − 7. n P1 P P n = 2 or 1 = 1 n1 n2 P2 n2 Mol F2 reacted 2.0991 g H2O × .924 atm 760 torr n N2 = = 0. % C = × 100 = 73.02 g H 2 O 0.2766 g CO2 × 7.20 × 10−3 mol N2 0.36 × 10−2 g nitrogen mol Mass of N in compound = 1.8 torr = 714 torr ⎛ 1 atm ⎞ ⎟ × 0.0% Mass % NaClO3 = 0.016 g H = 1. PV = nRT. so: Xe + 2 F2 → XeF4 Mol Xe reacted 1.62 atm = 2.11 × 10 −2 g 2.

195 Thus the molecular formula is C24H42N2O2.500 atm × = 0.144 mol C.02 g 0.23 × 10−3 mol N2 0.51 mol O 1.00 L = 1.510 mol N 12.2% O Out of 100.45 × 10−2 g nitrogen mol N 2 GASES 1.00 g of compound.14) = 8.00 L For O2: P2 = P1V1 1.00 g Dividing all values by 0.333 atm V2 3.01 g 10.00 L P1V1 = 0. V and T will be constant.6 × 10 −3 L = = 1.00 − (73.14% N 0.9 + 7. 7.23 × 10−3 mol N2 × Mass % N = 3.45 × 10 −2 g × 100 = 7. 4.08206 L atm RT × 273 K K mol 28.500 atm V2 3.51 gives an empirical formula of C12H21NO. For NH3: P2 = 2.08206 L atm × × 400.008 g 16.8 mol H.9 g H × 1 mol 1 mol = 10. 65.00 atm × 27.011 g 14. K dRT L K mol Molar mass = = = 392 g/mol 1 atm P 256 torr × 760 torr 392 Empirical formula mass of C12H21NO ≈ 195 g/mol and ≈ 2.00 L After the stopcock is opened. n N 2 = CHAPTER 5 PV 1.79 g C × 1 mol 1 mol = 6. there are: 73.50 atm × = 0.02 g N 2 = 3.2 g O H = 0.25 4 .14 g N × = 0.79 + 10. The balanced equation requires: n O2 n NH 3 = PO 2 PNH 3 = 5 = 1.4831 g Mass % O = 100. 8.110 PV = nRT. so P % n.

which will increase the total pressure. the pressure will decrease (by onehalf). PV = nRT.333 atm (the same as PNH 3 reacted).500 atm = 1. P n P1 P = 2 or 1 = 1 P2 n2 n1 n2 When V and T are constant. As the moles of gas particles decrease by a factor of 2. and pressure ratios are identical to mole ratios. so the density of the gas will not change because mass and volume do not change.00 atm H2O 2 atm H 2 Ptotal = PO 2 (excess) + PH 2O (produced) = 2. H2 is the limiting reagent. then pressure is directly proportional to moles of gas present. PO 2 (reacted) = 2. Rigid container (constant volume): As reactants are converted to products.00 atm H2 × 1 atm O 2 = 1. the partial pressure of NO produced is 0. H2O(g) is produced at 125°C. Density is the mass per unit volume. Mass is conserved in a chemical reaction. the moles of gas particles present decrease by one-half. The only gas present at 25°C after the reaction goes to completion will be the excess O2.00 atm O2 At 125°C: 2 H2(g) + O2(g) → 2 H2O(g). Therefore.50 0. 66. the volume of the container will decrease (by one-half). The balanced equation requires 2 mol H2 for every mol O2 reacted. V and T are constant.00 atm O2 2 atm H 2 PO 2 (excess) = PO 2 (initial) − PO 2 (reacted) = 3. PH 2O (produced) = 2. Flexible container (constant pressure): Pressure is constant because the container changes volume in order to keep a constant pressure.333 atm The actual ratio present is: The actual ratio is larger than the required ratio. At 25°C: 2 H2(g) + O2(g) → 2 H2O(l).00 atm H2O = 4.1. As n decreases.00 atm . so NH3 in the denominator is limiting. We have the same mass of gas in a smaller volume. The actual pressure ratio present is 2 atm H2 to 3 atm O2. The same ratio (2 : 1) holds true for pressure units.00 atm H2 × 2 atm H 2 O = 2. well below the required 2 : 1 ratio.00 atm 67. so the gas density will increase (is doubled). Because equal moles of NO will be produced as NH3 reacted. .CHAPTER 5 GASES PO 2 PNH 3 111 = 0.00 atm O2 + 2. The major difference in the problem is that gaseous water is now a product. H2O(l) is produced at 25°C.00 atm = 2.

In order to keep the pressure constant. which decreases the pressure). As we said earlier. CHAPTER 5 GASES Rigid container: As temperature is increased. As the volume increases. and pressure will decrease (Boyle's law). Therefore. We have the same mass of gas in a larger volume. as reactants are converted into products. Avogadro’s law: V % n at constant P and T . ⎛ RT ⎞ PV = nRT. so the pressure will double. Gas density will decrease in the flexible container as T increases. As T increases. 2 NH3(g) → N2(g) + 3 H2(g).112 68. and the volume of the container is constant. pressure is directly related to n at constant T and V. the total pressure will double from the initial pressure of NH3 as reactants are completely converted into products. Density = mass/volume. the internal pressure will be unaffected by an increase in temperature. The density of the gas. we go from 2 moles of gaseous reactants to 4 moles of gaseous products (1 mol N2 + 3 mol H2). there will be fewer collisions per unit area with the walls of the container. the volume of the gases will double (at constant P and T). PH 2 = 3/2 PNH 3 . so density must be temperature-independent (density is constant). Boyle's law: P % 1/V at constant n and T In the kinetic molecular theory (KMT). Because the moles of gas doubles as reactants are converted into products. 69. will be affected because the container volume is affected. Owing to the 3 to 2 o mole ratio in the balanced equation. the gas molecules move with a faster average velocity. Charles's law: V % T at constant n and P When a gas is heated to a higher temperature. the moles of gas will double. This results in more frequent and more forceful collisions. the velocities of the gas molecules increase and thus hit the walls of the container more often and with more force. however. o o o Note: Ptotal = PH 2 + PN 2 = 3/2 PNH 3 + 1/2 PNH 3 = 2 PNH 3 . Kinetic Molecular Theory and Real Gases 70. the moles of gas are constant. Flexible container: The flexible container is a constant-pressure container. P = ⎜ ⎟n = (constant)n. PN 2 = 1/2 PNH 3 . Because 1 o mol of N2 is produced for every 2 mol of NH3 reacted. the volume of the container must increase (this increases surface area. Therefore. ⎝ V ⎠ As the reaction occurs. The container expands its volume to reduce the internal pressure back to the external pressure. there is an immediate increase in P inside the container. which decreases the number of collisions per unit area. P is proportional to the collision frequency which is proportional to 1/V. resulting in an increase in pressure. volume and temperature are directly related at constant n and P (Charles’s law).

collide more frequently. Only temperature determines the average kinetic energy. and vii. iv. vi. Both these result in an increase in pressure. However.CHAPTER 5 GASES 113 As gas is added to a container (n increases). The order is ii = vi < i = iv = v = viii < iii = vii. c. P and n are directly related at constant V and T. gas B molecules must be heavier than gas A molecules. so n must be constant. Pressure and temperature are directly related at constant V and n. d. This results in an increase in pressure in the container. the container is such that it wants to keep the pressure constant. This is a direct relationship. and viii have twice the number of molecules present than containers i. a. Because we have equal moles of gas in each container. Because T is constant. or you can collectively group all the gases together to determine the total pressure. All have the same average kinetic energy because the temperature is the same in each container. and P are all constant. V is directly related to n at constant P and T. The heavier gas B molecules do collide more forcefully. Both gas samples have the same number of molecules present (n is constant). . P versus n relationship at constant V and T. but gas A molecules. In order to keep pressure constant. iii. T. One mole of an ideal gas behaves the same whether it is a pure gas or a mixture of gases. with the faster average velocity. v and viii) will have the same pressure between the two extremes. V. Containers iii. b. This increases the gas collision frequency as well as increases the force of each gas particle collision. v. All the other containers (i. a mixture of gases behaves as one big gas sample. You can concentrate on the partial pressures of the individual components of the mixture. b. which reduces the pressure. vii. iv. and vi. the gas molecules move with a faster average velocity. This is a direct relationship. the volume of the container increases in order to reduce the collision frequency. there will be an increase in the collision frequency. 72. The smallest container with the most moles of gas present will have the highest pressure (containers iii and vii both have the highest P). iv. resulting in an increase in pressure. Therefore. P versus T relationship at constant V and n. 71. The end result is that P is constant between the two containers. The lighter gas A molecules will have the faster average velocity. Gas molecules all behave the same way. KEave must be the same for both gases (KEave = 3/2 RT). ii. As gas is added to a container. The container with the lowest pressure will be the one which has the fewest moles of gas present in the largest volume (containers ii and vi both have the lowest P). there will be an immediate increase in the number of gas particle collisions with the walls of the container. a. v. As the temperature of the gas sample increases. Containers ii. Dalton’s law of partial pressure: Ptotal = P1 + P2 + P3 + … The KMT assumes that gas particles are volumeless and that they exert no interparticle forces on each other. and viii have volumes twice those of containers i.

3145 J and M = molar mass in kg K mol At 546 K: (KE)avg = ⎛ 3RT ⎞ urms = ⎜ ⎟ ⎝ M ⎠ 1/ 2 74. we will calculate the relative density of each. 2V1 v 2m1.3145 J ⎛ × 273 K ⎜3 × K mol ⎜ For CH4 at 273 K: urms = ⎜ 1.3145 J × × 546 K = 6. To determine average KE per molecule.604 × 10 − 2 kg/mol ⎜ ⎝ ⎞ ⎟ ⎟ ⎟ ⎟ ⎠ 1/ 2 = 652 m/s . The order is v = vi = vii = viii < i = ii = iii = iv. and d1 equals the density of the gas in container i. volume i m1. 2V1 density ⎛ ⎞ ⎜ ⎟ ⎝ volume ⎠ mass m1 V1 = d1 1 m1 = d1 2 2 V1 2 m1 V1 = 2d1 2 m1 2 V1 = d1 2 m1 V1 = 2d1 2 m1 2 V1 = d1 4 m1 V1 = 4d1 4 m1 2 V1 = 2d1 From the table.3145 J K−1 mol−1.65 × 10−21 J/molecule 2 K mol 3 8. For energy units of joules (J). The least dense gas will be in container ii because it has the fewest of the lighter Ne atoms present in the largest volume. the order of gas density is ii < i = iv = vi < iii = v = viii < vii. Container vii has the most dense gas because the largest number of the heavier Ar atoms are present in the smallest volume.022 × 1023 molecules/mol. m1 equals the mass of Ne in container i. V1 viii 4m1. In the table below.3145 J × × 273 K = 3.81 × 103 J/mol = 1. 73. the root mean square velocity only depends on the temperature and the molar mass.114 CHAPTER 5 GASES c. (KE)avg = 3/2 RT. µrms = (3RT/M)1/2. M = 2. 2V1 vii 4m1. At each temperature CH4 and N2 will have the same average KE. Container mass. 6. Because T is constant. the heavier argon molecules will have a slower root mean square velocity than the neon molecules. 8.604 × 10−2 kg and for N2. KE depends only on temperature. V1 vi 2m1. d. V1 equals the volume of container i. where R = For CH4: M = 1. use R = 8. divide by Avogadro’s number. To figure out the ordering for the other containers.802 × 10−2 kg. . At 273 K: (KE)avg = 3 8. V1 iv 2m1. V1 ii m1. 2V1 iii 2m1.40 × 103 J/mol = 5.13 × 10−20 J/molecule 2 K mol 8.

Xe (131. c. there is a distribution of energies. the numbers calculated in Exercise 74 are a special kind of average velocity. n (relative) A B C 1.CHAPTER 5 GASES 115 At 546 K: urms for CH4 is 921 m/s. the greater is the root mean square velocity (at constant T). at constant T. At each temperature. Flask C. Freq. .48 76. There is a distribution of velocities as shown in Figs. (relative) = n × uavg 1. They will all have the same average kinetic energy because they are all at the same temperature.3 g/mol) < Cl2 (70. the faster is the average velocity [uave % (1/M)1/2]. Similarly.90 g/mol) < O2 (32. No. At constant T and V. the number of collisions will double.0 0. b. 77.0 1. n is proportional to P.33 0. At constant T. the lighter H2 molecules have a faster average velocity than the heavier O2 molecules. and average velocity is proportional to (1/M)1/2. Flask A: collision frequency is proportional to average velocity × n/V (as the average velocity doubles. Separate samples of H2 and O2 can only have the same average velocities if the temperature of the O2 sample is greater than the temperature of the H2 sample. In general.0 0.00 g/mol) < H2 (2. All the gases have the same average kinetic energy because they are all at the same temperature [KEave = (3/2)RT]. the numbers calculated in Exercise 73 are the average kinetic energies at the various temperatures. the lighter the gas molecules. Note that the major reason there is a distribution of kinetic energies is because there is a distribution of velocities for any gas sample at some temperature.33 0. We use these relationships and the data in the exercise to determine the following relative values.016 g/mol) slowest fastest c. the average velocity of the gas molecules increases. Average kinetic energy depends only on temperature. As temperature increases. urms % (1/M)1/2. b. 75.17 of the text.0 3. 5. At constant T. the lighter the gas molecule.13 uavg (relative) 1. the number of collisions again doubles). For N2: urms= 493 m/s at 273 K and 697 m/s at 546 K.15 to 5. a.7 Coll. a. and as the number of molecules in the container doubles.

⎛M ⎞ Rate1 =⎜ 2⎟ ⎜M ⎟ Rate 2 ⎝ 1⎠ 1/ 2 12 80. C17 O ⎛ 30. it takes less time to move to the next collision) and the quantity n/V (as molecules per volume increases. Major disadvantages of using CO2 instead of CO: 1. freq.7 g = 0.4 ⎞ ⎟ =⎜ 1. Avg.0 mL 47.252 mol 24. ⎛M ⎞ Rate1 =⎜ 2⎟ ⎜M ⎟ Rate 2 ⎝ 1⎠ 1/ 2 . 12C16O18O and 12C17O2. Some species. 16. Advantage: CO2 isn't as toxic as CO. so Freon-12 is CF2Cl2. M1 = ? min min mol 16.00. 81. rate1 = 16. freq.04 The relative rates of effusion of 12C16O : 12C17O : 12C18O are 1. 1. Thus some species cannot be separated from each other. M1 = 121 g/mol M1 The molar mass of CF2Cl2 is equal to 121 g/mol. 79. KE (KEavg % T) u rms (u 2 ∝ T) rms Coll.502.0 ⎞ =⎜ ⎟ 12 18 C O ⎝ 29.0 ⎞ =⎜ ⎟ 12 18 C O ⎝ 28.02. Graham’s law of effusion: ⎛M ⎞ Rate1 =⎜ 2⎟ ⎜M ⎟ Rate 2 ⎝ 1⎠ 1/ 2 Let Freon-12 = gas 1 and Freon-11 = gas 2: 1.8 mL .02 : 1. M2 = .0 ⎛ 16.14 = 137.04 g 24.8 ⎜ M1 ⎟ ⎝ ⎠ 1/ 2 = 0.0 ⎠ 1/ 2 = 1. M1 = . would effuse (gaseously diffuse) at about the same rate because the masses are about equal.04 63.502)2 H M1.04 ⎞ ⎟ =⎜ 47.4 .07 ⎛ 137. C16 O ⎛ 30.04 : 1. for example.0 ⎠ 1/ 2 12 = 1.116 78. . gas Coll. 2. rate 2 = .00 ⎜ M1 ⎟ ⎝ ⎠ 1/ 2 . collision frequency increases). Can get a mixture of oxygen isotopes in CO2.04 = (0. wall Impact E (impact E % KE % T) a inc inc inc inc inc b dec dec dec dec dec c same same inc inc same CHAPTER 5 d same same inc inc same GASES Both collision frequencies are proportional to the root mean square velocity (as velocity increases.

39⎜ ⎟ atm ⎥ (1.0 L 1/ 2 4.13 atm 0.348 atm)(0.08206 L atm × 298. The ideal gas law is high by 0. a.91%.5 min ⎛ 70.5000 × 0. gas (2) = Cl2.003 ⎠ t 83.0000 ⎠ ⎢ ⎥ ⎣ ⎦ (P + 0.0 L ⎝ 4. a.13 P= nRT = V 0. 2 ⎡ ⎛n⎞ ⎤ 2 2 ⎢P + a⎜ ⎟ ⎥ (V − nb) = nRT. 1.CHAPTER 5 GASES 1/ 2 117 82.39 atm L /mol and b = 0. PV = nRT nRT = V t = 4.5000 mol × 0.0000 L b.000 ⎠ ⎢ ⎥ ⎣ ⎦ (P + 0.209.5000 ⎞ ⎢P + 1.2 K K mol = 1.0391 L/mol ⎝V⎠ ⎥ ⎢ ⎣ ⎦ 2 ⎡ ⎤ ⎛ 0.0000 L − 0.24 atm 1.11 atm.39⎜ ⎟ atm ⎥ (10.0391 L) = 12.9805 L) = 12.24 L atm ⎝ 10.11 × 100 = 0. or 84.348 atm = 12.5000 mol × P= 0. ⎛M ⎞ Rate1 =⎜ 2⎟ ⎜M ⎟ Rate 2 ⎝ 1⎠ where M = molar mass. 2 ⎡ ⎛n⎞ ⎤ 2 2 ⎢P + a⎜ ⎟ ⎥ (V – nb) = nRT.24 L atm P= 12.00348 atm)(10. 12.224 atm 10.5000 ⎞ ⎢P + 1. let gas (1) = He.000 L b.000 L − 0.2) K K mol = 12. for N2: a = 1.000 L − 0. PV = nRT 0.5 min 0. t = 19 min 4.08206 L atm × (25.348 = 12.0391 L/mol V⎠ ⎥ ⎝ ⎢ ⎣ ⎦ 2 ⎡ ⎤ ⎛ 0.90 ⎞ =⎜ ⎟ .48 − 0.39 atm L /mol and b = 0.0196 L) = 12. for N2: a = 1.0391 L) = 12.5000 × 0.24 L atm ⎝ 1.0 + 273.24 L atm .9805 L c.24 L atm − 0. 1.

O2(g) at 1273 K would behave most ideally. would be for the Cl2 sample. Therefore. with the faster average velocity. P = 1.223 atm 9. 2. The results agree to ±0. 0.24 L atm = 1. Real gas particles do exert attractive forces for each other. 1. N2. The values of a are: H2. Plot A would be for O2(g) at 273 K. a.25 86. would be for O2(g) at 1273 K. 87. d. the smaller He atoms must move at a faster average velocity than Cl2 molecules. the attractions are greatest for CO2. The kinetic molecular theory assumes that gas particles do not exert forces on each other and that gas particles are volumeless. CH4. At low pressure. and plot B would be for the He sample.08%). In Exercise 84 the pressure is around 1 atm and both gas laws show better agreement. This is due to the attractions gas particles do have for each other. CO2. . and real gas particles do have volumes.118 P + 0. The pressure measured for real gases is too low compared to ideal gases. At constant temperature. The effect of attractive forces is minimized at high temperatures because the gas particles are moving very rapidly. the average velocity of a gas will increase. Thus C3H8 should have the largest value of b because it has the largest molar mass (size).001 atm (0. Therefore. 3.244 atm L2 mol 2 . Note the average velocity in each plot is a little past the top of the peak.980 L GASES c.00348 atm = CHAPTER 5 12. The ideal gas law is valid at relatively low pressures. these attractions “hold” them back from hitting the container walls as forcefully. A gas behaves most ideally at low pressures and high temperatures. The van der Waals constant b is a measure of the size of the molecule.59. plot A. 88.39. Because a gas behaves more ideally at higher temperatures. A term is subtracted from the container volume to correct for the volume taken up by real gas molecules. and plot B. the average kinetic energy of the He gas sample will equal the average kinetic energy of the Cl2 gas sample.00348 = 1. with the slower average velocity. As temperature increases.226 atm. so the volume of the container taken up by the gas particles is negligible.226 − 0. 85. To make up for this slight decrease in pressure for real gases. In order for the average kinetic energies to be the same. 89. the container volume is relatively large (P and V are inversely related). The measured volume is too large. A fraction of the space of the container volume is taken up by the volume of the molecules themselves. the actual volume available to real gas molecules is slightly less than the container volume. Because a is a measure of intermolecular attractions. In Exercise 83 the pressure is relatively high and there is significant disagreement. b. a factor is added to the measured pressure.

) UF6 235 238 UF6 1526 × (1.00 × 1020 molecules) = 0.000 × 105 − 1526 235 238 UF6 1526 × 1. 1/ 2 = 615 m/s KEave = 3/2 RT per mol. is a large negative number. e-∞ → 0.3807 × 10−23 J/K) × 300.7 of the text. ⎛ m ⎞ f(u) = 4π ⎜ ⎟ ⎜ 2πk T ⎟ B ⎠ ⎝ 2 u 2 e ( − mu / 2 k BT ) As u → 0. At large values of u. the exponent term. As u → ∞. at small values of u. and e raised to a large negative number causes the function to decrease. K ) ⎥ ⎠ ⎥ =⎢ ⎝ ⎢ 28.CHAPTER 5 GASES 3/ 2 2 119 90.3145 kg m 2 ⎞ ⎤ ⎟ ⎢ 3⎜ ⎜ s 2 K mol ⎟ (227 + 273) K ⎥ ⎠ ⎥ =⎢ ⎝ ⎢ ⎥ 28.5358 = 98500 UF6 UF6 = 1. ⎛ 3 RT ⎞ urms = ⎜ ⎟ ⎝ M ⎠ 1/ 2 = 667 m/s ⎛ 2 RT ⎞ ump = ⎜ ⎟ ⎝ M ⎠ 1/ 2 = 545 m/s 1/ 2 ⎛ 8 RT ⎞ uavg = ⎜ ⎟ ⎝ πM ⎠ 92.003 94. KEave = 3/2 kBT per molecule KEtotal = 3/2 × (1.7097 4. Impact force (H 2 ) = Impact force (He) M H2 M He = 2. Diffusion rate Diffusion rate 235 235 238 UF6 = 1. K ) ⎥ ⎢ 8⎜ ⎜ s 2 K mol ⎟ ⎠ ⎥ =⎢ ⎝ ⎢ π (28. the force per impact at constant T is proportional to M × (1/M)1/2 = M. Because m % M. The force per impact is proportional to Δ(mu) = 2mu.3145 kg m 2 ⎞ ⎤ ⎟ (500.01 × 10−2 = initial 235U to 238U atom ratio UF6 .02 × 10 −3 kg/mol) ⎥ ⎢ ⎥ ⎢ ⎥ ⎣ ⎦ 1/ 2 1/ 2 91.621 J 93.3145 kg m 2 ⎞ ⎤ ⎟ ⎢ 2⎜ ⎜ s 2 K mol ⎟ (500. the u2 term causes the function to increase.02 × 10 −3 kg/mol ⎢ ⎥ ⎢ ⎥ ⎣ ⎦ ⎡ ⎛ 8. and u % (1/M)1/2 at constant T.0043 (See Section 5.016 = 0. -mu2/2kBT.0043)100 = . K × (1.02 × 10 −3 kg/mol ⎥ ⎢ ⎥ ⎢ ⎥ ⎣ ⎦ ⎡ ⎛ 8. e ( − mu / 2 k BT ) → e0 = 1. ⎡ ⎛ 8. the molar mass. 238 UF6 1.

Z 77 ⎛ 350. Δ (mu ) 77 Δ (mu ) 27 ⎛ 350.3537.827 The change in momentum per impact is 2.827 times as many impacts per second for He as for O2. Intermolecular collision frequency = Z = 4 N 2 ⎛ πRT ⎞ d ⎜ ⎟ V ⎝ M ⎠ 1/ 2 .08 1/ 2 ⎝ 300.827 1/ 2 1/ 2 ZO2 ⎛ 1 ⎞ ⎛ N ⎞⎛ RT ⎞ ⎜ A⎜ ⎟⎜ ⎜ 2 πM ⎟ ⎟ ⎜M ⎟ ⎟ ⎝ V ⎠⎝ He ⎠ ⎝ He ⎠ ⎛ N ⎞⎛ RT A⎜ ⎟⎜ ⎝ V ⎠⎜ 2 πM O 2 ⎝ There are 2. N ⎛ RT ⎞ ZA = A ⎜ ⎟ V ⎝ 2 πM ⎠ 1/ 2 . Because m is proportional to M. ⎠ ⎛ 300. ⎛T ⎞ Z 77 = ⎜ 77 ⎟ ⎜T ⎟ Z 27 ⎝ 27 ⎠ 1/ 2 . ⎠ 1/ 2 = 1. ⎞ =⎜ ⎟ Z 27 ⎝ 300.08 times as many impacts per second for Ar at 77°C as for Ar at 27°C.827 times larger for O2 molecules than for He atoms.120 95. CHAPTER 5 GASES Δ(mu) = 2mu = change in momentum per impact.08 There are 1.998 ⎛ 4. Δ(mu) = 2mu and u % (T/M)1/2.003 ⎞ ⎜ ⎟ 4.003 ⎝ 31. ZA = A N ⎛ RT ⎞ ⎜ ⎟ V ⎝ 2πM ⎠ 1/ 2 = collision rate 1/ 2 1/ 2 ZO2 Z He ⎞ ⎛ 1 ⎞ ⎟ ⎜ ⎟ ⎟ ⎜ MO ⎟ Z 2 ⎠ ⎠ = = ⎝ = 0.998 ⎠ 1/ 2 = 2.08 times greater for Ar at 77°C than for Ar at 27°C.08206 L atm V RT × 300.0 atm = = = 0. 96. K ⎞ 2 m⎜ ⎟ ⎝ M ⎠ 1/ 2 The change in momentum is 1. where d = diameter of He atom n P 3.12 mol/L 0. 97. the molar mass. K ⎞ 2 m⎜ ⎟ 1/ 2 ⎛ 350. ⎞ ⎝ M ⎠ = =⎜ ⎟ = 1. He = 2. K K mol . and u is proportional to (T/M)1/2: ⎛ T ∝ 2M O 2 ⎜ ⎜ MO 2 ⎝ ⎞ ⎟ ⎟ ⎠ 1/ 2 Δ(mu ) O 2 and Δ (mu ) He ⎛ T ⎞ ∝ 2M He ⎜ ⎜M ⎟ ⎟ ⎝ He ⎠ 1/ 2 1/ 2 Δ(mu ) O 2 Δ(mu ) He ⎛ T ⎞ ⎟ 2M O 2 ⎜ ⎜ MO ⎟ M O2 2 ⎠ ⎝ = = 1/ 2 M He ⎛ T ⎞ ⎟ 2M He ⎜ ⎜M ⎟ ⎝ He ⎠ 1/ 2 ⎛ M He ⎜ ⎜ MO 2 ⎝ ⎞ ⎟ ⎟ ⎠ = 31.

PCO = × 628 torr = 0.2 × 10 −6 atm = = 0. RT VCO 3.08206 L atm V RT × 298 K K mol = 2.6 × 10 21 molecules ⎛ 1 m ⎞ 6. PHe = χHe × Ptotal = 5.) ⎞ 7.3145)(300.12 mol 6.24 × 10 −6 from Table 5.2 × 10 −6 atm n P 5.1 × 10 −7 mol 1L 6. × 10 −12 m) 2 × ⎜ 3 ⎜ 4.022 × 10 23 atoms = 1.1 × 10−2 mol × c.0 × 102 L of CO. If we have 1.0 × 106 L of air.0 atm = 5.19 torr Vtotal 1.022 × 10 23 molecules 1000 L 7.0 × 10 6 b.4.2 × 10 25 molecules × × = = V L mol m3 m3 ⎛ π(8. λ = 1260 m/s = 1. PCO = χCOPtotal. χHe = 5.0 × 103 L) 760 = = 1.19 atm × (1.0 m3 air.00 × 10 −3 ⎟ m ⎝ ⎠ = 1.0 m3 of air mol 3 1. a.0 × 10 s Atmospheric Chemistry 98.0 H 109 collisions/s Mean free path = λ = u avg Z .3 × 1014 atoms He/cm3 × × L mol 1000 cm 3 99.08206 L atm × 273 K K mol 6.0 × 10 2 because V % n.3 × 10−6 m 9 −1 1.2 × 10 25 molecules ⎟ Z= 4× × (50.CHAPTER 5 GASES 121 N 0. 1 m3 = 1000 L: nCO 0. then there are 3.02 × 10 23 molecules = 6. u avg ⎛ 8 RT ⎞ =⎜ ⎟ ⎝ πM ⎠ 1/ 2 1/ 2 = 1260 m/s.1 × 10−2 mol CO 0.6 × 1021 CO molecules in 1. nCO = Assuming 1.1 × 10 −7 mol He/L 2.6 × 1015 molecules CO ⎟ = ×⎜ ⎜ 100 cm ⎟ m3 cm 3 ⎝ ⎠ .24 × 10 −6 × 1. χCO = PCO V . 6.

47 × 10−3 ppmv 3.47 ppbv total vol.022 × 10 23 molecules × × 3. reaction with atmospheric H2O 2 HNO3(aq) + CaCO3(s) → Ca(NO3)2(aq) + H2O(l) + CO2(g) H2SO4(aq) + CaCO3(s) → CaSO4(aq) + H2O(l) + CO2(g) GASES 101. combustion of coal 2 SO2(g) + O2(g) → 2 SO3(g). reaction with atmospheric H2O S(s) + O2(g) → SO2(g).15 × 10−9 mol benzene 78.31 × 1011 molecules benzene/cm3 For toluene: 153 × 10−9 g C7H8 × 1 mol = 1.00 L 1. 3. automobile combustion or formed by lightning 2 NO(g) + O2(g) → 2 NO2(g).66 × 10−9 mol toluene 92.13 g .84 × 10 −8 L = × 109 = 9.00 L or ppbv = vol.84 × 10 −8 L × 106 = 9. of X × 109 2. reaction with atmospheric O2 2 NO2(g) + H2O(l) → HNO3(aq) + HNO2(aq).84 × 10−8 L 1 atm 748 torr × 760 torr Vbenzene = n benzene RT = P Mixing ratio = 2. For benzene: 89.08206 L atm × 296 K K mol = 2.11 g 1. reaction with atmospheric O2 H2O(l) + SO3(g) → H2SO4(aq).00 L mol 1000 cm 3 = 2.15 × 10 −9 mol benzene 1L 6. CHAPTER 5 N2(g) + O2(g) → 2 NO(g).6 × 10-9 g × 1 mol = 1.122 100.15 × 10 −9 mol × 0.

=) 75 mL not occupied by the liquid (headspace). Because k = nRT.00 L mol 1000 cm 3 = 3. we can assume that Boyle’s data and the Example 5.10 × 10 −8 L × 106 = 1.0 g 1. enough CO2 will dissolve in the wine to lower the pressure of CO2 to a much more reasonable value. 14. mL C2H5OH present 100 mL juice 90. from Example 5.CHAPTER 5 GASES 1.00 L 1.54 cm 10 mm 1 atm 1L ⎛ 2. mL juice × 12 mL C 2 H 5 OH = 90.10 × 10−8 L Mixing ratio = 4.1 data were taken at different temperatures and/or had different sample sizes (different moles).08206 L atm × 310.8 × 10 −3 mol × 0.54 cm ⎞ × × × ⎜ ⎟ × in 1 cm 760 mm ⎝ in ⎠ 1000 cm 3 = 0.8 × 10−3 mol O2 mL 32.07 C 2 H 5 OH 2 mol C 2 H 5 OH The CO2 will occupy (825 − 750.5 mol × = 0.08206 L atm × 298 K K mol = 490 atm 75 × 10 −3 L PCO 2 = n CO 2 RT V Actually. 1.1 of the text.149 g 1 mol O 2 × = 1.1 × 102 in Hg C in3 × 2.022 × 10 23 molecules × × 3.08206 L atm × 296 K K mol 1 atm 748 torr × 760 torr 123 Vtoluene = n toluene RT = P = 4. where k = nRT.79 g C 2 H 5 OH 1 mol C 2 H 5 OH 2 mol CO 2 × × = 1.37 × 10−2 ppmv (or 13. mL C2H5OH × 0. the k values are around 22 atm L.0 atm V= nRT = P 104. .6 × 10−2 L = 46 mL 1. 0. 750.66 × 10 −9 mol × 0.050 mL × 1. K K mol = 4.7 ppbv) 3.66 × 10 −9 mol toluene 1L 6. 103.772 atm L 3 Boyle’s law: PV = k.5 mol CO2 mL C 2 H 5 OH 46.33 × 1011 molecules toluene/cm3 Additional Exercises 102.

4 m3 3 3 (Note: Radius = diameter/2 = 5.200 mol Cl Mol Cl = = = 4.00 1 mol Mn Mol Mn 0.100 mol H2 × 0.31 × 103 mol air n= 0.200 mol Cl 0.70 × 104 g mol 745 atm × 6.100 mol H2 0.200 mol Cl x mol H 2 2 Mol Cl in compound = mol HCl = 0.951 atm × 3.00/2 = 2.22 L = = 0. Volume of hot air: V = 4 3 4 πr = π( 2.54 × 10 4 L PV 760 = = 2.54 × 10 4 L ⎜ 760 torr ⎟ PV ⎠ = ⎝ = 2.66 × 103 mol × 29.4 m3 × ⎜ = 6.71 × 104 g mol Lift = 7.50 m) 3 = 65.08206 L atm RT × (273 + 65) K K mol Mass of hot air = 2.05000 mol Mn 2. 106. a.08206 L atm RT × ( 273 + 21) K K mol Mass of air displaced = 2.747 g Mn × 54.66 × 103 mol air Air displaced: n = 0.70 × 104 g = 1.50 m) 1L ⎛ 10 dm ⎞ 65. Mn(s) + x HCl(g) → MnClx(s) + n H2 = x H 2 (g) 2 CHAPTER 5 GASES PV 0.124 105.01 × 104 g .0 g = 6.94 g Mn The formula of compound is MnCl4.0 g = 7.54 × 104 L ⎟ × m ⎠ dm 3 ⎝ 3 ⎛ 1 atm ⎞ ⎜ 745 torr × ⎟ × 6.71 × 104 g − 6.08206 L atm RT × 373 K K mol x mol Cl = 0.31 × 103 mol × 29.

08206 L atm RT × 265 K K mol 29. because P.25 × 103 mol air Air displaced: n = 0.66 × 103 mol.65 × 104 g 630. 2. Mass of He = 2. Hot air: n = = = 1. V and T are constant. Mass of air displaced is the same. The reactant that produces the smallest amount of product will run out first and is the limiting reagent.70 × 104 g (from part a) 745 atm × (6.56 × 104 g of air displaced 2.66 × 104 g of hot air mol 630. Moles of He in balloon will be the same as moles of air displaced.06 × 104 g mol Lift = 7.53 × 104 g − 5.86 × 104 g 107.0 g = 6.53 × 104 g of air displaced mol Lift = 6.25 × 103 mol × 29.6.003 g = 1. 7.56 × 104 g . 2 = 2 n1 n 2 P1 n1 We will do this limiting-reagent problem using an alternative method than described in Chapter 3. atm × (6.95 × 103 mol air 0. .95 × 103 mol × mol Lift = 8.0 g = 8. PV = nRT.7 × 103 g d.95 × 103 mol × 29.54 × 10 4 L) PV 760 c.66 × 104 g = 8.CHAPTER 5 GASES 125 b.0 g = 5.70 × 104 g = 1. Mass of hot air = 6.06 × 104 g = 6.08206 L atm RT × 338 K K mol 1. Let's calculate the partial pressure of C3H3N that can be produced from each of the starting materials assuming each reactant is limiting.54 × 10 4 L) PV 760 = = 2.54 × 10 4 L) PV 760 Air displaced: n = = = 2. V.66 × 103 mol × 4. atm × (6.71 × 104 g − 1.71 × 104 g.95 × 103 mol air 0. P1 P P n = 2.08206 L atm RT × 294 K K mol 2. and T are the same.

3 mol C3H3N 0.08206 L atm RT × 298 K K mol 53.800 MPa × CHAPTER 5 2 MPa C 3 H 3 N = 0.94 atm 1. L = = 30.94 atm × 150. Ptotal = PH 2 + PH 2O . 1.32 g MgO 1 mol CO 2 mol MgO 2.56 × 10−3 mol H2 × . = 350.990 atm = PH 2 760 torr 109.042 = 0.85 g 1 atm .00 L PV 760 n= = = 5.013 × 105 Pa n = PV 4.990 atm × 0.75 × 10−2 mol CO2 0. Although more product could be produced from NH3 and O2.38 g Zn × = 0.08206 L atm RT × 293 K K mol 5.06 g = 1.31 g MgO × = 2. torr.500 × 106 Pa × 1 atm = 4.75 × 10−2 mol CO2 × Mass % MgO = 1 mol MgO 40.032 atm = PH 2 + 32 torr × n H2 = PH 2 V RT = 0.500 MPa × 2 MPa C 3 H 3 N = 1. .08206 L atm × 303 K K mol 1 mol Zn 65.500 MPa of C3H3N. 1.3 mol × 108.126 PC3H 3 N = 0.390.4% MgO 2. The partial pressure of C3H3N in atmospheres after the reaction is: 0.500 MPa × PC3H 3 N = 0. mol 30.800 MPa if NH3 is limiting 2 MPa NH 3 GASES PC3H 3 N = 1.32 g × 100 = 81.000 MPa if O2 is limiting 3 MPa O 2 C3H6 is limiting.61 × 103 g C3H3N can be produced. atm × 3. Thus the number of moles of CO2 that reacts is given by: 350. there is only enough C3H6 to produce 0.56 × 10−3 mol H2 0.032 − 0.625 g Zn mol H 2 mol Zn 9. The partial pressure of CO2 that reacted is 740.240 L = 9.500 MPa if C3H6 is limiting 2 MPa C 3 H 6 2 MPa C 3 H 3 N = 0.

00 atm and the total pressure is 2. From the balanced equation. V % n because P and T are constant. GASES 127 a. Initially PN 2 = PH 2 = 1.0 L) = 10. The total pressure after reaction will also be 2.00 L + 2. there must be equal moles of N2 and H2 present initially.0 torr He V2 4.00 atm because we have a constant-pressure container.00 atm = PN 2 + PNH 3 . solving: PN 2 = 1. N2(g) + 3 H2(g) → 2 NH3(g). torr H = 50. equal moles of N2(g) and NH3(g) are present (2x/3). The moles of gas present initially are: n N 2 + n H 2 = x + x = 2x mol After reaction. H2 will be limiting because three times as many moles of H2 are required to react as compared to moles of N2. Because equal moles are present. Let x = mol N2 = mol H2 that are present initially.00 L .00 L. the total volume is 1. Ptotal = 2. Mol NH3 produced = x mol H2 × 2 mol NH 3 = 2x/3 3 mol H 2 Mol N2 reacted = x mol H2 × 1 mol N 2 = x/3 3 mol H 2 Mol N2 remaining = x mol N2 present initially − x/3 mol N2 reacted = 2x/3 mol N2 After the reaction goes to completion. Because V and T are constant before the reaction takes place. none of the H2 remains (it is the limiting reagent). After the reaction occurs.00 atm = PNH 3 b. so: V = 2/3(15. P1V1 = P2V2.CHAPTER 5 110.00 L = 200.00 L = 4. the partial pressure of each gas must be equal (PN 2 = PNH 3 ). the moles of gas present are: n N 2 + n NH 3 = 2x 2x + = 4x/3 mol 3 3 Vafter n 4 x/ 3 2 = after = = 2x 3 Vinitial n initial The volume of the container will be two-thirds the original volume.0 L 111.00 L + 1.00 atm (Ptotal = PN 2 + PH 2 ). For He: P2 = P1 V1 1.

100 atm H atm 4.0 + 76. 2 H2(g) + O2(g) → 2 H2O(g).75.0 + 90. Mol O2 reacted = x mol H2 × 1 mol O 2 = x/2 mol O2 2 mol H 2 Mol O2 remaining = x mol O2 initially − x/2 mol O2 reacted = x/2 mol O2 Mol H2O produced = x mol H2 × 2 mol H 2 O = x mol H2O 2 mol H 2 Total moles gas initially = x mol H2 + x mol O2 = 2x Total moles gas after reaction = x/2 mol O2 + x mol H2O = (1.0% theoretical yield 268 g Percent yield = b.5)x nf V (1.3 kPa atm = 90.45 g HSiCl 3 4 mol HSiCl 3 This is the theoretical yield. volume ratios will equal mole ratios (Vf /Vi = nf /ni).0 torr Ar Ptotal = 50.5) x 1. no H2 will be present after the reaction goes to completion. Vf/Vi = 0.386 mol SiH4 135. excess O2(g) will be present as well as the H2O(g) produced.0 kPa × × 4.00 L = 76. 0. because P and T are constant. 12. but only a 1 : 1 mole ratio is present.400 atm H CHAPTER 5 GASES 760 torr 1.128 For Ne: P2 = 0.0 kPa × = 12. Therefore.75 : l or 3 : 4 ni Vi 2x 2 113.45 g HSiCl 3 × = 268 g HSiCl3 3 mol HCl mol HSiCl 3 actual yield 209 g × 100 = × 100 = 78.1%. Let x = mol H2 = mol O2 present initially.00 L 1 atm 760 torr For Ar: P2 = 24.08206 L atm RT × 308 K K mol 5. H2 will be limiting because a 2 : 1 H2 to O2 mole ratio is required by the balanced equation.0 = 216.0 kPa.34 g = 209 g HSiCl3 = actual yield of HSiCl3 mL nHCl = PV 10. 209 g HiSCl3 × 1 mol HSiCl 3 1 mol SiH 4 × = 0. a.0 L = = 5. If the percent yield is 93.00 L 101. However.100 atm.0 atm × 15.00 L 2. then the actual yield is: .93 mol HCl 0. 156 mL × 1.93 mol HCl × 1 mol HSiCl 3 135.0 torr Ne = 0.0 torr 112.5 = f = = = 0.

359 mol × 0.01 mg C 9.60 mg × 100 = 13.1% C 44. 2.00 14.01 mg CO 2 35.00 2.6 × 10 −3 L 760 = = = 1.0 1 mol = 5.1 mg H2O × n N2 740. 33.02 g N 2 = 3.02 mg H 2 O 35.0 g: 26.14 mg = 9.907 L = 907 mL SiH4 114.2 mg Or we can get % N by difference: % N = 100.14 mg C.4 = 1.17 13. M = (1.386 mol SiH4 × 0. 12.8 mg × 100 = 61.CHAPTER 5 GASES 0.01 g 2.008 g 1 mol 4.08206 L atm × 308 K K mol 10.1 g C × 1 mol = 2.0 mol H.60 mg H.6 Empirical formula mass of CH6N2 ≈ 12 + 6 + 28 = 46.34 = 4.17 mol C. % C = × 100 = 26.8% Out of 100.7 g/mol 24.8 mg nitrogen mol N 2 1. = 2.016 mg H 4. Thus the molecular formula is also CH6N2.07)2 × 39.359 mol SiH4 0.08206 L atm RT × 298 K K mol PN 2 V 28. .5 mg CO2 × 12.07.1 g H × 13.0 atm 129 VSiH 4 = nRT = P = 0.17 1.0 mg 2.95 ⎠ 1/ 2 = 26.98 × 10−2 g nitrogen = 39.0% N 65.931 = 0.1) = 60. % H = 18.42 × 10−3 mol N2 0.(26.0 .42 × 10-3 mol N2 × Mass % N = 39.17 60. atm × 35.1% H = 4.0 mg 41.8 g N × Empirical formula is CH6N2. Rate1 ⎛ M ⎞ =⎜ ⎟ Rate 2 ⎝ 39.95 = 45.01 g 2.17 = 1.1 + 13.99 = 13.34 mol N.

y = mx + b.00 L). However.5 of a balloon. Average velocity % (1/M)1/2 at constant T.0 atm of He in the tank. 0. Condition (2) will correspond to the filled balloons with P2 = 1.650( n CH 4 + 5. where constant = . 1490 balloons.0 L = 1. 3.00 = 199 atm and V1 = 15. each at a volume of 2. .71 = (0. y = b + mx) b. = α + βP n (straight line. where N is the number of filled balloons. so N = 1492 balloons. We must leave 1. or to 3 significant figures. PV = nRT = constant.6 kJ 1/ 2 118. 199 atm × 15.350)n CH 4 . so P1 = 200. P1V1 = P2V2 GASES Let condition (1) correspond to He from the tank that can be used to fill balloons.650 = 39. we can't fill 0. nAr = n CH 4 n CH 4 228 g = 5.71 mol Ar.00 atm and V2 = N(2. χ CH 4 = . PV a.130 115.00 L). Δ (mu ) ⎛T⎞ = 2mu ∝ M⎜ ⎟ impact ⎝M⎠ = M at constant T PV n slope = m = β y intercept = b = α P c.06 × 104 J = 60.71) = n CH 4 . 0.71 mol) × 3/2 × 8.0 L.95 g/mol n CH 4 + n Ar n CH 4 + 5.00 atm × N(2. N = 1492. CHAPTER 5 We will apply Boyle’s law to solve.3145 J K−1 mol−1 × 298 K = 6.6 + 5. P = Δmu impact α M nR (T° C + 273) nR = constant (T°C + 273).71 117. − 1. 116. the pressures will eventually equalize once the gases have had time to mix thoroughly. V V This is in the form of the straight line equation.00 L. n CH 4 = 10.5. TK = TEC + 273. the pressure in container A will increase initially because the lighter H2 molecules will effuse into container A faster than air will escape container A.6 mol CH4 KEavg = 3 RT for 1 mol 2 Thus KEtotal = (10.

00 g of Z.01) + 4(16.5858 mol Ni 58. d.000 15.CHAPTER 5 GASES 131 P 273 nR V slope = m = nR V y intercept = b = T(oC) 273 nR V 119. V= 120.960 − 1. we have: 34.648 × 10-2 .13 g C × 37.342 = 2.8 g/mol c.95 ⎞ =⎜ ⎟ ⎜ M ⎟ Z ⎠ ⎝ 1/ 2 1/ 2 .16 × 10 −5 mol) × 0.250 atm = 7.4837 = ⎜ ⎜ M ⎟ ⎟ Z ⎠ ⎝ .00 × 10−3 L V 0. Mz = 170. = 4.999 g 0.69 + 4(12. b.250 atm. Mol of He removed = PV 1. because initial mol Ar = mol Z: ⎛ 39.343 = 2.4837.011 g 1 mol 2. 7.75 × 10 −3 L) = = 7. The original concentration of Z molecules to Ar atoms is a 1 : 1 ratio. Out of 100.342 mol C.08206 L atm RT × 298 K K mol In the original flask. Each effusion step changes the concentration of Z in the gas by a factor of 0.95 ⎞ 0. ⎛M ⎞ Rate Z = ⎜ Ar ⎟ Rate Ar ⎜ M Z ⎟ ⎠ ⎝ 1/ 2 ⎛ 39.00 atm × (1.08206 L atm K −1 mol −1 × 298 K = = 7.16 × 10−5 mol of He exerted a partial pressure of 1.38 g Ni × 28.73 g/mol Molecular formula is also NiC4O4.4837)5 = 2.48 g O × 1 mol = 0.710 = 0.5858 The empirical formula is NiC4O4. = 3.16 × 10−5 mol He 0. After 5 stages: nZ/nAr = (0. NiC4O4: M = 58.00) = 170.00 mL a.998 0. nRT (7.5858 12.69 g 1 mol 2.343 mol O.

41 mol(29 g/mol − 4. L = = 0. we need at least 23. methane and ammonia are in stoichiometric amounts and oxygen is in excess. This is a lot of balloons. In 1 second: n CH 4 = PV 1. The difference in this mass is the lift of the balloon. To lift 23 kg = 23.576 mol CH 4 2 mol HCN 27. 123. 2a = b + 2c + d (O balance) 2d = 4 (H balance).08206 L atm K −1 mol −1 × 423 K 0. We assumed a pressure of 1.576 mol CH4 RT 0.00 atm . The balloon displaces air as it is filled. but the displaced air has more mass than the helium. 2 CH4(g) + 2 NH3(g) + 3 O2(g) → 2 HCN(g) + 6 H2O(g) CHAPTER 5 GASES b. Volumes of gases are proportional to moles at constant T and P. b.fig. d = 2 = 2.00 mol CH4 (16.6 L (1 extra sig .0 atm and a temperature of 25°C (298 K). as does the helium in the balloon.0 g/mol = molar mass).0 L = = 0. a. 50.000 g.454 kg/lb = 23 kg n= PV 1.00 (C balance).) P 1. a.00 mol H2O Vinitial = nRT 3.132 121. the difference in mass is directly related to the difference in density between air and helium. Because volume is constant.003 g/mol) = 10.00 mol × 0.6 g HCN/s s 2 mol CH 4 mol HCN Challenge Problems 122. lb × 0. The displaced air has mass.000/10 = 2300 balloons. g. Initially we have 1.08206 L atm K −1 mol −1 × 425 K = = 104.41 mol gas 0.0 g/mol = molar mass) and 2.08206 L atm RT × 298 K K mol The lift of one balloon is: 0.00 mol O2 (32. Using the balanced equation.03 g HCN × × = 15.00 atm × 20. CH4(g) + a O2(g) → b CO(g) + c CO2(g) + d H2O(g) b + c = 1.0 atm × 10.

solving gives b = 0. an expression for the total moles of gas present at completion is: b + c + 2. Because b + c = 1. From the O balance equation: 2a = 3.00 mol CH4 = 0. fig. Thus: ZA ∝ N T N T Z1 = 1 1 = 2.15 total moles of gas 0. 124.00.00.30 (or 30. a. V= volume of container.7648 g/L (1 extra sig.9 L = = 3.) nfinal = PV 1. P ∝ nT (also.70 Because b + c = 1.70 = b + 2c + 2. and N1T1 = N2T2 Z2 N 2 T2 .00 mol H2O was determined previously.00.% by moles of the reacted methane forms CO).15. n ∝ N). Note: d = 2. Vfinal = Vinitial × Vfinal = 109. Because both He samples are in separate containers of the same volume.00 – a) = 3.30 mol CO/1. O2 is in excess. solving gives a = 1. and M = molar mass of gas particles in kilograms. b + 2c = 1.CHAPTER 5 GASES 80.7648 g/L = 104.) 104.30 mol CO and c = 0.6 L 133 Densityinitial = Because mass is constant: mass = Vinitial × dinitial = Vfinal × dfinal.70 mol CO2. Indeed. fig. Because pressure and volume are constant.85 mol O2 reacted.7282 g/L Assuming an excess of O2 is present after reaction.08206 L atm RT × 425 K K mol d initial 0.9 L (1 extra sig. The fraction of methane that reacts to form CO is 0.00 + (2.00 atm × 109. T = temperature (Kelvin). V and M are constant. The number of collisions of gas particles with the walls of the container is proportional to: ZA ∝ N V T M where N = number of gas particles.0 g = 0.6 L × d final 0.

b. the balloon will expand (P and n remain constant). the balloon will rise. The mass of the balloon is the same. . Assuming the balloon has no mass. Above this temperature. 2 T1 = T2 N2 T1 T1 T1 T2 CHAPTER 5 GASES Thus: Solving: 4T1 = T2.105 g × 100 0.01355)x.02 × 10−3 mol H2 = mol H2 from Cr reaction + mol H2 from Zn reaction From the balanced equation: 9. b.225 L ⎜ 750.257 g 0. the balloon will float in air.01530)y −0. Cr(s) + 3 HCl(aq) → CrCl3(aq) + 3/2 H2(g). When the balloon is heated. and P is constant.48 × 10 −3 = 0.02885)x + (0. because P ∝ nT.105 g Zn. then: x + y = 0.134 2 T2 N1 T 2T1 T = = 2.01530)y 3.362 g − 0. the balloon will rise. so the density of the argon in the balloon decreases.02 × 10−3 mol H2 0.01530)x − (0.02 × 10−3 = (0.362 g and 9. = 2 .257 g = 0.362 = −(0.02 × 10−3 mol H2 = mol Cr × (3/2) + mol Zn × 1 Let x = mass of Cr and y = mass of Zn. the gas particles are hitting with less forceful collisions.08206 L atm RT × (273 + 27) K K mol 9. There are two times the number of collisions.48 × 10−3 = (0. Solving by simultaneous equations: 9.38 We have two equations and two unknowns. T1 = 1/4 T2. but the volume increases.02 × 10−3 = y (1.01355 y = mass of Zn = 0. mass % Zn = 0. when the density of the argon equals the density of air. a. n1 = 4n2. the temperature is onefourth that of container 2.362 g = 29. x = mass of Cr = 3. This is so because there are four times the number of moles of helium gas in container 1. When the density is less than that of air. torr × ⎜ 760 torr ⎟ PV ⎠ ⎝ Mol H2 produced = n = = = 9.01530 × 0. Although the number of collisions in container 1 is twice as high.00 65.0% Zn 126. 125. Zn(s) + 2 HCl(aq) → ZnCl2(aq) + H2(g) ⎛ 1 atm ⎞ ⎟ × 0. Overall.5) x + 52. but because the temperature is lower. the pressure is the same in each container.

6 From these data.00 g/mol = 28.9 g/mol = 1. (0.08 g/mol. 127.08206 L atm RT × 303.210 × 32.15°C.9460(x + 100.2 K K mol 230.3 and 56.00 atm × 28. CaO(s) + CO2(g) → CaCO3(s) 750.0595 mol CO2 ni = 0. P and molar mass are constant. 1.18 g/L 0.2 K K mol 0. BaO(s) + CO2(g) → BaCO3(s). T = x + °C.00 atm × 39.0) (1. the mixture contains 0.33 153. The molar masses of BaO and CaO are 153. x = 272.0413 mol CO2 reacted Because each metal reacts 1 : 1 with CO2. Let x = mass of BaO and y = mass of CaO. 128.3470)x = 94. The actual value is −273. atm × 1.9 g/mol dair = 1.60.6°C. where T is in kelvin (K). atm × 1.2930)x = (0.CHAPTER 5 dair = GASES P • MM air .2930(x + 0.18 g/L. T = 413 K 0. Molar mass = dRT P × molar mass .50 L Pf V 760 nf = = final moles of CO2 = = 0.02 g/mol + 0.60.08 .3 56. respectively.734)y = 6.08206 L atm RT × 303. where MMair = average molar mass of air RT 135 MMair = 0.790 × 28.0413 mol of BaO and CaO. absolute zero would be −272.0595 − 0.°C and the balloon will float. so: x + y = 5. dT = = constant P R d = constant(1/T) or d1T1 = d2T2.0) = 0.08206 L atm × 298 K K mol 1.9460)x + 94.0413 mol or x + (2.50 L Pi V 760 = initial moles of CO2 = = 0.95 g/mol = 1.14 g and x y + = 0.0182 = 0.0182 mol CO2 0.08206 L atm ×T K mol dargon = Heat the Ar above 413 K or 140.

Thus. The equation that determines the probability that a gas molecule has a certain velocity is: ⎛ m ⎞ f(u) = 4π ⎜ ⎜ 2 πk T ⎟ ⎟ B ⎠ ⎝ 3/ 2 u 2 e − mu 2 / 2 k BT Let Tx = the unknown temperature.00°C.19/1. y = 1. = = = 87.686 g CaO and 5. % CaO = 100.0 = 2.93 T1 M1 THe M He 4.6% BaO. since the probability of the gas particle with the most probable velocity decreased by one-half.0 − 86.19.08206 × 273.33 −y = −5. × molar mass = d nRT V P RT βRTP molar mass P = 1 + βP . then the temperature must be higher than 300. we get a y intercept = b = 1.136 Solving by simultaneous equations: x + (2. At 0.398 130.14 −x (1.14 g 129.686 y = 0. K. then: . = × + d molar mass molar mass RT d This is in the equation for a straight line: y = b + mx.14 − y = x = 4.734)y = 1. PV n = 1 + βP.6 = 13.398 = RT/molar mass. ZA 1/ 2 ⎛ N ⎞ ⎛ RT ⎞ = A⎜ ⎟⎜ ⎟ . M1T2 = M2T1 M UF6 T2 M TUF6 352.16 shows the effect of temperature on the Maxwell-Boltzmann distribution of velocities of molecules. Figure 5. ⎝ V ⎠ ⎝ 2πM ⎠ ⎛ T1 ⎞ ⎜ ⎜M ⎟ ⎟ Z1 = ⎝ 1 ⎠ 1/ 2 Z2 ⎛ T2 ⎞ ⎜ ⎜M ⎟ ⎟ ⎝ 2⎠ 1/ 2 ⎛M T ⎞ = ⎜ 2 1⎟ ⎜M T ⎟ ⎝ 1 2⎠ 1/ 2 = 1. Note that as temperature increases.4% CaO 5.00.45 g BaO CHAPTER 5 GASES Mass % BaO = 4. 1.45 g BaO × 100 = 86.734 = 0. If we plot P/d versus P and extrapolate to P = 0.03 g/mol. molar mass = 0.15 = 16. the probability that a gas particle has the most probable velocity decreases.734)y = 6.003 131.

. + Pk.6 of the text. for k different types of gas molecules in a mixture. the volume of the individual particles can be assumed to be negligible. Tx = 1.CHAPTER 5 GASES 3/ 2 137 ⎛ m ⎞ − mu 2 . x e ⎟ f (u mp. there exist k different types of gas molecules. 300 ) 2 ⎛ ⎞ m − mu 2 / 2k T ⎟ u 2 . x / 2 k B Tx 2 mp 4 π⎜ ⎜ 2πk T ⎟ u mp. K ⎞ 1 3 =⎜ ⎜ T ⎟ . Tx is higher than 300. For a mixture of gases in a cube. the force on the cube = Fi = (2mi/L)ui2. the average kinetic energy of a collection of gas particles is assumed to be directly proportional to the Kelvin temperature of the gas. 132. For each type (i) of gas molecule. 300 B 300 4 π⎜ mp ⎜ 2πk T ⎟ B 300 ⎠ ⎝ Because ump = ⎛ 1 ⎜ ⎜T ⎝ x 2k B T . the total force for all the gas molecules in the mixture is: Ftotal = ∑ 2m i 2 (u i ) i =1 L k . the collisions of the particles with the walls of the container are the cause of the pressure exerted by the gas.20 × 10 K ⎟ 2 x ⎝ ⎠ As expected. Solving for Tx: mp ⎛ 300. 3. 300 e mp . the temperatures cancel. x ) 1 B x ⎠ ⎝ = = 3/ 2 f (u mp. Dalton’s law states: Ptotal = P1 + P2 + . the particles assert no forces on each other. the equation reduces to: m 3/ 2 ⎞ ⎟ (Tx ) 1/ 2 ⎟ ⎛ T300 ⎞ 1 ⎠ = =⎜ 3/ 2 ⎜ T ⎟ ⎟ 2 ⎛ 1 ⎞ ⎝ x ⎠ ⎜ ⎜ T ⎟ (T300 ) ⎟ ⎝ 300 ⎠ Note that the overall exponent term cancels from the expression when 2kBT/m is substituted for u 2 in the exponent term. 2.. The derivation is very similar to the ideal gas law derivation covered in Section 5. K. Because the gas particles are assumed noninteracting. 4. The postulates of the kinetic molecular theory are: 1.

00 × 1018. where NA = Avogadro’s number ⎞ ⎛1 Because molar KEi.00 × 1018 where ZA is the collision frequency of the gas particles with the walls of the container and Z is the intermolecular collision frequency. Note that no additional assumptions are necessary other than the postulates of the kinetic molecular theory and the conclusions drawn from the ideal gas law derivation.2 × 10−11 m) = 6. the expression for total pressure can be written as: ⎠ ⎝2 k 2 3 Ptotal = ∑ n i N a ( 1 m i u i2 ) 2 V = i =1 ∑ k 2 3 n i KE i . where V is the volume of the cube Total pressure due to the number of moles of different gases is: Ptotal = ∑ n i N a m i (u i2 ) i =1 k 3V .1 dm. which is: Ftotal = GASES ∑ 2m i 2 (u i ) i =1 L k Pressure due to the average particle in this gas mixture of k types is the average total force divided by the total area. avg is proportional to T and is equal to Ptotal = ∑ k i =1 n i RT = V ∑ Pi i =1 k because Pi = n i RT V This is Dalton’s law of partial pressure. avg V 3 RT . then: 2 i =1 Assuming molar KEi. From the problem.11 m = 1. . From the text: ZA = Z A 4 N RT V 2π M N 2 π RT d V M = 1. 1. and then for R gives R = 0.4 × 10−11 m. Solving the above expression for A. avg = N a ⎜ m i u i2 ⎟. we want ZA/Z = 1. He diameter = d = 2(3. then the area A of one cube face is R2 and the total area in the cube is 6R2 (6 faces/cube). 133.138 CHAPTER 5 Now we want the average force for each type of gas particle. The expression for pressure is: P= ∑ 2m i 2 (u i ) i =1 L 6L 2 k = ∑ m i (u i2 ) i =1 k 3V .00 × 1018 = A 4d π 2 2 If R = length of the cube edge container.

3 L 134. then the volume of products will be 4.196 (moles of products) (0.00) _______________________ n O2 = 0.000 L = = 0.0%.0392)x(44.CHAPTER 5 GASES 139 Volume = R3 = (1.564 g products Mol CxHy = n C x H y = PV 0.0%. moles of CO equals twice the moles of O2 present ( n CO = 2n O 2 ). P = n ⎜ ⎟ = n(constant) ⎝ V ⎠ Because the pressure has increased by 17. the number of moles of gas has also increased by 17.00) = 5.0392(y/2) = 0. nfinal = (1.959 atm × 1.0392 mol RT 0. If all C were converted to CO.1 dm)3 = 1.000 L = 5.170(5. .000 L = = 0.0392(y/2)(18.170)ninitial = 1.02 g/mol) = 5.3 dm3 = 1.85 mol gas = n O 2 + n CO + n CO 2 n CO + n CO 2 = 5.000 L of the hydrocarbon (CxHy). The reactions are: C(s) + 1/2 O2(g) → CO(g) and C(s) + O2(g) → CO2(g) ⎛ RT ⎞ PV = nRT. we would get 5 mol CO and 2.196 mol 0. 135.5 mol excess O2 in the reaction mixture.564 g (mass of products) Solving: x = 2 and y = 6.000 L and the mass of products (H2O + CO2) will be: 1.08206 L atm RT × 375 K K mol Mol products = np = CxHy + oxygen → x CO2 + y/2 H2O Setting up two equations: (0. Solving by simultaneous equations: n O 2 + n CO + n CO 2 = 5.08206 L atm × 298 K K mol PV 1.85 If all C were converted to CO2.85 − (n CO + n CO 2 = 5.391 g/L × 4.0392)x + 0.00 (balancing moles of C).51 atm × 4. Assuming 1. In the final mixture. no O2 would be left. so the formula of the hydrocarbon is C2H6.01 g/mol) + 0.

0000 ⎞ = = final . 0.13 Solving: x = 0.4443 mol SO3. d = mass 1 and V % n at constant P and T. In a reaction. For three times as much oxygen. V n n initial d 1.15 5. then: x + x + z = 1. 5. Therefore.13 g 2x + z = 1.924 g/L = 1. Because SO2 is limiting.140 CHAPTER 5 n CO = 2n O 2 = 1. n CO 2 = 3.924 g/L. 2 SO2(g) + O2(g) → 2 SO3(g) Initially.21)nair. we would need 6 mol O2 per mol of CH4 reacted (n O 2 = 6n CH 4 ). The reaction is: CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) PV = nRT.4443 mol and z = 0. so d % .000 and (96. PCH 4 VCH 4 P V PV = RT = constant.07 g/mol × x + 32. dfinal = 2. and 0.85 = 0.0000 mol and nfinal = 0.70 3.07)x + (4. mass is constant. a. Let x = moles SO2 = moles O2 and z = moles He. we end up with 0.85 5. assume 0.000 atm × MM .0000 ⎛ 1. d final = ⎜ ⎟ × 1. χ CO 2 = = 0.003)z = 43.4443 mol SO2. a.1114 mol Thus: χHe = 0.473 g/L n final 0.70 mol CO. P • MM where MM = molar mass RT 1.4443 mol O2 and 0.000 mol = 0. 1. MMmixture = 43.85 χ O2 = 0. so n O 2 = (0.1114 mol/1.13 g/mol 0.2222 mol O2.000 total moles of mixture is present.1114 mol He. This gives: ninitial = 1.08206 L atm × 273.2 K K mol Assuming 1.30 = 0.291.564.1114 mol He in the gaseous product mixture. 0.7779 ⎠ 137.000 and: 64.1114 b.7779 mol.30 mol CO2 χ CO = 1. the moles of air we would need to delivery the excess O2 are: .85 GASES 136. = air air n n CH 4 n air The balanced equation requires 2 mol O2 for every mol of CH4 that reacts.7779 d initial ⎝ 0.70 + n CO 2 = 5.145 ≈ 0. Air is 21% mole percent O2.00 g/mol × x + 4.00.003 g/mol × z = 43.

77 atm.)x mol of gas total χ CO = (0.032.067. Because Ptotal = 1. L × 29 × = 8.08206 L atm RT × 300.032 atm.0017. and PN 2 = 0.) x (30.00)x mol H2O + 23x mol N2 = (30.050) x (0. PCO = 0. PCO 2 = 0.20 × 10 −6 atm) × 1.00 atm.00)x mol O2 × The reaction mixture contains: (0.13 atm.CHAPTER 5 GASES n O 2 = (0.5 mol O 2 = (0.050)x mol CO × 1.050)x mol of CO. In addition. CH4(g) + 3/2 O2(g) → CO(g) + 2 H2O(g) Amount O2 reacted: (0.950)x mol CO2 + (0. K K mol .950)x mol CO2 × 2 mol O 2 = (1.87 × 10-8 mol 0.) x (2. χ CO 2 = = 0.00) x = 0.00 atm n CH 4 Pair b.6)x ≈ 23x mol N2 21 mol O 2 χ H 2O = c. PO 2 = 0.00)x − (1. nair = 29n CH 4 .00 L = = 4. The partial pressures are determined by P = χPtotal. 138.0017 atm. PH 2O = 0.90)x − (0.03)x mol O2 + (2.90)x mol O2 mol CO 2 (0.075)x mol O2 mol CO Amount of O2 left in reaction mixture = (6.950) x (4. ntotal = total number of moles of gas that have effused into the container: ntotal = PV (1.075)x = (4. χ O 2 = = 0. then 6x mol O2 were added. n air = 29 n CH 4 141 In 1 minute: Vair = VCH 4 × PCH 4 1.13 (30.950)x mol CO2 and (0.7 × 103 L air/min 1. producing (0. CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g).050)x mol CO + (4.) x χ N2 = 23 x = 0.77 (30.03) x = 0. If x mol of CH4 were reacted.) x (30.) x 79 mol N 2 = (22.21)nair = 6n CH 4 .50 atm n air × = 200. (30.067 atm. 2x mol H2O must be produced to balance the hydrogens.03)x mol O2 Amount of N2 = (6.

44 × 1025) = 1.4 × 10 ⎜ ⎟ ⎥ = A ⎢1. Z total = 3.78)(2. 8.40 × 1011 molecules + = A⎢ ⎥ s m2 s m2 s ⎣ ⎦ 3.3 × 10 27 molecules 6.0 × 10 −3 ) ⎟ ⎥ ⎢ ⎝ ⎠ ⎝ ⎠ ⎦ ⎣ 3. ⎞ ⎟ + 5.9 × 10 ⎜ ⎜ 2 π(28.40 × 1011 molecules/s = Z N 2 + Z O 2 11 1/ 2 1/ 2 ⎡ ⎤ 25 ⎛ 8.44 × 1025) = 5.0 × 10 26 molecules ⎤ 3.06 × 10−2 mol/L 0.40 × 1011 molecules/s s mol The frequency of collisions of the gas with a given area is: ⎛N Z = A⎜ ⎜V ⎝ ⎞ ⎛ RT ⎞ ⎟⎜ ⎟ ⎜ 2 πM ⎟ ⎟ ⎠⎝ ⎠ 1/ 2 .2 × 10 −16 m 2 ⎞ ⎜ ⎟ ⎜ ⎟ π ⎝ ⎠ 1/ 2 = 6.022 × 10 23 molecules × = 3.44 × 1025 molecules/m3 3 V L mol m For N2 : N = (0.3145 × 300.2 × 10−16 m2 = πr2.40 × 1011 molecules = Z N 2 + ZO2 s n P 1.08206 L atm V RT × 300.9 × 10 27 ⎛ 1.64 × 10-13 mol/s have entered the container.64 × 10 −13 mol 6.0 × 10 −3 ) ⎟ ⎜ 2 π(32.87 × 10 −8 mol = 5.2 × 10−9 m) = 1.3145 × 300.40 × 10 ⎡ 2.64 × 104 s × 1h 1 min CHAPTER 5 GASES Thus: 4.00 atm = = = 4.2 nm Diameter of hole = 2r = 2(6. K K mol N 4.40 × 1011 2 m = 1.142 This amount has entered over a time span of 24 hours: 24 h × 60 min 60 s = 8. r = A= 2.64 × 10 4 s 5.2 × 10−9 m = 6.9 × 1025 molecules/m3 V N = (0.4 × 1024 molecules/m3 V For O2: Ztotal = 3.06 × 10 −2 mol 6.22)(2. ⎞ 24 ⎛ 8.022 × 10 23 molecules 1000 L = × × = 2.2 × 10−8 m = 12 nm .

08206 × 300.84 × 1010 collisions/s Therefore.022 × 10 23 atoms/mol 2.001 ⎞ ⎟ = 1. N = 140.12 × 10−8 mol 0.1 × 102 stages are needed.3145 × 300. After the hole develops.50 × 109 collisions/s . K K mol N ⎛ RT ⎞ × ⎜ ⎟ V ⎝ 2 πM ⎠ 1/ 2 Z He = A × . 4.88 × 10 N log(1.990 12 CO 2 99.00 (carrying extra significant figures) 1. 6.10 13 CO 2 1. ⎞ ⎟ ×⎜ ⎜ 2 π (4. assume each He that collides with the hole goes into the Rn side and that each Rn that collides with the hole goes into the He side. each successive stage will have less 13CO2. 10. 99.998 ⎠ CO2 moves slightly faster. −3 4. N P = × NA × 1000 L/m3 and A = πr2 V RT ZHe = π(1.89 × 10−9 mol He leave in 10.00 × 10−6 m)2 × 2.84 × 1010 atoms × × = 1.999.74 × 1015 atoms = 2.00 × 10 −6 × (6. ⎛ 8.0113) = log(10.0113 ⎝ 43.84 × 1010 atoms/s leave the He side. GASES 143 Each stage will give an enrichment of: Diffusion rate Diffusion rate Because 12 12 ⎛ M 13 CO CO 2 2 =⎜ 13 ⎜ M 12 CO 2 CO 2 ⎝ ⎞ ⎟ ⎟ ⎠ 1/ 2 =⎜ ⎛ 45.CHAPTER 5 139.003 × 10 −3 ) ⎟ ⎠ ⎝ 1/ 2 = 4.0 = 10.3145 × 300.0 h.05 × 102 ≈ 2. Assume no molecules return to the side in which they began. ⎞ ⎟ ×⎜ ⎜ 2 π (222 × 10 −3 ) ⎟ ⎝ ⎠ 1/ 2 ZRn = π(1.08206 × 300.00 × 10 −6 atm) × 1.90 12 CO 2 × 1.08206 L atm RT × 300.74 × 1015 atoms 1h 1 min s or: 1.009).000391 = 2.022 × 1023) × 1000 0.0113N = 0.00 × 10−6 m)2 × = 6. Initial moles of each gas: n = PV (2.010 13 CO 2 0.0 h × 60 min 60 s 4.009 999. ⎛ 8.00 × 10 −6 × (6.022 × 1023) × 1000 0.0113N = 9.00 L = = 8.

and because the initial pressures were equal and the pressure in one of the sides decreased by 0.50 × 109 atoms/s leave Rn side. Because no gas has escaped.89 × 10−9 mol He = 8. molar mass of helium = 4.50 × 109 atoms 1 mol × = 3. T = 2150 K (a very high 0.94 × 10−6 atm V 1. The Rn side contains: 8.00 L We can determine the pressure in the Rn chamber two ways.08206 L atm ×T temperature) K mol . b. K = = 2.06 × 10−6 atm.60 × 104 s × CHAPTER 5 GASES 6. P in the second side must increase by 0.87 × 10 −8 mol) × 0. a.08206 L atm K −1 mol −1 × 300.08 × 10−8 mol Rn + 2.0 h Side that began with He now contains: 8.9 g/mol.87 × 10−8 moles total The pressure in the He side is: P= nRT (7.89 × 10−10 = 8.83 × 10−8 mol He + 3.12 × 10−8 − 2.003 g/mol A given volume of air at a given set of conditions has a larger density than helium at those conditions. solving: mass He = 0.00 g/mol = 28.06 × 10−6 atm.00 atm).37 × 10−8 mol total P= 141.89 × 10−10 mol Rn = 7.00 L .06 × 10−6 atm V 1.9 g/mol × 1.89 × 10−9 = 7.00 atm × 1.164 g = 28.89 × 10−10 mol Rn leave in 23 s 6. 3.02 g/mol + 0.144 6.00 L). To provide the same lift as the helium balloon (assume V = 1.790 × 28. the mass of air in the hot-air balloon (V = 1. Thus the pressure on the side that originally contained Rn is 2.022 × 10 atoms 10.00 L) must be the same as that in the helium balloon.08206 L atm K −1 mol −1 × 300.12 × 10−8 − 3.06 × 10−6 atm.00 L Average molar mass of air = 0.164 g RT Mass air = 0.210 × 32.87 × 10 −8 mol) × 0. nRT (8. Let MM = molar mass: PCMM = dRT. mass = MM • PV . Or we can calculate P the same way as with He. K = = 1. We need to heat the air to a temperature greater than 25°C in order to lower the air density (by driving air out of the hot air balloon) until the density is the same as that for helium (at 25°C and 1.

Any number larger than 1 would not fit the data given in the problem.00 − (1.00 = 2x. any change in density must be due to a change in volume of the container as the reaction goes to completion.50)x Because x and y are whole numbers. y must be 1 because the above equation does not allow y to be 2 or greater. When y = 1. Because P and T are constant. In both possible products. the equations dictated that only one mole of either A or B had to be present in the formula. 3.CHAPTER 5 142. Density = d % d n 1 and V % n. We need to determine both possible products. Thus the two formulas determined are both molecular formulas and not just empirical formulas. and then determine what happens to the initial total moles of gas as it is converted into the product. A2 or B2. Because mass is conserved in a chemical reaction. The procedure we will use is to assume one reactant is limiting. . x = 3 giving a formula of A3B if A2 is limiting. GASES 145 a.50 = initial = density before n after y−x+2 Solving gives x = 1 and y = 3 for a molecular formula of AB3 when B2 is limiting. let’s consider when A2 is limiting with x moles each of A2 and B2 in our equimolar mixture. The formula of the compound AxBy depends on which gas is limiting. volume % n.50)y = (0. First. x A2(g) + y B2(g) x mol −y mol (x − y) mol → 2 AxBy(g) 0 mol +2 mol 2 mol Initial Change Final x mol −x mol 0 d after n 2x = 1. b.50)y + 3.50)x − (1.50 = initial = d initial n after x− y +2 (1. Note that the coefficient in front of AxBy in the equation must be 2 for a balanced reaction. Assuming B2 is limiting with y moles in the equimolar mixture: x A2(g) + y B2(g) y −y 0 → 2 AxBy(g) 0 +2 2 Initial Change After y −x y−x density after n 2y = 1. so: after = initial V d initial n after Assume the molecular formula of the product is AxBy where x and y are whole numbers.

00 g/mol) = 44.714 L 1 atm 790.226 mol AxHy Mol H = 16. Use the first set of data to determine the identity of element A.0285 mol A 0. torr × 760 torr ⎛ 1 atm ⎞ ⎜ 745 torr × ⎟ × 0. at constant P and T.226 mol A x H y The mass of the x moles of A in the AxH8 formula is: 44. C3H8.08206 L atm × 288 K K mol = 0. Molar mass = 1.714 L ⎜ 760 torr ⎟ ⎝ ⎠ Moles of A = n = = 0.880 g N2 × 1 mol N 2 = 0. Let AxHy be the formula for unknown compound. Marathon Problem 144.02 g mol H 2 O 1.0314 mol × 0. the density of gas is directly proportional to the molar mass of the gas.452 g − 658.008 g) = 36.0 g AxHy × 1 mol A x H y 44.81 mol H = 8 mol H/mol AxHy . the unknown must contain hydrogen.2 g − 8(1.0314 mol N2 28. C3H8 is the best possible identity from the data in this problem.2 g = 0.880 g N2 0. We must determine the identities of element A and compound B in order to answer the questions.146 143. Mol AxHy = 10. and Be4H8.1 g From the periodic table and by trial and error.38(32. AxHy = AxH8 0. C3H8 and Be4H8 fit the data best and because C3H8 (propane) is a known substance.572 g = 0.08206 L atm K −1 mol −1 × (273 + 26) K .38 times that of the molar mass of O2.81 mol H 18.2 g/mol Because H2O is produced when the unknown binary compound is combusted. F2H8. Mass N2 = 659. CHAPTER 5 GASES d = molar mass(P/RT).02 g N 2 nRT V = = P 0. some possibilities for AxH8 are ClH8. Thus the molar mass of the gas has a value which is 1.3 g H2O × 1 mol H 2 O 2 mol H × = 1.

6 g C × 14.3 g = 81.13 12.13 1 mol C = 1. The remainder of the information is used to determine the formula of compound B. 7.4 g Because mol CO2 = mol H2O = x (see balanced equation): 81.63 mol O2 Total moles gaseous reactants before reaction = PV 11.4 g = x mol CO2 × 44.59 − 658.3 mol H.31 mol CO2 × 1.29 mol RT 0.13 = 14.01 g CO 2 18. molecular formula = CxH2x where x is a whole number.68 L = = 5.98 atm × 10.008 g H 7.08206 × 295 K .08206 L atm K −1 mol −1 × (273 + 22) K Mol O2 present initially = 1.0285 mol A The only element that is a gas at 26°C and 745 torr and has a molar mass close to 70.7 g − 765.02 g A Molar mass of A = 2.01 1.66 mol excess O2 RT 0.66 mol = 4.13 mol C.02 atm × 10.CHAPTER 5 GASES 147 Mass of A = 660.50 mol O 2 = 1. Mass of CO2 + H2O produced = 846.4 g H × 7.01 g C 1 mol H 14. we can calculate the moles of excess O2 because only O2(g) remains after the combustion reaction has gone to completion.02 g A = 70.572 g = 2.00 g of B: 85. = 2.13 Empirical formula of B = CH2.9 g/mol is chlorine = Cl2 = element A. The balanced combustion reaction of CxH2x with O2 is: CxH2x(g) + 3x/2 O2(g) → x CO2(g) + x H2O(l) To determine the formula of CxH2x. we need to determine the actual moles of all species present.9 g/mol 0.02 g H 2 O + x mol H2O × .31 mol mol CO 2 mol H 2 O Mol O2 reacted = 1.97 mol O2 mol CO 2 From the data.97 mol + 2.00 = 7. x = 1.68 L = = 2. Assuming 100. n O2 = PV 6.

446 mol V = 10.446 mol × 0. CxH2x must be C2H4 = compound B.31 mol H2O Dividing all quantities by 0. The reaction is: C2H4(g) + Cl2(g) → C2H4Cl2(g) B + A C Mol Cl2 = n = PV 1.446 mol Cl2 − 0.00 atm × 8. ntotal = 0.08206 L atm K −1 mol −1 × 273 K PV 1. Now we can answer the questions.0 L = = 0.08206 L atm K −1 mol −1 × 273 K Mol C2H4 = n = Because a 1 : 1 mol ratio is required by the balanced reaction.384 mol C2H4 RT 0.537 atm 18.00 atm × 10.31 mol CO2 + 1.60 L = 18.0 g C2H4Cl2 b.95 g × mol C 2 H 4 mol C 2 H 4 Cl 2 = 38.446 mol Cl2 RT 0.384 mol C2H4Cl2 produced + 0.08206 L atm K −1 mol −1 × 273 K = 0.97 mol O2 → 1.66 mol CxH2x + 1.60 L = = 0.6 L . Excess mol Cl2 = 0.0 L + 8.66 mol CxH2x Summarizing: CHAPTER 5 GASES 0.384 mol Cl2 reacted = 0.29 mol total − 4.384 mol C2H4 × 1 mol C 2 H 4 Cl 2 98.062 mol Cl2 Ptotal = n total RT .6 L Ptotal = 0. a.148 Mol CxH2x = 5.63 mol O2 = 0.062 mol Cl2 excess V = 0. Mass C2H4Cl2 produced = 0.66 gives: CxH2x + 3 O2 → 2 CO2 + 2 H2O To balance the equation. C2H4 is limiting.

however. 2 NOCl(g) ⇌ 2 NO(g) + Cl2(g) K = 1. Thus 14C atoms will be distributed between CO and CO2. Both experiments will give the same equilibrium position because both experiments started with stoichiometric amounts of reactants or products. 12. equilibrium is a dynamic process. ⇌ H2(g) + CO2(g) K= [H 2 ][CO 2 ] = 2. There is no net change in the composition (as long as temperature is constant). 2 NO(g) ⇌N2(g) + O2(g) K = 1 × 1031 When K has a value much greater than one. H2O(g) + CO(g) 14. and the reactant concentrations are relatively large. In both cases. No. Both reactions: H2O + CO → H2 + CO2 and H2 + CO2 → H2O + CO are occurring at equal rates. the product concentrations are relatively small. the rate of the forward reaction equals the rate of the reverse reaction at equilibrium (this is a definition of equilibrium). 149 . Therefore. 11.6 × 10−5 mol/L The expression for K is the product concentrations divided by the reactant concentrations. it doesn't matter which direction the equilibrium position is reached.0 [H 2 O][CO] K is a unitless number because there is an equal number of moles of product gases as moles of reactant gases in the balanced equation. When K has a value much less than one. and the reactant concentrations are relatively small.CHAPTER 6 CHEMICAL EQUILIBRIUM Characteristics of Chemical Equilibrium 10. b. No. 13. a. The rates of the forward and reverse reactions are equal. the product concentrations are relatively large. we can use units of molecules per liter instead of moles per liter to determine K.

0 for this reaction mixture. so let’s assume 3 molecules of CO react. and 1 B2 molecule present.0 K= ⎛ 4 molecules H 2 O ⎞ ⎛ 2 molecules CO ⎞ ⎜ ⎟⎜ ⎟ L L ⎝ ⎠⎝ ⎠ Because K = 2. 0 + 3 = 3 molecules of H2. 8 ! 3 = 5 molecules of H2O. and 0 + 3 = 3 molecules of CO2 present. 2 A2 molecules and 1 B2 molecule are present (along with 4 A2B molecules). 2 A2 molecules. the first diagram cannot represent equilibrium because there was a net change in reactants and products. From the balanced reaction. This will be an equilibrium mixture if K = 2. Is the second diagram the equilibrium mixture? That depends on whether there is a net change between reactants and products when going from the second diagram to the third diagram. The second diagram has 2 A2B molecules. 4 A2 molecules. Let’s try 4 molecules of CO reacting to reach equilibrium. If 3 molecules of CO react. From the first diagram. An equilibrium position is a set of concentrations that satisfies the equilibrium constant expression.0: ⎛ 3 molecules H 2 ⎞ ⎛ 3 molecules CO 2 ⎞ ⎜ ⎟⎜ ⎟ L L ⎝ ⎠⎝ ⎠ = 3 K= 5 ⎛ 5 molecules H 2 O ⎞ ⎛ 3 molecules CO ⎞ ⎜ ⎟⎜ ⎟ L L ⎝ ⎠⎝ ⎠ Because this mixture does not give a value of K = 2. The Equilibrium Constant 16. 15. When equilibrium is reached. the initial number of A2B molecules present equals 4 + 2 = 6 molecules A2B. The first diagram has 4 A2B molecules. and 2 B2 molecules. so the second diagram is the first illustration that represents equilibrium. this is not an equilibrium mixture. Therefore. we are at equilibrium. . then 3 molecules of H2O must react. there is no net change in the amount of reactants and products present because the rates of the forward and reverse reactions are equal to each other. Therefore.0. and 3 molecules each of H2 and CO2 are formed. Molecules CO remaining = 6 ! 4 = 2 molecules of CO Molecules H2O remaining = 8 ! 4 = 4 molecules of H2O Molecules H2 present = 0 + 4 = 4 molecules of H2 Molecules CO2 present = 0 + 4 = 4 molecules of CO2 ⎛ 4 molecules H 2 ⎞ ⎛ 4 molecules CO 2 ⎞ ⎜ ⎟⎜ ⎟ L L ⎝ ⎠⎝ ⎠ = 2 . More than one equilibrium position can satisfy the same equilibrium constant expression. We would have 6 ! 3 = 3 molecules of CO.150 CHAPTER 6 CHEMICAL EQUILIBRIUM We need to start somewhere. The third diagram contains the same number and type of molecules as the second diagram. The equilibrium constant is a number that tells us the relative concentrations (pressures) of reactants and products at equilibrium. The reaction container initially contained only A2B. these 2 A2 molecules and 1 B2 molecule were formed when 2 A2B molecules decomposed.

9(0. and for Kp. [CO][H 2 ]2 (0. When Q ≠ K. Solutes have (aq) written after them. concentration units of mol/L are used. that is. Solids and liquids do not appear in equilibrium expressions. they just have to be present. K = 18. only reaction d has Δn = 0. Heterogeneous equilibria involve more than one phase. For K. each experiment has different equilibrium concentrations. all reactants and products are included in the K expression. initial concentrations are used to calculate the Q value. When Q = K (or when Qp = Kp). Since there are an infinite number of initial conditions. Δn = 3 ! 1 = 2. 17.6 × 103 atm2 . Kp = 2 2 [ NH 3 ] [CO 2 ] PNH 3 × PCO 2 3 b. gases and solutes are always included in K expressions. Q has the exact same form as K or Kp. partial pressures in units of atm are used (generally). However. equilibrium does not depend on the amounts of pure solids or liquids present. so only reaction d has Kp = K. Only gases and dissolved solutes appear in equilibrium expressions.24)(1.CHAPTER 6 CHEMICAL EQUILIBRIUM 151 Table 6. We use Q to determine if a reaction is at equilibrium. Each of the three experiments in Table 6. In heterogeneous equilibria. Kp = K(RT)Δn. K= 21. However. each experiment gives the same value for K. but instead of equilibrium concentrations.15) [CH 3OH] Kp = K(RT)2 = 1.1 of the text illustrates this nicely. PH 2O [ H 2 O] . The amounts of solids and liquids present are not included in K expressions. the reaction is at equilibrium. a.08206 L atm K−1 mol−1 × 600.1) 2 = = 1. When reactants and products are all in the same phase. 19. Kp = PN 2 × PBr2 3 c. In general. where Δn equals the difference in the sum of the coefficients between gaseous products and gaseous reactants (Δn = mol gaseous products ! mol gaseous reactants). and one can deduce the net change that must occur for the system to get to equilibrium. these are homogeneous equilibria. K)2 = 4. K and Kp are equilibrium constants as determined by the law of mass action. Kp = [H 2 ] PH 2 20. For this reaction. K = [O2]3. for a homogeneous gasphase equilibrium. the reaction is not at equilibrium. Kp = PO 2 d. When Δn = 0. where Δn = sum of gaseous product coefficients ! sum of gaseous reactant coefficients.9 mol2/L2 (0. Kp = K(RT)Δn. each of these infinite equilibrium positions will always give the same value for the equilibrium constant (assuming temperature is constant). there are an infinite number of equilibrium positions. In Exercise 19. On the other hand. K = [N2][Br2]3. K = PH 2O [ H 2 O] . then Kp = K. Q is called the reaction quotient.1 has different equilibrium positions. The equilibrium position depends on the initial concentrations one starts with. when these equilibrium concentrations are inserted into the equilibrium constant expression.

.00 L 2.00 L 2 ⎛ 2.00 × 10 − 4 ) 2 (0. one can conclude that the given set of partial pressures does not represent a system at equilibrium.8 × 104 atm−2 (0.00 ⎝ ⎠ ⎝ ⎠ = 4. 2 HBr ⇌ H2 + Br2 ' K 'p = (PH 2 )(PBr2 ) 2 PHBr = 1 1 = = 2.200) 2 = 4. Therefore.00 × 10 − 2 ) 2 ⎝ ⎠ K= = = [ N 2 ]2 [O 2 ] ⎛ 2.152 CHAPTER 6 CHEMICAL EQUILIBRIUM 22. H2(g) + Br2(g) ⇌ 2 HBr(g) Kp = 2 PHBr = 3.50 × 10 −5 mol . [N2O] = 2.80 × 10 −4 mol 2. then they should give a value of K = 4.00 2.00245) Because the given concentrations when plugged into the equilibrium constant expression give a value equal to K (4. 1/2 H2 + 1/2 Br2 ⇌ HBr ' K 'p' = (PH 2 ) PHBr 1/ 2 (PBr2 )1/ 2 = (K p )1/ 2 = 190 23.08 × 108 L/mol If the given concentrations represent equilibrium concentrations.525) (0. [O2] = 2.1 × 10 −3 ) 3 (0.00 [ N 2 O ]2 (1.00 × 10 − 2 ⎞ ⎜ ⎟ ⎜ ⎟ 2. the value does not equal the Kp value of 3. (0.08 × 108).40 × 10 − 4 ) 2 (1.00 × 10 −2 mol 2.50 × 10 −5 ⎞ (1.8 × 104.3 × 10−3 b.08 × 108 (2.167) 2 = 1. Kp = 2 PNH 3 3 PN 2 × PH 2 = (3. HBr ⇌ 1/2 H2 + 1/2 Br2 K 'p = (PH 2 )1/ 2 (PBr2 )1/ 2 PHBr ⎛ 1 ⎞ ⎟ =⎜ ⎜ Kp ⎟ ⎝ ⎠ 1/ 2 ⎛ ⎞ 1 ⎟ =⎜ ⎜ 3.5 × 10 c. [N2] = .1 × 10 −2 ) 2 = 3. this set of concentrations is a system at equilibrium 24.9 × 10−5 4 Kp 3.5 × 10 4 ⎟ ⎝ ⎠ 1/ 2 = 5.5 × 104 ( PH 2 ) ( PBr2 ) a.08 × 108.85)(3.00761) When the given partial pressures in atmospheres are plugged into the Kp expression.25 × 10 −5 ) ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ 2.21 × 103 3 (0.00 L 2.80 × 10 − 4 ⎞ 2 ⎛ 2.

00 atm = PN 2 + PH 2 + PNH 3 2. 26.0 torr × ⎟ ⎜ 760 torr ⎟ ⎝ ⎠ Note: Solids and pure liquids are not included in K expressions.00 − 3x = 2. We must determine the change in partial pressures necessary to reach equilibrium.00 – x) + (2.00 ! 3x 2x 1. some of the PCl5 reacts to produce some PCl3 and Cl2.0 torr + PH 2 .00 – 2x.500)[2.00) 2 (2 x) 2 [2(0.500) = 0. Ptotal = PH 2O + PH 2 . with only reactants present initially. Initially. if we let x = atm of PCl5 that reacts to reach equilibrium.00 – 3(0. PH 2 = 21.00 − x)(2. x = 0.00 – 3x) + 2x = 3.500 atm PH 2 = 2. Let’s summarize the problem in a table that lists what is present initially. n ∝ P. all in a 1 : 1 mole ratio. At constant volume and temperature. PCl5(g) ⇌ PCl3(g) + Cl2(g) Kp = PPCl3 × PCl 2 PPCl5 To determine Kp. The equilibrium partial pressures of each gas will be the initial partial pressure of each gas plus the change necessary to reach equilibrium. To reach equilibrium.50 atm and PPCl3 = PCl 2 = 0 atm. 2 PNH 3 N2(g) + 3 H2(g) ⇌ 2 NH3(g) Kp = 3 PN 2 × PH 2 Initial Change Equil. we must determine the equilibrium partial pressures of each gas.00 − 3(0. N2(g) + 3 H2(g) ⇌ 2 NH3(g).CHAPTER 6 CHEMICAL EQUILIBRIUM 4 PH 2 153 25. Thus if x atm of N2 reacts to reach equilibrium.00 atm 2.00 atm = (1.50) 3 27.50)(0.3 torr × ⎟ ⎜ 760 torr ⎟ ⎝ ⎠ = 4. this will produce x atm of PCl3 and x atm of Cl2 at equilibrium.00 − 3 x) 3 (1.00 atm 0 x atm of N2 reacts to reach equilibrium !x !3 x → +2x 2. the net change that must occur to reach equilibrium is a conversion of reactants into products.500)]3 (0. change. and equilibrium.3 torr = 15.00 ! x From the setup: Ptotal = 2. PPCl5 = 0. The equilibrium partial pressures are: . and what is present at equilibrium (initial + change). Because moles % P at constant V and T.07 Because l atm = 760 torr: Kp = 4 ⎛ 1 atm ⎞ ⎜15. then 3x atm of H2 must also react to form 2x atm of NH3 (from the balanced equation).00 − 0. This table is typically called an ICE table for initial.50 atm Kp = (1.3 torr 4 ⎛ 1 atm ⎞ ⎜ 21. what change in terms of x that occurs to reach equilibrium. 1. Kp = 4 PH 2O .500)]2 = 16 atm−2 = = (1. 36.

34 atm Kp = PPCl 3 × PCl 2 PPCl 5 = (0. Therefore. PPCl 3 = PCl 2 = 0. Because there is a 4 : 1 mole ratio between S2 and S8 (from the balanced reaction).0 atm. S8(g) ⇌ 4 S2(g) Kp = Initially: PS8 = 1.50 − x + x + x.154 PPCl5 = 0.50 atm − x. a common method to summarize all the information in the problem is to set up a table.16) K= Kp (RT ) Δn . PPCl3 = PCl 2 = x CHAPTER 6 CHEMICAL EQUILIBRIUM Now we solve for x using the information in the problem: Ptotal = PPCl5 + PPCl3 + PCl 2 .50 + x. changes that must occur to reach equilibrium. PS2 = 0 + 3. Equilibrium: PS8 = 0.0 atm of S2 must have been produced when the reaction went to equilibrium (moles and pressure are directly related at constant T and V).00 atm − 0. and equilibrium concentrations (the sum of the initial and change columns).25 atm.34) = 0.25 atm of S8 remain at equilibrium.0 atm = 3.34 atm The equilibrium partial pressures are: PPCl 5 = 0. 4(0.017 mol/L (0.25 29. and we use the coefficients in the balanced equation to relate the net change in SO3 to the net change in SO2 and O2.25 atm = 0. we will generally use the variable x.08206)(523) 28. Solving for Kp: Kp = (3.34)(0. Δn = 2 − 1 = 1.72 = 0.00 atm and PS2 = 0 atm Change: Because 0.75 atm) = 3. 0.0) 4 = 3.50 − 0. In this problem. x = 0.34 = 0. 0.84 atm = 0.16 atm. For the change column.2 × 102 atm3 0. which will be defined as the amount of reactant (or product) that must react to reach equilibrium.84 atm = 0.75 atm of S8 must have reacted in order to reach equilibrium. the reaction must shift right to reach equilibrium because there are no products present initially. We commonly call this table an ICE table because it summarizes initial concentrations.72 atm (0. K p = PS42 PS8 0. When solving equilibrium problems. The general ICE table for this problem is: . x is defined as the amount of reactant SO3 that reacts to reach equilibrium. 1.

[O2]e = x = 0. −2x → +2x +x 4. −x → +x +x/2 4.50 M These are exactly the same equilibrium concentrations as solved for previously.0 = 3. then the ICE table setup is: [SO 2 ]2 [O 2 ] O2(g) K= 2 SO3(g) ⇌ 2 SO2(g) + [SO 3 ]2 Initial Change Equil. K= [SO 2 ]2 [O 2 ] (1.0 − 2x 2x x Solving: 2x = [SO2]e = 1.0 M ) 2 Alternate method: Fractions in the change column can be avoided (if you want) be defining x differently.0 − 2(0. .50 M ) = 0. [SO2]e = x. Because Δn = 0.0 mol/3. From the ICE table setup.0 M). Solving for the other equilibrium concentrations: [SO3]e = 4. If Q = K. If Q > K. Equilibrium Calculations 30. K = Kp. then the reaction shifts left to reach equilibrium.0 mol/3. so x = 1. If we were to let 2x mol/L of SO3 react to reach equilibrium.056 mol/L = [SO 3 ]2 (3.0 L = 1.50 M. then the reaction does not shift in either direction because the reaction is at equilibrium.CHAPTER 6 CHEMICAL EQUILIBRIUM 2 SO3(g) 155 + O2(g) K= [SO 2 ]2 [O 2 ] [SO 3 ]2 ⇌ 2 SO2(g) Initial Change Equil.0/2 = 0.50) = 3. we are told that the equilibrium SO2 concentration is 3. [SO3]e = 4.0 M. 0 0 4.0 − 1. then the reaction shifts right to reach equilibrium. thus K will be the same (as it must be).0 M ([SO2]e = 1. x = 0.0 − x = 4. initial concentrations given in a problem are used to calculate the value for Q.0 M. [ NO]2 Use the reaction quotient Q to determine which way the reaction shifts to reach equilibrium. [O2] = x/2 = 1. The moral of the story is to define x in a manner that is most comfortable for you.0 M ) 2 (0. 2 NO(g) ⇋ N2(g) + O2(g) K = [ N 2 ][O 2 ] = 2.4 × 103.0.0 L 0 0 Let x mol/L of SO3 react to reach equilibrium. If Q < K.0 − x x x/2 From the problem. 12. For the reaction quotient.50 M. Your final answer is independent of how you define x initially.0 M Let 2x mol/L of SO3 react to reach equilibrium.0 M.

[NO] = = 0. reaction shifts right to reach equilibrium. e.0 L Q= [ N 2 ]0 [ O 2 ]0 (2. [O2] = = 2.156 a.4 mol 1.80 M.0 M.36 atm)(0.51 atm)(0.0 L 1.0 atm) = 2.2 × 103 (0. [NO] = = 0.4 g CO 2 0.0 L 2.04 atm We only need to calculate the initial partial pressure of CO2 and compare this value to 1.80 M )(0.0 × 103 > Kp.04 atm.0 M. Q = PN 2 × PO 2 2 PNO = (0.57 M ) = 1.0078 atm) 2 (0. n CO 2 RT V 58.0 L 3.62 mol 4.020 M 3 . Q= 31. b.18 atm) = 2. [N2] = 2. PV = nRT.016 M ) c.0 L 2. Q = (0.032 mol = 0. the mass of CaO will decrease.010 atm) 2 Q < Kp (2. [O2] = = 0.31 M ) (2. Q = PCO 2 = Reaction will shift to the left because Q > Kp.024 mol = 2.0 M ) (2. .4 × 103).0 M ) = 2.1 × 103 < K.55 atm > Kp a.01 g/mol K mol = = 50.7 mol 0.024 M 1. so the reaction shifts left to produce more reactants in order to reach equilibrium. (0.0 L (0.0 L Q= (0.020 M ) 2 Q= d.0062 atm) 2 f.060 mol = 0.11 atm)(2. at equilbrium (0. [N2] = 0.6 M. [NO] = = 0.0 L 1.6 mol 0. reaction shifts left to reach equilibrium.4 × 103 = K.016 M 2.57 M. At this temperature.0 mol 0. at equilibrium 2 (0.0 L 3 .31 M.4 × 103 = Kp.0 L 2. [N2] = CHAPTER 6 CHEMICAL EQUILIBRIUM 2. [O2] = = 2. (0.0 × 103 2 [ NO]0 (0. CaCO3(s) ⇌ CaO(s) + CO2(g) Kp = PCO 2 = 1.024 M ) 2 Q > K.08206 L atm × × 1173 K 44. so the reaction shifts right to reach equilibrium.0 mol 2.67 atm) = 4. all CO2 will be in the gas phase.6 M ) = = 9.

H2O(g) + Cl2O(g) ⇌ 2 HOCl(g) K = 0.94)x = 0. which is less than K. 32.54 M 33.82) (0.75.94.800 + x 0.26 M 0.94)x.800 − x) 2 for x: 0.3 × 10−2 mol/L 1 .04 atm = Kp (44.0) 157 b. The reaction shifts to the right to reach equilibrium. mass of CaO will not change.0 L 86.800 ! x Plug the equilibrium concentrations into the equilibrium constant expression: K= [SO 3 ][ NO] (0. 3.75 0.08206)(1173) = 1. c.800 − x The equilibrium concentrations are: [SO3] = [NO] = 0.08206)(1173) = 0.211 atm < Kp (44.6 × 10−2 mol/L. Summarizing the equilibrium problem in a table: SO2(g) Initial Change Equil.800 ! x = 0.800 + 0.800 M x mol/L of SO2 reacts to reach equilibrium !x !x → +x +x 0.800 M 0. (2.06 M.01)(50.26 = 1.01)(50.76) (0.9 g Because only reactants are present initially. mass of CaO will not change.55 ! (1. take the square root of both sides and solve [SO 2 ][ NO 2 ] (0.0 g 2. At equilibrium.800 + x 0. [SO2] = [NO2] = 0.0) Reaction will shift to the right because Q < Kp. Q = PCO 2 = (4. P = 1.0 g H 2 O 1 mol × = 5.800 + x = 0.CHAPTER 6 CHEMICAL EQUILIBRIUM (23.800 + x = 1. + NO2(g) ⇌ SO3(g) + NO(g) K = 3. x = 0.0 g Cl 2 O 1 mol × = 2. Mass of CO2 is the same as in part b. 1 .090 = [HOCl]2 [H 2 O][Cl 2 O] a.800 + x) 2 .04 atm = KP.800 + x = 1. Q = PCO 2 = At equilibrium because Q = Kp.800 M 0. d. Summarizing the problem in a table: .0 L 18.800 ! x 0. Q = 1.00. the mass of CaO will increase. 0.800 M 0. the reaction must proceed to the right to reach equilibrium. The initial concentrations of H2O and Cl2O are: 1.75 = .

we can't have less than nothing.434 = 0.3 × 10−2 − x 2x 5.090 = + CHAPTER 6 Cl2O(g) CHEMICAL EQUILIBRIUM ⇌ 2 HOCl(g) 5. so we can take the square root of each side: 0.11 × 10−3)x + (0.50 − 2 x . (0.82 A negative answer makes no physical sense.16 × 10−4 − (7.6 × 10−2 − x = 0.11 × 10−3)x − 1.8 × 10−2 M [H2O] = 5.0046 = 1.07 M .0 mol/2.2 × 10−3 M.30)x = 0.217 M (We carried extra significant figures. K = 0.056 − 0.6 × 10−3 M or −6.) Solving using the quadratic formula (see Appendix 1 of the text): x= − 7.11 × 10 −3 ± (5.) x = [H2O] = [Cl2O] = 0.090)x2 = 4x2 (3.50 − 2 x) 2 = [H 2 O][Cl 2 O] x2 The expression is a perfect square.30 = 0.0 L = 0.090 = H2O(g) + Cl2O(g) ⇌ 2 HOCl(g) 0 0 1.023 − 0.158 H2O(g) Initial Change Equil. K = 0.50 x x = 0.16 × 10−4 = 0 (We carried extra significant figures.50 − 2x = 0.50 M 2x mol/L of HOCl reacts to reach equilibrium +x ← −2x +x x x 0. [HOCl] = 2x = 9.6 × 10 − 2 1.50 − 0.3 × 10−2 − x = 0.91)x2 + (7.6 × 10−2 M 2.3 × 10−2 M 0 x mol/L of H2O reacts to reach equilibrium −x −x → +2x 2. (2.6 ×10−3 M. [HOCl] = 0.22 M.30)x = 0. [Cl2O] = 2.217 = 0. Thus x = 4.06 × 10 −5 + 1.50 − 2x [HOCl]2 (0.50 − 2x.0046 = 5.6 × 10−2 − x (2 x) 2 − x)(2.81 × 10 −3 )1/ 2 = 4. Initial Change Equil.3 × 10 − 2 − x) (5.4 × 10−3 M 7.1 × 10−2 M b.

50 − 2 x) 2 (0.050)]2 − [0.40) 2 (0. We continue this process until the estimated value of x and the calculated value of x converge on the same number. H2(g) Initial Change Equil.495. K= CHEMICAL EQUILIBRIUM 159 [ HF]2 (0. 0.400 + 2 x . an alternative method for solving a cubic equation is to use the method of successive approximations (see Appendix 1 of the text).050 atm.200 mol F2/5.25 = 2 SO2(g) + O2(g) ⇋ 2 SO3(g) Kp = 0. For equilibrium problems.0500 − x [HF] = 0.50 atm 0 2x atm of SO2 reacts to reach equilibrium −2x −x → +2x 0.0249 = 0.0500 M. Applying the method of successive approximations and carrying extra significant figures: 4x2 4x2 = = 0.0251 M 35.400)2/(0.50 − x) This will give a cubic equation.400 + 2x.50 − x 2x 0. x = 0. we will substitute the estimated value for x into the denominator.45) . Kp = 0.50 − 2(0. Let’s guess that x = 0. not much of the forward reaction will occur to reach equilibrium.400 + 2 x) 2 .400 + 2(0.0500 − x 0.0500 M 0. [H2] = [F2] = 0.0249 mol/L 0.400 M 0.CHAPTER 6 34.450 M. x = 0. = 17.50 atm 0.00 L = 0.0500)2 = 64.895 − (17.9)x = 0. [H2] = [F2] = 0.0500 − x) 2 0..0500 − 0.067 [0. the concentrations of species present are [HF] = 0.0500 − x 0. Because the value of K is small (K < 1).400 M ) 2 = = 320. If you don’t have a graphing calculator. Q = (0. 0. because Q < K.0249) = 0. The first step is to guess a value for x.0400 M F2 added [H 2 ][F2 ] (0. K = 320. Now we take this estimated value for x and substitute it into the equation everywhere that x appears except for one.50 − (0.50 − 2x 2 PSO 3 2 PSO 2 × PO 2 = (2 x) 2 (0.25 0. the reaction will shift right to reestablish equilibrium. (19. This tells us that x is small. Initial Change Equil.0100 M ) After F2 has been added.0.9)x = 0.0500 M )(0. and then solve for the numerator value of x.25 . taking the square root of each side: (0. This is the same answer we would get if we were to solve the cubic equation exactly. Graphing calculators can be used to solve this expression.9 = + F2(g) ⇋ 2 HF(g) 0.0500 M x mol/L of F2 reacts to reach equilibrium −x −x → +2x 0.400 M.400 + 2x (0.050)] (0.

PSO 3 = 2x = 0. The assumption comes from the value of K being much less than 1. Instead.124 = 0.050 ± [(0.95)x2 + (0.433) 4x2 4x2 = 0. + O2(g) ⇌ 2 NO(g) Kp = 0.437) x = 0. = 0.50 − 2(0.00)x + x2] = 4x2 (0.067)]2 [0. Summarizing the problem in a table: N2(g) Initial Change Equil.25.80 − x)(0. so we don’t assume x = 0.376 = 0. so the equilibrium NO concentration is: PNO = 2x = 2(3. If we define the change that must occur in terms of x as the amount (molarity or partial pressure) of a reactant that must react to reach equilibrium.0 × 10−3 = 0 Solving using the quadratic formula (see Appendix 1 of the text): x= − b ± (b 2 − 4ac)1/ 2 − 0.160 CHAPTER 6 CHEMICAL EQUILIBRIUM 4x2 4x2 = = 0. x = 0.25.5 – 3x. the equilibrium mixture will not have a lot of products present.366) 2 (0.050)]2 − 4(3.44 atm.0 × 10−3 − (0.062 atm. we concentrate on the equilibrium row in the ICE table. the reaction must proceed to the right to reach equilibrium. (0.060 [0.50 − (0. x = 0. (3.050)x − 8.438 = 0. etc.10 – x or 0.374) 2 (0.9 × 10−2 atm makes sense (x cannot be negative). mostly reactants are present at equilibrium.2 × 10−2 atm. 0.50 − 2(0.9 × 10−2 atm) = 7.062) = 0.38) 2 (0. Because only reactants are present initially. Those reactants (or products) that have equilibrium concentrations in the form of 0.80 − x 2 PNO (2 x) 2 = . For these reactions.95) x = 3.25 . only x = 3.050[0. They are: PSO 2 = 0.9 × 10−2 atm or x = −5.062 The next trial gives the same value for x = 0.95)(−8..050 = 4x2 = 8.44) (0.38 atm PO 2 = 0. The .50 − x = 0.25 + x or 3.0 × 10 −3 )]1/ 2 = 2a 2(3.063.12 atm 36.20 atm 0 x atm of N2 reacts to reach equilibrium −x −x +2x 0.067)] (0.050 0. We want to know the value of x in order to solve the problem.8 × 10−2 atm 37. We are done except for determining the equilibrium concentrations. is where an important assumption can be made.50 − 2x = 0.20 − x) PN 2 × PO 2 Kp = 0.16 − (1.80 atm 0. then x must be a small number because K is a very small number.050)x2.20 − x 2x 0.050)x + (0.

0 − 2x = 1.97 = 1.6 × 10−5 2. For our example above (0.0 − 2x ≈ 1.032 M. etc. it will make little or no difference.016) = 0. if the error we introduce by making simplifying assumptions is less than 5%. We saved time and energy.25 or 3. a. Summarizing the problem in a table: 2 NOCl(g) Initial Change Equil.6 × 10−2 M.0 (to proper significant figures) Our error is about 3%.20) × 100 ≤ 5%.0 L 2x mol/L of NOCl reacts to reach equilibrium −2x → +2x +x 1.016 M. if (x/0.0 M Note: If we were to solve this cubic equation exactly (a longer process). Whenever K is a very small value.25 + x ≈ 0. always make . [NOCl] = 1. ⇌ 2 NO(g) + Cl2(g) K = 1.20 – x ≈ 0.20 – x ≈ 0. if x is less than 5% of the number the assumption was made against.10 – x ≈ 0. we know that the product concentrations will be small.0 mol 0 0 = 1.0 − 2 x) 2 If we assume that 1. This assumption makes the math much easier and usually gives a value of x that is well within 5% of the true value of x (we get about the same answer with a lot less work). x = 1. 1 . we assume that the initial concentration of a substance is equal to the final concentration. so x will be small).6 × 10−5 = 4x 3 . See Appendix 1 for details regarding the method of successive approximations.2% of 1. Solving for the equilibrium concentrations: [NO] = 2x = 0. Generally. that is. 2x is 3. we assume that 0.0 M 2.016. then: 1. now we must check the assumption. [Cl2] = x = 0.5 – 3x ≈ 3. the assumption is said to be valid. and when we add x or subtract x from some initial concentration. x will be small (x << 1).20 is made. then we must solve the equation exactly or use a math trick called the method of successive approximations. The reaction must proceed to products to reach equilibrium because only reactants are present initially.0 2 1. We call this the 5% rule. then our final answer is within acceptable error limits of the true value of x (as determined when the equation is solved exactly).6 × 10 = [ NO]2 [Cl 2 ] [ NOCl]2 = (2 x) 2 ( x) (1.0 − 2(0.20).97 M ≈ 1.0 (from the small size of K. That is. If the error is greater than 5%.CHAPTER 6 CHEMICAL EQUILIBRIUM 161 assumption is that because K << 1. we go no further.0 M. as well as for a review in solving quadratic equations exactly.0 − 2x = 0.0 − 2x 2x x −5 K = 1. then our assumption is valid by the 5% rule. 38. it is found that when an assumption such as 0.5.10 or 0. This is the exact same answer we determined by making a simplifying assumption. we get x = 0.. We check the assumptions for validity using the 5% rule. From doing a lot of these calculations.

0 React completely 2. [NO] = 0. then we are faced with solving a cubic equation.0 2 .0 M 0 2. then the answer you calculated making the assumption will be considered the correct answer.0 M. Summarizing these steps in a table: 2 NOCl(g) Before Change After Change Equil. +2. . we cannot make any simplifying assumptions.6 × 10−5. [NOCl] = 2. The setup would be: 2 NOCl Initial Change Equil.0 M (K is small.5% of 2.0 − 2y + Cl2 1. the reaction will contain mostly reactants at equilibrium (the equilibrium position lies far to the left).0 −1. Because K for this reaction is very small (K << 1). This is impossible! 4y2 To solve this equation. then: 1.0 0 0 New initial conditions 2x mol/L of NOCl reacts to reach equilibrium −2x → +2x +x 2.0 M −y 1.0 2 (assuming 2.) Let 1. We get y = 250.0) K = 1.025 M Note: If we do not break this problem into two parts (a stoichiometric part and an equilibrium part). x = 2. we have to find a way to solve a cubic equation.0 − 0.0 − y (2.0 mol/L Cl2 react completely.0 − 2 y ) 2 (1.050 = 1. b. Or we can use some chemical common sense and solve the problem the easier way. If the assumption introduces an error of less than 5%. assumption good by the 5% rule (2x is 2.162 CHAPTER 6 CHEMICAL EQUILIBRIUM the assumption that x is small.6 × 10−5 = x3 = 1.0 − 2x ≈ 2.0 ← −2. reactants dominate. and then we will solve the forward equilibrium problem to determine the equilibrium concentrations.0 − 2 x) 2 2.5 × 10−2 M. There is a little trick we can use to solve this problem in order to avoid solving a cubic equation.0 M −2y 2.6 × 10−5 = 2 .0). ⇌ 2 NO(g) + Cl2(g) K = 1.6 × 10−5 = 0 +2y 2y ⇌ ← 2 NO 2.95 M = 2. [Cl2] = 0.0 − 2x 2x x (2 x) 2 ( x) 4x3 ≈ ( 2.0 − y ) (2 y ) 2 If we say that y is small to simplify the problem.6 × 10−5 1. We will let the products react to completion by the reverse reaction.050 M. 1.

6 × 10−5 = 1.6 × 10−5 = 2 NOCl(g) ⇌ 2 NO(g) + Cl2(g) 2. [NOCl] = 4.0).0) 2 (assuming 2x << 1.080 M. x = 4.6 × 10−5 M.0) x = 1.0 − 2x (2 x) 2 ( x) 4 x3 ≈ . +2.0 −1.040 M.0 M 1.0 − 2x x (1.0 × 10−2 M.6 × 10−5 = 2 NOCl(g) ⇌ 2 NO(g) + Cl2(g) 1. Before Change After Change Equil. [Cl2] = 1.92 M ≈ 3.0).6 × 10−5 M and [NOCl] = [NO] = 1.0 M 2.0 M e.0 − 2 x ) 2 [Cl2] = 0.0 + 2x x 1.0 + 2x x 2.0 M.0 − 2(0.0 + 2 x) 2 ( x) ≈ . Before Change After Change Equil.0 M Let 1. 1.0 (2. 1.0 React completely 4. [NOCl] = 2.0 + 2 x) 2 ( x) (1. Assumptions are great (2x is 3. 16 ( 4 .0 0 New initial 2x mol/L NOCl reacts to reach equilibrium −2x → +2x +x 1.0 M 2x mol/L NOCl reacts to reach equilibrium −2x → +2x +x 1. 1.0 0 0 New initial 2x mol/L NOCl reacts to reach equilibrium −2x → +2x +x 2x x 4.4 × 10−5 M.CHAPTER 6 c.2 × 10−3% of 1.3 × 10−2% of 1.0 − 2 x) Assumptions are great (2x is 1.0 ← −2. [NO] = 0. CHEMICAL EQUILIBRIUM 2 NOCl(g) 163 + Cl2(g) ⇌ 2 NO(g) Initial Change Equil.0 React completely 2.0 1. assumption good (2% error). +2.0 − 2x (1.0 M Let 1.0 M d.0 mol/L Cl2 react completely.0 −1.0 − 2 x) 2 (2.040) = 3.4 × 10−5 M 2 4.0 M 0 3. [Cl2] = 6.0 ← −2.0) 2 (x) ≈ (1. solving: x = 6.9 M . [NO] = 1.0 M 0 1.0 mol/L Cl2 react completely.

00 −0.0057) = 1.40) 2(4.00 − 2 x) (2.6 × 10−3 M.2%. so x is (0.50).51 M [NOCl] = 2. [Cl2] = 0.00) Assumptions are good (x is 1. assumption is valid by the 5% rule.40 − 2x = 0. [O2] = x = 4.00 M 1.16 (0. 2.0057 = 0. 4.00 − 2x 2x 0.00 M Let 1. 2 CO2(g) ⇌ 2 CO(g) + O2(g) K= [CO] 2 [O 2 ] [CO 2 ] 2 = 2.500 React completely 2.40 − 2x [CO] 2 [O 2 ] [CO 2 ] 2 = (2 x) 2 ( x) .) K = 2. x = 5. Summarizing the problem in a table where x atm of N2O4 reacts to reach equilibrium: N2O4(g) Initial Change Equil. a.6 × 10−5.99 M 39.1% of 0.0 × 10−6 = .00 ← −1.7 × 10−3 M 2 2 (2.3 × 10−3) = 8.1 × 10−2 M.50 + 0.40 Checking assumption: [CO2] = 0.50 + x (2 x) 2 (0.0 × 10-6 ≈ 4x3 4 x3 .39 M [CO] = 2x = 2(4. Initial Change Equil.0 × 10−6 2.40 (K is small. +1. [NO] = 2x = 1.5 − x ⇌ → 2 NO2(g) 0 +2x 2x Kp = 0. 0.00 M 1.50 + x) 4 x 2 (0.40 − 2(4.0 mol/5. assuming 2x << 0. x = 4. The reaction must proceed to products to reach equilibrium because no product is present initially.50 New initial 2x mol/L NOCl reacts to reach equilibrium → +2x +x −2x 2.00 − 2(0. K= 2 NOCl(g) CHAPTER 6 CHEMICAL EQUILIBRIUM ⇌ 2 NO(g) + Cl2(g) 1.00 0 0.3 × 10−3) = 0.5 atm −x 4.40 − 2 x) 2 small.3 × 10 −3 ) × 100 = 2.0 × 10−6 = 2.3 × 10−3 M 2 0.164 f.00 mol/L NO react completely (the limiting reagent). Before Change After Change Equil.3 × 10−3 M 40.0 L 0 0 2x mol/L of CO2 reacts to reach equilibrium −2x → +2x +x 2x x 0.50) ≈ = 1.25 .

Kp = 4. 4x2 − (36.) x − (−36.0 atm c. No.0 + x 1.25 ± 4.25. figs.25)x − 1. PN 2O 4 = x = 4.0 atm.0 atm −2x 9.1.25. From part a. PN 2O 4 = 4. x = 4.125 − (0. d.0 = 0 (carrying extra sig.25. 4x2 + (0. N2O4(g) Initial Change Equil.25) 2 − 4(4)(81)]1/ 2 .0 atm b.0 − 2 x) 2 = 0.125)]1/ 2 − 0.0 + x .0 atm 2.0 − 2 x) 2 = 0.5 − x We carried extra significant figures in this expression (as will be typical when we solve an expression using the quadratic formula).25 = . The reaction must shift to reactants (shift left) to reach equilibrium. 4x2 = 1.25) ± [(−36.0 atm 8.0 − 2x = 1.) 8 . Kp = 0 +x x ⇌ ← 2 NO2(g) 9.) PNO 2 = 2x = 1. N2O4(g) ⇌ 2 NO2(g) Initial New Initial Change Equil.0 atm and PN 2O 4 = 4. Solving using the quadratic formula (see Appendix 1 of text): x= − 0.0 = 0. 4x2 − (8.125 = 0 4 .0 atm 2( 4) Solving: x = The other value.5 − x = 4.50.0 atm.CHAPTER 6 CHEMICAL EQUILIBRIUM 2 PNO 2 165 Kp = PN 2O 4 = (2 x) 2 = 0. PNO 2 = 9.25)x.0 − 2x (9. the equilibrium partial pressures are PNO 2 = 1. the reaction will shift left to reestablish equilibrium.25 ± [(0. Halving the container volume will increase each of these partial pressures by a factor of 2.0 +x 8. we get the same equilibrium position starting with either pure N2O4 or pure NO2 in stoichiometric amounts.0 − 2x ← ( 2. figs.0 −2x 2.25)x + 81 = 0 (carrying extra sig.0)2/8. is impossible. 5. x = 0.0 atm.50 2( 4) 8 (Other value is negative.25) 2 − 4(4)(−1. Because Q > Kp.25)x + 2. Q = (2.

0% 20.0 − 2x = 1.0 L = 0.2 g CaCO3 mol CO 2 mol CaCO3 13. − 2x x 2 Kp = 2.9 × 10−3 − 0 0 Some NH4OCONH2 decomposes to produce 2x atm of NH3 and x atm of CO2. where Δn = 1 − 2 = −1 a. NH4OCONH2(s) Initial PCO 2 V ⇌ 2 NH3(g) + CO2(g) Kp = 2. PNO 2 = 2.0 + x = 8.2 g Mass % CaCO3 reacted = × 100 = 66.28 atm PN 2O 4 = 8. 1.9 × 10 −3 ⎞ ⎟ x= ⎜ ⎜ ⎟ 4 ⎝ ⎠ 1/ 3 = 9.132 mol CO2 × × = 13.132 mol CO2 0.0 g n CO 2 = = 42. PCO 2 = x = 9.08206 L atm RT × 1073 K K mol 1 mol CaCO3 100. This is a typical equilibrium problem except that the reaction contains a solid.166 CHAPTER 6 Solving using the quadratic formula: x = 0.27 atm 43. PNH 3 = 2x = 0.5 × 109 L ⎛ 0. Whenever solids and liquids are present.4 atm CHEMICAL EQUILIBRIUM 41. Kp is so large that at equilibrium we will have almost all COCl2.3 atm. .0 g of CaCO3 will react to reach equilibrium.0 × 10−2 atm Ptotal = PNH3 + PCO 2 = 0.08206 L atm ⎜ × 373 K ⎟ .9 × 10−3 = PNH3 × PCO 2 = (2x)2(x) = 4x3 ⎛ 2. Kp = K(RT) = ⎜ ⎟ mol K mol ⎝ ⎠ Δn −1 Kp = 1.09 g Mass CaCO3 reacted = 0. CaCO3(s) ⇌ CaO(s) + CO2(g) Kp = 1. ⎞ 4.5 × 108 atm−1 b. we basically ignore them in the equilibrium problem.16 = PCO 2 Some of the 20. The amount that reacts is the quantity of CaCO3 required to produce a CO2 pressure of 1.16 atm (from the Kp expression). Change − → +2x +x Equil.16 atm × 10.18 atm + 0.090 atm = 0.0 atm. Assume Ptotal ≈ PCOCl 2 ≈ 5.18 atm.0 × 10−2 atm.

0 − x 5.CHAPTER 6 CHEMICAL EQUILIBRIUM CO(g) + Cl2(g) 167 Kp = 1.020 → +0.08 + 2 × 10−4 = 0.0 − x = 5.0.020 −0.020 M Let 0.8 × 10-4 atm. .08 0. −0. the reaction just reaches equilibrium more quickly. then the value of K is constant.020.020 = ≈ 3+ − ( x)(0.08 + x) (0. 46.020 React completely 0 0. Check assumptions: 5.0 − 1. Only statement d is correct. products dominate).0 atm x atm COCl2 reacts to reach equilibrium +x +x ← −x x x 5.8 × 10−4 = 5.0 ≈ 2 x2 x (Assuming 5. A decrease in volume will favor the side with lesser gas-phase particles.8 × 10−4 atm and PCOCl2 = 5.0 − x 5.5 × 108 ⇌ COCl2(g) Initial Change Equil. 0 0 5. Before Change After Change Equil.1 × 103 = x = 2 × 10−4 M. Assumptions are good by the 5% rule.020 − 2 × 10−4 = 0.10 M 0 0. a change in volume will not shift the equilibrium. [SCN-] = 0.0 atm 44.1 × 103 0.020 M Le Chatelier's Principle 45. A change in volume will change the partial pressure of all reactants and products by the same factor.5 × 108 = Solving: x = 1.08) x [Fe ][SCN ] K = 1. Assumptions are good (well within the 5% rule). x is 1% of 0. Statement c is false for exothermic reactions where an increase in temperature decreases the value of K. The shift in equilibrium depends on the number of gaseous particles on each side.0 − x ≈ 5.08 M [FeSCN2+] = 0.08 + x 0.020 − x [FeSCN 2 + ] 0. If temperature remains constant. PCO = PCl2 = 1. Fe3+(aq) + SCN−(aq) ⇌ FeSCN2+(aq) K = 1. x = [Fe3+] = 2 × 10−4 M. Statement a is false for reactants that are either solids or liquids (adding more of these has no effect on the equilibrium).020 mol/L Fe3+ react completely (K is large.0 atm.020 New initial x mol/L FeSCN2+ reacts to reach equilibrium +x +x ← −x x 0. Addition of a catalyst has no effect on the equilibrium position. An increase in volume will shift the equilibrium to the side with the greater number of particles in the gas phase.020 − x 0. If there are the same number of gas-phase particles on each side of the reaction.) Kp = 1. Statement b is false always.

H+ + OH− → H2O. we do not change the partial pressures (or concentrations) of any of the substances in equilibrium with each other since the volume of the container did not change.168 CHAPTER 6 CHEMICAL EQUILIBRIUM When we change the pressure by adding an unreactive gas. The moles of SO3 will increase because the reaction will shift left to use up some of the added O2(g). 49. decreasing T will remove heat. c. sodium hydroxide (NaOH) will react with the H+ on the product side of the reaction. c. Because more CrO42− is produced. As HF(g) is removed. 47. the reaction will shift left to produce more HF(g). c. Reaction shifts to the right as Fe3+ is added. d. the reaction is still at equilibrium. Doubling the volume will decrease all concentrations by a factor of one-half. This effectively removes H+ from the equilibrium. shifting this endothermic reaction to the left. as H2O(g) is removed. a. . a. No effect. so the reaction is still at equilibrium. Increase. which will shift the reaction to the right to produce more H+ and CrO42-. Shifts left. Decrease 50. the partial pressures of sulfur trioxide. No effect.through the formation of AgSCN(s). Heat + 2 SO3 ⇌ 2 SO2 + O2. a. and oxygen are unchanged. adding more of a pure solid or pure liquid has no effect on the equilibrium position. 48. because there are fewer reactant gas molecules than product gas molecules. 1 [FeSCN 2 + ] eq 2 = 2 K. b. If the partial pressures (and concentrations) are unchanged. the reaction shifts left with a decrease in volume. Shifts right. b. the solution turns yellow. Q > K Q= ⎛1 ⎞⎛ 1 ⎞ − 3+ ⎜ [Fe ] eq ⎟⎜ [SCN ] eq ⎟ ⎝2 ⎠⎝ 2 ⎠ The reaction will shift to the left to reestablish equilibrium. sulfur dioxide. d. The reaction will shift to the left to produce more SCN-. Removing Fe3+ as Fe(OH)3(s) will shift the reaction to the left to produce more Fe3+. e. Increase. HF(g) will be removed by reaction with the glass. Adding Ag+ will remove SCN. b. the reaction will shift right to produce more H2O(g).

because the moles of gaseous reactants equals the moles of gaseous products (2 mol versus 2 mol). No change because there are equal reactant and product molecules of gas. e. a. an increase in temperature will shift the equilibrium to the right. a. c. heat is a product: CO(g) + H2O(g) → H2(g) + CO2(g) + heat Increasing T will add heat. c. Reaction shifts right. Right c. The equilibrium shifts to the left to use up the added heat. No effect. Shift to left b. No effect d.CHAPTER 6 51. We make the same assumption when liquids are present (only worry about the gas molecules). Left d. Shift to right. d. No effect (reactant and product concentrations are unchanged) e. Reaction shifts left (to reactants) because the reactants contain 4 molecules of gas compared with 2 molecules of gas on the product side. When the molecules of gas are equal on both sides of the reaction. Shift to right e. a change in volume will have no effect on the equilibrium. He(g) is neither a reactant nor a product. No effect. because the reaction is exothermic. 52. a change in volume has no effect on the equilibrium position. One can ignore the solids and only concentrate on the gases because gases occupy a relatively huge volume compared with solids. Right. f. the reaction itself will want to increase its own volume by shifting to the side of the reaction that contains the most molecules of gas. the equilibrium will shift right with an increase in volume. When the volume of a reaction container is increased. No effect. Left b. . a. Shift to right. a decrease in temperature will shift the equilibrium to the right because heat is a product in this reaction (as is true in all exothermic reactions). because there are equal numbers of product and reactant gas molecules. Right CHEMICAL EQUILIBRIUM b. Reaction shifts right to produce more CO2(g). 53. Reaction shifts right (to products) because there are more product molecules of gas (2) than reactant molecules (1). because the reaction is endothermic (heat is a reactant). Left. a. b. because there are more gaseous product molecules than gaseous reactant molecules. 54. Right c. e. then the reaction will remain at equilibrium no matter what happens to the volume of the container. 169 d.

Additional Exercises 57. As temperature increases. a. Therefore. a. In an exothermic reaction. The answer must lie in the rates of the reaction. can be produced in high-energy or hightemperature environments because the production of NO is endothermic. Once the NO gets into a more normal temperature environment. In nature.170 55. Very strong bonds must be broken. CHAPTER 6 CHEMICAL EQUILIBRIUM An endothermic reaction. and the rates of the reaction will also increase. 58. There is more NO in the atmosphere than we would expect from the value of K. so the smell of ammonia will increase.0 × 10 −3 L) = = 4 × 10−21 mol NO RT ⎛ 0. the rates of both reactions: N2 + O2 → 2 NO and 2 NO → N2 + O2 are so slow that they are essentially zero. the reaction essentially doesn’t occur at low temperatures. At 25°C.08206 L atm ⎞ ⎟ (298 K ) ⎜ ⎟ ⎜ K mol ⎠ ⎝ Kp = 1 × 10−31 = 2 2 PNO PNO = (0. and an increase in temperature shifts the equilibrium to the reactant side (as well as lowering the value of K). The amount of NH3(g) will increase as the reaction shifts right. the activation energy is very high. Na2O(s) ⇌ 2 Na(l) + 1/2 O2(g) K1 Na2O(s) + 1/2 O2(g) ⇌ Na2O2(s) K= 2 Na(l) + O2(g) ⇌ Na2O2(s) 1/K3 ___________________________________________________ K = (K1)(1/K3) 2 × 10 −25 = 4 × 103 L1/2/mol1/2 − 29 5 × 10 . At these high temperatures. will shift right to products with an increase in temperature. resulting in a higher production of NO.2) PN 2 × PO 2 4 × 10 −21 mol NO 6. heat is a product. N2(g) + O2(g) ⇌ 2 NO(g) PNO = 1 × 10−16 atm In 1. it doesn’t go back to N2 and O2 because of the slow rate. 56. Nitric oxide. This is consistent with an exothermic reaction.8)(0.02 × 10 23 molecules 2 × 103 molecules NO × = mol NO cm 3 cm 3 b. the value of K decreases. some NO is produced by lightning and the primary manmade source is automobiles. where heat is a reactant.0 cm3 of air: nNO = PV (1 × 10 −16 atm)(1. K will increase. however.

NO2(g) + O2(g) ⇌ NO(g) + O3(g) K = 1/5.7 × 1033 __________________________________________________________________________ K = (1.5 × 1048 2 NaO(g) ⇌ 2 Na(l) + O2(g) K2 2 Na2O(s) ⇌ 2 Na(l) + 1/2 O2(g) 59.50 – x 0. x = 0.00 atm PB = χBPtotal. ⇌ 2 A(g) + D(g) ⇌ 2 A(g) + 2 B(g) K1 = (1/3.5 × 1048)(1.50 − x PB (at equilibrium) = 2x = 2(0.00 atm . 1/K3 2 Na(l) + O2(g) ⇌ Na2O2(s) ________________________________________________________________ K = K 2 (1/K 3 ) = 8 × 1018 L2/mol2 2 NaO(g) ⇌ Na2O2(s) 2 O(g) + NO(g) ⇌ NO2(g) O2(g) + O(g) ⇌ O3(g) 2 C(g) K = 1/6.8 × 10−49 = 1.50 – 0.6 × 1081 L/mol 60.275 Ptotal 3.8 × 10−34 = 1.826 atm = = 0.50 atm 1. Kp = K = 0.10 ____________________________________________________________ C(g) + D(g) ⇌ 2 B(g) K = K1 × K2 = 0. CHEMICAL EQUILIBRIUM NaO(g) ⇌ Na(l) + 1/2 O2(g) K2 K1 171 1/K3 2 Na(l) + O2(g) ⇌ Na2O2(s) ________________________________________________________________ K = K2(K1)(1/K3) = 8 × 10−2 L/mol NaO(g) + Na2O(s) ⇌ Na2O2(s) + Na(l) c.579 Kp = K(RT)Δn.413 atm 1.579 = K = + D(g) 1.826 atm Ptotal = PC + PD + PB = 2(1.413) = 0.50 − x) 2 2x = (0. 1. χB = PB 0.826 = 3.50 − x)(1.761.50 – x ⇌ 2 B(g) 0 2x (2 x) 2 (2 x) 2 = (1.7 × 1033) = 2.579. C(g) Initial 1.50 atm Equil.50)2 = 8.16 × 10 −2 C(g) K2 = 7.CHAPTER 6 b. Δn = 2 – (1 + 1) = 0.413) + 0.579)1/2 = 0. because Δn = 0.50 − x) (1.

7 torr P0 = n PCl5 RT V 2.2 = 169.0 M = [H2]0 − 3(2. [N2]e = 8.0 M = [H2]0 −3x. N2(g) + 3 H2(g) ⇌ 2 NH3(g) Kp = 5. 8.000 L x = Ptotal − P0 = 358.0 M.00)x 2. x = 5.5 torr PPCl 3 = PCl 2 = 169.3 × 10−4 atm) = 2.1 × 10−3 atm 63.0 M = [N2]0 − 2.2230 atm 760 torr . P0 − 2x = Kp = [(4. 3 H2(g) + N2(g) CHAPTER 6 CHEMICAL EQUILIBRIUM ⇌ 2 NH3(g) [H2]0 [N2]0 0 x mol/L of N2 reacts to reach equilibrium −3x −x → +2x [H2]0 − 3x [N2]0 −x 2x From the problem: [NH3]e = 4. Initial Change Equil.7 − 189.2 K 208.3 × 105 P0 = initial pressure of NH3 0 0 P0 2x atm of NH3 reacts to reach equilibrium +x +3x ← −2x x 3x P0 − 2x P0 .00(5. x = 2.00 From problem. Initial Change Equil.0 M). PCl5(g) P0 −x P0 − x ⇌ → PCl3(g) 0 +x x + Cl2(g) 0 +x x Kp = (PPCl3 × PCl 2 ) / PPCl5 P0 = initial PCl5 pressure Ptotal = P0 − x + x + x = P0 + x = 358.00) x 2 4.0 M = [N2]0 − x 5.2490 atm (or 189. [H2]0 = 11. [N2]0 = 10.0 M 62.00) x]2 (4.4156 g 0. Initial Change Equil.3 × 10−4 atm 3 3 4 ( x)(3x) ( x)(3x) 27 x 27 x 2 P0 = (4.08206 L atm × × 523.00) x − 2 x]2 [(2.172 61.0 M = 2x.0 M. so P0 = (4.0 M.22 g/mol K mol = = 0.3 × 105. a.00 = = = = 5.00)x = 4.2 torr) 2. [H2]e = 5.5 torr × 1 atm = 0.

P0 = (8.5 = 19.0650 atm.37 +x 5.900 = P0 + x = (9. SO2Cl2(g) P0 −x P0 .250 mol Cl2 increases PCl 2 by 5.700 . PCl 2 = 5. Initial Change Equil.0650 atm PPCl3 = 0.2 = 5.37 + x React completely New initial (5.2230 atm Adding 0.43 × 10−2 atm 0.29)x − 0.100 = 0.37 atm Cl2 added 2.2489 −x → 0.59 −0.44 atm 64.CHAPTER 6 CHEMICAL EQUILIBRIUM 1 atm = 0.100) 2 = 1.2489 − x) Solving using the quadratic formula: x = 0. P0 − x = 0. 0.2489 − x 0.0650 = 0. ⇌ PCl3(g) + Cl2(g) (from a) 0.2230 5.0259 atm 760 torr 173 PPCl5 = 189.0259 atm 0. x = 0. PPCl5 = 0.1839 atm.800 − 0.900 atm = P0 − x + x + x = P0 + x x × 100 = 12.92 atm 0.x ⇌ → Cl2(g) 0 +x x + SO2(g) 0 +x x P0 = initial pressure of SO2Cl2 Ptotal = 0.2230 ← 0.2230 0 +x x 5.000 PCl5(g) Initial Initial' Change After Change Equil.478 = 0 (0.700 atm = PSO 2Cl 2 Kp = PCl 2 × PSO 2 PSO 2Cl 2 = (0. PCl 2 = = 0. x2 + (7.0259 n Cl 2 RT V b.00)x.2 − 169.37 + x)( x) = 1.92.100 atm x = 0.0259 +0.37 + 0.2230 atm 0.100 atm = PCl 2 = PSO 2 .2489 − 0.0650 = 5.37 atm.2230) 2 = 1.00)x P0 Solving: 0.250 × 0.7 torr × Kp = (0.08206 × 523.2230 −0.5.

Kp = PN 2O 4 (1.4% 1.600) 2 = 2.22 atm d.704 atm. equilibrium will shift to the right.2 atm 0. Percent dissociation = x 1.5 Initial 1.16 . Q= (0.052) = 0.052 = 0. a.) (0.17 atm Equil. 0. 4x2 + (6. b.1. PPCl5 = 0.16 atm 0.20) 2 = 4.600 atm and PN 2O 4 = 0.5)x − 13.06 = 0.450 g PCl 5 0.17 N2O4(g) Initial 0. 0.06 atm.052 atm PNO 2 = 0. PN 2O 4 = 0.06 = 2.12 atm 2. 1.500 L 66.10 + 1.5.17 − x) Solving using the quadratic formula: x = 0.06 × 100 = × 100 = 91.16 atm 0 0 x atm of PCl5 reacts to reach equilibrium Change −x → +x +x Equil. PNO 2 = 0. Q < K.06 + 1.10 atm Ptotal = PPCl5 + PPCl3 + PCl 2 = 0.600 atm 0.16 − x Using the quadratic formula: x = 1.600 + 2(0.17 .3 = 0 1.22 g/mol K mol = = 1.6)x − 0.174 N2O4(g) ⇌ 2 NO2(g) 2 PNO 2 CHAPTER 6 = CHEMICAL EQUILIBRIUM 65.17 atm are the new partial pressures.06 atm PPCl5 = 1.0. PPCl3 = PCl 2 = 1.10 atm c. K 208.16 − 1.16 1.354 = 0 (carrying extra sig. PPCl5 = n PCl5 RT V PCl5(g) ⇌ PCl3(g) + Cl2(g) Kp = PPCl3 × PCl 2 PPCl5 = 11.08206 L atm × × 600.2 = ⇌ 2 NO2(g) 0. figs.34 Doubling the volume decreases each partial pressure by a factor of 2 (P = nRT/V). x2 + (11.600 + 2x (0.600 + 2 x) 2 .16 − x x x Kp = x2 = 11.17 − x Kp = 4.

5 = 7.786 atm = 597 torr × 2 760 torr (200.0 torr = 392.00 L) = 1. nRT (5. CHEMICAL EQUILIBRIUM 2 NaHCO3(s) 175 + CO2(g) + H2O(g) Kp = 0.0 torr PH 2 = 3x = 3(96.08206 L atm K −1 mol −1 )(398 K ) Mass of Na2CO3 produced: 1.95 × 10−2 mol CO2 84.50 atm (from a). a.5 g c.CHAPTER 6 67.0) = 288 torr.01 g NaHCO3 × = 2.0 − 2x + 3x. − − x x Initial Kp = 0.0 g Na 2 CO 3 × = 1.08206 L atm K −1 mol −1 )(398 K ) = = 3. +x Change − → − +x Equil. V = 68.01 g NaHCO 3 2 mol NaHCO 3 When all the NaHCO3 has just been consumed.9 L P 0.0 − 2.0 g NaHCO3 × 1 mol NaHCO 3 1 mol CO 2 × = 5.6 g Na2CO3 mol CO 2 mol Na 2 CO 3 Mass of NaHCO3 remaining = 10. Kp = (PH 2 ) 3 (PAsH3 ) 2 = ( 288) 3 1 atm = 0. 0.25 = PCO 2 × PH 2O .50 atm b.0) .5 g NaHCO3 mol CO 2 mol 1 mol Na 2 CO 3 106.25 = x2. Initial Equil.50 atm 2 AsH3(g) 392. 10.0 .5 × 10−2 mol CO2 (0. we will have 5.50 atm)(1. PAsH3 = 392.95 × 10−2 mol CO2 gas at a pressure of 0.2x ⇌ 2 As(s) − − + 3 H2(g) 0 3x Ptotal = 488.0 torr 392. x = PCO 2 = PH 2O = 0. x = 96.5 × 10−2 mol CO2 × 2 mol NaHCO3 84.5 × 10−2 mol CO2 × Mass of NaHCO3 reacted: 1.0 − 2(96.95 × 10 −2 mol)(0. n CO 2 = PCO 2 V RT = (0.25 ⇌ Na2CO3(s) − − 0 0 NaHCO3(s) decomposes to form x atm each of CO2(g) and H2O(g) at equilibrium.0 torr b.0) = 200. a.

00 L x mol/L of NH3 reacts to reach equilibrium Change !x !x − 0. − − ⇌ C10H8(g) 0 x K = 4. Initial NH3(g) + H2S(g) CHAPTER 6 CHEMICAL EQUILIBRIUM 1 [ NH 3 ][H 2S] ⇌ NH4HS(s) K = 400.011 g 1 mol H = 6.24 Empirical formula = (C1.400 ! x = ⎜ ⎟ (0.400 M – x = 0.75 mol L mol NH 3 Total mol NH4HS(s) = 2.400 ! x 1 ⎛ 1 ⎞ K = 400.08 g/mol) is one-half of 128.050 M H2S PH 2S = 70.050 mol 0. the molecular formula is C10H8.256 mol Because the empirical mass (64.75 mol NH4HS × 51.24 mol H.0500.29 × 10 −6 = [C10H8] = x .350 mol NH 3 1 mol NH 4 HS × = 1.75 mol produced = 3.25H) × 4 = C5H4.29 × 10 −6 = [C10H8] K = 4.00 mol initially + 1. n H 2S RT V = n H 2S V × RT = 0.350 M Mol NH4HS(s) produced = 5.400 − x) ⎝ 400.8 g = 128 g/mol 0.25 6. = 2.176 69.3 atm L K mol Assuming 100. C10H8(s) Initial Equil.00 L 5.008 g 7. 0. 1. x = 0.00 mol − 5. 0.400 − x)(0.29 g H × 1 mol C = 7.802 mol C 12.400 M – 0.400 ! x − Equil.75 mol total 3.12 g NH 4 HS = 192 g NH4HS mol NH 4 HS [H2S]e = 0.00 mol 2.350 M = 0.802 = 1.00 g naphthalene: 93.00 L × 0.2 K = 1. molar mass = 32. = .08206 L atm × × 308.71 C × 6. ⎠ 1/ 2 = 0.

0186) mol CO ⎤ ⎢ ⎥⎢ ⎥ 3 2.0493 ! x 0.33 atm (= PNO 2 ) .63 g C5H6O3 × 1 mol C 5 H 6 O 3 = 0.105 mol = 0.16)x (0.34 × 10 − 2 mol 71.00 g × 1 mol C10 H 8 = 2. y y2 = 0. Equil.63 atm × 2. Initial Change Equil.0493 + 3x.08206 L atm RT × 473 K K mol C2H6(g) + 3 CO(g) ⇌ 0.0493 – x + x + 3x = 0.32)x (0.50 L ⎣ ⎦ 3 Challenge Problems 72. Kp = b. x = 1.0186 mol C 2 H 6 ⎤ ⎡ 3(0.1 (0.5 atm.32)x (0. a.50 L 2. x = 0.0186 mol ⎡ 0.105 mol total = 0.15 × 10 −5 mol C10H8 sublimed Mol C10H8 initially = 3. N2O4 x ⇌ 2 NO2 .67 atm (= PN 2O 4 ) and y = 0. 5. x + y = 1.74 × 10 −6 mol3/L3 K= 2 6 = ⎣ [C 5 H 6 O 3 ] ⎡ (0.50 L = 0.0186) mol C 5 H 6 O 3 ⎤ ⎢ ⎥ 2.0 atm.32)x = 1.0493 mol 0 0 Let x mol C5H6O3 react to reach equilibrium.10 g Total moles of gas = ntotal = at equilibrium C5H6O3(g) Initial Change Equil.0493 mol C5H6O3 initially 114.16 atm 1.42) 2 = 0. Ptotal V 1.34 × 10 −2 mol C10H8 initially 128. !x → +x +3x x 3x 0.50 L [C H ][CO] ⎦⎣ ⎦ = 6.0493 − 0.0919% 2.84)x ⇌ 2 NO2(g) 0 +(0.00 L × 4.15 × 10 −5 mol × 100 = 0.29 × 10 −6 mol/L = 2.16 x Solving: x = 0. N2O4(g) x !(0.3 atm.16 g Percent C10H8 sublimed = 2.CHAPTER 6 CHEMICAL EQUILIBRIUM 177 Mol C10H8 sublimed = 5.84)x + (0.

+ Br2 ⇌ 2 NOBr 0.) P0 ! x = 0.7 − x Ptotal = 110.2 torr.4 torr 41. x = 29.4 .0768 atm Kp = b.3 − x) + 2x = 139.30 atm NO react completely.30 − 2x 0.165 = 0. Initial Change Equil.67. Because Kp is pretty large.4 − 2x 41.3 torr 0 2x torr of NO reacts to reach equilibrium −2x −x → +2x 98.% dissociated 0.33. PNOBr = 2(29.2 = 12. 2 PNOBr (0. and then solve the back equilibrium problem.33 atm P0 = initial pressure of N2O4 P0 !x 0. Initial Change Equil.3 − 29. x = 0.2x) + (41.4 .2(29.0526 atm PBr2 = 41.7 − x.30 atm 0.15 0. P0 = 0.30 atm 0.15 → +0. let’s approach equilibrium in two steps: Assume the reaction goes to completion. PNO = 98.30 React completely 0 0.0768 atm) 2 = = 134 atm−1 2 2 PNO × PBr2 (0. a. 2 NO(g) + Br2(g) 0.0159 atm) 2 NO(g) + Br2(g) ⇌ 2 NOBr(g) 0.2) = 58.67 atm 2x = 0. 73.3 − x 2x Ptotal = PNO + PBr2 + PNOBr = (98. −0.84 atm.165 (using extra sig.30 − 2y 2y .67 + 0.2) = 40.5 = 139.0 torr = 0. N2O4 CHAPTER 6 CHEMICAL EQUILIBRIUM ⇌ 2 NO2 0 +2x 0. which can be difficult to solve unless you have a graphing calculator.1 torr = 0.30 − x 2x This would yield a cubic equation. Initial Change Equil.4 torr = 0.165 × 100 = 20. figs.0526 atm) (0.30 atm 0 Let 0.84 ⇌ 2 NOBr(g) 98.0159 atm.15 + y 0. 2 NO Before Change After Change Equil.178 c.30 New initial 2y atm of NOBr reacts to reach equilibrium +2y +y ← −2y 0.30 −0.30 atm 0 2x atm of NO reacts to reach equilibrium −2x −x → +2x 0.

PBr2 = 0.15 + y ) 179 K p = 134 = If y << 0. y = 0.010 0. 2x = 2.15 + 0.0025 0.046) 2 = 536y2.5 × 10−11 atm3 2 (0. PNOBr = 0.034 as an approximation for y. Kp = 2 N2O5 ⇌ 4 NO2 0 +0. y = 0.100) 2 2.15).30 − 2 y ) 2 (0.023. 0. Initial Change Equil. b. so the mole percent of N2O5 decomposed will be greater than 0.30 − 0.026 answer.0 × 10−3 atm = PN 2O5 decomposed (0.068) 2 = 536y2.5 × 10−11 = (4 x) 4 ( x) (4 x) 4 ( x) ≈ .100 − 2 x) 2 (0. PN 2O5 = 1.30 − 0.026 0.30 − 2y = 0.010 + O2 0 +0. 1. If the volume is increased.) So: PNO = 2y = 0. 2 (0.0 times the old volume. y = 0.30 − 0.0025 1.995 (0.25 atm 74.052 atm.15 Use 0.15 + 0. 0.0.30) 2 ≈ 536y2 and y = 0.034.CHAPTER 6 CHEMICAL EQUILIBRIUM (0. equilibrium will shift to the right. Therefore. assumptions are poor (y is 23% of 0.100 − 2x 2.010) 4 (0.15 + y = 0.026 atm (We have converged on the correct 0.30 − 2 y ) 2 = 134 × 4y2 = 536y2 .00 atm × 2 N2O5 Initial Change Equil. a. and solve by successive approximations (see Appendix 1): (0.100 .18 atm.995) The new volume is 10.0025) = 2.0 × 10 −3 × 100 = 2.023 (0.0 ⇌ 4 NO2 + O2 0 +x x 0.50%.034 (0.00 = 0.000 atm −0. the initial partial pressure of N2O5 will decrease by a factor of 10.15: (0.15 + y ) ( 2 y ) (0.100 atm 0 −2x → +4x 4x 0.0% N2O5 decomposed (moles and P are directly related) 0.100 atm 10.052) 2 = 536y2.0050 → 0.15 + 0.

50(10.00 3.25 4 CO2 + 6 H2O 1. and 10.25 atm +2x 3.00 10. we need the initial pressure of P4.00 − y Let y = PP2 at equilibrium.50 – 2x K p = 1.50 atm CO2. P0 0.50 + 2 H2O 0 3. 0 +x x 4 + 2 O2 3.50 atm H2O.180 P4(g) ⇌ 2 P2(g) Kp = 0.25 atm O2.270 atm = PP2 = 2x.0 × 10 = 2 PCO 2 × PH 2O 2 PCH 4 × PO 2 = (6.50 After 0 12.50 − x)(10.50 ) 2 ≈ x(3. x = 0. PP4 = 1.00 → CO2 0 1.00 − 0.73 atm To solve for the fraction dissociated.25) 2 .00 atm 2 C2H6 + 7 O2 → Before 2.100 1.00 atm.50 6.135 atm. then Kp = Solving: y = 0. we have 3. P4(g) Initial Change Equil. PP4 = 1.135 = 0.00 atm = P0 + x Solving: 0.50 atm −2x 10.50 − 2 x) 2 6.50 atm Thus after we let the two reactions go to completion. and then solve the back equilibrium problems. 6.00 − 0.100 = 2 PP2 CHAPTER 6 CHEMICAL EQUILIBRIUM 75. ⇌ 2 P2(g) P0 0 P0 = initial pressure of P4 x atm of P4 reacts to reach equilibrium −x → +2x P0 − x 2x Ptotal = P0 − x + 2x = 1.25 + 2 x) 2 x(3.270 atm = PP2 .87 atm Fraction dissociated = 76.87 Equilibrium lies to the right (Kp values are very large). 0. PP4 . P0 = 1. Let each reaction go to completion initially. PP4 + PP2 = Ptotal = 1.50 – x + 2 H2O 10.50 3.270 = 0.25 + 2x ⇌ ← CO2 6.50 atm −x 6.00 After 0 12. CH4 + 2 O2 Before 1.00 − PP2 y2 = 0. Let’s solve the back equilibrium problems to determine the equilibrium concentrations.135 x = = 0. or 16% of P4 is dissociated to reach equilibrium.50 15.16. CH4 Initial Change Equil.

50 ) 6 ≈ ( 2 x) 2 (3. 77.50 atm −6x 10.18 0.80 = 0.50 − 4 x) 4 (10.80 PO3 = Kp = 78.00)PO3 = 6.00)PO 2 − (32. 2 C2H6(g) + Initial Change Equil.18 − (32. 0.8 × 10−3 atm. d = density = PO ( molar mass O 2 ) + PO3 (molar mass O3 ) P × (molar mass) = 2 RT RT 0.00)PO 2 + (48.5 atm−1 (0.118 atm 16.50 – 6x Kp = 1.25 + 7 x) 7 4 x 2 (3.50) 4 (10.9071 and χ O 2 = 0.0929 183 .00 g / mol) .0 × 108 = 4 6 PCO 2 × PH 2O 2 7 PC 2 H 6 × PO 2 = (6.50 − 6 x) 6 (6.CHAPTER 6 CHEMICAL EQUILIBRIUM 181 x = PCH 4 = 6.50 – 4x + 6 H2O(g) 10.00)PO 2 + (48. 0 +2x 2x 7 O2(g) 3.50 atm −4x 6. Solving using simultaneous equations: (32. assumptions are good. Thus: χO = 166 = 0.00 2 PO3 3 PO 2 = (0.00 g / mol) + PO3 (48.168 atm 760 torr Ptotal = PO 2 + PO3 = 128 torr × We have two equations in two unknowns. Initial Change Equil. assumptions are good.25 atm +7x 3.25) 7 2x = PC 2 H 6 = 0.118) 3 O2(g) 100 !83 17 ⇌ 2 O(g) 0 +166 166 Assume exactly 100 O2 molecules.050 atm and PO 2 = 0.38 ____________________________ (16.079 atm.08206 L atm × 448 K K mol 1 atm = 0.050) 2 = 1.00)PO3 = 6.25 + 7x ⇌ ← 4 CO2(g) 6.168 g/L = PO 2 (32. (32.00)PO3 = 0.00)PO3 = −5.

86. 4.016 The effused mixture has 33.72 g CH3OH × 1 mol = 0.9071 atm. n H2 n CH 3OH = 8.04 = 3. we have two equations and two unknowns. respectively. the effused mixture will have 33.0 times as much H2 as CH3OH.117 atm. Kp = 2 PO (0.9071) 2 = 8.240 atm 79. 0. and PO = χOPtotal CHAPTER 6 CHEMICAL EQUILIBRIUM Because initially Ptotal = 1.0929 atm and PO = 0.0 times as much H2 as CH3OH. Let n H 2 and n CH 3OH equal the equilibrium moles of H2 and CH3OH.0929 PO 2 O2 Initial Change Equil.182 PO 2 = χ O 2 Ptotal .118 mol n CH 3OH 2x 0. = 8.28 = Solving: x = 0.147 mol −x 0. x− y x Solving: x = 0. Ptotal = (x − y) + 2y = 0. PO 2 = 0.123 atm and y = 0.147 mol CH3OH initially 32. 33.147 − x ⇌ → CO(g) 0 +x x n H2 = + 2 H2(g) 0 +2x 2x From the ICE table.0.86 atm = 0.987 2. 8.000 atm.147 − x .987 × n H2 n CH 3OH .04 g Rate1 = Rate 2 M2 M1 Graham’s law of effusion: Rate H 2 Rate CH 3OH M CH 3OH M H2 = = 32. ⇌ 2O 0 +2y 2y x !y → x!y (2 y) 2 y × 100 = 95.0 = 3.28 CH3OH(g) Initial Change Equil. When the effusion rate ratio is multiplied by the equilibrium mole ratio of H2 to CH3OH.

0876 − 0.41 × 10−3 mol/L K= ⎝ ⎛ 0. Equilibrium moles Cl2 = x + 0.0 L ⎟ ⎟⎜ ⎟ ⎠⎝ ⎠ = 2.168 mol Cl added = 2 ⎛ 0.100 mol × 0.0 L ⎟ ⎟ ⎝ ⎠ b.0876 Cl2(g) 0 +0. 89.0438 = 0.328 atm → −x 0.0876 mol 0.0876 mol ⎞ ⎛ 0.08206 L atm × 480.0 ⎠ .256 ⎞ ⎜ ⎟ ⎝ 15.1 g SbCl5(g) Initial Change Equil.328 − x .300) 0. solving: x = 0. a.212 mol ⎞ ⎜ ⎜ 15.212 ⎛ 0. reaction shifts left after Cl2 is added.300 mol SbCl5 initially 299.212 + 0.0 L + Cl2(g) 0 +x x Kp = 0.0876 = 0.0438 mol 2 Therefore.23 mol2/L2 1 mol = 0. ⇌ SbCl3(g) + 0 +0.0438 ⎞ ⎛ 0.328 atm 12.00 L ⎟⎜ ⎟ 2 [CO][H 2 ] ⎝ ⎠⎝ ⎠ K= = (0. Let x = moles Cl2 added.267 atm 2.118) mol [CH 3OH] 1.0876 0. K K mol = 0.300 mol −(0. PPCl5 = n PCl5 RT V = PCl5(g) Initial Change Equil.0438 Equilibrium moles SbCl5 = 0.0438 mol SbCl3 was reacted.CHAPTER 6 CHEMICAL EQUILIBRIUM 2 183 ⎛ 0.0 ⎠ 0.0876 mol ⎞ ⎜ ⎜ 15.0438 = x + 0.0876 0.0 L ⎟ ⎜ 15.00 L 80.41 × 10−3 81. a. ⇌ PCl3(g) 0 +x x 0. Equilibrium moles SbCl3 = 0.118 mol ⎞ ⎛ 2(0.256 mol ⎛ x + 0.00 L ⎟ ⎜ 1. 0.0 ⎝ ⎠ ⎝ 15.7 g SbCl5 × = 0.0438 ⎞ ⎜ ⎟⎜ ⎟ 15.292)(0.118 mol) ⎞ ⎜ ⎟ ⎜ 1.147 − 0.

50 L) = 4.511 atm 2 P0 = 2.511 = 1.49 atm)(5.4 g PCl5 was initially introduced.328 − x Solving using the quadratic formula: x = 0.137 atm b.534) = (1.184 CHAPTER 6 CHEMICAL EQUILIBRIUM Kp = x2 = 0.00 − x = 2.49 atm. x2 = 0. = 0.534 − (0.189 mol PCl5 × 208.189 mol PCl5 (0.191 atm.08206 × 684 K)/(32.45 atm H2O Solving using simultaneous equations: 2x + 2y = 4.08206 L atm K −1 mol −1 )(480. PCl5(g) P0 −x P0 − x ⇌ → PCl3(g) 0 +x x + Cl2(g) 0 +x x P0 = initial pressure of PCl5 Ptotal = 2. x= = 0.534 = 0.49 atm.534)x P0 − x 2.22 g PCl5/mol = 39. x2 + (0.00 − 2 x solving using the quadratic formula: x2 + (0.00 − 0.16 atm O2 and 2x + 2y = 4. PPCl5 = 0.16 atm O2 2x + 3/2 y = 4.00 atm = (P0 − x) + x + x = P0 + x.50)y = 0.00 L) = 0.267.00 g/mol × 2.191 atm PPCl3 = PCl 2 = 0.267)x − 0.267. the initial pressure of PCl5 was 1. P0 (for O2) = n O 2 RT / V = (6. 82.16 (0.534 ± (0.45 −2x − (3/2)y = −4. n PCl5 = PPCl5 V RT − 0.49 atm − 0.29. K ) 0.08758 = 0 (carrying extra sig.400 g × 0.) 0. P0 = 2.534)x − 0.49 atm CH4(g) + −x 2 O2(g) → CO2(g) + 2 H2O(g) −2x → +x +2x Change Change CH4(g) + 3/2 O2(g) → CO(g) + 2 H2O(g) −y −3/2 y → +y +2y Amount of O2 reacted = 4.191 = 0. figs.326 atm = 4. Initial Change Equil.328 − 0. y = 0.58 atm = PCO .534) 2 + 4(0.267.00 − x Kp = x2 x2 = 0.

PN 2 = 3.21 To solve for the equilibrium concentrations of all gases (not required to answer the question).21)Ptotal. N2(g) (3. x = PNO = PNO 2 = 0.7)p equilibrium PNO = x equilibrium PNO 2 = y Kp = 1.58) = 4.35 atm . PNO = PNO 2 = 0.5 × 10−4 = N2 Equil.35 atm 15[3. Taking the ratio of the two Kp expressions: 2 PNO PO 2 × PN 2 2 PNO 2 2 PO 2 × PN 2 = 1.65 atm = PCO 2 2 185 2x + 2(0. 1. Ptotal = 15 atm = 71 atm 0.7)p + O2(g) p ⇌ 2 NO(g) x Let: equilibrium PO 2 = p equilibrium PN 2 = (78/21)PO 2 = (3.0 × 10 −5 Air is 21 mol % O2.0 × 10−5 = 2 PO 2 × PN 2 We want PNO 2 = PNO at equilibrium. because PNO = PNO 2 : PO 2 = = 15 atm 1. Equil.45 − 1. solve one of the Kp expressions where p = PO 2 = 15 atm.5 × 10−4 = x2 .45.5 = 56 atm. so: PO 2 = (0. x = 83. so x = y.7(15)] Equilibrium pressures: PO 2 = 15 atm.7(15) = 55. 2 PNO PO 2 × PN 2 + 2 O2 p ⇌ 2 NO2 y (3.CHAPTER 6 CHEMICAL EQUILIBRIUM 4.7)p 2 PNO 2 Kp = 1.0 × 10 −5 1.16 = 1.5 × 10 −4 .5 × 10 −4 1.

20. substituting into P0 − x 0.7 g/mol The average molar mass is determined by: average molar mass = n SO3 (80.88 atm 2(5.76)P0 − (0. CCl4(g) P0 −x P0. Initial Change Equil.20 atm Kp = (2 x) 2 4 x 2 + (0.07 g/mol) + n O 2 (32.07) + PSO 2 (64.76)x. P0 = 1.76) x = 0. ⇌ → SO2(g) + 1/2 O2(g) 0 +x x 0 +x/2 x/2 P0 = initial pressure of SO3 Average molar mass of the mixture is: average molar mass = dRT (1.20 atm.80 atm.00) Ptotal Ptotal = P0 − x + x + x/2 = P0 + x/2 = 1.07) + x (64.80 atm = 63.x/2 (P0 − x) (80.4)1/ 2 = 0.186 84.07 g/mol) + n SO 2 (64. (5. P0 −x P0 − x x= 85.08206 L atm K −1 mol −1 ) (873 K ) = P 1.76 − 2 ± (4 + 25.x CHAPTER 6 CHEMICAL EQUILIBRIUM ⇌ → C(s) + − − − 2 Cl2(g) Kp = 0.32 atm.60 g / L) (0.3) SO3(g) Initial Change Equil.7 = .20: 2 4x + x + x = 1.20 = 0.07) + PO 2 (32. P0 = 0.76 0 +2x 2x P0 = initial pressure of CCl4 Ptotal = P0 − x + 2x = P0 + x = 1. P0 + 0.80 x (32.76 P0 + x = 1.80 .07) + 1.00) 2 63.00 g/mol) n total Because χA = mol fraction of component A = nA/ntotal = PA/Ptotal: 63.7 g/mol = = PSO 3 (80. 4x2 = (0.76.3)x2 + 2x − 1. P0 = . solving using the quadratic formula: 0.32 = 1.

Using the second reaction.75 atm 0.73) (0.CHAPTER 6 CHEMICAL EQUILIBRIUM (1.161 atm2 For SO3(g) ⇌ SO2(g) + 1/2 O2(g): Kp = 1 PSO 2 × PO/22 PSO3 = (0. PSO 2 = P0 + x = 0.1)x + (64. SO3(g) Initial Change Equil.00)x.75 − 3x .71) The first reaction produces equal amounts of SO3 and SO2. N2(g) + 3 H2 (g) 1.218 atm1/2 (0. Ptotal = P0 − x + P0 + x + x/2 = 2P0 + x/2 = 0.73 atm PSO 3 = P0 − x = 1.7 = 1. calculate the SO3.80 115 = 144 − (120. PSO 2 = 0.63 atm1/2 (0. x = 0.350) = 0.0)x = 29.836 − 0. 2P0 = 0.0550 atm 2P0 + x/2 = 0. 1 PSO 2 × PO/22 PSO3 = (0.73 atm.25 − x ⇌ 2 NH3(g) 0 2x 0.350 atm.405 + 0.836 atm. (40. ⇌ 2 NH3(g) + 3 H2(g) Kp = PN 2 × 3 PH 2 = 6.07) + x (32.405 atm PSO 3 = P0 − x = 0.350) 2 PNH 3 87. PO 2 = x/2 = 0.37 atm Kp = 86.0275 atm.460) (0.07) + x (64. P0 −x P0 − x → ⇌ SO2(g) P0 +x P0 + x + 1/2 O2(g) 0 +x/2 x/2 P0 = initial pressure of SO3 and SO2 after first reaction occurs.0550 = 0.460)(0.460 atm For 2 FeSO4(s) ⇌ Fe2O3(s) + SO3(g) + SO2(g): Kp = PSO 2 × PSO 3 = (0.0275)1/ 2 = 0. x = 0.405 − 0.37)1/ 2 = 0.25 atm 0.80 − 3/2 x) (80.5 × 10−3 N2(g) 0.0 atm Initial Equil. and O2 partial pressures at equilibrium.0550 = 0.809 atm.00) 2 187 63. SO2. P0 = 0.07)x + (16.0275 = 0.71 atm.80 − (3/2)x = 0.836 atm PO 2 = x/2 = 0.

PNH 3 = 2x = 0.5 × 10−3.024 atm 10 atm Initial Equil.5 − x) x = 0.5 × 10−3 3 (75 − 3x) (25 − x) Solving by successive approximations: x = 16 atm. PNH 3 = 32 atm 1000 atm N2(g) Initial New initial Equil. 0 0 5.5 × 10−3.5 × 10−3.25 − x) x = 1.0 × 102 − 2x (5.69 atm.4 atm 100 atm Using the same setup as above: 4x2 = 6.5 − 3x ⇌ 2 NH3(g) 0 2x (2 x) 2 = 6. using successive approximations: 3 (0.5 atm 2. PNH 3 = 1.0 × 102 x 3x 5.0 × 10 2 − 2 x) 2 = 6.5 − 3 x) (2. using successive approximations: 3 (7.188 CHAPTER 6 CHEMICAL EQUILIBRIUM (2 x) 2 = 6.2 × 10−2 atm.5 − x + 3 H2(g) 7. N2(g) 2.75 − 3x) (0. Using successive approximations: 3 (3x) x x = 32 atm.5 atm 7. PNH 3 = 5.0 × 102 − 2x = 440 atm . + 3 H2(g) ⇌ 2 NH3(g) 250 atm 750 atm 0 Let 250 atm N2 react completely.

a larger fraction of N2 and H2 is converted to NH3.04090 mol NOBr initially 109. = equil.086 g/L Vinitial n initial Assuming an initial volume of 1.100.CHAPTER 6 CHEMICAL EQUILIBRIUM 189 The results are plotted as log PNH 3 versus log Ptotal. Notice that as Ptotal increases.100 L . [NO] = = 0.00818 mol = 0.110 L.110(1.495 g/L = = 1. then the equilibrium volume will be 1. that is. the reaction shifts further to the right. solving: x = 0. 88.000 L. n initial 0. Density (equil. V n Density (initial) 4.100 L 1. as predicted by LeChatelier’s principle.04090 − 2 x + 2 x + x = 1.02975 M .91 g 2 NOBr(g) Initial Change Equil.100 = equil. a.04090 If the initial volume is 1. Solving for the equilibrium concentrations: [NOBr] = 0.000 L: 4.495 g NOBr × 1 mol NOBr = 0.00409 mol 0.) 4. as Ptotal increases (V decreases).04090 − 2x ⇌ → 2 NO(g) + Br2(g) 0 +2x 2x 0 +x x = 0.000 L) = 1. The volume increases because the number of moles of gas increases (V ∝ n at constant T and P).03272 mol 0. n equil.00744 M 1. volume must increase. Because density (mass/volume) decreases while the mass remains constant (mass is conserved in a chemical reaction).04090 mol −2x 0.

so: Vfinal n 0. 2. K is a constant as long as temperature is constant.02975) b. 89.0079 mol ⎞ ⎜ ⎜ 0.008206 L atm K −1 mol −1 )(298 K ) nRT = = 0.0121 mol XY (initially) 165 g/mol (0. This causes Q < K and the reaction shifts right to get back to equilibrium.0164 mol = final = = 1. Because there are more moles of product gases versus reactant gases (3 mol versus 2 mol).0121 mol Vinitial = (0.0121 mol) = 4. The argon gas will increase the volume of the container.00424 + 0.416 L ⎟ ⎝ ⎠ = 5.0079 mol → → X + Y 0 0 +0.36) = 0. the volume must increase. This is because the container is a constant-pressure system.0079 + 0.416 L 2 ⎛ 0.190 [Br2] = K= CHAPTER 6 0.00372) = 2.00409 mol = 0.00424 mol ⎞ ⎜ ⎟ [X ][Y] ⎜ 0.967 atm P Vfinal = 0.350)(0. the value of K will not change. Because temperature was unchanged.416 L ⎟ ⎟ ⎝ ⎠ .306 L(1.00424 +0.00424 = 0.00 g = = 4. Because mass is conserved in a chemical reaction: density (final) = mass 2. and if the number of moles increases at constant T and P.33 × 10−4 mol/L 2 (0.00424 mol 0.00 g = 0.416 L.00424 mol Total moles of gas = 0.5 × 10 −3 mol/L K= = [XY] ⎛ 0.24 × 10−3 mol XY dissociated XY Initial Change Equil.00372 M 1. An increase in volume will dilute the concentrations of all gaseous reactants and gaseous products.81 g/L volume 0.36 Vinitial n initial 0. the dilution will decrease the numerator of K more than the denominator will decrease.00424 0.0164 mol V ∝ n.306 L 0.00744) 2 (0.100 L CHEMICAL EQUILIBRIUM (0. 0.0121 mol)(0.00424 0.0121 mol −0.

1648 − x2)24.406 + 0. Concentration units involve both moles and volume and since both quantities are changing at the same time.6 L/mol Substituting into the equilibrium expression for Veq: K = 130.406 + x)24. Let’s simplify the setup of the problem initially by only worrying about the changes that occur to the moles of each gas.)x2 = (0.6 x2 Solving for x (we will carry one extra significant figure): (130.00 atm . At equilibrium: ntotal = mol A(g) + mol B(g) + mol C(g) = x + x + 0.406 + x Therefore: Veq = n total RT (0. x = 0.406 mol Let x mol of C(g) react to reach equilibrium +x +x ← −x x x 0.054. we need the total moles of gas present at equilibrium.406 − x)(0. [C]eq = Veq Veq 0. = (0.406 − x Let Veq = the equilibrium volume of the container.0 K ) = 14.08206 L atm K −1 mol −1 )(300.6)x2 = 4.406 − x .162 mol Solving for the volume of the container at equilibrium: Veq = (0. + B(g) ⇌ C(g) K = 130.0 K ) = P 1.162 mol)(0. (154.046 − x Veq (0.406 + x)(0.CHAPTER 6 CHEMICAL EQUILIBRIUM 191 Marathon Problem 90. we have a complicated system.406 + x)24.6. A(g) Initial Change Equil.00 atm Veq = (0.0 L 1.x = 0. so: [A]eq = [B]eq = x 0. 0 0 0. To calculate the equilibrium volume from the ideal gas law.406 .406 − x) Veq [ C] K = = = x x [A ][B] x2 × Veq Veq From the ideal gas equation: V = nRT/P.08206)(300.

C5H5N(aq) + H2O(l) ⇌ C5H5NH+(aq) + OH−(aq) K = Kb = [C 5 H 5 NH + ][OH − ] [C 5 H 5 N ] 17. Propanoic acid is a weak acid. Acid a. HF(aq) + H2O(l) ⇌ F−(aq) + H3O+(aq) or [H + ][F − ] HF(aq) ⇌ H+(aq) + F−(aq) K = Ka = [ HF] c. NH4+ is a weak acid. the dissociation reaction is: NH4+(aq) + H2O(l) ⇌ H3O+(aq) + NH3(aq) or NH4+(aq) ⇌ H+(aq) + NH3(aq) 192 . The common abbreviation for this reaction is HClO4(aq) → H+(aq) + ClO4−(aq). the dissociation reaction is commonly written without water as a reactant. b. c. c.CHAPTER 7 ACIDS AND BASES Nature of Acids and Bases 16. H2CO3 C5H5NH+ C5H5NH+ Base H2O H2O HCO3− Conjugate Base of Acid HCO3− C5H5N C5H5N Conjugate Acid of Base H3O+ H3O+ H2CO3 18. A conjugate acid-base pair differs by only a proton (H+) in the formulas. The dissociation reaction is CH3CH2CO2H(aq) + H2O(l) ⇌ H3O+(aq) + CH3CH2CO2−(aq) or CH3CH2CO2H(aq) ⇌ H+(aq) + CH3CH2CO2−(aq). For acids. and a base is a proton acceptor. An acid is a proton (H+) donor. HClO4(aq) + H2O(l) → H3O+(aq) + ClO4−(aq). b. a. This reaction is also called the Ka reaction because the equilibrium constant for this reaction is designated as Ka. Similar to propanoic acid. a. Only the forward reaction is indicated because HClO4 is a strong acid and is basically 100% dissociated in water. H2O(l) + H2O(l) ⇌ H3O+(aq) + OH−(aq) or H2O(l) ⇌ H+(aq) + OH−(aq) K = Kw = [H+][OH−] b. so it is only partially dissociated in water.

HClO4 is a strong acid. d. and H2SO4. The beaker on the left represents a strong acid in solution. However.5 × 10−8). there are only a few common strong acids so if you memorize the strong acids.CHAPTER 7 19. d. HClO4. Co(H2O)63+(aq) ⇌ H+(aq) + Co(H2O)5(OH)2+(aq) Ka = [H + ][C 2 H 3O 2 ] [HC 2 H 3O 2 ] − Ka = [H + ][Co(H 2 O) 5 (OH) 2+ ] [Co(H 2 O) 3+ ] 6 [H + ][CH 3 NH 2 ] [CH 3 NH 3 ] + c. The strong acids to memorize are HCl.2 in the text lists some Ka values for weak acids. H2SO4 is a strong acid. ACIDS AND BASES 193 The dissociation reaction (the Ka reaction) of an acid in water commonly omits water as a reactant. HI. a. We will follow this practice. All Kb reactions refer to the base reacting with water to produce the conjugate acid of the base and OH−. c. a. HC2H3O2(aq) ⇌ H+(aq) + C2H3O2−(aq) b. Ka = Strong acids have a Ka >> 1 and weak acids have Ka < 1. HNO3. so the acid exists mostly as undissociated HB molecules in water. HBr. CH3NH3+(aq) ⇌ H+(aq) + CH3NH2(aq) 20. HOCl is a weak acid (Ka = 3. a. then all other acids will be weak acids. The beaker on the right represents a weak acid in solution. CN−(aq) + H2O(l) ⇌ HCN(aq) + OH−(aq) c. H2SO3 is a weak diprotic acid because the Ka1 and Ka2 values are less than 1. only a little bit of the acid HB dissociates into ions. b. b. the acid HA is 100% dissociated into the H+ and A− ions. HNO2: weak acid beaker HNO3: strong acid beaker HCl: strong acid beaker HF: weak acid beaker HC2H3O2: weak acid beaker 22. c. Table 7. Ka values for strong acids are hard to determine so they are not listed in the text. All dissociation reactions produce H+ and the conjugate base of the acid that is dissociated. e. a. NH3(aq) + H2O(l) ⇌ NH4 (aq) + OH (aq) + − [OH − ][ NH 4 ] Kb = [ NH 3 ] Kb = [OH − ][HCN] [CN − ] [OH − ][C 5 H 5 NH + ] [C 5 H 5 N ] + b. 21. C5H5N(aq) + H2O(l) ⇌ C5H5NH+(aq) + OH−(aq) Kb = .

The Ka values are: HClO4: strong acid (Ka >> 1). Ka = 5. The ordering is NH3 > ClO2− > H2O > ClO4− . H2SO4 is a strong acid and water is a very weak acid with Ka = Kw = 1. As Ka increases.6 × 10−10. H2O.2 × 10 −2 NH4+: Ka = 5. the conjugate bases of weak acids are weak bases (10−14 < Kb < 1). When we put acetate ion into solution as the only major basic species. a. H2O and CH3CO2− b. OCl− . HC2H2ClO2 is a stronger acid than NH4+ because Ka for HC2H2ClO2 > Ka for NH4+. the ordering is: HClO4 > HClO2 > NH4+ > H2O 24. H2O: Ka = Kw = 1. for a conjugate acid-base pair. Ka = 3. c. H2SO4 is a much stronger acid than H2O. HOCl. these are the conjugate bases of the acids in the preceding exercise. 25. ClO4− is the conjugate base of a strong acid. In general. Ka = 1. even though they are designated as weak bases. Ka × Kb = Kw.5 × 10−8. it is a terrible base (worse than water).0 × 10−14. C6H5NH2(aq) + H2O(l) ⇌ C6H5NH3+(aq) + OH−(aq) Kb = ACIDS AND BASES [OH − ][C 6 H 5 NH 3 ] [C 6 H 5 NH 2 ] + 23.6 × 10 −10 . Except for water. Because HC2H2ClO2 is a stronger acid than NH4+ (Ka for HC2H2ClO2 > Ka for NH4+). a. NH4+ . the reaction is: CH3CO2− + H2O ⇌ CH3CO2H + OH− . H2O. the stronger the conjugate base. CH3CO2− is a stronger base than H2O. a. An acid-base reaction can be thought of as a competition between two opposing bases. HClO2: Ka = 1. For water. c. the conjugate bases of weak acids are all better bases than H2O.35 × 10−3. c. the conjugate bases of strong acids are terrible bases (Kb < 10−14). Because this equilibrium lies far to the left (Ka < 1). b. HOCl is a stronger acid than H2O because Ka for HOCl > Ka for H2O.0 × 10−14. 26. the stronger the acid. From this relationship. HC2H2ClO2. the weaker is the conjugate base (Kb decreases as Ka increases). The acetate ion is a better base than water and produces basic solutions in water. the weaker the acid. Ka = Kw = 1. acid strength increases. b.0 × 10 −14 From the Ka values. The Ka value is directly related to acid strength. NH3. 27. NH3 will be a stronger base than C2H2ClO2− . use Kw when comparing the acid strength of water to other species.194 CHAPTER 7 d.

47 × 10−14 = [H+][OH−] In pure water [H+] = [OH−].38 × 10−4) weak base (Kb = 1. g. the reaction is endothermic. In deciding whether a substance is an acid or a base. a. HNO3.2 × 10−4) strong base 29.3 for Kb values for some weak bases. i. CsOH. you should keep in mind a couple ideas: 1. h.°C has: [H+] = [OH−]. The preceding equilibrium lies far to the left resulting in a Kb value of less than 1. Sr(OH)2. Weak bases are stronger bases than water but are weaker bases than OH−.47 × 10−14 = [H+]2.631 Obviously. KOH.631 A neutral solution of water at 50. f. and Ba(OH)2.0 × 10−4) weak base (Kb = 4. Therefore. Weak acids only partially dissociate in water and have Ka values of between 10−14 and 1. They are weak acids because they are not as strong as H3O+ (H+). c. Those species we specifically call weak bases (10−14 < Kb < 1) lie between H2O and OH− in base strength. use the tables of Ka and Kb values to help you identify weak acids and weak bases. Ca(OH)2. [H+] = 2. so 5. HBr. a. e. Common strong acids = HCl. Reference Table 7. Weak acids are better acids than water.34 × 10−7) = 6. In endothermic reactions. There are only a few common strong acids and strong bases all of which should be memorized. HI. thus their aqueous solutions are acidic. d. All other acids and bases are weak and will have Ka and Kb values of less than 1 but greater than Kw (10−14).CHAPTER 7 ACIDS AND BASES 195 Now the competition is between CH3CO2− and OH− for the proton.34 × 10−7 M pH = −log[H+] = −log(2. HClO4.2 for Ka values for some weak acids and Table 7. There are too many weak acids and weak bases to memorize them all. weak acid (Ka = 4. heat is a reactant. 28. [H+] = 2. Autoionization of Water and pH Scale 30. strong acid strong base weak acid (Ka = 7.34 × 10−7 M.8 × 10−4) strong acid b. . 2. Appendix 5 contains more complete tables of Ka and Kb values.8 × 10−5) weak acid (Ka = 1. H2O(l) ⇌ H+(aq) + OH−(aq) Kw = 5. strong or weak. NaOH. Hydroxide ion is the strongest base possible in water. b. Common strong bases = LiOH. so an increase in temperature (heat) shifts the reaction to produce more products and increases K in the process. the condition that [H+] = [OH−] is the most general definition of a neutral solution. Because the value of the equilibrium constant increases as the temperature increases. and H2SO4. RbOH. pH = 6. The NH4+ ion is a weak acid because it lies between H2O and H3O+ (H+) in terms of acid strength.

499 −31.767 c.10 × 10−3 CHAPTER 7 Kw 1. At 25°C.0 × 10 −7 M.71 × 10 −7 ) = 6. At 25°C. 50.537 From the graph: 37°C = 310. an acidic solution has [OH−] < 1.23 × 10−3 K−1 ln Kw = −31.92 × 10 −14 )/0.0 × 10 −7 M.0 × 10 −7 M. the solution is neutral.00.236 −31. the relationship [H+][OH−] = Kw = 1. pH = !log[H+] = !log(1. the solution is basic.165 −30. . At 37°C.14 × 10−15 1.0 × 10 −7 M. H2O(l) ⇌ H+(aq) + OH−(aq) Kw = 2. when [H+] = 1.53 × 10−7) = 6. Kw = e−31. Temp (K) 273 298 308 313 323 1/T (K−1) 3.0 × 10 −7 M.9 × 10 −13 M.54 32.408 −32. When [H+] is greater than 1.35 × 10−14 = [H+][OH−] = [H+]2.36 × 10−3 3.71 × 10 −7 M = [OH−] b. 2. Temp (°C) 0 25 35 40. In terms of [OH−].92 × 10 −14 = [H+][OH−] In pure water: [H+] = [OH−].19 × 10−3 3. pH + pOH = 14. Kw = 2.09 × 10−14 2.47 × 10−14 ACIDS AND BASES ln Kw −34. K.9 × 10 −13 ) = 12.25 × 10−3 3.66 × 10−3 3. when [H+] is less than 1. the solution is acidic.38 = 2. a. a basic solution has [OH−] > 1.0 × 10 −14 always holds for aqueous solutions.0 × 10 −7 M. pH = !log(2. [H+] = 1. [H+] = Kw/[OH−] = (2. [H+] = 1.196 c.815 31.38. and a neutral solution has [OH−] = 1.92 × 10 −14 = [H+]2.00 × 10−14 2. 1/T = 3.35 × 10−14 d.53 × 10−7 M pH = −log[H+] = −log(1.92 × 10−14 5.10 = 2.

0 = 1 × 10−15 M.0 − (−1.0 × 10 −14 = 1. + −7 [H ] 1.3) = 20 M.63 = 4.59 3. basic f.40 = 4.0 = 9. the solution is basic. [OH−] = 10−pOH = 10−6. basic c. pOH = 14. [OH−] = 10−10.5 × 10−7 M or [OH−] = Kw 1.73 33.59 = 5.0) = 15.3 × 10 −5 M.00 = 7.20 = 6. [OH−] = 1.3 × 10 −16 M.08) = 15.41.40 = 6. this solution is basic since pH > 7.9 × 10 −10 M.6 × 10 −9 M.08.00 − pH = 14.0 × 10 −7 ) = 7.3 = 5 × 10−16 M.00 − 4.5 × 10−7 M. [OH−] = 10−9.40 = 4.00.CHAPTER 7 ACIDS AND BASES Kw 1. pH = 14. basic b. acidic a.00 − 9. 34. pH = 14.00 − 7.27.60 = 4.0 − 5.63 = 2. [OH−] = 10−5.0 × 10 b. pOH = 14. the solution is neutral.80 = 1. pOH = 14.0 × 10 −14 = 12 M.0) = 10 M.37.3 × 10 −10 M [OH−] = 10 −4.4 × 10 pH = −log(5.20 = 10. pOH = 14. 12 pH = −log(12) = −1. pOH = 14.40.60. the solution is acidic.00 – 8.60 = 2.0 × 10 −14 = 8. pOH = 14.00.27 = 9. pOH = 14.0 × 10 −14 = = 1.6 × 10−11 M. [H+] = 10−15. [OH−] = 1.9 × 10 −6 pOH = 14. acidic d.0 × 10−8 M pOH = 14. [H+] = 10−9.0 × 10 −14 = 2.00 − 3.0 = 1 × 10−9 M.0 × 10−5 M.0 × 10 197 a. [OH−] = pH = −log[H+] = −log(1. + −8 [H ] 4.0 × 10 −14 = = 2. the solution is acidic.00 − 15.5 × 10−10 M.80.6 × 10 −9 ) = 8. [OH−] = 10-15. [H+] = 10− (−1. −5 5.3 × 10−4 M.0 × 10-7 M. [OH−] = 10− (−1. acidic e. 8.08 d. [OH−] = 1.0.00 – 9.60 = 2.08 c. pOH = 14.37 = 4. pH = −log(2. [H+] = 10−4.00 − 7.3 × 10 −16 pH = −log(8.00 − 15. [H+] = 1. [H+] = 10−pH.0. a. [H+] = 10 −9.00 − (−1. basic .08 = −1.0 = 1 × 10−5 M.0 − pOH = 14. [H+] = 10−7. [H+] = 10−3.3.3 × 10 −16 ) = 15.4 × 10 −5 ) = 4.3 = −1.08.00 b.

HCl soln 36.57.1 × 10−14 M 0. HNO3 soln × HCl(aq) → H+(aq) + Cl−(aq) and HNO3(aq) → H+(aq) + NO3−(aq) (Both are strong acids. pH = −log(5. acidic d.10 M Cl− because HCl completely dissociates.00 b. If you take the negative log of 1. g HNO 3 1 mol HNO 3 1.0 M H+ is produced when 5.10) = 1.94 mol = 0.) c.) So we will have 0.62 mol HCl mL 100 g conc.0 × 10−11 M H+ is produced when 1.43 = 3.0 g HNO 3 20. for example.0 × 10 −14 = = 1. this gives pH = 11.94 [H + ] . pOH = 14. pH = −log[H+] = −log(0. [H+] = 0. 5.32 mol HNO3 × × mL 100 g soln 63.94 M. We can normally ignore the small amount of H+ from H2O except when we have a very dilute solution of an acid (as in the case here). 36.42 g = 0. This is impossible! We dissolved an acid in water and got a basic pH. a.8 = 1.00. acidic ACIDS AND BASES Solutions of Acids 35.6 × 10 −2 M [OH−] = 10 −12. A 0.7 × 10 −13 M. 50. pH = −log[H+] = −log(0.94 mol of H+ in the final solution.0) = −0.0 mL conc.62 + 0. HCl(aq) + H2O(l) → H3O+(aq) + Cl−(aq) or HCl(aq) → H+(aq) + Cl−(aq).2 = 6 × 10 −13 M. pH = –log(0. HCl soln × 1.19 g 38 g HCl 1 mol HCl × × = 0. the pH is that of neutral water (pH = 7.0 M HClO4 completely dissociates. pH = 14.027) = 1.0 – 12.10 M H+ and 0.0 × 10−11 M HI completely dissociates.2 = 1.57 = 12.03 1. Therefore. The amount of H+ from H2O will be insignificant. [H+] = 10 −1.00) because the amount of HI present is insignificant. 1.0 mL conc.5 g 70. The amount of H+ from H2O will be insignificant.00 L [OH−] = Kw 1. What we must consider in this problem is that water by itself donates 1.94) = 0.00 – 1.70 (Negative pH values just indicate very concentrated acid solutions.32 = 0.10 M HCl solution gives 0.43 [OH−] = 10 −12.0 × 10−11.027 = 0. Strong acids are assumed to completely dissociate in water.198 CHAPTER 7 c.8.0 × 10−7 M H+.

so it only partially dissociates in water. ClO4−(aq). 0. (HNO3 is a strong acid. we have a 7.50 = 3.50.10 = 7. H+(aq). [H+] = 10 −5.250) = 0.) M1V1 = M2V2. Major species: H+(aq).2500 L × 39. if we assume x << 0. HNO2 (Ka = 4.0 × 10 − 4 (0. fig.2 × 10 −2 M and pH = 1. (HBr is a strong acid.250 We must check the assumption: . we will summarize the initial. 4.9 × 10 −6 M HNO3 solution. 38. However.010 M x 0. (HClO4 is a strong acid.250.602 c.0% 0.250 M ~0 0 x mol/L HNO2 dissociates to reach equilibrium −x → +x +x 0. Ka = ⇌ H+(aq) + NO2−(aq) 0.0 × 10−14) are the major species.2 mL of 12 M HCl with enough water added to make 1600 mL of solution will result in a solution having [H+] = 3. V1 = M 2 V2 3.250) = 0.9 × 10 −6 mol HNO 3 63. In this Solutions Guide. Solving the weak acid problem: HNO2(aq) Initial Change Equil. ACIDS AND BASES 199 HCl is a strong acid. 0. HNO3(aq) → H+(aq) + NO3−(aq) Because HNO3 is a strong acid.9 × 10 −6 M. 7.0 × 10−4) and H2O (Ka = Kw = 1. so it is the major source of H+. HNO2 is a weak acid (Ka < 1).010 × 100 = × 100 = 4. Br−(aq). HNO2 is much stronger acid than H2O. [H+] = 10 −1.16 × 10 −2 mol/L × 1. and H2O(l).) [H+] = 0.16 × 10 −2 M (carrying one extra sig.0 × 10-4 ≈ x2 .2 × 10 −4 g HNO3 L mol HNO 3 a. We must solve an equilibrium problem to determine [H+].0 × 10-4 = .250 M pH = −log[H+] = −log(0. NO3−(aq). and H2O(l). change and equilibrium concentrations into one table called an ICE table.CHAPTER 7 37.6 L = = 4.250 − x x x − x2 [H + ][ NO 2 ] .) pH = 0.602 b.2 × 10 −3 L M1 12 mol/L 4. H+(aq). then: [HNO 2 ] 0.250 x = 4.602 d. and H2O(l).250 − x 4.250 0.02 g HNO 3 × = 1.) pH = 0.

0100 mol H + = 1.250 − x 0.0100 L × 0.000: 1.1 × 10−3 M. Assumptions good.250 − x x x − [H + ][CH 3CO 2 ] x2 x2 ≈ (assuming x << 0. HCN Initial Change Equil. CH3CO2H is the major source of H+.8 × 10−5 = [CH 3CO 2 H] 0.84%. pH = −log(2.000.000 = 1.00 × 10−4 M Mol H+ present = 0.99 L = 990 mL . Solving the weak acid problem: CH3CO2H Initial Change Equil.0 × 10−14) are the major species.0100 L = 0. at pH = 4.00 L − 0.00 ×10−4 mol/L = 0.1 × 10−3) = 2.8 × 10−5) and H2O (Ka = Kw = 1. [H+] = 10−2.000. The H+ contribution from water (10−7 M) is negligible and x is small compared to 0. CH3CO2H (Ka = 1.250 (percent error = 4. 1. V = 1. Ka = ⇌ H+ + CH3CO2− 0.0100 mol H + .250) [HCN] 0.0%). At pH = 2. ⇌ H+ + CN− 0.92 40.000 = 1.2 × 10−5 M. checking assumption: [H+] = x = 2. HCN (Ka = 6.68 f.00 × 10−2 M.1 × 10 −3 × 100 = 0.250 M ~0 0 x mol/L HCN dissociates to reach equilibrium −x → +x +x 0.250 x = 2. Finishing the problem: x = 0. [H+] = 10−4.250 2. pH = −log[H+] = −log(0.250.250 − x 0.2 × 10−5) = 4.010) = 2.2 × 10−10 = x = [H+] = 1.250 M ~0 0 x mol/L CH3CO2H dissociates to reach equilibrium −x → +x +x 0.200 CHAPTER 7 ACIDS AND BASES All the assumptions are good. pH = −log(1.1 × 10−3 M.00 × 10−4 mol H+ L Let V = total volume of solution at pH = 4.250) .010 M = [H+].250 Ka = 6. we will consider it a valid assumption (called the 5% rule).00 L V Volume of water added = 1. checking assumption: x is 0.250 − x x x [H + ][CN − ] x2 x2 = ≈ (assuming x << 0. HCN is the major source of H+.0048% of 0.2 × 10−10) and H2O are the major species. 0.00 e. If the percent error is less than 5% for an assumption. Assumptions good.

4 × 10−5 >> 1.0 × 10−7 M H+ already present in neutral H2O. In future problems we will always begin the problem solving process by making these assumptions.5 − x x x .5 × 10−8 = (assuming x << 0. Major species: HOCl (Ka = 3. 0. If the percent error in the assumption is less than 5%. we can ignore 1. ⇌ H+(aq) + OCl−(aq) ~0 0 0. and we will always check them. that is. We will always state when the assumptions are not valid and we have to use other techniques to solve the problem.20 − x 0.6 × 10−10 ~0 0 1.4 × 10−5 M.042%. 2. Remember. Because Ka for HOCl is less than 1. [H+] from HOCl = 8.20 M. Solving the weak acid problem: HOC6H5 Initial Change Equil.20) × 100 = 0. pH = −log[H+] = −log(8.20 M x mol/L HOCl dissociates to reach equilibrium −x → +x +x 0.08 b. Answering the question: [H+] = [OCl−] = 8. anytime we make an assumption. The setup is: HOCl (aq) Initial Change Equil. ⇌ H+ + OC6H5− Ka = 1.20) × 100 = (8.4 × 10−5) = 4.CHAPTER 7 41. [OH−] = Kw/[H+] = 1.20 − x x x x2 x2 [H + ][OCl − ] = ≈ [HOCl] 0. ACIDS AND BASES 201 a. major source of H+ = HOCl. HOC6H5 (Ka = 1. HOCl is a weak acid and we must solve an equilibrium problem to determine [H+].5 × 10−8) and water. Great assumption.2 × 10−10 M [HOCl] = 0.20) x = [H+] = 8.6 × 10−10) is the dominant producer of H+.20 (x/0. However.0 × 10−7.20 Ka = 3. 1.20 − x = 0.4 × 10−5/0. HOCl is the major source of H+. then the assumption is valid. this assumption is valid.4 × 10−5 M We have made two assumptions that we must check. we must check its validity before the solution to the problem is complete. we may not explicitly state that the assumptions are valid.5 M x mol/L HOC6H5 dissociates to reach equilibrium −x → +x +x 1.20 − x ≈ 0.

pH = −log(1. In this case it is. we let 0.).020 − 0.9 × 10−12 M .020 The assumption x << 0.2 × 10−4.202 Ka = 1.0166 We repeat.020 − 0. We must solve x2/(0. assumptions good: 1.020 − x 0.4 × 10−3 0.020 0.020) x2 x2 [H + ][F − ] = ≈ [HF] 0.2 × 10−4 = x 3.020 − x = 0.5 × 10−3 0.2 × 10−4 ~0 0 0.020 M x mol/L HF dissociates to reach equilibrium −x → +x +x 0. in the denominator try x = 0. that is.5 × 10−5 M.5 × 10−3. ⇌ H+ + F− Ka = 7.5 × 10−5 M. fig.020). Solving the weak acid problem: HF Initial Change Equil.5 ACIDS AND BASES (assuming x << 1.8 × 10 −3 × 100 = H 100 = 19% 0.0038 (the value of x we calculated making the normal assumption) so that 0.5) x = [H+]= 1. until we get a self-consistent answer.8 × 10−3 M.0166 (carrying an extra sig.6 × 10−10 = − CHAPTER 7 [H + ][OC 6 H 5 ] x2 x2 = ≈ [HOC6 H 5 ] 1 .020 − x x x (assuming x << 0. That is.016 M be a new approximation for [HF].016 We use this new value of x to further refine our estimate of [HF]. Check assumptions: Ka = 7. then solve for a new value of x in the numerator.5 M. x = 3.020 x = [H+] = 3. Thus: [H+] = [F−] = x = 3.7 × 10−10 M [HOC6H5] = 1.0 × 10−7 << 1.2 × 10−4. x2 x2 ≈ = 7. [OH−] = 6. x2 x2 ≈ = 7.5 × 10−3 M. [OH−] = Kw/[H+] = 2. This is a weak acid in water.020 − x) = 7.82 c. 0.5 − x = 1.2 × 10−4 exactly by using either the quadratic formula or the method of successive approximations (see Appendix 1 of the text). x = 3.020 − x 0.0034 = 0.5 × 10−5 << 1.016.5 [H+] = [OC6H5− ] = 1.0038 = 0. This would be the same answer we would get solving exactly using the quadratic equation.020 is not good (x is more than 5% of 0.020 − x 0.5 − x 1 . Using successive approximations.5 × 10−5) = 4. x = 3.

Using either method gives x = [H+] = 1.17 = ⇌ H+ + IO3− ~0 0 0. H2O.02 .17)x − 1.020 − 0. x = 9.189 = .0035 = 0. major source of H+: HIO3 (a weak acid. When the assumption is this poor.020 − x = 0.7 × 10−3 = 0 0.17 = x2 . [HIO3 ] 0.17(0. it is generally quickest to solve exactly using the quadratic formula (see Appendix 1 in text). Major species: HIO3. x = 0.010 − x − x x [H + ][IO3 ] x2 x2 = ≈ .1 × 10−2) = 1. We must solve 1.5 × 10−3) = 2. Ka = 0.10 − x) exactly using either the method of successive approximations or the quadratic equation.7 × 10 −3 )]1/ 2 − 0.10 which fails the 5% rule.10 M x mol/L HC2H2ClO2 dissociates to reach equilibrium −x → +x +x 0.35 × 10−3 = Checking the assumptions finds that x is 12% of 0.35 × 10−3 = x2/(0. x = 1. pH = −log[H+] = −log(1.2 × 10−2 M 0.46 203 Note: When the 5% assumption fails. major source of H+: HC2H2ClO2 HC2H2ClO2 Initial Change Equil. pH = −log(9.010 − x).17 ± 0.10 − x x x x2 x2 ≈ .17 ± [(0. Major species: HC2H2ClO2 (Ka = 1.010 − x 0.1 × 10−2 M.017 M.010 M x mol/L HIO3 dissociates to reach equilibrium −x → +x +x 0. check assumption. The method of successive approximations is probably fastest when the percent error is less than ~25% (unless you have a graphing calculator). 42.17) HIO3 Initial Change Equil.10 − x 0.35 × 10−3) and H2O. 43. Using the quadratic formula and carrying extra significant figures: 0.010 − x x= − 0. Ka = 0.17) 2 − 4(1)(−1.041. ⇌ H+ + C2H2ClO2− ~0 0 0.96.5 × 10−3 M 2(1) 2 (x must be positive) x = 9. x2 = 0.10 Ka = 1.010 Assumption is horrible (x is more than 400% of 0.010). use whichever method you are most comfortable with to solve exactly.5 × 10−3 M = [H+]. x2 + (0.CHAPTER 7 ACIDS AND BASES [HF] = 0. pH = 2.

[HBz]0 = 4. [H + ] 1.0 × 10−14) are the major species present.100).100 − x x x [H + ][C3 H 5 O 2 ] x2 x2 = ≈ [HC3 H 5 O 2 ] 0. [OH−] = Kw/[H+] = 9. Solving the weak acid problem: HC3H5O2 Initial Change Equil.6 × 10−3).6 × 10 −3 − x) 4.1 × 10−3 = 0. HC3H5O2 will be the dominant producer of H+ because HC3H5O2 is a stronger acid than H2O.6 × 10−3 M ~0 0 x mol/L HBz dissociates to reach equilibrium −x → +x +x 4. We must solve a weak acid problem.100 − Ka = 1.100 This is a weak acid in water. Let HBz = C6H5CO2H.6 × 10 −3 4.1 × 10−3) = 2. When assumption(s) fail.204 44.3 × 10−5 = x = [H+] = 1.100 M x mol/L HC3H5O2 dissociates to reach equilibrium −x → +x +x 0.1 × 10−3 M.1% of 0.1 × 10−12 M [HC3H5O2] = 0.4 × 10−4. 0.6 × 10 −3 Assumption is not good (x is 12% of 4.96 Assumption follows the 5% rule (x is 1.6 × 10 −3 Ka = 6.6 × 10−3 mol.100 − x 0. CHAPTER 7 ACIDS AND BASES HC3H5O2 (Ka = 1.4 × 10−5 = x = [H+] = 5. ⇌ H+ + C3H5O2− ~0 0 0.1 g HBz Initial Change Equil.56 g HBz × 1 mol HBz = 4. we must solve exactly using the quadratic formula or the method of successive approximations (see Appendix 1 of text). Using successive approximations: .1 × 10 −3 × 100 = × 100 = 1.3 × 10−5) and H2O (Ka = Kw = 1.1 × 10−3 M.1% [HC3 H 5 O 2 ]0 0. ⇌ H+ + Bz- 4.100 − 1.6 × 10−3 − x x x x2 x2 [H + ][Bz − ] ≈ = [HBz] (4.6 × 10−3 M 122. pH = −log(1. check assumptions: x 5. [H+] = [C3H5O2−] = 1.4 × 10 −4 × 100 = × 100 = 12% 4.099 M Percent dissociation = 45.

6 × 10 −3 ) − (5. C = (4.6 × 10−3 M + C − [H ] (1.CHAPTER 7 ACIDS AND BASES x2 = 6. x = 5. 4. ⇌ ~0 0 0.2 × 10−2 M 6.9 × 10−11 M 46.0152 ! x . pH = 2.1 × 10−4 M (consistent answer) (4. [H+] = 10−2.15 g = 0.2 × 10−2 mol/L. [OH−] = 10−10.80.71.6 × 10 ) − (5.80 = 1.71 = 1. Ka = HBz C ⇌ H+ ~0 + Bz0 HBz = C6H5CO2H C = [HBz]0 = concentration of HBz that dissolves to give saturated solution.4 × 10−5.4 × 10−5.100 L = 0.51 g per 100.1 × 10−4 −3 −4 (4.0 × 10−2.6 × 10−3 − x = 4.0152 M 0.1 × 10 − 4 ) 205 Thus: x = [H+] = [Bz−] = [C6H5CO2−] = 5.4 × 10−5 = .0 × 10−2) + (1.1 × 10−4) = 3. pOH = 14.0152 M x mol/L HC9H7O4 dissociates to reach equilibrium !x → +x +x x x 0. x mol/L HBz dissociates to reach equilibrium −x → +x +x x x C−x x2 [H + ][Bz − ] = 6.00 − pH = 10.237 L H+ + C9H7O4− 47. [HC9H7O4] = HC9H7O4 Initial Change Equil.2 × 10 −2 mol C 6 H 5 CO 2 H 122. mL solution L mol C 6 H 5 CO 2 H 2 tablets × 0.6 × 10 −3 ) 2 = 4. where x = [H+] [HBz] C−x 6.4 × 10 ) x2 = 6.1 × 10−4 M [HBz] = [C6H5CO2H] = 4.29. Initial Change Equil.4 × 10 −5 C − 1.6 × 10−3) = 4.325 g HC9 H 7 O 4 1 mol HC9 H 7 O 4 × tablet 180.1 × 10−3 M pH = −log(5.6 × 10−3 = The molar solubility of C6H5CO2H is 4.1 g C 6 H 5 CO 2 H × × 0. x = 5.4 × 10−5 = [ H + ]2 .

0152 – x ≈ 0.10 M 0.206 Ka = 3.3 × 10 −4 = − CHAPTER 7 ACIDS AND BASES [ H + ] [C 9 H 7 O 4 ] x2 x2 = ≈ .0 − x 1.7 × 10 −2 )[OC 6 H 5 ] = .10 − x 0. [H+] = x = 2.68 48.10 M 0 x mol/L HOCl dissociates to reach equilibrium −x → +x +x 0.0152 2. ⇌ H+ + F− 1.6 × 10−10.2 × 10−4 = x2 x2 [H + ][F − ] = ≈ 1 . [HOC 6 H 5 ] 1. 49. HF and HOC6H5 are both weak acids with Ka values of 7.0 [OC6H5−] = 5.1 × 10 −3 ) = 2. x = 2.7 × 10−2) = 1.2 × 10 −3 × 100 = 14% 0. HF will be the dominant producer of H+ (we can ignore the amount of H+ produced from HOC6H5 because it will be insignificant).0 M ~0 0 x mol/L HF dissociates to reach equilibrium −x → +x +x 1.57. which indicates that HF is truly the only significant producer of H+ in this solution.10 + x x .9 × 10−9 M − − Note that this answer indicates that only 5. It will produce 0. respectively. Because the Ka value for HF is much greater than the Ka value for HOC6H5. HOCl is a weak acid.0152 Assumption that 0.0152 − x 0.6 × 10−10 = [H + ][OC 6 H 5 ] (2.1 × 10 −3 M. Let's consider the equilibrium: HOCl Initial Change Equil.0152 fails the 5% rule: Using successive approximations or the quadratic equation gives an exact answer of x = 2. HCl is a strong acid.0 − x x x Ka = 7. assumptions good.2 × 10 −3 M [HC9 H 7 O 4 ] 0.7 × 10−2 M. Solving for [OC6H5−] using HOC6H5 ⇌ H+ + OC6H5− equilibrium: Ka = 1. pH = !log(2.10 M H+. a.2 × 10−4 and 1.9 × 10−9 M HOC6H5 dissociates. pH = −log(2.0 [ HF] x = [H+] = 2.5 × 10−8 0.1 × 10 −3 M. ⇌ H+ + OCl− Ka = 3. HF Initial Change Equil.

Let HA symbolize the weak acid.50 − x) 0.30 50.00.050 + x = 0.15 M x mol/L HA dissociates to reach equilibrium !x → +x +x 0.5 × 10 ) HX ⇌ H+ + X− I ~0 0 where I = [HX]0 x mol/L HX dissociates to reach equilibrium −x → +x +x I−x x x From the problem.50 − x 0. We are really assuming that HCl is the only important source of H+. ⇌ H+ + C2H3O2− Ka = 1.050 M 0 x mol/L HC2H3O2 dissociates to reach equilibrium −x → +x +x 0.5 × 10 −3 M. b. Consider the equilibrium: HC2H3O2 Initial Change Equil. pH = 1.050 + x x −5 [H + ][C 2 H 3O 2 ] (0.050) x = ≈ Ka = 1. Set up the problem like a typical weak acid equilibrium problem.050 M and pH = 1. ( 4. x = 3. Initial Change Equil.5 × 10−8 = Assumptions are great (x is 0.10 − x 207 Ka = 3. then x = [H+] is 3.25(I) and I − x = 0. Ka = 51.8 × 10−4. The [H+] contribution from HOCl.10 + x)( x) = ≈ x. ⇌ H+ + A− ~0 0 0.030 × (0.15 ! x x x If the acid is 3. [H+] = 0.5 × 10−8 M [HOCl] 0.0% of 0. we can solve for Ka.10 M.8 × 10−5 0.5 × 10 −3 ) 2 x2 [H + ][A − ] = = = 1. x = 0.4 × 10 −4 −3 0. [H+] = 0. is negligible. HNO3 is a strong acid. x.15 M) = 4.0% dissociated.8 × 10 = [HC 2 H 3O 2 ] (0.000035% of 0.10). assumptions are good (well within the 5% rule).050 M. which it is. giving an initial concentration of H+ equal to 0.050 + x) x (0.50 − x = 1. HA Initial Change Equil.15 − ( 4.CHAPTER 7 ACIDS AND BASES [H + ][OCl − ] (0.30 M.15: x = 0. .15 − x [HA] 0. Now that we know the value of x. Therefore.50 M 0.

40 M and x = 0.050 x2 x2 ≈ 0. Initial Change Equil.9 × 10−4 0.050 x = [H+] = [C2H3O2−] = 9.0 × 10 −3 H 100 = H 100 = 0.50 − Ka = 1. I = 0.050 − x 0.50 b. assumptions good.8 × 10−5 = . We must solve a weak acid problem. assumptions good.10) 2 x2 [H + ][X − ] = = = 0.40 M) = 0.30 M.208 CHAPTER 7 I − 0. Percent dissociation = [H + ] 3. Percent dissociation = c. acetic acid (HC2H3O2) is the best weak acid present.0050 − (3. Using the method of successive approximations (see Appendix 1 of the text): x2 x2 = 1.25(I) = 0. Ka = 1.0 × 10−4 M. HC2H3O2 ⇌ H+ + C2H3O2− 0.9% 0.50 − x 0.30 [HX] ACIDS AND BASES 52.0% error).10 M Ka = (0. Assumption that x is negligible is borderline (6.8 × 10−5 = x = [H+] = [C2H3O2−] = 3.60% [HC 2 H 3O 2 ]0 0.0 × 10 − 4 ) Next trial also gives x = 2.8 × 10−5 = 9. The setup for solutions b and c are similar to solution a except that the final equation is different because the new concentration of HC2H3O2 is different.5 × 10−4 M.0050 − x 0.25(0. x = 2. In all parts of this problem.50 − x x x [H + ][C 2 H 3O 2 ] x2 x2 = = [HC 2 H 3O 2 ] 0. a.9 × 10−4.5 × 10 −4 × 100 = 1. check assumptions.0047 0.0 × 10−3 M.033 I −x 0.0050 x = [H+] = [C2H3O2−] = 3.8 × 10−5 = x2 x2 ≈ 0. We should solve exactly. .50 M ~0 0 x mol/L HC2H3O2 dissociates to reach equilibrium −x → +x +x 0. Ka = 1.

8% 5. [CCl 3CO 2 H ] 0. x = [H+] = 4.7 × 10−3 M HOCN Initial 0.77.CHAPTER 7 ACIDS AND BASES 2. suppose we double the volume of an equilibrium mixture of a weak acid by adding water. pH = 2.0100 − x ⇌ H+ ~0 x + OCN− 0 x x = [H+] = [OCN−] = 1.9 × 10 −4 × 100 = 5.0 × 10 −3 209 Percent dissociation = d.050 M 0.0 × 10 − 2 ) Ka = 55. Major species: HCOOH and H2O.77 = 1. [H+] depends on the initial concentration of weak acid and on how much weak acid dissociates. the initial concentration of acid decreases more rapidly than the percent dissociation increases.5 × 10−4 −3 [HOCN] 8. 53. 0. major source of H+: HCOOH . Set up the problem using the Ka equilibrium reaction for CCl3CO2H.7 × 10−3 M. e. Dilution will shift the equilibrium to the side with the greater number of particles. then: ⎛ [H + ]eq ⎞ ⎛ [X − ]eq ⎟⎜ ⎜ ⎜ 2 ⎟⎜ 2 ⎠⎝ Q= ⎝ ⎛ [HX]eq ⎞ ⎜ ⎜ 2 ⎟ ⎟ ⎝ ⎠ ⎞ ⎟ ⎟ ⎠ = 1 K a 2 Q < Ka.040 M. from the problem. [H+] = 10−2.050 − x − ⇌ H+ ~0 x + CCl3CO2− 0 x Ka = [H + ][CCl 3CO 2 ] x2 = . HClO4 is a strong acid with [H+] = 0.0083 M (1.0017 = 0.050 − x (4.0100 − x = 0. CCl3CO2H Initial Equil. all concentrations are decreased.0100 Equil. [HOCN] = 0. For example.0 × 10 −2 ) 2 = 0.050 − ( 4.3 × 10 Ka = 54.0100 − 0. This equals the [H+] in the trichloroacetic acid solution. For solutions a-c. so the equilibrium shifts to the right or toward a greater percent dissociation.7 × 10 −3 ) 2 [H + ][OCN − ] = = 3.16 0. Thus [H+] decreases.0 × 10−2 M. 0. As we dilute a solution.

because pH = 2.) 58. the stronger the base.70 = 2. they are still weak acids with Ka values between Kw and 1.0 × 10−3 M C − [H + ] ( 2.75 = 1. All conjugate bases of strong acids have no base strength in water.8 × 10−5. C − (2.8 × 10 −6 ) 1 mol 1L 1000 mL × × = 340 mL 183.8 × 10 −6 M I−x (1. C = 2. Prove this to yourself by calculating the Ka values for NH4+ and C5H5NH+ (Ka = Kw/Kb). base strength increases.8 × 10 − 4 A 0. H2O: Kb = Kw = 1.19 g 1.70 = 2. 56. I = 1.8 × 10 −6 ) 2 . I − (1.70: [H+] = 10−2. I I!x ⇌ H+ ~0 x + Sac− 0 x Ka = 10−11. Let HSac = saccharin and I = [HSac]0.6 mol L 100. NO3−: Kb << Kw because HNO3 is a strong acid. CHAPTER 7 ACIDS AND BASES ⇌ H+ + HCOO− C ~0 0 where C = [HCOOH]0 x mol/L HCOOH dissociates to reach equilibrium → +x +x −x C−x x x Ka = 1.8 × 10−4 = 1.0 × 10−3) = .0 × 10 −3 ) 2 4.0 × 10 −12 = 2. where x = [H+] C−x [HCOOH] [ H + ]2 .0 g HC7H4NSO3 × Solutions of Bases 57.7 × 10−9 Base strength = NH3 > C5H5N > H2O > NO3− (As Kb increases.6 M = [HSac]0. In general.0 × 10 −12 = x2 .0 × 10 −3 ) 1.024 M formic acid solution will have pH = 2.210 HCOOH Initial Change Equil.0 × 10 −12 Ka = 2. Note: Even though NH4+ and C5H5NH+ are conjugate acids of weak bases.8 × 10−4 = 1. Excluding water.70.4 × 10−2 M C − (2.8 × 10−4 = x2 [H + ][HCOO − ] = . x = [H+] = 10 −5. these are the conjugate acids of the bases in the preceding exercise.0 × 10−14. NH3: Kb = 1. the weaker is the conjugate acid. C5H5N: Kb =1. HSac Initial Equil.0 × 10 −6 . Acid strength = HNO3 > C5H5NH+ > NH4+ > H2O .

C6 H 5 NH 2 = 3.CHAPTER 7 59. pOH = −log[OH−] = −log(0. so [OH−] = 0.0 × 10−7 M.30) = 14.5740 Although we are justified in calculating the answer to four decimal places.0 × 10−7 M. The [OH−] concentration donated by the NaOH is 1.4 × 10 −4 ).0 g NaOH 1 mol × = 3. pH = 14. 61. pH = 13. NaOH is a strong base. [OH−] = 0. pOH = −log[OH−] = 3. L 40. a.30. NaOH is a strong base that completely dissociates into Na+ and OH−.00 = 13. pH = 10.8 × 10 −10 .45 M. 25 g KOH 1 mol KOH × = 0.5740) = 14.45) = 0.30 62.0 × 10−10 M.01 pH units. and [OH−] = 1. pOH = −log(2.45 mol KOH/L L 56. OH− is the strongest base possible in water.00 Note that H2O is also present. [OH−] = 10−3. b.50. Water by itself donates 1.0 × 10−4 M.50. K b .50 = 3. pH = 14. pOH = −log(1.00 − 7.65 c.00 = 7. NaOH(aq) → Na+(aq) + OH−(aq).0) = −0. [OH−] = 2(0. a.00040) = 8.2 × 10−4 M .00 − pOH = 10.00 g pOH = −log(3.750 M. water is the major OH− contributor. pH = 14. pOH = −log(0. To calculate Ka values for C6H5NH3+ and CH3NH3+.00. C6H5NH3+ The acid with the largest Ka value is the strongest acid. ACIDS AND BASES b.0000 − (−0.00 − 1. CH 3 NH 2 = 4. C6H5NH2 c. C6H5NH3+ c.750) = −0. CH3NH2 211 a.10 M OH− produced from the NaOH.0 × 10−7) = 7. pOH = 14.0 M. C6H5NH2 The base with the largest Kb value is the strongest base (K b . OH− d.10 M. Ca(OH)2 is a strong base and dissociates completely. 63. Ca(OH)2 → Ca2+ + 2 OH−.1 g KOH KOH is a strong base. in reality the pH can only be measured to ±0. so [OH−] = 3. a. 60. HClO4 (a strong acid) b.50 = 3.5740 and pH = 14. [OH−] = 2. where Kb refers to the bases C6H5NH2 or CH3NH2.35. The initial concentration of NaOH will equal the concentration of OH− donated by NaOH.10) = 1.00 − pOH = 14.00 c.90 b. use Ka = Kw/Kb .00 − 10.750 M.00 − (−0. In this exercise. but the amount of OH− produced by H2O will be insignificant compared to the 0. 150.10.00 pH = 14.

⇌ (C2H5)3NH+ + OH− Kb = 4.2 × 10−4 M OH− × 1 M Ba (OH) 2 = 1.6 × 10 −3 M 0.50 solution.68 67. [OH−] = 8. Ba(OH)2 donates 2 mol OH− per mol Ba(OH)2. 0. . x = [OH−] = 8.1 × 10 −8 = x2 x2 ≈ .20 ! x [(C 2 H 5 ) 3 NH + ][OH − ] x2 x2 = ≈ . pH = 11. pOH = 14. 64.00 – 11.20 ! x ⇌ HONH3+ 0 x + OH− ~0 x Kb = 1.44. [OH−] = [KOH] = 10 −2. 3.212 CHAPTER 7 ACIDS AND BASES Ba(OH)2(aq) → Ba2+(aq) + 2 OH−(aq).16 g KOH L mol KOH Neutrally charged organic compounds containing at least one nitrogen atom generally behave as weak bases.0 × 10 −14 = = 1. (C2H5)3N + H2O 66.5% of 0. This lone pair of electrons is used to form a bond to H+.6 × 10−4 M Ba(OH)2 2 M OH − A 1. This is a solution of a weak base in water.1 × 10 −10 M.20 − x 0. Kw 1. we must solve an equilibrium weak base problem. Initial Change Equil.0 × 10 −4 0.9 × 10 HONH2 + H2O 0.9 × 10 −3 M [H+] = b.20 [H+] = 2. pH = 9. These are solutions of weak bases in water.1 × 10 −8 Kb = 1. assumptions good.6 × 10−4 M Ba(OH)2 solution will produce a pH = 10.44 = 3.56 = 2.20). a.0 × 10 −4 = Assumptions good (x is 4.1 g KOH × = 0. [Ba(OH)2] = 3. x = [OH−] = 4.20 M 0. Initial Equil.20 Kb = 4.1 × 10 −12 M. The nitrogen atom has an unshared pair of electrons around it.20 M 0 ~0 x mol/L of (C2H5)3N reacts with H2O to reach equilibrium !x → +x +x x x 0.7 × 10 −5 M.20 − x 0. We must solve a weak base equilibrium problem.8000 L × 65.9 × 10 −3 M [(C 2 H 5 ) 3 N ] 0. In each case.96 − −3 [OH ] 8.6 × 10 −3 mol KOH 56.

checking assumption: x2 x2 = = 5.4 g . Initial Change Equil.189 x = [OH−] = 1.CHAPTER 7 ACIDS AND BASES C2H5NH2 + H2O 213 ⇌ C2H5NH3+ + OH− Kb = 5.6 × 10−4. [H+] = Kw/[OH−] = 1.0 × 10 −14 = 1.074 [OH−] = x = 7.1 × 10 −3 .3 × 10 −3 = x2 .20 ! x x x + [C 2 H 5 NH 3 ][OH − ] x2 x2 = ≈ (assuming x << 0.050 − x 0. 5.3 × 10 −3 = .20 − 0.20 The assumption fails the 5% rule.1 × 10 −2 × 100 = 5.20 M 0 ~0 x mol/L C2H5NH2 reacts with H2O to reach equilibrium !x → +x +x 0.20 1. We must solve exactly using either the quadratic equation or the method of successive approximations (see Appendix 1 of the text).0100 L 299. Using successive approximations and carrying extra significant figures: x = 1.85 69.0 × 10 −2 M (consistent answer) 0.011 0.050 M 0 ~0 x mol/L (C2H5)2NH reacts with H2O to reach equilibrium !x → +x +x x x 0. assumption is bad (x is 16% of 0.3 × 10 −3 = x = 8. x = 1. let cod = codeine (C18H21NO3). Kb = 0.4 × 10 −3 0.20) [C 2 H 5 NH 2 ] 0. x = 7.7 × 10−3 M = [codeine]0. Using successive approximations: x2 1.4 × 10 −12 M.00 = − −2 [OH ] 1.4 × 10 −3 M.081 1.050 + Kb = 1.1 × 10 −2 .3 × 10 −3 0.050 − 0.0 × 10 ⇌ (C2H5)2NH2+ + OH− Kb = 1.050 − 0. x = 7.0 × 10 −3 g 1 mol × = 1. [H+] = 68.20).4 × 10 −3 (consistent answer) 0. pH = 12. pH = 11.5% 0.0 × 10 −2 M. 0.0 × 10 −12 M.6 × 10−4 Initial Change Equil. (C2H5)2NH + H2O Kw 1.050 ! x [(C 2 H 5 ) 2 NH 2 ][OH − ] x2 x2 = ≈ [(C 2 H 5 ) 2 NH] 0.20 − x 0.

assumptions good.3 × 10 −3 M × 100 = × 100 = 1. To solve for percent ionization. assumptions good. Initial Equil.7 × 10 −3 − x) 1.6 × 10−10 M. Two codeine molecules are protonated by H2SO4. x = 3. [H+] = Kw/[OH−] = 2.3 × 10−3 M.010 M 0.8 × 10−5 x2 x2 ≈ .8 × 10−5 = ⇌ NH4+ 0 x + OH− ~0 x Kb = 1. CHAPTER 7 ACIDS AND BASES ⇌ codH+ + OH− Kb = 10−6. 71.9 × 10−5 .010 − x 0. where codeine H+ = HC18H21NO3+.8 × 10−5 = NH3 + H2O 0.2% 0.7 × 10−3 M x mol/L codeine reacts with H2O to reach equilibrium −x → +x +x x x 1.2 × 10 −4 × 100 = 4. a. codeine sulfate = C36H44N2O10S The formula for codeine sulfate works out to (codeine H+)2SO42−. ≈ (1. x = [OH−] = 4. 0. Codeine = C18H21NO3.9 × 10−7 = x2 x2 . NH3 + H2O Initial 0. 0.2 × 10−4 M.10 − x Kb = 1.214 Solving the weak base equilibrium problem: cod + H2O Initial Change Equil.10 M Percent ionization = b. allowing more of the drug into the bloodstream. .010 Percent ionization = Note: For the same base.05 = 8.10 − x 0.9 × 10−5 M.7 × 10 −3 [OH−] = 3. the percent ionization increases as the initial concentration of base decreases. pH = −log[H+] = 9. 0.7 × 10−3 − x Kb = 8.9 × 10−7 0 ~0 1. Codeine sulfate is an ionic compound that is more soluble in water than codeine. assumptions good.59 70. x = [OH−] = 1.010 4. forming the conjugate acid of codeine. The SO42− then acts as the counter ion to give a neutral compound.10 M Equil.010 − x ⇌ NH4+ 0 x + OH− ~0 x x2 x2 ≈ .10 [OH − ] 1.3% [ NH 3 ]0 0. just solve the weak base equilibrium problem. 1.

10).6 × 10 −3 Kb = 8 × 10−6 = x = 1 × 10−4.0016).38 × 10−4 Initial Equil.0066 0.6% of 0. x = 6.6 × 10−3 M 0 ~0 x mol/L quinine reacts with H2O to reach equilibrium → +x +x −x −3 1.9000 L 324. 1. Using successive approximations and carrying extra significant figures: 4.6 × 10−3.0 g quinine 1 mol quinine × = 1.016 − x x x . pOH = 4.38 × 10−4. Using the Kb reaction to solve where PT = p-toluidine (CH3C6H4NH2): PT Initial Change Equil.6 × 10 − 1 × 10 ) x = [OH−] = 1 × 10−4 M. x = 6.10 6.0. ACIDS AND BASES CH3NH2 + H2O 215 ⇌ CH3NH3+ 0 x + OH− ~0 x Kb = 4.38 × 10−4 = x2 x2 = = 4. + H2O ⇌ PTH+ + OH− 0. x = 1 × 10−4 M (consistent answer) −3 −4 (1.4 × 10 −3 × 100 = 6.6 × 10 − x x x [QH + ][OH − ] x2 x2 ≈ = [Q ] (1.016 M 0 ~0 x mol/L of PT reacts with H2O to reach equilibrium −x → +x +x 0.0 73. assumption fails the 5% rule (x is 0.10 (consistent answer) 72. 1. pH = 10.4 × 10−3 0.10 − 0.093 Percent ionization = 6.10 − x x2 x2 ≈ .6 × 10 −3 − x) 1.6 × 10−3 M quinine.4 g quinine Q Initial Change Equil.CHAPTER 7 c. + H2O ⇌ QH+ + OH− Kb = 10−5. let Q = quinine = C20H24N2O2.1 = 8 × 10−6 1.10 − x 0.10 M 0. assumption fails 5% rule (x is 6% of 0. 0. Using successive approximations: x2 = 8 × 10−6.4% 0.

60: pOH = 14.10 M H2CO3 will dissociate into HCO3− and H+. (4. Because K a1 << 1. I = 0. . Statement c is best for a 0.91 mol HONH 2 33.20 M because only some of 0. K a 2 = 1.10 M H2SO4 solution will dissociate into 0. All of the 0.2500 L × Polyprotic Acids 75.0 × 10−6 M Kb = 74.0 × 10 −6 ) 2 = 1.10 M H2SO4 solution.3 × 10 −7 and K a 2 = 4. some of the 0.40 and [OH−] = x = 10−5. only a small percentage of the 0.5 g HONH2 L mol HONH 2 Mass HONH2 = 0. pH = 10.10 M HSO4−.10 M but will not reach 0. The [H+] concentration in solution will be determined from the K a1 reaction because K a1 >> K a 2 . Initial Equil.00 − 8.91 M I − (1. because HSO4− is a good weak acid due to the relatively large Ka value. H2SO4 is a strong acid as well as a very good weak acid ( K a1 >> 1.216 Kb = CHAPTER 7 x2 [PTH + ][OH − ] = 0.1 × 10 −8 I = [HONH2]0 Kb = 1.2 × 10 −2 ).10 M H+ and 0. So statement a best describes the 0.016 − x [PT ] ACIDS AND BASES Since pH = 8. H3C6H5O7(aq) ⇌ H2C6H5O7 (aq) + H (aq) − + [H 2 C 6 H 5 O 7 ][H + ] K a1 = [ H 3C 6 H 5 O 7 ] Ka2 = K a3 = [HC 6 H 5 O 7 ][H + ] [H 2 C 6 H 5O 7 ] [C 6 H 5 O 7 ][H + ] [HC 6 H 5 O 7 ] 2− 3− − 2− − H2C6H5O7−(aq) ⇌ HC6H5O72−(aq) + H+(aq) HC6H5O72−(aq) ⇌ C6H5O73−(aq) + H+(aq) 76. the [H+] will be greater than 0.016 − ( 4.00.40 = 4.10 M H2CO3 solution.10 M HSO4− will dissociate into some more H+ and SO42−. H2CO3 is a weak acid with K a1 = 4. so pOH = 4.0 × 10 −6 ) HONH2 + H2O I I–x ⇌ HONH3+ + OH− 0 x ~0 x Kb = 1.1 × 10 −8 = (1.0 × 10−9 0.0 × 10 −4 M.10 M.8 × 10 −11 . 1. However. Therefore.0 × 10 −4 ) 2 .60 = 5.10 M HSO4− will dissociate.1 × 10 −8 = x2 I−x From problem.03 g HONH 2 × = 7. the [H+] < 0.00 and x = [OH−] = 1.0 × 10 − 4 ) 0.

20 .03). assumption good.20 0. x = 3 × 10−2 (consistent answer) [H+] = [H2AsO4−] = 3 × 10−2 M. Therefore. very little of H2AsO4 (and HAsO42−) dissociates compared to H3AsO4. beginning with the largest Ka. assumption fails the 5% rule.x ⇌ H+ ~0 x + H2AsO4− 0 x K a1 = 5 × 10−3 = [H + ][H 2 AsO 4 ] [H 3 AsO 4 ] − x2 x2 ≈ . [H+] and [H2AsO4−] will not change significantly by the K a 2 reaction. [H3AsO4] = 0.20 M 0.17 M Because K a 2 = − [H + ][HAsO 4 ] [H 2 AsO 4 ] − 2− = 8 × 10−8 is much smaller than the K a1 value.03 = 0. [HAsO42−] = 8 × 10−8 M 8 × 10 = −2 3 × 10 −8 2− The assumption that the K a 2 reaction does not change [H+] and [H2AsO4−] is good. 5 × 10−3 = 0. We repeat the process using K a 3 to get [AsO43−].20 . K a1 .20 − 0.CHAPTER 7 77.0. Using the previously calculated concentrations of H+ and H2AsO4− to calculate the concentration of HAsO42−: (3 × 10 −2 )[HAsO 4 ] . . −x 0. ACIDS AND BASES 217 The reactions are: H3AsO4 ⇌ H+ + H2AsO4− K a1 = 5 × 10−3 H2AsO4− ⇌ H+ + HAsO42− K a 2 = 8 × 10−8 HAsO42− ⇌ H+ + AsO43− K a 3 = 6 × 10−10 We will deal with the reactions in order of importance.6 × 10−15 ≈ 2 × 10−15 M. H3AsO4 Initial Equil. x = 3 × 10−2 M. K a 3 = 6 × 10−10 = [H + ][AsO 4 ] [HAsO 4 ] 2− 3− = (3 × 10 −2 )[AsO 4 ] 8 × 10 −8 3− [AsO43−] = 1.20 Solving by the method of successive approximations: 5 × 10−3 = x2/(0.

20 M analytical concentration of H3AsO4: CHAPTER 7 ACIDS AND BASES [H3AsO4] = 0.010 − x 0.010 x = 6. then [H+] = [HCO3−] and K a 2 = 4. We should write H2O(l) + CO2(aq) or CO2(aq) for what we call carbonic acid. .8 × 10−11 = ≈ y.17 M. and then let those results control values of concentrations in the second reaction.010 − x ⇌ H+ ~0 x − + HCO3− 0 x K a1 = 4. that we write H2CO3(aq). we would have to treat both equilibria simultaneously. If the second dissociation contributed a significant amount of H+. [H+] = [H2AsO4−] = 3 × 10−2 M. assumptions good. HCO3− ⇌ H+ + CO32− K a 2 = 4.6 × 10−5 M = [H+] = [HCO3−].3 × 10−7 = [H + ][HCO 3 ] x2 x2 = ≈ [H 2 CO 3 ] 0. [AsO43−] = 2 × 10−15 M. The relevant reactions are: H2CO3 ⇌ H+ + HCO3− K a1 = 4.8 × 10−11 Initially.3 × 10−5 % −5 6. [HAsO42−] = 8 × 10−8 M.3 × 10−7. we deal only with the first reaction (since K a1 >> K a 2 ). The reaction that occurs when acid is added to a solution of HCO3− is: HCO3−(aq) + H+(aq) → H2CO3(aq) → H2O(l) + CO2(g) The bubbles are CO2(g) and are formed by the breakdown of unstable H2CO3 molecules. 0. HCO3− Initial Equil.6 × 10−5 M 6. It is for convenience. 6.218 So in 0.8 × 10 −11 × 100 = 7. however. y = [CO32−] = 4. H2CO3 Initial Equil.6 × 10−5 M 6.6 × 10 This result justifies our treating the equilibria separately.010 M 0.6 × 10−5 + y + CO32− 0 y [H + ][CO 3 ] [HCO 3 ] − 2− If y is small. The amount of H+ from the second dissociation is 4.6 × 10−5 − y ⇌ H+ 6. [OH−] = Kw/[H+] = 3 × 10−13 M 78.8 × 10−11 M or: 4.8 × 10−11 M. assumptions good.

we can ignore the H+ contribution from the K a 2 reaction.2000 L H2C6H6O6(aq) Initial Equil.0142 M 0.12 g = 0.0 × 10 −4 ) = 4. x = 1.0 × 10 −4 M 1. 80.6 × 10 −12 . 0.0 × 10 −4 ! x ⇌ H+ + −4 1.9 × 10 −5 K a1 = 7. 0. ACIDS AND BASES 219 For H2C6H6O6.0 × 10 −4 )x ≈ (1.9 × 10 −5 = x2 . Because K a 2 for H2S is so small.1 × 10 −3 .0142 − x Solving by the method of successive approximations: 7. .9 × 10 −5 = x2 x2 ≈ . K a1 = 7. assumptions good.00 Use the K a 2 reaction to determine [S2−]. Initial Equil.1 × 10 −3 Because H+ produced by the K a 2 reaction will be negligible.0 × 10 − 4 − x) 1.00. 0.0 × 10 −4 . HS− 1. assumptions good. Because K a1 >> K a 2 .0142 0.10 pH = !log(1.0 × 10 −19 = (1.0 × 10 −3 M (consistent answer) 0. the amount of H+ produced by the K a 2 reaction will be negligible. H2S Initial Equil.0 × 10 −4 + x S2− 0 x K a 2 = 1.10 M 0. 0.0 × 10 −7 K a1 = 1.0142 − 1.9 × 10 −5 and K a 2 = 1.0142 M 0. assumption fails the 5% rule.0 × 10 − 4 x = [S2−] = 1. [H+] = 1. 0. x = 1.0 × 10 −3 and pH = 3.0 × 10 −7 = x2 x2 ≈ .CHAPTER 7 79.500 g × [H2C6H6O6]0 = 1 mol H 2 C 6 H 6 O 6 176.10 − x 0.0142 ! x ⇌ HC6H6O6−(aq) 0 x + H+(aq) ~0 x K a1 = 7.10 ! x ⇌ H+ ~0 x HS− 0 x K a1 = 1.0 × 10 M 1.0 × 10 −19 M. x = [H+] = 1.0 × 10 −4 + x) x (1.

10 Note: We had to consider both H2SO4 and HSO4− for H+ production in this problem.012)x = x2 + (0.2 × 10−2) = 2.012. ⇌ H+ + SO42− 2. We will consider this equilibrium for additional H+ production: HSO4− Initial Change Equil. HSO4− is a weak acid that could also add H+ to the solution. the assumption is valid by the 5% rule. The amount of additional H+ from HSO4− is 1. ⇌ H+ + SO42− 0. . 0.60% of 2.0.0050 M 0 x mol/L HSO4− dissociates to reach equilibrium −x → +x +x 0.0 M H2SO4 solution produces 2.0 × 10−3 M 2 2 [H+] = 0.4 × 10 −4 )1/ 2 − 0.012 = Using the quadratic formula: 6. x = 3. CHAPTER 7 ACIDS AND BASES The dominant H+ producer is the strong acid H2SO4. The hydrogen sulfate ion.0 − x 2 .017)x − 6.0030 = 0.2 × 10−2 M 2.9 × 10 −4 + 2. pH = −log(2.0050 M 0. the first dissociation occurs to completion.0 − x 2. However.0080 M. assumption is horrible (240% error). A 2.0 Because x is 0.0 + x) x 2. 82.0 M HSO4.0) = -0.and 2.220 81.30 Note: In this problem H+ from HSO4− could have been ignored. For H2SO4.0050 − x K a 2 = 0.017 ± (2. pH = 2.0050)x.0050 + x x (0.2 × 10−2 M.0 + x x [H + ][SO 4 ] [HSO 4 ] − 2− K a 2 = 1. x2 + (0.0 × 10−5 = 0 x= − 0.2 × 10−2.0050 − x 0.0( x) ≈ .2 × 10−2 = = (2.0 M H+.0 + (1. However.0 M 2.0050 + x) x ≈ x. this is not usually the case in more dilute solutions of H2SO4.017 ± 0. is a weak acid with K a 2 = 1. x = 0.0050 + x = 0.0 M 0 x mol/L HSO4− dissociates to reach equilibrium −x → +x +x 2.0050 + 0.023 = . HSO4− Initial Change Equil.0 × 10−5 − (0. The total amount of H+ present is: [H+] = 2. x = 1. HSO4−.0 M.

Memorize the following strong acids: HCl. b. KC2H3O2. HNO3. then the salt will produce a neutral solution. If the Ka for the weak acid ion is equal to the Kb for the weak base ion. or HClO4. d. RbOH. The easiest way is to combine a conjugate base of a strong acid (except for HSO4−) with one of the cations from a strong base. Na+. and H2SO4 Memorize the following strong bases: LiOH. 84. Some weak acids are listed in Table 7. and Ba(OH)2 Weak acids have a Ka value of less than 1 but greater than Kw. a. These ions have no acidic/basic properties in water. . c. This salt at any concentration produces a neutral solution. Ka × Kb = Kw. Ka for NH4+ = Kb for C2H3O2− = 5. These are salts of the conjugate acids of the bases in Table 7. HClO4. Ca(OH)2. NH4Cl. pKa + pKb = pKw = 14. or a neutral species. which has weak acid properties). KNO3. One difficult aspect of acid-base chemistry is recognizing what types of species are present in solution. weak acid. There are two ways to make a neutral salt. Weak bases have a Kb value of less than 1 but greater than Kw.0 × 10−14 at 25°C) 85. The conjugate bases of weak acids are weak bases themselves.00 (Kw = 1. or Ba2+ because these cations have no acidic or basic properties in water. c. KOH. Ca(OH)2. HBr. Sr(OH)2.6 × 10 −10 . Sr2+. These conjugate acids are all weak acids. whether a species is a strong acid. Some weak bases are listed in Table 7. a. These are salts of the conjugate bases of the neutrally charged weak acids in Table 7. and C2H5NH3Br are three examples.CHAPTER 7 ACIDS AND BASES 221 Acid-Base Properties of Salts 83. so salts of these ions are neutral.3 of the text. and CaF2.3. CsOH. Below are some ideas and generalizations to keep in mind that will help in recognizing types of species present. For this salt. NaOH. Three examples are NaCl. KOH. e. K+. −log(Ka × Kb) = −log Kw −log Ka − log Kb = −log Kw. this is so because they have no acidic or basic properties in water (with the exception of HSO4−. Cs+. Three examples are NaClO2. strong base. Another type of strong electrolyte that can produce neutral solutions are salts that contain an ion with weak acid properties combined with an ion of opposite charge having weak base properties. HNO3. and SrI2. Ca2+. The most common example of this type of salt is ammonium acetate (NH4C2H3O2). b. Notice that these are the cations of the strong bases you should memorize. HI. HI. weak base.2 of the text. that is. These are strong acids like HCl. HBr. RbOH. H2SO4. and Ba(OH)2. These are strong ases like LiOH. Sr(OH)2. NaOH. Rb+. CH3NH3NO3. The cations used to form these salts are Li+.2. Note that the anions used to form these salts are conjugate bases of strong acids.

0). Cs+) and some alkaline earth metal ions (Ca2+. K+.2 of the text.6 × 10−10). that is. Alkali metal ions (Li+. Na+ and NO3− have no acidic/basic properties. HOC6 H 5 = 6. Strong acid.8 × 10−5 Increasing pH: HBr < NH4Br < KBr < NH3 Most Most acidic basic c. Ba2+) have no acidic or basic properties in water. Weak base.6 × 10−10) OC6H5− is a weak base (K b = K w /K a. Na+ and I− have no acidic/basic properties.2 × 10−4) F− is the conjugate base of the weak acid HF.4 × 10−11. HF = 1. and K+ is a neutral species. all have a Ka value of less than 1 but greater than Kw. and Br. Kb = 1.8 × 10−10) Strong acid .0 × 10−14/3. all have a Kb value of less than 1 but greater than Kw. e. HSO4−) have no basic properties in water (Kb << Kw). NH4Br: HBr: KBr: NH3: NH4+ is a weak acid (Ka = 5. NO3−. K+ and Br.is a neutral species. Strong base Weak acid (Ka = 1. ClO4−. In order of increasing pH. Na+ has no acidic or basic properties. and NO3− is a neutral species. Rb+. Neutral. a. Increasing pH: HI < HF < NaI < NaF. Br-. we place the compounds from most acidic (lowest pH) to most basic (highest pH). Strong acid Neutral.has any acidic properties in water.222 d.have no acidic/basic properties. Let’s apply these ideas to this problem to see what types of species are present. CHAPTER 7 ACIDS AND BASES Conjugate bases of weak acids are weak bases. Some examples of these are the conjugate acids of the weak bases listed in Table 7. The Kb value for F− = Kw/Ka. I−. C6H5NH2: HNO3: Weak base (Kb = 3. Some examples of these are the conjugate bases of the weak acids listed in Table 7. g. Conjugate bases of strong acids (Cl−. Sr2+. Neutral (pH = 7. f.3 of the text. C6 H 5 NH 2 = 1. Conjugate acids of weak bases are weak acids.8 × 10−10 = 2. Na+. so F− is a weak base. and only HSO4.6 × 10−5). HI: NaF: NaI: b. that is.3 × 10−5). HF: weak acid (Ka = 7. C6H5NH3NO3: NaNO3: NaOH: HOC6H5: KOC6H5: C6H5NH3+ is a weak acid (K a = K w /K b.

c.0 × 10−4 (c) HONH3+ is a weak acid. Increasing pH: HNO3 < C6H5NH3NO3 < HOC6H5 < NaNO3 < C6H5NH2 < KOC6H5 < NaOH Most acidic Most basic 86. NO2− is a weak base.0 × 10−14/5. the solution of C5H5NHF will be acidic.6 × 10−4 = 1.6 × 10−5). Reference Table 7. K+ and Cl− have no effect on pH.0 × 10−14/6.C5 H 5 N = 5. HF = 1. Because K b . NH4NO2: NH4+ is a weak acid.1 × 10−7 (c and e). Ka = K w /K b. The letters in parenthesis is(are) the generalization(s) listed in Exercise 85 that identifies that species. C2H5NH3CN → C2H5NH3+ + CN− basic. C6H5NH3+ is a stronger weak acid than HOC6H5 since the Ka value for C6H5NH3+ is larger than the Ka value for HOC6H5. Ka = 5.9 × 10 −6 ) . the ordering is: Most acidic → most basic: HClO4 > HNO2 > HONH3ClO4 > NH4NO2 > CaBr2 > KNO2 87.C 2 H 5 NH 2 = 1.2 × 10−10 = 1. the solution will be slightly acidic with a pH a little lower than 7. Ca2+ and Br.4 × 10−11). and CN− is a weak base (Kb = Kw/Ka. C 2 H 5 NH3+ . b.5 × 10−11 (c and d).CHAPTER 7 ACIDS AND BASES 223 This is a little more difficult than the previous parts of this problem because two weak acids and two weak bases are present. Using the information above (identity and the Ka or Kb values). .8 × 10−11). C5H5NHF → C5H5NH+ + F− acidic.6 of the text and the solution to Exercise 85 for some generalizations on acid-base properties of salts. HCN = 1.5 × 10−11 (c and d). Between the two weak bases. because the Kb value for OC6H5.1 × 10−8 ) = 9.have no acidic/basic properties (f and g). Reference Table 7.0 × 10−4) = 2.0 × 10−14)/(4. Kb = (1. CN − > K a . Ka = 4. Strong acid (a) Weak acid. HONH 2 = (1. Because K a . F− . NO2− is a weak base.0 × 10−14)/(1. the solution of C2H5NH3CN will be basic. Ignore ClO4− (g). CaBr2: KNO2: HClO4: HNO2: HONH3ClO4: Neutral. OC6H5− is a stronger weak base than C6H5NH2. Ignore K+ (f). C5 H5 NH + > K b. KCl → K+ + Cl− neutral. C2H5NH3+ is a weak acid (K a = K w /K b.is larger than the Kb value for C6H5NH2. Between the weak acids. C5H5NH+ is a weak acid (K a = K w /K b.6 of the text and the solution to Exercise 85 for some generalizations on acid-base properties of salts.6 × 10−10 (c and e).0. a. Kb = 2. and F− is a weak base (Kb = Kw/Ka. Because the Ka value for NH4+ is a slightly larger than Kb for NO2−.

050 [CN − ] x = [OH−] = 8. ignore Na+. Na+ has no acidic (or basic) properties.6 × 10 −10 ). HSO3− is a stronger acid than a base because Ka > Kb. a. NH4C2H3O2 → NH4+ + C2H3O2− neutral. C 2 H 3O 2 − .2 × 10 −10 0.05.8 × 10−11). H 2SO 3 = 1. and HSO3− is also a weak base (K b = K w /K a1 .0 × 10 −14 = Ka 6.6 × 10 −5 x mol/L CN− reacts with H2O to reach equilibrium !x → +x +x 0. assumptions good.7 × 10−13). CH3NH3Cl → CH3NH3+ + Cl−: CH3NH3+ is a weak acid. and C2H3O2− is a weak base (K b = K w /K a. ⇌ HCN + OH− Kb = Kw 1.10 x = [H+] = 1.5 × 10 −6 M.28 × 10 −11 = 0. HCO3− is a stronger base than an acid because Kb > Ka. and HCO3− is a weak base (Kb = K w /K a1 .5 × 10−2 = 6. CN− + H2O Initial Change Equil. Therefore.10 − x 0. the solution of NH4C2H3O2 will have pH = 7.38 × 10 − 4 = 2. NaHSO3 → Na+ + HSO3− acidic.10) Ka = 2.28 × 10 −11 CH3NH3+ Initial ⇌ CH3NH2 0 ~0 0. b. Because K a . f. .224 CHAPTER 7 ACIDS AND BASES d.9 × 10 −4 M.050 M 0 ~0 Kb = 1.3 × 10−8) . pOH = 3. HCO3− is a weak acid (K a 2 = 4.00 × 10 −14 = Kb 4.0 × 10−14/1.6 × 10 −5 = x2 [HCN][OH − ] x2 = ≈ 0. H 2CO3 = 2.6 × 10−10).10 ! x x x 2 2 x x ≈ (assuming x << 0.00.10 M x mol/L CH3NH3+ dissociates to reach equilibrium Change !x → +x +x Equil. Cl− has no basic (or acidic) properties. 88. HC 2 H 3O 2 = 5. pH = 10. NaCN → Na+ + CN−: CN− is a weak base. e. Therefore.82. pH = 5. HSO3− is a weak acid (K a 2 = 1.0 × 10−7).050 − x 0. the solution is acidic. NaHCO3 → Na+ + HCO3− basic. Cl− is the conjugate base of a strong acid. NH + = 4 K b. assumptions good.95. Na+ has no acidic/basic properties.050 ! x x x Kb = 1. 0. the solution is basic. NH4+ is a weak acid (Ka = 5. CH3NH3+ ⇌ CH3NH2 + H+ Ka = [CH 3 NH 2 ][H + ] [CH 3 NH 3 ] + H+ + = Kw 1.

0 × 10 [OH − ][HNO 2 ] [ NO 2 ] − x2 x2 ≈ 0. 0.6 × 10 −4 M.45 − x 0.0 × 10 −14 = = 2. KNO2 → K+ + NO2−: NO2− is a weak base. b.6 × 10 −10 Kb 1. assumptions good.7 × 10 −6 M. 0. Solving the weak acid problem: HSO4− Initial Equil.56. −14 K NH4+ ⇌ NH3 + H+ Ka = w = 1.10 .CHAPTER 7 89. Solution is acidic from HSO4− ⇌ H+ + SO42−.9 × 10 −7 Ka 3.0 × 10 −5 = 5.12 − x 0.12 x = [OH−] = 1.2 × 10−2 . OCl− + H2O Initial 0. NaOCl → Na+ + OCl−: OCl− is a weak base.10 M 0. ClO4− is the conjugate base of a strong acid.5 × 10 −11 = −4 Ka 4. pH = 10.44.5 × 10 −11 = ⇌ HNO2 + OH− 0 x ~0 x = Kb = Kw 1. Ignore Na+.12 M Equil. pOH = 5.5 × 10 −5 M. NH4ClO4 → NH4+ + ClO4−: NH4+ is a weak acid.40 M Equil.12 ! x Kb = 2.8 × 10 Initial 0. NO2− + H2O Initial 0.40 − x 0. ACIDS AND BASES 225 a.0 × 10 −14 = 2.6 × 10 −10 = 0 x [ NH 3 ][H + ] [ NH 4 ] + ~0 x = x2 x2 ≈ 0. 0. pH = 4.40 x = [H+] = 1. 90. ClO4− has no basic (or acidic) properties.5 × 10 −8 x2 x2 [HOCl][OH − ] = ≈ 0.45 M Equil.23.82.40 ! x Ka = 5.9 × 10 −7 = ⇌ HOCl + OH− 0 x ~0 x Kb = Kw 1. 0.45 [OCl − ] x = [OH−] = 3.77.45 ! x Kb = 2. pH = 8. assumptions good. assumptions good. c.x ⇌ H+ ~0 x + SO42− 0 x Ka = 1. pOH = 3. Ignore K+.

035 x2 = 1.010 x = [OH−] = 2.10 Assumption is not good (35% error). N3− + H2O Initial Change Equil.035 0.0 × 10 −14 = = 5. Kb = ⇌ HN3 + OH− Kb = Kw 1.9 × 10 0. −6 2. x = 0.010 − 2. x = 0. [H+] = 1. As is true for all conjugate acids of weak bases. [N3−] = 0. All conjugate bases of weak acids are weak bases (Kw < Kb < 1).010 M 0 ~0 x mol/L of N3 reacts with H2O to reach equilibrium −x → +x +x 0.010 M. Ignore Na+.3 × 10−9 M.028 x = [H+] = 0.54 If we add Na2CO3 to a solution of NaHSO4.10 − 0.029 M. pH = 1. C2H5NH3Cl → C2H5NH3+ + Cl−.010 − x 0. Azide (N3−) is a weak base since it is the conjugate base of a weak acid.226 Ka = 1. two reactions are possible. CO32−(aq) + HSO4−(aq) or ⇌ HCO3−(aq) + SO42−(aq) CO32− (aq) + 2 HSO4−(aq) ⇌ 2 SO42−(aq) + H2O(l) + CO2(g) 91.029 M (consistent answer) 0.010) 0.6 × 10−4).0 × 10 −14 = 4.3 × 10−6 M.028 0. 5. Cl− has no basic (or acidic) properties.3 × 10−10 = [HN 3 ][OH − ] [N3 ] − x2 x2 ≈ (assuming x << 0.3 × 10−6 = 0.010 − x x x .2 × 10−2.10 − x 0. Depending on relative amounts.3 × 10−6 M. x = 0.3 × 10 [HN3] = [OH−] = 2. NaN3 → Na+ + N3−.010 M 92. Solving the weak acid problem: . assumptions good. the base CO32− will react with the acid HSO4−. [Na+] = 0. C2H5NH3+ is a weak acid. Ignore Cl−.2 × 10−2 = [H + ][SO 4 ] [HSO 4 ] − 2− CHAPTER 7 = ACIDS AND BASES x2 x2 ≈ . C2H5NH3+ is the conjugate acid of the weak base C2H5NH2 (Kb = 5. Using successive approximations: x2 x2 ≈ = 1.3 × 10−10 −5 Ka 1.2 × 10−2.10 − 0.10 − x 0.

which has no acidic/basic properties and a conjugate base of a weak acid (except for NaCl.100 mol/1. pH = 8.8 × 10−11 ⇌ C2H5NH2 Initial Change Equil.93. 0 ~0 0. Kb = ⇌ HA + OH− 0. we can identify the conjugate base present by calculating the Ka value for the weak acid.4 × 10−11 = Kb value for the conjugate base of a weak acid. pH = 5.25 x = [H+] = 2. this Ka value is closest to HF.00 − 8.100 − x x2 [HA ][OH − ] = .07: 0.25 M. All these salts contain Na+.2 of the text.2 × 10 −6 ) 2 = 1. [C2H5NH2] = [H+] = 2.2 × 10 ) 1.2 × 10−6 M Kb = (1.8 × 10−9 M 93. We will use A. A− + H2O Initial Change Equil.1 × 10−6 M.07 = 5.4 × 10 −11 The Ka value for the weak acid equals Kw/Kb: Ka = From Table 7. [OH−] = x = 10−5.100 − x [A − ] pOH = 14. where Cl− is a neutral species).8 × 10−11 = = x2 x2 ≈ (assuming x << 0. assumptions good.25 M x mol/L C2H5NH3+ dissociates to reach equilibrium −x → +x +x 0.25) 0. from the problem.93 = 1.0 × 10 −14 = 7.2 of the text.00 L 0 ~0 x mol/L A− reacts with H2O to reach equilibrium −x → +x +x x x 0.68.1 × 10−4 1.25 − x 0.25 − x x x [C 2 H 5 NH 2 ][H + ] [C 2 H 5 NH 3 ] + Ka = 1. [C2H5NH3+] = 0. −6 0. Therefore. the unknown salt is NaF. .6 × 10−4) = 1.CHAPTER 7 ACIDS AND BASES C2H5NH3+ 227 + H+ Ka = Kw/(5. we will use the data given to determine the Kb value for the weak conjugate base. [Cl−] = 0. To identify the species. All conjugate bases of weak acids are weak bases since Kb values for these species are between Kw and 1.100 − (1. From the Kb value and data in Table 7.as an abbreviation for the weak conjugate base.25 M [OH−] = Kw/[H+] = 4.1 × 10−6 M.

x ⇌ Co(H2O)5(OH)2+ 0 x + H+ ~0 x Ka = 1.0 × 10−5).0 × 10−14).5 × 10 −6 ) 2 = 2. from the problem.2 × 10−4) = 1.200 − x .0 × 10−14)/(7.10 . CHAPTER 7 ACIDS AND BASES BHCl → BH+ + Cl−.10 − x 0.0 × 10−3 M 0.0 × 10−5 = x2 x2 ≈ . Major species: Co(H2O)63+ (Ka = 1.200 M −x → 0. HF = (1. BH+ is a weak acid because it is the conjugate acid of a weak base B. Determining the Ka value for BH+: BH+ Initial Change Equil. Co(H2O)63+ will determine the pH since it is a stronger acid than water. assumptions good. From Table 7.0 × 10−14)/(1. Let’s solve by first setting up an ICE table. so Cl− has no acidic/ basic properties. 96.0 × 10−14)/(2.3 × 10−11 −6 0.3 × 10−4.0 × 10−5 Ka = 1.4 × 10−11]. and F− [Kb = K w /K a.9 × 10−6]. 0.10 pH = −log(1.3 × 10−11) = 4. C5H 5 N = (1.82: 0.5 × 10 ) [H+] = x = 10−5. Solving the weak acid problem in the usual manner: Co(H2O)63+ Initial Equil.228 94. Major species present are H2O. The reaction to consider is the best acid present (C5H5NH+) reacting with the best base present (F−). Cl− is the conjugate base of the strong acid HCl.200 M −x 0.00. this Kb value is closest to CH3NH2. Ka = ⇌ B + H+ 0 ~0 0.10 M 0. C5H5NH+(aq) Initial Change Equil.3 of the text.10 M x mol/L BH+ dissociates to reach equilibrium −x → +x +x x x 0.5 × 10−6 M. pH = 5.82 = 1. 95.7 × 10−9) = 5.10 − x [BH + ] (1. and H2O (Kw = 1.10 − x x2 [B][H + ] = .200 − x + F−(aq) ⇌ C5H5N(aq) + HF(aq) 0 +x x 0 +x x 0. C5H5NH+ [Ka = K w /K b. 0. Ka = Kb for the base B = Kw/Ka = (1.0 × 10−3) = 3.10 − (1. so the unknown salt is CH3NH3Cl. x = [H+] = 1. Cl− (neutral).

058)[H + ] . because the Ka for the weak acid is larger than the Kb for the weak base.50 − x)(0. The dominant equilibrium is the best acid (NH4+) reacting with the best base (OCl−) present.016 x(x) (0. OCl−. use any pertinent Ka or Kb value. x = [C5H5N] = [HF] = 0.200 − x From the setup to the problem.058 M 2 0.8 × 10−5) = 5. NH 4 + = 5. To solve for the [H+]. taking the square root of both sides: [C 5 H 5 NH + ][F − ] (0.058 .200 − x = 0. [H+] = 6. the solution will be basic. C H 5 5 = 5.016 = [ NH 3 ][HOCl] [ NH 4 ][OCl ] + − = x2 x = 0. we can use either the Ka equilibrium for C5H5NH+ or the Ka equilibrium for HF.016 = 0.5 × 10−8) = 2.184 M = [C5H5NH+] = [F−].200 − 0. x = 0.6 × 10 −10 = [ NH 3 ][H + ] [ NH 4 ] + = (0.8 × 10−5 M + 0.6 × 10 −10 and Kb for OCl− = (1. x = 0.2 × 10 − 4 229 K = K a.50 – x 1 K a .0 × 10−14)/(1.17 As one would expect. 0. Using C5H5NH+ data: K a.2 × 10−3 = . 8.200 − x) 2 0. x = 0.5 × 10−8) = 0.091 = x . C H 5 5 NH + K= [C 5 H 5 N][HF] x2 . a solution of this salt should be acidic.016 M.13.016.50 – x K = K a .091)x. pH = 8. 97.37 0. Using Ka for NH4+: K a . Ka for NH4+ = (1.016 M 0.016)[H + ] = .9 × 10−6 = NH + [C 5 H 5 N ][H + ] (0. HF = 5. and H2O. Because OCl− is a better base than NH4+ is an acid. and 0.9 × 10−6 × 1 = 8. HOCl + OCl− ⇌ NH3 0 +x x + HOCl 0 +x x 0. NH4+ Initial Change Equil.50 M –x 0.9 × 10 −7 .0 × 10−14)/(3.3 × 10 −9 M.184 [C 5 H 5 NH ] pH = −log(6. Major species: NH4+.018 − (0.50 − 0.50 − x) K = 0.50 M –x → 0.50 − x) To solve for the H+.CHAPTER 7 ACIDS AND BASES × 1 K a .8 × 10−5) = 4.016)1/2 = 0. [H+] = 4.6 × 10−10)/(3. NH + × 4 = (5. = (0.50 − x (0.2 × 10−3 7.

021 Kb = 0. 0.10 M 0.0 × 10−6 M x mol/L HBrO dissociates to reach equilibrium −x → +x +x −6 x x 1.021 = x2 . CHAPTER 7 ACIDS AND BASES Major species: Na+. Initial Change Equil.6 × 10 −7 and Kb for H2PO4− = K w /K a1 = 1.230 98. HBrO ⇌ H+ + BrO− Ka = 2 × 10−9 ~0 0 1. This answer is impossible! We can't add a small amount of an acid to a neutral solution and get a basic solution.10 ! x ⇌ HPO42− + OH− 0 x ~0 x Kb = 0. pH = 7.3 × 10 −12. the Kb value for PO43− is much larger than the Kb values for HPO42− and H2PO4−.0 × 10−5 M Equil. Kb for PO43− >> Kb values for HPO4− and and H2PO4−. the 5% assumption will not hold. pOH = 1. PO43− + H2O Initial Equil. 100. The highest pH possible for an acid in water is 7.0 × 10−5 − x ⇌ C6H5O− 0 x + H+ ~0 x C6H5OH = phenol .0 × 10 −14 = = 0.7 × 10 −2 .0 × 10 Let’s check the assumptions. K b for PO 4 3− = Kw 1.021)x – 0. x = [OH−] = 3.0. 4.43.0 × 10 − x) 1. Solving 0.0 × 10 − x Ka = 2 × 10−9 = x2 x2 ≈ . PO43− (a weak base).021 K a3 4.4 −6 −6 (1. pH = 12. and H2O. C6H5OH Initial 4.8 × 10 −13 Note: Kb for HPO4− = K w /K a 2 = 1.10 − x using the quadratic equation: x2 + (0.0021 = 0.57 Solutions of Dilute Acids and Bases 99. because Kb is so large. We can ignore the contribution of OH− from the Kb reactions for HPO42− and H2PO4− . Indeed. x = [H+] = 4 × 10−8 M. In the correct solution we would have to take into account the autoionization of water.

0 × 10−4 M Equil.0 × 10−14)]1/2.7 × 10−7) = 6. try [H+] = (Ka[HA]0 + Kw)1/2 . [H+] = 5. From Section 7.89 [ H + ]2 − K w = 5.0 × 10−4 − x Ka = ⇌ H+ ~0 x + CN− 0 x Ka = 6. Whenever the calculated pH is greater than 6. the water contribution to [H+] must be considered.6 × 10−10 ≈ . we first determine the charge balance equation and then manipulate this equation to get into one unknown.0 × 10−14 = 0 . pH = −log(5. Charge balance: [H+] = [NO3−] + [OH−]. Whenever the calculated pH is greater than 6. Assumption [H + ] Note: If the assumption that ([H+]2 − Kw)/[H+] << Ka is bad. then the full equation derived in Section 7.7 × 10−7 M Checking assumptions: [ H + ]2 − K w = 5. + [H ] Using this formula: [H+] = [(6.2 × 10−10)(5.0 × 10−8)[H+] − 1. 5.10 of the text. 1. From Section 7.0 × 10−14)]1/2 = 1. The assumption that the H+ contribution from water is negligible is poor.6 × 10−10)(4. then we can use [H+] = (Ka[HCN]o + Kw)1/2. the H+ contribution from water should be considered.0 × 10 The assumption that the H+ contribution from water is negligible is poor. x = [H+] = 8. [H+] = [NO3−] + Kw/[H+] [H+]2 − 1.6 × 10−7.3 × 10−7 M This equation will work if [HA]0 = 4. check assumptions.5 × 10−7 << 5. [H+] = 1.0 ([H+] < 1 × 10−6 M) for an acid solution.3 × 10−8. ≈ −4 −4 (5.0 × 10−5 >> good.0 × 10−4.0 × 10 − x) 4. 101.0 × 10−4 + [H ] Assumptions good.9 of the text.0 × 10 Check assumptions.2 × 10−10.0 × 10−4) + (1.CHAPTER 7 Ka = ACIDS AND BASES 231 x2 x2 . pH = 6.0 for a weak acid. [H+] = [(1.0 × 10−8 M −5 −5 (4. We can't neglect the [H+] contribution from H2O since this is a very dilute solution of the strong acid.0 × 10−14 = [H+](5.3 × 10−7 M.24 102. x = 5. Following the strategy developed in Section 7.9 in text: if [ H + ]2 − K w << [HCN]0 = 5. HCN Initial 5. [H+]2 − (5.0 × 10 − x) 5.0 × 10−5) + (1.0 × 10−8).9 of the text should be used.2 × 10−10 x2 x2 = 6.

that is. we first determine the charge balance equation and then manipulate this equation to get into one unknown.0 × 10−7 + 1. NaOH → Na+ + OH− H2O ⇌ H+ + OH− Kw = [H+][OH−] = 1.0 × 10−7 M and [H+] = Substituting into the charge balance equation: 1. we must worry about the amount of OH− donated from the autoionization of water. [H+]2 − (7. [OH−]2 − (1.0 × 10−14 = 0 − [OH ] Kw [OH − ] Using the quadratic formula to solve: [OH−] = − (−1.1 × 10−7) = 6.0 × 10−14 = 0 + [H ] Using the quadratic formula to solve: [H+] = − (−7. like all solutions.15 104.0 × 10−7 and [OH−] = ) + [H ] [H + ] [ H + ]2 − K w = 7. pOH = −log(1.0 × 10−14 This solution. where [Na+] = 1.6 × 10−7) = 6.0 × 10−7 + Kw Kw (because [Cl−] = 7.1 × 10−7 M.20 . pH = 6. the charge balance equation is: [Na+] + [H+] = [OH−]. Following the strategy developed in Section 7.0 × 10−7)[OH−] − 1. [positive charge] = [negative charge].0 × 10 −14 )]1/ 2 2(1) [H+] = 7. pH = 7.0 × 10−7.0 × 10 −7 ) 2 − 4(1)(−1.89 ACIDS AND BASES 103.10 of the text.0 × 10−7)[H+] − 1. pH = −log(7.3 × 10−7 M.0 × 10 −7 ) 2 − 4(1)(−1. [Positive charge] = [negative charge] [H+] = [Cl−] + [OH−] = 7. Because this is a very dilute solution of NaOH.6 × 10−7 M.0 × 10 −7 ) ± [(−7.0 × 10 −14 = [OH−]. must be charged balanced.0 × 10 −7 ) ± [(−1. We can't neglect the [H+] contribution from H2O since this is a very dilute solution of the strong acid. For this problem.0 × 10 −14 )]1/ 2 2(1) [OH−] = 1.232 CHAPTER 7 Using the quadratic formula: [H+] = 1.80.

5 × 103 Ka 4.CHAPTER 7 ACIDS AND BASES 233 Additional Exercises 105.0 × 10 [ NH 3 ][H ] K a for NH 4 b. NH4+ + CH3CO2− ⇌ NH3 + CH3CO2H + [ NH 3 ][CH 3CO 2 H ] [ NH 4 ][CH 3CO 2 ] + − × [H + ] [H + ] K a for NH 4 Kw = Keq = K a for CH 3CO 2 H (K b for NH 3 )(K a for CH 3CO 2 H) Keq = 1. Breathing into a paper bag increases CO2 in the blood. Bicarbonate ion acts as a base in water and neutralizes the excess acidity.8 × 10 −5 ) (1. driving the equilibrium to the left. H3O+ + OH− ⇌ 2 H2O e. c. which shifts the reaction left. NH4+ + OH− ⇌ NH3 + H2O HNO2 + OH− Keq = 1 = 5. NH3 + H3O+ ⇌ NH4+ + H2O Keq = + K 1. .0 × 10 − 4 c.0 × 1014 Kw d. a.1 × 10−5 (1. and the equilibrium favors Hb(O2)4.8 × 10 −5 ) Keq = 1 = 1. CO2 + H2O ⇌ HCO3− + H+.0 × 10 −14 = 3.8 × 10 −5 [ NH 4 ] 1 = = b = = 1. b. and the equilibrium favors HbH44+. Removing CO2 essentially decreases H+. CO2 builds up in the blood. Hb(O2)4 is then favored. ⇌ − H2O + NO2− K for HNO 2 [ NO 2 ] 4. and O2 is not released by hemoglobin in the cells.0 × 10 [HNO 2 ][OH ] [H ] 106.8 × 109 + + −14 Kw 1.6 × 104 K b for NH 3 f.0 × 1010 × Keq = − + −14 Kw 1. a. In the cells there is a deficiency of O2.0 × 10 −4 [H + ] = a = = 4. CO2 is a weak acid. and it becomes too acidic. Hemoglobin can't bind O2 as strongly in the lungs. In the lungs there is a lot of O2. thus increasing [H+]. NO2− + H3O+ ⇌ H2O + HNO2 Keq = [HNO 2 ] [ NO 2 ][ H ] Keq = − + = 1 1 = = 2.

9 × 10 −3 M 1 . C7H4ClO2− is a weak base. pOH = 5. 10. HCB.5 × 10 −6 ) 2 = = = 1.65.35 and [OH−] = 10−5.20 .20 − x ⇌ H+ ~0 x + CB− 0 x Kw x2 x2 1. Ca(OH)2(aq) → Ca2+(aq) + 2 OH−(aq) 0.08 g 1 mol CaO mol Ca (OH) 2 = 5. + H2O 108. pH = 14. and the NaOH solution would have a pH close to 14. NaOH (strong base).5 × 10−3 M. ⇌ HCB 0 x + OH− ~0 x 0.x Because pH = 8.35.0). pH = 2.0 × 10 − 4 = = ≈ Kb 0. chlorobenzoic acid.9 × 10 −3 ) = 2. The pH meter value of 4.20 M 0.25 g CaO × [OH−] = 1 mol CaO 1 mol Ca (OH) 2 2 mol OH − × × 56. so it has no basic (or acidic properties) in water.0 M. Kb = x2 [HCB][OH − ] (4.35 = 4. NH4Cl is the solute. From the pH. the pH would be close to zero. NH4+.0 × 10−10 − −6 0. so NH4+ is a weak acid and would produce a solution with a pH = 4.6 when the concentration is ~1. CHAPTER 7 ACIDS AND BASES The light bulb is bright because a strong electrolyte is present.23.154 mol NaOCN 65. is the conjugate acid of the weak base NH3. CB− Initial Equil.0 g NaOCN × 1 mol = 0.0 × 10 −14 . only NH4Cl contains a weak acid (the HCl solution would have a pH close to zero.) Of the possible substances.0 × 10 −10 x = [H+] = 4.6 indicates that a weak acid is present. Ka = 0. Use the weak base data to determine Kb for C7H4ClO2− (which we will abbreviate as CB−).ions when dissolved in water. is a weak acid. Of these three substances.20 1. 1. and NH4Cl are strong electrolytes.5 L pOH = !log(5.77 110. (If a strong acid were present.5 × 10−6 M = x.20 − x 0.234 107.20 M 0. CaO(s) + H2O(l) → Ca(OH)2(aq). Solving the weak acid problem: HCB Initial Equil. Cl− is the conjugate base of a strong acid. that is. a solute is present that dissolves to produce a lot of ions in solution. 109. only HCl (strong acid). NH4Cl dissociates into NH4+ and Cl.20 − (4.20 − x [CB ] 0. assumptions good.00 – 2.5 × 10 ) Because CB− is a weak base.23 = 11.01 g . however.

04 g 235 10.1 × 10 −14 = 2. 112. 1.4 × 10 −4 M 0. assumptions good. ⇌ H+ ~0 x + NCO− 0 x Ka = 1.0792 M Equil. Initial Equil.10 − x ⇌ H+ ~0 x + acr0 x . x = [H+] = 4.2 × 10 −4 0.4 × 10 −2 M 1.100 L 1. Therefore.154 mol (actual) = = 1.4 × 10 −4 ) = 3. For this problem we will abbreviate CH2=CHCO2H as Hacr and CH2=CHCO2− as acr−. pap = 2.54 mol HNCO will be produced.4 × 10 −2 ) = 1.33 × 10 −9 x2 x2 ≈ . assumptions good. 30. x = [H+] = 1.39 Mol H 2 C 2 O 4 0.0 mg papH + Cl − 1000 mL 1g 1 mol papH + Cl − 1 mol papH + × × × × mL soln L 1000 mg 378.5 × 10 −6 8.85.0792 − x 0. HNCO Initial Equil.54 ! x Ka = 1.154 mol/0. Because there is a 2 : 2 mole correspondence between mol NaOCN reacted and mol HNCO produced.2 × 10 −4 = x2 x2 ≈ .36.0792 M papH+ Initial 0. Hacr 0.0792 ! x Ka = 2.0792 pH = -log(4.54 − x 1.85 g mol papH + Cl − = 0.111 mol The balanced reaction requires a larger 2 : 1 mole ratio. a.54 pH = –log(1.CHAPTER 7 ACIDS AND BASES 1 mol = 0. NaOCN in the numerator is limiting.10 M 0. ⇌ pap + H+ 0 x ~0 x Ka = Kw K b.111 mol H2C2O4 90. 0.0 g H2C2O4 × Mol NaOCN 0.5 × 10 −6 = 111.

10 − 0. 0.022 0.4 × 10−2 M.0 × 10−5 M Ka = [ H + ] (1. acr− is a weak base and the major source of OH− in this solution.050 − x 0.52.0 × 10 −5 ) d.024 x2 x2 = 6. assumption is poor (24% error). For 0. x = [H+] = 2.6 × 10−5 = .0 × 10 −14 = Ka 5.010% dissociation: [acr−] = 1.10 − 0.10 − x 0.10 M 0.022 M.48.0 × 10−3.4 × 10 −3 × 100 = 2. Ka = Fe(H2O)63+ + H2O 0.050 x = [OH−] = 3. b. pH = 8. assumptions good.6 × 10−5 ≈ .10 x = 2.0 × 10−4(0.62 0.66 .0 × 10−3.10 − 0.8 × 10−10 = Kb = 1. Initial Equil.6 × 10 −5 Initial 0. pH = 1. x = 0.0 × 10−3 = x2 x2 ≈ 0. x = 0.0 × 10−6 M.10 − x 0. Percent dissociation = 2.56 M [Hacr] 0.8 × 10−10 x2 x2 ≈ 0.021 0. 5. 6.0 × 10 −5 ) [H + ][acr − ] .10 c.022. 1. 5.050 M Equil. acr+ H2O ⇌ Hacr 0 x + OH− ~0 x Kb = Kw 1.10) = 1.0 × 10−3.4% 0.10 Assumptions good. Using successive approximations: x2 = 6.021 0.10 − (1. = 6.050 − x Kb = [OH − ][ Hacr] [acr − ] .022 x = [H+] = 0.4 × 10−3 M.10 − x [H 3O + ][Fe( H 2 O) 5 (OH ) 2 + ] [Fe(H 2 O) 6 ] 3+ ⇌ Fe(H2O)5(OH)2+ 0 x + H3O+ ~0 x . x = 0. 113. pH = 2. [H+] = 0. pOH = 5. a.236 Ka = CHAPTER 7 ACIDS AND BASES x2 x2 .

50 M 0.50 mol/L. × 100 = 4.1 × 10−10 M For HB: 1. [B−] = 9.45 M = 0.0 mol HCl total to achieve pH = 0.10 M HC.00. 116.0 M.45 Since NH3 is so concentrated. [HA]0 = 1.0 mol HCl to neutralize the OH− plus an additional 1.05 M.0 mol excess to reduce to a pH of 0.022 M.CHAPTER 7 b.0 mol/L NaOH = 2. 2 .022 M = [H+]. 114.0 × 10−12 Major source of H+ is HA because its Ka value is significantly larger than other Ka values. [HA] = 0. (0.9990 0. Because of the lower charge. [H+] = 0. 0. At a pH = 0. We will need 2.50 0.0 × 10−3 = 0. pH = −log(6. the [H+] = 10−0. x = 0.50 M HA.0 L × 2. Ka = 6. we need to calculate the OH− contribution from the weak base NH3. 0. Begin with 1.0010 [H + ] (0. (0.0010) .0 × 10−3. Thus our original assumption was good.0 × 10−10. Even less will be produced by HC. Let's check out the assumption that only HA is an important source of H+. . solve using the Ka equilibrium reaction. Ka = 0. Ka = 1.00 = 1.78 c.0 × 10−10 = (0.00. A solution of iron(II) nitrate will be less acidic (have a higher pH) than a solution with the same concentration of iron(III) nitrate.0 L HA Initial Equil. ⇌ H+ ~0 x + A− 0 x x2 x2 0. We need 3.50 − x 115.50 M − x. HB will produce an additional 9.20) At most.4% error 0. Fe2+(aq) will not be as strong an acid as Fe3+(aq).50 Assumption good. in this problem.022 . 1.50 − x ⇌ H+ ~0 x + A− 0 x x2 [H + ][ A − ] = . Ka = 1.022) [B − ] . Ka = 0. Ka = 117.0 mol = 0.00.50 M 0. Ka = 1. x = 0. 0.20 M HB.0) = −0. ACIDS AND BASES = 0.45 M so: [HA] 0.9990 237 [Fe(H 2 O) 5 (OH) 2 + ] [Fe( H 2 O) 6 ] 3+ Solving: [H+] = 6.05) 2 = 6 × 10−3 0.0 M.50 − x [HA] = 0. HA Initial Equil.1 × 10−10 M H+.50 − x 0.0 × 10−3 ≈ .0 mol OH−.

010 M 0. assumption is horrible.0 M Equil.8 × 10−5 0.020 + x + SO42− 0 x Ka = 0.6 × 10−3.8 × 10−6 = 0 x = 1.027. HSO4− is a good weak acid (Ka = 0. Ka = ⇌ H+ 0. NH4(HCO3) → NH4+ + HCO3− .00 × 10 −4 ) ≈ 0.0 − x Kb = 1.80 b. HCN is a poor weak acid (Ka = 6.0 (x is 270% of 0.238 NH3 + H2O Initial 15.100 − x 0.6 × 10−3 M. pH = 2.0 × 10−2) = 2.0 − x) = (0.0100).) 0.8 × 10−5)(15.64 119.032)x − 1.010 − x 0. 0.7 × 10−4 = 0 x = 1. x2 + (0. assumption poor (60% error).0100) ≈ . a.4 × 10−3 M [H+] = 0.0 × 10−2) + (1.010 Using the quadratic formula: x2 + (0.100 M 0. 15. HC2H3O2 Initial Equil.0100 = 0.0100 M (Assume no volume change.0100)x + x2.1 × 10−3 M. assumption is horrible 15.012). x = 0.012 ≈ . x = 3.020) .8 × 10−5 = CHAPTER 7 ACIDS AND BASES ⇌ NH4+ 0 x + OH− Kb = 1.00 × 10 −4 + x) x(5.0060. Using the quadratic formula: (1. 0. [OH−] = (1.2 × 10−10) and can be ignored.012 0. a.100 x = 3. Calculating the H+ contribution from HSO4-: HSO4− Initial Equil. [H+]0 = (1.1 × 10−3 M 120.0100 + x x(0.2 × 10−4 = 0. 0. The initial concentrations are halved since equal volumes of the two solutions are mixed.2 × 10−2) + 0.0100)x − 2.4 × 10−3) = 0. x = [C2H3O2−] = 1. pH = 1.020 + x = 0.023 M.2 × 10−2 M.100 − x ⇌ H+ + C2H3O2− 0 x 5.010 − x x(0.00 × 10−4 M 5. However.00 × 10−4 + x = 1.0 × 10−2 M from strong acids HCl and H2SO4.0100 + x) x(0. [H+] = 5.0 − x 15.022 M 118.00 × 10−4 + x Ka = 1.8 × 10−5 = x(5.020 M 0.020 + x) x(0.18 × 10−4)x − 1. Using the quadratic formula: x2 + (5. x = 0.020 + (3.

NH + = 5.4 × 10−4 = x2 .8 × 10−13.3 × 10 239 K a . Because the values of K a1 and K a 2 are fairly close to each other. x = 1. ignore Na+.2 × 10−8.6 × 10−10.15 − x 0. K b . HPO = Kw 1.15 assumption fails the 5% rule. K b .4 × 10−4 = .0 × 10 −14 = 1. we should consider the amount of H+ produced by the K a1 and K a 2 reactions.8 × 10−11). K b . H3C6H5O7 Initial Equil. Ka = 4. c. 121.3 × 10−12 K a .15 M x 0. K a . K 1. from Appendix 5. 0. HCO 2 H = 1. .8 × 10 4.6 × 10−7 Ka2 6.8 × 10−4.15 − 1. HCO − = w = = 2.0 × 10 −14 = = 1. x = 1.0 × 10 −14 = = 5.1 × 10 − 2 ) Now let’s solve for the H+ contribution from the K a 2 reaction.6 × 10−10.2 × 10 −8 3.1 × 10−2 M (consistent answer) (0. e. ⇌ H2C6H5O7− + H+ ~0 x K a1 = 8. d.0 × 10 −14 = 5.15 .6 × 10−11 Ka 1.8 × 10 − 4 Solution is acidic since NH4+ is a stronger acid than HCO2− is a base. ignore Na+.3 × 10−8 −5 −7 3 K a1 1. K b . K a . Solving more exactly using the method of successive approximations: 8. NH4(HCO2) → NH4+ + HCO2−.CHAPTER 7 ACIDS AND BASES K 1.x 2 2 x x ≈ 8. b. NH4(H2PO4) → NH4+ + H2PO4− NH4+ is weak acid and H2PO4− is also acidic (see part b). Solution with both ions present will be acidic. NH + = 4 Solution is basic since HCO3− is a stronger base than NH4+ is as an acid.5 × 10 −3 Solution is acidic since Ka > Kb. HCO − = 4 2 Kw 1. The acidic properties of HCO3− were ignored because K a 2 is very small (4. NaH2PO4 → Na+ + H2PO4−. H PO − = w = 2 2 4 2 4 K a1 7.1 × 10−2. HPO 4 2− 4 2− Solution is basic since Kb > Ka. Na2HPO4 → 2 Na+ + HPO42−.0 × 10 −14 1.4 × 10−4 0 0. H PO − = 6.

0833 L = 83. [H+]total = (1. At most.00 × 10 − 4 )(7.50 × 10 −5 ⎞ ⎟ ⎟⎜ ⎜ ⎟ ⎟⎜ V V [H + ][A − ] ⎜ ⎠ ⎠⎝ ⎝ −4 = 1.50 × 10 −5 )(V) (1.00 × 10 = Ka = −5 [ HA] ⎛ 7.1 × 10−2 + x x (1. a.1 × 10−2) + (1. x = 1.1 × 10 −2 + x) x (1. mL to 83.50 × 10 −5 ) 2 (2.50 × 10 −5 ) 2 . 1.1 × 10−2) = 1.00 × 10−4) = 2. 123.00 × 10−4) = 7.50 × 10−5 mol mol HA− = 0.000 L × 1. HCO3− + HCO3− ⇌ H2CO3 + CO32− . 1. Therefore.00 × 10−4) = 2.2% error). Solving: pH = −log(1.50 × 10 −5 ) The volume goes from 1000.8 × 10−5 ⇌ HC6H5O72− 0 x + H+ 1.00 × 10−4 = (2.50 × 10 −5 ⎞ ⎛ 2. V= = 0.1 × 10−2 M Note that the H+ contribution from the K a 2 reaction was negligible compared to the H+ contribution from the K a1 reaction even though the two Ka values only differed by a factor of 50.00 × 10−4 mol HA L 25. 1.240 H2C6H5O7− Initial Equil.3 mL (7.8 × 10−5 = 1.00 × 10 −4 mol HA = 1.1 × 10−2 M 1. the H+ contribution from the K a 3 reaction will also be negligible since K a 3 < Ka2 .3 mL.1 × 10−2 − x CHAPTER 7 ACIDS AND BASES K a 2 = 1.8 × 10−5 M. so 917 mL of water evaporated.1 × 10 − x) 1.0% dissociation gives: mol H+ = 0.750 × (1.1 × 10 (0.1 × 10 −2 ) ≈ .8 × 10−5) = 1.50 × 10−5 mol mol A− = 0. assumption good −2 −2 (1.1 × 10−2 M 1.50 × 10−5 mol ⎛ 2.250 × (1.8 × 10−5 M H+ will be added from the K a 2 reaction.96 Challenge Problems 122.50 × 10 ⎞ ⎜ ⎟ ⎜ ⎟ V ⎝ ⎠ 1.250 × (1.

[H+] = [(4. c. The pH of HSO4− solutions does depend on the concentration of HSO4− present. Thus bicarbonate solutions are concentration independent. [H+] = 4. HSO4− is the conjugate base of the strong acid H2SO4. or taking the −log of both sides: pH = pK a1 + pK a 2 2 d. HCO3− is amphoteric.8 × 10−11)]1/2. HCO3− is a weak acid with Ka = 4. adding more HCO3− adds both the acid and the base to the equilibrium at the same time.8 × 10 −11 = a2 = = 1. HCO3− is also the conjugate base of the weak acid H2CO3.5 × 10−9 M. H2CO3 ⇌ 2 H+ + CO32− Keq = [H + ]2 [CO 3 ] = K a1 × K a 2 [H 2 CO 3 ] 2− Because [H2CO3] = [CO32−] from part b. a. When more HSO4− is added. resulting in a more acidic pH. The H2CO3 and CO32− concentrations are increased by the same proportions as more HCO3− is added. The dominant equilibrium reaction is: HCO3−(aq) + HCO3−(aq) ⇌ H2CO3(aq) + CO32−(aq) .35 124.8 × 10−11. The proportional increase is determined only by the Ka value for HCO3− and the Kb value for HCO3−. For HSO4− solutions. more H3O+ will be produced. which makes it a weak base. Water is the best base present in bisulfate solutions. NaHSO4 → Na+(aq) + HSO4−(aq) Na+ has no acidic (or basic) properties. pH = 8. [H+] = (K a1 × K a 2 )1/ 2 . so HSO4− is a much worse base than water. [H2CO3] = [CO32−] since the reaction in part a is the principal equilibrium reaction.1 × 10−4 + −7 K a1 [H ] 4. the dominant equilibrium of the best acid reacting with the best base present in a bicarbonate solution is: HCO3−(aq) + HCO3−(aq) ⇌ H2CO3(aq) + CO32−(aq) Because the best acid and best base present are the same species.3 × 10 b.3 × 10−7) × (4. [H+]2 = K a1 × K a 2 . b.CHAPTER 7 Keq = ACIDS AND BASES [H 2 CO 3 ][CO 3 ] [HCO 3 ][HCO 3 ] − − 2− 241 × K [H + ] 4. the dominant equilibrium of the best acid reacting with the best base present is: HSO4−(aq) + H2O(l) ⇌ SO42−(aq) + H3O+(aq) This is just the Ka reaction for HSO4−. NaHCO3(aq) → Na+(aq) + HCO3−(aq).

242 CHAPTER 7 ACIDS AND BASES From this reaction. x = [H+] = 4. C2H3O2−.) 1. If we add the K a1 reaction for H2CO3 to the K a 2 reaction for HCO3−. pK a1 + pK a 2 2 HSO4− 0. . For a pH = 4. the result is: 2− [H + ]2 [CO 3 ] K = K a1 × K a 2 = H2CO3 ⇌ 2 H+ + CO32− [H 2 CO 3 ] 2− + 2 Because [H2CO3] = [CO3 ]: [H ] = K a1 × K a 2 [H+] = ( K a1 × K a 2 )1/2 or taking the −log of both sides: pH = pH = c. the equilibrium concentrations of H2CO3 and CO32− must be equal to each other.010 − x x = [H+] = 6. solving using the quadratic equation: 0. they are so good that we can assume they accept protons 100% of the time.00 pH = !log(4. fig.37. pH = = 8.00 M Equil.3 × 10 −7 ) − log(4. As is true with all strong bases.37 + 10.00 − x 1.2 × 10 −2 1.5 × 10−3 M. HC2H3O2 Initial 1.24 × 10 −3 ) = 2. they are great at accepting protons.19 125.35 2 2 ⇌ H+ + SO42− ~0 x 0 x Ka = 1. let’s calculate the ratio of [C2H3O2−]/[HC2H3O2] necessary to achieve this pH. 1.24 × 10 −3 M (using one extra sig. assumptions good. The initial reaction that occurs when the strong base is added is: HC2H3O2 + OH− → C2H3O2− + H2O Note that this reaction has the net effect of converting HC2H3O2 into its conjugate base.8 × 10 −5 x2 x2 ≈ .00 − x 1.8 × 10 −5 = ⇌ H+ + ~0 x C2H3O2− 0 x Ka = 1. This is HC2H3O2.74 by addition of the strong base NaOH.37) = 4. We want to double the pH to 2(2.8 × 10 −11 ) 6. The best acid present will react the strong base.32 .74. In fact.010 M 0. pH = 2.010 − x = pK a1 + pK a 2 2 − log(4. Initial Equil.2 × 10 −2 = x2 .

the principal equilibrium is: . Therefore. g NaOH L mol 0.50 M From the preceding stoichiometry problem.08206 L atm × 298 K K mol = 125 g/mol 1.5 × 10−3 [HA] 0. Mass NaOH = 1.50 M 0 !0.120 − x Ka = 127.016 Major species: BH+.8 × 10 −5 )[C 2 H 3O 2 ] [C 2 H 3O 2 ] . 0.6 × 10 −2 ) 2 = = 2. [H+] = 10−1.8 × 10 −5 . we need to add an amount of NaOH that will convert onehalf of the HC2H3O2 into C2H3O2−.120 − 0.74.74. we need to have equal concentrations (equal moles) of C2H3O2− and HC2H3O2.0 [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] − − Ka = 1.6 × 10−2 M Initial 0.74 = 1. because BH+ is the best acid and X− is the best base in solution. adding enough NaOH(s) to produce a 0. dRT Molar mass = = P 1.50 g × [HA]0 = HA 5.00 atm 126. this results in a solution with pH = 4.80 = 1.50 M NaOH.120 M Equil. HC2H3O2 + OH− → C2H3O2− + H2O Before 1.11 g / L × 1 mol 125 g = 0. X−.8 × 10 −5 = For a solution having pH = 4.CHAPTER 7 ACIDS AND BASES 243 − HC2H3O2 ⇌H + + C2H3O2 − [H + ][C 2 H 3 O 2 ] Ka = [ HC 2 H 3 O 2 ] When pH = 4.50 → +0.100 L ⇌ H+ + A− ~0 x 0 x where x = [H+] = 1.80.50 mol NaOH 40.50 After 0.74.00 g NaOH × = 20.00 M Change !0.00 L × 0.50 0 0. (1. and H2O. [H+] = 10 −4.50 M completion 0. = 1.6 × 10−2 M 0. pH = 1. [H + ][A − ] (1. This amount is 0.50 M OH− solution will convert one-half the HC2H3O2 into C2H3O2−.120 M.

[ H + ]2 = K × K a .100 − x K = 9.3 × 10 −4 ) .200 − x + C2O42− ⇌ NH3 + HC2O4− 0 +x x 0 +x x K= K a .3 × 10−4 M (0. = [HX] K a . K= 0.00 and Ka for HX = 10−5. pK a .100 − 4. HX Taking the −log of both sides: pH = 2 K a . HX X− CHAPTER 7 ACIDS AND BASES ⇌ B + 0 x HX 0 x 0. Ka for BH+ = pH = 8. HX a . HX ⎠ pK a . HX = [HX ]2 [H + ][X − ] [HX] [H + ] . BH + K a . 0. [H+] = 2. solving: x = 4. (4.2 × 10−6. Solving the problem: Kb for B = 1. where [B] = [HX] and [BH+] = [X−] + − [BH ][X ] To solve for the Ka of HX.0 × 10−3. . K a 2 = 6. let’s use the equilibrium expression to derive a general expression that relates pH to the pKa for BH+ and to the pKa for HX.100 M −x → 0.244 BH+ + Initial 0. BH + This is a general equation that applies to all BHX type salts.6 × 10−7 M. and H2O.100 − x) Use either Ka expression to solve for [H+]. K a .0 × 10−5 Major species: NH4+. K a . C2O42−.3 × 10 − 4 ) pH = 6.100 − x = [B][HX ] . HC O 2 4 − 0.100 M Equil. 11.00 = 128. HX [ X − ]2 ⎝ .200 M −x 0. BH + K a .00 = 1.0 × 10−11 Kb ⎛ [H + ] [HX]2 = =⎜ ⎜ K a .00 + pK a .100 − x K= K a . HX = 5. BH + ⎟ K a .2 × 10−6 ( x)( x) = 9. reacting the best acid with the best base: NH4+ Initial Change Equil.100 M 0. HX 2 Kw = 1.59 We get the same answer using the Ka equilibrium for NH4+.200 − x)(0. HX [ X − ]2 [X − ] 2 ⎞ ⎟ . BH + + pK a . NH 4 + K a .1 × 10−5 = [H + ][C 2 O 4 ] [HC 2 O 4 ] − 2− = [H + ](0. HX = .

150 = [HB] + [B−] [H + ][A − ] [H + ][B − ] = 1. Initial Equil.00 × 10−4 M C C − 1. The HB assumption is good (0. [H+] = 3.6 × 10−10 = 129.85 × 10−6. = 0.30 × 10−3 mol/L 8.6 × 10 −7 M.77 × 10−4.0500.200 − 4.4% error).0500). They do. This assumption is borderline (2. [H+]2 = [H+][A−] + [H+][B−] + Kw [H+][A−] = (1. then [H+][A−] ≈ (1.CHAPTER 7 ACIDS AND BASES [H + ][ NH 3 ] [ NH 4 ] + 245 [H + ](4. [H+] = 2. pH = 6. pH = −log(3.00 × 10−14.3 × 10−3 M = [H+]total This assumes the acids did not suppress each other’s ionization. HA ⇌ H+ + A− 0 1.3 × 10−3 M. Ka = 1.00 × 10−4 .0500 M HCO2H (HA). 0.85 × 10−6 + 2. = 1. Similarly.0500 − [A−]) If [A−] << 0.68 × 10−3 Check assumptions: [H+][A−] ≈ 8.150 M CH3CH2CO2H (HB).30 × 10 Assumed 0.77 × 10 − 4 .150) = 2.000 x = [H+] = 1. each contributes to the total pH.492 Note: If we treat each acid separately: H+ from HA = 2.3 × 10 −4 ) .77 × 10−4) (0. and we expect the [H+] to be less than 4.85 × 10−6.85 × 10 −6 ≈ 2.77 × 10−4)[HA] = (1.59 −4 (0.22 × 10−3 M. Charge balance: [H+] = [A−] + [B−] + [OH−] = [A−] + [B−] + Kw/[H+] Mass balance for HA and HB: 0. Ka = 1. [H+] = [A−] + [B−] + Kw/[H+].01 × 10−6 + 1.0500 = [HA] + [A−] and 0. Manipulate the equations to solve. We get such an answer. [A−] ≈ −3 3.01 × 10−6.0500) = 8.00 × 10−6 C = [HA]0 for pH = 4.77 × 10−4) (0.9 × 10−3 H+ from HB = 1.0500 − [A−] ≈ 0. assume [H+][B−] ≈ (1.34 × 10−5 [HA] [HB] We have five equations and five unknowns.68 × 10−3 is 5. Using successive approximations to refine the [H+][A−] value: [H+] = 3.00 × 10−4 Ka = 1.22 × 10−3) = 2. [H+]2 = 8.00 × 10−4 ~0 1.0500.3 × 10 ) Ka = 5.34 × 10−5 Because two comparable weak acids are present.4% of 0.4 × 10−3 _________________________________________________ 4.34 × 10−5)(0. 130.

x = [H+].650. so we need to add 4540 mL of water.00 × 10−5) ~0 1. We then dilute to a total volume V in liters. [HA]0 = 1.00 × 10−4 = (5. and H2O. HSO4−. The resulting pH = 5. so: HA Initial Equil. NH3. so [H+] = x = 10−5.59 L.00 × 10−6 (5.05 × 10−4/V) − (1.00 × 10 − 2 )⎜ ⎜ 0.00 × 10 ) ACIDS AND BASES The solution initially contains 50. Ka = ⇌ H+ + A− 0 1.0500 ⎞ (2. 131.00 × 10−5 (1.24 × 10−7 M Let V = volume of water added: 5.00 × 10−10 From the problem: pH = 5.650. so [H+] = 1.00 × 10−10 = (2.00 × 10−10 = x2 (2. solving: C = 0. HA [HA]0 −x [HA]0 − x ⇌ → H+ ~0 +x x + A− 0 +x x Ka = 5.00 × 10−6.05 × 10 − 4 /V) − (1.24 × 10 −6 ) 2 = .650 = 2. V = 6.05 × 10−4 mol HA.00 × 10−2 M [HA]0 − x ([HA]0 − 2.0 × 10−3 L × 0.650 = 2.24 × 10 −7 ) 2 − (1.24 × 10 −7 ⎝ ⎠ Solving.00 × 10 −5 ) 1.00 × 10 −5 ) 2 = 1.0 mL are present initially.000.00 × 10 −14 ) ⎛ 0.05 × 10−4 mol/V (5.00 × 10 −14 ) (1. 132.24 × 10 −6 ) After the water is added. [H+] = 10−6.05 × 10−4/V) − 1.0101 M −4 (C − 1.24 × 10−6 M 5.00 × 10 −4 ) 2 = 1.00 × 10−5. so the water contribution to the [H+] must be considered.00 × 10−5 V = 4.246 Ka = CHAPTER 7 (1. Major species = Na+.24 × 10 −7 ) 2 − (1.00 × 10−5 5.0500 + V ⎟ − ⎟ 2. the pH of the solution is between 6 and 7. The general expression for a very dilute weak acid solution is: Ka = [ H + ]2 − K w [ H + ]2 − K w [HA]0 − [H + ] pH = 6. Initial Change Equil.0101 mol/L = 5.16 L of water were added. In the typical weak acid problem. 50. reaction: HSO4− + NH3 ⇌ SO42− + NH4+ .

40 × 10−2 mol CO2/L = 5.135 mol CO 2 = 5.40 × 10−2 M H2CO3. x = 2.10 M ← −x 0.2 × 10−5 M. ≈ 2 2 x x [HSO4−] = 2. pH = 5.5 × 10−5 M. our assumption that the reaction goes to completion is good (2. [H+] = 2. H 2CO3 = 4.2 × 10 −2 = 2.40 × 10−2) = 0.105 M CO32− 2. let the reaction go to completion. Whenever K >> 1.40 × 10−2 mol/L CO32− is converted into HCO3−.051).10 M 0 0. [HCO3−] = 2(5.10) 2 = 2. HSO4− + NH3 Before After 0. 0.10 M Using one of the Ka equilibrium expressions to solve for [H+]: K a .0 × 103 4.108 M. [CO32−] = 0.2 × 10−5 M. assumptions good.1 × 107 5.5 × 10−5 is 0.6 × 10−6 M.10 − x 0. [SO42−] = 0.10 M 0 ⇌ SO42− 0 0. . H2CO3 + CO32− → 2 HCO3− K= K a1 . 5.05% of 0.3 × 10 −7 = 9.10 M −x 0. 0. 0 +x x NH3 0 +x x ⇌ SO42− + NH4+ 0.10 M + NH4+ 0 0. and then solve the back equilibrium problem.105 .2 × 10 − 2 .0540 = 0.50 L The best acid (H2CO3) reacts with the best base present (CO32−) for the principal equilibrium.6 × 10 −10 Because K is a large number.2 × 10−5 M.2 × 10 −5 133.59 2. H 2CO 3 K a 2 . HSO K a . [NH3] = 2. NH 4 − = 4 + 1. we get [H2CO3] = 2. assume all CO2 (H2CO3) is converted into HCO3−. HSO − = 4 [H + ] (0. that is.1 × 107.10 M Allow the reaction to attain equilibrium: HSO4− + Initial Change Equil. always assume the reaction goes to completion.10 M [NH4+] = 0.051 M Note: If we solve for the [H2CO3] using these concentrations.CHAPTER 7 ACIDS AND BASES 2− + 247 K= [SO 4 ][ NH 4 ] [HSO 4 ][ NH 3 ] − = K a .10) = 1.0.10 − x) 2 (0.8 × 10 −11 Because K >> 1.10 − x (0.

8 × 10−11 = 2− K a 2 = 4.108 [H+] = 1.0 × 10 −14 . 134.0 × 10 −5 [OH−] = 1. pH = 7. NO2− is a weak base. Kb = [HB+ ][OH − ] [B] material balance: [B]o = [B] + [HB+] Charge balance: [H+] + [HB+] = [OH−]. So: [OH−] = [H+] + [HB+] [OH−] = Kw Kw + [HB+] or: [HB+] = [OH−] − − [OH ] [OH − ] [B] = [B]0 − [HB+] ⎛ Kw [B] = [B]0 − ⎜ [OH − ] − ⎜ [OH − ] ⎝ ⎛ Kw ⎞ ⎟ [OH − ] ⎜ [OH − ] − − ⎟ ⎜ [OH ] ⎠ Kb = ⎝ ⎛ Kw ⎞ ⎟ [B]0 − ⎜ [OH − ] − ⎜ [OH − ] ⎟ ⎠ ⎝ Assuming [B]0 >> ⎞ ⎟ ⎟ ⎠ [OH − ]2 − K w [OH − ]2 − K w [B]0 − [OH − ] = [OH − ]2 − K w . HCO3− ⇌ H+ + CO32− 4. NO2− + H2O ⇌ HNO2 + OH−.1 × 10−11 = [B]0 2. and NO2−. pH = 10.051) 0. use the Ka expression for HCO3−.1 × 10−7. assumptions good.96. then: [OH − ] Kb ≈ [OH − ]2 − K w [OH − ]2 − 1.00.248 CHAPTER 7 ACIDS AND BASES To solve for the [H+] in equilibrium with HCO3− and CO32−.04 (assumption good) 135.8 × 10−11 [H + ][CO 3 ] [HCO 3 ] − = [H + ] (0. Na+. B + H2O ⇌ HB+ + OH− Kw = [H+][OH−]. Major species: H2O. H2O ⇌ H+ + OH−. 6. .0 × 10−10. pOH = 6.

0 × 10 ) ⎟ ⎝ ⎠ − 1/ 2 = 1.00 × 10−7 M ).0 × 10 −14 −4 −14 ⎞ ⎟ Try: [OH ] = ⎜ ⎜ 4.00 × 10−7) − [SO42−] + 2[SO42−].00 × 10−7) + [H ] [H + ] ⎞ ⎛ Kw [H + ]⎜ [H + ] − − (1.00 × 10 −7 ) ⎟ + ⎟ ⎜ [H ] [H ][SO 4 ] ⎠ ⎝ 1. For A− type bases (A− + H2O Kb = ⇌ HA + OH−).0 × 10 − 4 × (6.0 × 10−14 Material balance: Ka = 1. the Ka equilibrium expression for HSO4− dictates that [SO42−] >> [HSO4−].2 × 10−2 = [H+] = [H + ][SO 4 ] [HSO 4 ] − 2− .00 × 10 −7 ) [H + ] + 2− This is a complicated expression to solve. [SO42−] = [H+] − − (1.6 × 10 Assumption good.CHAPTER 7 ACIDS AND BASES 249 Because this is a very dilute solution of a weak base. the OH− contribution from H2O must be considered.6 × 10 −7 ) 2 − (1.8 × 10−8 −7 1. then Kb = [OH − ] [A − ]0 and: When [A−]0 >> [OH−] = (Kb[A−]0 + Kw)1/2 ⎛ 1.0 × 10−4 >> (1.0 × 10 −14 ) = 9.9 of the text.00 × 10−7) − [SO42−] Kw Kw + (1. The weak base equations for dilute solutions are analogous to the weak acid equations derived in Section 7. Because this is such a dilute solution of H2SO4 (1.20 136.80.2 H 10−2 = = − Kw [HSO 4 ] (1. pOH = 6.00 × 10−7 M (from the 1. the general equation is: [OH − ]2 − K w [OH − ]2 − K w [A − ]0 − [OH − ] [OH − ]2 − K w [OH − ]2 − K w . Major species: H+. [HSO4−] = (1. and H2O (water is important!) Charge balance: [H+] = [OH−] + [HSO4−] + 2[SO42−] [HSO4−]0 = [SO42−] + [HSO4−] = 1. HSO4−.00 × 10−7 M (assume most of the HSO4− dissociates): .00 × 10−7 M H2SO4) Kw = [H+][OH−] = 1. pH = 7.00 × 10 −7 ) − [H + ] + + (1.0 × 10 ) + (1. Let’s assume that [SO42−] = 1. [OH−] = 1.6 × 10−7 M Checking assumption: 6.6 × 10−7 M.

0 × 10−4 M NH3 and 1. x = 1. The reaction is: NH3 + H+ → NH4+ Because equal volumes of 1.6 × 10−10 NH4+ Kb −5 Initial 5. then: [H+] = (Ka[HA]0 + Kw)1/2 = 1.0 × 10 −5 We cannot neglect [H+] that comes from H2O. If this is the case. Cl− has no basic properties since it is the conjugate base of a strong acid. + −7 [H ] 2. The H+ from the strong acid will react with the best base present (NH3). a weak acid. 137.62 Assumption good: [SO 4 ] [HSO 4 ] − 2− = Ka 1. that is.0 × 104.4 × 10−7 M.0 × 10−4 M H+ are mixed. the only species with acid-base properties is NH4+. Because strong acids are great at donating protons. Therefore. checking assumption: [ H + ]2 − K w = 1.0 × 10−5 >> ([H+]2 − Kw)/[H+].2 × 10 −2 = = 5. pH = 6. After reaction. so we can't ignore the OH− contribution from H2O. H+. only NH4+ and Cl− remain. until one or both of the reactants runs out. NH3.0 × 10 −5 − x) 5.00 × 10−7 + [H ] [H + ] ACIDS AND BASES Solving: [H+] = 2.6 × 10−10. and Cl−.250 [H+] = CHAPTER 7 Kw Kw + (1. assume 5.0 × 10−5 (assumption good) [H + ] So: [H+] = 1. K ⇌ H+ + NH3 Ka = w = 5. 2[Ca2+] = [OH−]. check assumptions. Ca(OH)2 (s) → Ca2+(aq) + 2 OH−(aq) This is a very dilute solution of Ca(OH)2. The initial concentration of NH4+ will be exactly one-half of 1. As discussed in Section 7. Including the H2O autoionization into H+ and OH−.7 × 10−7 M.0 × 10−5 − x Ka = x2 x2 ≈ = 5. both reactants are in stoichiometric amounts.9 × 10−7 M.0 × 10 M ~0 0 x x Equil. and both reactants will run out at the same time. the overall charge balance is: . 5.9 of the text. the reaction between H+ and NH3 essentially goes to completion. Major species: H2O.9 × 10−7 M. From the dissociation of Ca(OH)2 alone. pH = 6.0 × 10−4 M since equal volumes of NH3 and HCl were mixed.0 × 10−5 M NH4+.4 × 10-7 << 5.72 138. Now we must solve the weak acid problem involving 5.4 × 10 We do have mostly SO42− at equilibrium.00 × 10−7) + [SO42−] = + 2. (5.

pH = 4.0 × 10−14)/(2. using quadratic formula: [OH−] = 6. and OH−. the OH− from the strong base is exceptional at accepting protons. So let’s work with moles of each reactant initially. and we can assume that OH− will react to completion with HX. x = [H+] = 6. X − = (1. Kb = + H2O ⇌ → HX 0 +x x + OH− ~0 +x x Kb = [HX][OH − ] [X − ] 0.5 × 10−8 = [H + ][X − ] [HX] 0.0500 − x (10 −3.2 × 10−7) = 4.0 × 10−14 = 0.0 × 10−7)[OH−] + Kw [OH−]2 − (6. which can then be used to calculate Ka for HX (Ka = Kw/Kb).98 0. Use solution B to determine Kb for X−.5 × 10−8 = x2 x2 ≈ .100 − x 0. HX (Ka = 4.17 Solution C: Major species: H2O. from the problem.02. . ⇌ H+ ~0 +x x + X− 0 +x x Ka = 4. until one (or both) of the reactants runs out.5 × 10−8 HX Initial Change Equil.2 × 10−7 M Marathon Problems 139.2 × 10−7 −3. we have diluted both solutions from their initial concentrations.100 M −x → 0. that is.98 0. HX = K w /K b.067% of 0. the Ka value for HX must be determined. Because we have added one volume of substance to another.100 − x Ka = 4. What hasn’t changed is the moles of each reactant.5 × 10−8). Solution B: X− Initial Change Equil. so pOH = 3. pH = 10.0 × 10−7 M) + Kw/[OH−] = [OH−]. To determine the pH of solution A.100 Assumptions good (x is 0.98 ) 2 = 2.0500 − x x2 . OH− will react with the best acid present (HX).7 × 10−5 M 0. [OH−]2 = (6.0500 M −x 0. Na+.0 × 10−7)[OH−] − 1.100).98 and [OH−] = x = 10−3.CHAPTER 7 ACIDS AND BASES 251 2[Ca2+] + [H+] = [OH−] 2(3.0500 − 10 Kb = Solution A: Ka.

we will use the Kb reaction.250 mol NaOH 1 mol OH − × = 3. assumptions great (x is 0.0150) L 0. The Na+ (like most +1 metal ions) has no effect on the pH of water. HX is a weak acid and its conjugate base.0192) x = [OH−] = (2.0192) x ≈ 0.20 M NaNO2.0192 M. major species = H+. pOH = 6. X−. HX Before 5. Since both Ka and Kb reactions refer to these species. we need to convert to concentration units since Kb is in concentration units of mol/L.75 × 10−3 Change After 1.75 × 10−3 0 → → X− + H2O 0 +3.00 = 6.) X− Initial Change Equil.20 M HCl + 0.0192 0.0577 − x 0.0192 + x (0.0150 L × CHAPTER 7 0.0192 + x)x (0.00 × 10−3 mol HX L ACIDS AND BASES 0. [OH−] = 6.25 × 10−3 mol completion + OH− 3.25 × 10 −3 mol 3. Na+ and H2O.0577 Kb = 2.0577) = 6.252 Mol HX = 0.0500 + 0.0034% of 0.75 × 10−3 − After reaction. Cl−.0577 − x 0.0192 M x mol/L of X− reacts to reach equilibrium −x → +x 0. the solution contains HX.75 × 10−3 3. X−. Na+. weakest base (smallest Kb) from group II = NaNO2 0.100 mol HX = 5.0577 M 0.75 × 10−3 mol −3. However. To solve the equilibrium problem using the Kb reaction. and H2O .0192).75 × 10 −3 mol = 0. pH = 14.2 × 10−7 = (assuming x is << 0. Strongest acid from group I = HCl.18 = 7. + H2O ⇌ HX + OH− 0 +x x Kb = 2.2 × 10−7 0.75 × 10−3 mol OH− L mol NaOH Now lets determine what is remaining in solution after OH− reacts completely with HX.82 = pH of solution C The combination is 4-17-7-82. [HX] = 1. NO2−. Note that OH− is the limiting reagent.6 × 10−7 M.0577 M (0. we could use either reaction to solve for the pH.18.2 × 10 −7 )(0. a. 140.00 × 10−3 mol −3.0500 L × Mol OH− = 0. [X−] = = 0.75 × 10−3 mol − +3. is a weak base.0650 L [OH−] = 0 (We reacted all of it to completion.6 × 10−7 M.

10 − x ⇌ HOI 0 x + (C2H5)3N 0 x K= K a .10 M Change −x Equil. solving.21 0.10 − x 0.64 (0.10 − x (0. H+ Before After 0.053 M 2 0.053) 1.1 × 10−3 M.047 M.10 − x b. OI− + (C2H5)3NH+ Initial Equil.12.0 × 10 −11 x2 x = 1. fig. best base from group II = KOI. 0.10 M 0 → HNO2 0 0. [H+] = 2.00.053 M and [OI−] = 0.0 × 10 − 4 c.10 M 0 HNO2 Initial 0. mixing (C2H5)3NHCl with NaNO2 will result in a solution with pH = 7.) Ka = 4.0 × 10 −14 = 2.5 × 10−11 4.0 × 10−4.10 M 0. Ka for (C2H5)3NH+ = Kb for NO2− = 1.10 – x = 0.3 × 10−11 M. (C 2 H 5 ) 3 NH + K a . x = 0.0 × 10 −14 1 × = 1. pH = 10.10 M 0.0 × 10−4 ⇌ → H+ + 0 +x x x2 = 4.) −4 4.5 × 10−11 4. pH = 2.0 × 10−11 = [H + ](0.25. HOI = 1.047) .0 × 10 − 4 Because Ka = Kb. . 0. = 1. The dominant equilibrium will be the best base reacting with the best acid.CHAPTER 7 ACIDS AND BASES 253 Let the H+ react to completion with the NO2−.10 − x + NO2− 0. using the Ka equilibrium constant for HOI to solve for [H+]: 2.25 (carrying extra sig.0 × 10 −14 = 2. Weakest acid from group I = (C2H5)3NHCl.10 − x) So: [HOI] = 0. x = [H+] = 6. then solve the back equilibrium problem.10 M NO2− 0 +x x (Molarities are halved due to dilution.0 × 10 2.

0 × 10 −4 (Kb = Kw/Ka for conjugate acid-base pairs). A buffer solution is one that resists a change in its pH when either hydroxide ions or protons (H+) are added. When [HA] = [A−] (or [BH+] = [B]) for a buffer. which translates into a Kb value of the base close to 1. The pH of a buffer depends on the [base]/[acid] ratio. we would want the acid component of the buffer to have a Ka close to 10 −10. the greater is the buffer capacity. the pH will be on the acidic side of the pKa value. The 1. OH−(aq) + HCO3−(aq) → H2O(l) + CO32−(aq) 16. the 0. For a pH = 10. the [base]/[acid] ratio does not change a lot (unless a large quantity of OH− is added). when [acid] > [base]. This translates into a pH that doesn’t change much. so the pH does not change much.00 buffer. the pH of the solution is equal to the pKa value for the acid component of the buffer (pH = pKa because [H+] = Ka).0 × 10 −10 .00 buffer. Of course. When H+ is added to a buffer.00 = 1. When OH− is added to a buffer. Any solution that contains a weak acid and its conjugate base or a weak base and its conjugate acid is classified as a buffer. the more strong acid or strong base that can be neutralized with little pH change.0 × 10 −4 (pH = pKa for a best buffer). if the log term is negative.01 M buffer the least capacity. The capacity of a buffer is a measure of how much strong acid or strong base the buffer can neutralize. the weak base component of the buffer reacts with the H+ and forms the acid component of the buffer. A best buffer has equal concentrations of the acid and base components so it is equally efficient at absorbing H+ and OH−. we would choose the acid component having a Ka close to 10 −4. the larger the concentrations of weak acid and conjugate base. Again. then pH < pKa. For a pH = 4. ⎟ [acid] [acid] ⎝ ⎠ From the Henderson-Hasselbalch equation. In general. the ratio of [base]/[acid] does not change that much.74) because they all have a 1 : 1 concentration ratio between the weak acid and the conjugate base. that is.0 × 10 −10 .CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA Buffers 15.00 = 1.00 buffer. we can have a buffer solution made from a weak base and its conjugate acid. H+(aq) + CO32−(aq) → HCO3−(aq). For a pH = 10. All the buffers listed have the same pH (= pKa = 4. Even though the concentrations of the acid and base components of the buffer change some. the weak acid component is converted into the base component of the buffer. pH = pKa + log ⎛ [base] ⎞ [base] [base] . then < 1 and log ⎜ ⎜ [acid] ⎟ < 0. 17. When one has more acid than base in a buffer.0 M buffer has the greatest capacity. 254 . our conjugate acid should have Ka ≈ 1.

the pH is at a value lower than the pKa value.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 255 that is. assumptions good. −log[OH−] = −log Kb + log [ NH 3 ] [ NH 3 ] + + + −log Kb = −log[OH−] − log + pOH = pKb + log [acid] [ NH 4 ] or pOH = pKb + log [ NH 3 ] [base] 19.8 × 10−6 M.7 × 10−10 = x = [OH−] = 8.100 M x mol/L HOPr dissociates to reach equilibrium −x → +x +x 0. HOPr(aq) Initial Change Equil.96.100 M 0 ~0 − x mol/L OPr reacts with H2O to reach equilibrium −x → +x +x 0. When one has more base than acid in a buffer. Let HC3H5O2 = HOPr and C3H5O2− = OPr−. that is.0 × 10−7 M. pH = 7. the pH is at a value greater than the pKa value. ⇌ HOPr(aq) + OH−(aq) Kb = Kw = 7. the log term is equal to zero.100 − x 0. and pH = pKa.7 × 10−10 Ka 0.06. The other scenario you can run across in a buffer is when [acid] = [base]. Here.100 − x 0.3 × 10−5 ~0 0 0. assumptions good by the 5% rule. b. taking the −log of the Kb expression: [ NH 3 ] [ NH 4 ] [ NH 4 ] . 18. pH = 2. This is a weak acid problem.00 . pOH = 5. the pH is on the basic side of the pKa value.100 − x x x [H + ][OPr − ] x2 x2 = ≈ [HOPr] 0.94.100 Ka = 1. resulting in pH > pKa.1 × 10−3 M. pH = 8. c. This is a weak base problem. ⇌ H+(aq) + OPr−(aq) Ka = 1.3 × 10−5 = x = [H+] = 1. a. NH3 + H2O ⇌ NH4 + OH + − [ NH 4 ][OH − ] Kb = . Pure H2O. then the log term in the Henderson-Hasselbalch equation is positive. [H+] = [OH−] = 1. When one has more base than acid in a buffer ([conjugate base] > [weak acid]).100 [OPr − ] Kb = 7. OPr−(aq) + H2O(l) Initial Change Equil.100 − x x x [HOPr][OH − ] x2 x2 = ≈ 0.

3 × 10−5 0. We will solve for the pH through the weak acid equilibrium reaction.89.020 M. b.100 M 0. Note: The Henderson-Hasselbalch equation can only be used to solve for the pH of buffer solutions. this will almost always be true for useful buffer solutions.100)( x) = x = [H+] ≈ 0.020 + x x [H+] = 0.100 + x)( x) (0. 20. From a practical standpoint. we can use the Henderson-Hasselbalch equation to calculate the pH of buffer solutions. pH = 1. pH = pKa + log [base] ⎛ 0. .020). the solution will have such a low buffering capacity it will not be of any use to control the pH.100 − x 0. pH = 4. We have a weak acid (HOPr = HC3H5O2) and a strong acid (HCl) present.89 0.100 M 0. assumptions good.3 × 10−5 = ⇌ H+(aq) + OPr−(aq) Ka = 1. Alternately.020 M 0 x mol/L HOPr dissociates to reach equilibrium −x → +x +x 0.1 that we just made in this problem is valid. HOPr(aq) Initial Change Equil. If the assumption is not valid. Note: The H+ contribution from the weak acid HOPr was negligible.1 + x ≈ 0.256 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA d. This is a buffer solution.100 − x x 0. 1.020 + x ≈ 0.3 × 10−5 M.100 + x (0.5 × 10−5 is << 0. a.100 ⎠ [acid] ⎝ The Henderson-Hasselbalch equation will be valid when an assumption of the type 0. assumption good (x = 6.100 M x mol/L HOPr dissociates to reach equilibrium −x → +x +x 0.100 ⎞ 5 = pKa + log ⎜ ⎟ = pKa = −log(1.70. To prove it lets consider the weak acid equilibrium reaction: HOPr Initial Change Equil. This solution contains a weak acid and its conjugate base.100 − x 0. OPr−.3 × 10−5 ~0 0. Added H+ reacts completely with the best base present.100 [H+] = 1. The pH of the solution can be determined by only considering the amount of strong acid present. ⇌ H+ + OPr− Ka = 1.3 × 10− ) = 4. The amount of H+ donated by the weak acid will be negligible.

020 0.080) b.100 M −0. [acid] (0. This is a strong acid problem.020 → 0 After reaction.120) [acid] a. HOPr. assumptions good.020) = 4. OH− will react completely with the best acid present.020 + H2O Reacts completely A buffer solution results after the reaction.020 0. Using the Henderson-Hasselbalch equation where pKa = −log (1.70 d.100 M −0. HOPr Before Change After 0. To prove it.020 0 → → OPr0 +0.020 Reacts completely 0. HOPr . assumptions good.020) c.080) = 4.020 0. are present.71. [acid] (0. Using the HendersonHasselbalch equation: pH = pKa + log 21. [H+] = 0.020 0 → → HOPr 0.89: pH = pKa + log [base] (0. OPr− Before Change After 0. We have a weak base and a strong base present at the same time.020 M.3 × 10−5) = 4.120 A buffer solution results (weak acid + conjugate base).020 0.29. pH = 1.020 M −0.020 M −0. This is a buffer solution. Added H+ reacts completely with the best base present.89 + log = 4. (0.020 M Reacts completely 257 Before Change After 0.020 0. assumptions good. OPr−.89 + log (0. The amount of OHadded by the weak base will be negligible.89 + log = 5.49.100 M +0. Using the Henderson-Hasselbalch equation: pH = pKa + log [base] (0. = 4.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA OPr− + H+ → HOPr 0 +0.100 M −0. a weak acid. let’s consider the weak base equilibrium: .080 0. and its conjugate base.080) [base] = 4.080 + H+ 0. OPr−.020 M −0.080 + OH− 0.

pOH = 1.7 × 10−10 ⇌ 0. it contains both a weak acid (HC3H5O2) and a weak base (C3H5O2−).30 5.07 The solution in Exercise 19d is a buffer.from the strong base). This is a solution containing a weak acid and its conjugate base.020 M OH. For this problem.020 M.89 + log = 5.080) Consider all the results to Exercises 19. However. the best acid present.96 8.120 + H2O Reacts completely 0. you could also use the Kb reaction for F− and come up with the same answer.70 4. which contains both HF and F−. HOPr Before Change After 0.100 M +0.020 M − x mol/L OPr reacts with H2O to reach equilibrium −x → +x +x 0. The pH can be determined by only considering the amount of strong base present. This is a buffer solution. 20. [base] (0. and H2O. 23.100 − x x 0.70.020 0. K+.29 12.020 M.020 0. which is the primary property of buffers. One appropriate equilibrium reaction you can use is the Ka reaction of HF. assumptions good.49 1. F−.94 7. pH = 12.30. pOH = 1. Solution d shows the greatest resistance to changes in pH when either a strong acid or a strong base is added.07.100 M −0. pH = 12.70. you could use the Henderson-Hasselblach equation to solve for the pH.020 + x [OH−] = 0. This is a strong base in water.020 + x ≈ 0. [OH−] = 0.30 d. Alternately. we will use the Ka reaction and set up an ICE table to solve for the pH.70 5. [acid] (0. .00 4.89 After Added H+ 1.258 CHAPTER 8 OPr− Initial Change Equil. + H2O APPLICATIONS OF AQUEOUS EQUILIBRIA HOPr + OH− Kb = 7.080 + OH− → OPr− 0. Note: The OH− contribution from the weak base OPr− was negligible (x = 3. and 21: Solution a b c d Initial pH 2.020 M −0. assumption good. Major species: HF.120) = 4.30 12. OH− will react completely with HOPr.100 M 0 0. c. K+ has no acidic or basic properties.020 → 0 Using the Henderson-Hasselbalch equation to solve for the pH of the resulting buffer solution: pH = pKa + log 22.9 × 10−9 M as compared to 0.71 After Added OH− 4.

.60 M 1. and H2O.1 × 10 −8 ). One could also use the Kb equilibrium reaction or use the Henderson-Hasselbalch equation to solve for the pH.00 M ~0 x mol/L HF dissociates to reach equilibrium !x → +x +x 1. Cl− has no acidic/basic properties.60 M !0.10 mol/1.60 − x x = [H+] = 0. we are left with a solution containing a weak acid (HF) and its conjugate base (F−). Any reaction involving a strong base is assumed to go to completion.1 × 10−7) + log ⎜ ⎟ = 6. F−.10 M 0 0.100 ⎠ Note that pH = pKa for a buffer solution when [weak base] = [conjugate acid].10 + H2O Reacts completely 0.60) 0. OH−. Major species: HONH2 (Kb = 1. or use the Henderson-Hasselbalch equation. The stoichiometry problem is: OH− Before Change After + HF → → F− 1.04 ⎝ 0. pH = −log(4.00 M +0.00 = 6. HONH3+.1 × 10 −8 ⎟ + log [HONH + ] [acid] ⎝ ⎠ 3 ⎛ 0. 25. Na+.2 × 10 −4 = [F − ][ H + ] (1.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA HF 259 ⇌ F− + H+ Initial Change Equil.10 M !0.00 + x)( x) (1. and H2O.00 L 0.0 × 10 −14 ⎞ [HONH 2 ] [base] ⎟ = − log ⎜ ⎜ 1.60 × (7. K+.37 24. or set up an ICE table using the Kb reaction for HONH2.04 + 0.50 After all the OH− reacts. This is what we call a buffer problem. Major species after NaOH added: HF. We have a weak base and its conjugate acid present at the same time in solution.100 ⎞ pH = −log(9.3 × 10−4) = 3.10 M 1.00)( x) = ≈ (assuming x << 0. 0. assumptions good. The OH− from the strong base will react with the best acid present (HF).60 [ HF] 0. one can set up an ICE table using the Ka reaction for HONH3+. we can use molarity units to do the stoichiometry part of the problem (instead of moles). To solve for the pH of a buffer. Because all species present are in the same volume of solution. We have a buffer solution.2 × 10−4) = 4.60 ! x Ka = 7.00 + x x 0. We will solve this buffer problem using the Ka equilibrium reaction.3 × 10 −4 M. Cl−. Using the Henderson-Hasselbalch equation: pH = pKa + log ⎛ 1.

3 × 10 −4 M. x = [H+] = 7. HONH3+. K+. Solving the buffer problem: HF Initial Equil. 26.37 to 3. 0.70. Using the Henderson-Hasselbalch equation: .80 0.48.2 × 10 −4 = Note: The added NaOH to this buffer solution changes the pH only from 3.260 HF Initial Change Equil. H+.2 × 10 −4 M. If the HCl were added to 1.00 to 0. the pH would change from 7.50 − x assumptions good.60 M +0. pH = 3.00 M → HF 0.080 + OH− → HONH2 0. the pH would change from 7.10 + x)( x) (1.20 M → 0.80 + x)( x) (0.50 M 1.0 L of pure water.2 × 10 −4 = (0.020 0.20 M 0 + F− 1.50 0.50 ! x (1.80 ! x ⇌ F− 0. Cl−.100 M +0. pH = 3.14.37 to 3.80 M 0.00. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA + H+ ⇌ F− 0. x = [H+] = 3. Major species after HCl added: HF. Cl−. HONH3+ Before Change After 0.00 to 13. HONH2. Note: The added HCl to this buffer solution changes the pH only from 3. and H2O.80 + x + H+ 0 x Ka = 7. If the NaOH were added to 1.14.20 mol 1.80)( x) ≈ . Na+.10 M ~0 x mol/L HF dissociates to reach equilibrium !x → +x +x 1. Let the OH− react completely with the best acid present (HONH3+).80 M 0.120 + H2O Reacts completely 0.10 + x x 0.020 M !0.00 L !0. H+ Before Change After 0.80 After all the H+ has reacted. Ka = 7.48.80 − x assumptions good.020 0. the added H+ from the strong acid will react completely with the best base present (F−). 0. 0.20 M 0. and OH−. F−.10)( x) ≈ .100 M !0.0 L of pure water.020 → 0 A buffer solution results.80 Reacts completely !0. Major species: H2O. the added strong base dominates the initial reaction mixture. we have a buffer solution (a solution containing a weak acid and its conjugate base).

31 M 0.04 + log = 6.31 M acid and its conjugate base present at reaction to solve. pK a = − log ⎜ ⎜ K b .080) = 6.04 + 0.880 − x pH = !log(4.10 g − [C7H5O2 ] = 0.18 = 5.2000 L We have a buffer solution since we have both a weak the same time.31) ≈ .880 0.020 0 → → HONH3+ 0.22 (0. . and H+.880 M 0.3 × 10 −5 ) = 4. Cl−.04 ! 0.3 × 10 −5 M 0.120) 21.31 + x) x(1.100 M +0.04 + log [HONH 2 ] [HONH 3 ] + = 6. Let the H+ react completely with HONH2. x = [H+] = 4.0 × 10 ⎟ = 6. we can use the Henderson-Hasselbalch equation to calculate the pH of buffer solutions.880 M x mol/L of HC7H5O2 dissociates to reach equilibrium !x → +x +x x 1.04 + log (0.86 (0.120 A buffer solution results after reaction. [HC7H5O2] = 1 mol HC 7 H 5 O 2 122.04 ⎜ 1.18 = 6.1 × 10 −8 ⎟ ⎟ ⎝ ⎠ ⎠ pH = 6.100 M !0. 1 mol C 7 H 5 O 2 mol NaC 7 H 5 O 2 − = 1. HONH3+. the added strong acid dominates the initial reaction mixture.080) Major species: H2O.04 + log (0. 37. We will use the Ka ⇌ H+ + C7H5O2− ~0 1.2000 L 1 mol NaC 7 H 5 O 2 × 144.080 + H+ 0. assumptions good.020 Reacts completely 0.7 g NaC 7 H 5 O 2 × HC7H5O2 Initial Change Equil. Using the Henderson-Hasselbalch equation: pH = 6. the best base present.020 0. One can use the Ka reaction or the Kb reaction for the acid component of the buffer.31 + x 0.880 – x Ka = 6. HONH2 Before Change After 0.4 × 10 −5 = x(1.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA ⎛ Kw [base ] .020 M !0. Alternatively. HONH [acid ] 2 ⎝ [HONH 2 ] [HONH 3 ] + 261 pH = pKa + log −14 ⎞ ⎛ ⎞ ⎟ = − log ⎜ 1. HONH2.12 g = 0.120) = 6.37.5 g HC 7 H 5 O 2 × 27.

262 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA − pH = pKa + log [C H O ] [base] = pKa + log 7 5 2 [HC 7 H 5 O 2 ] [acid] ⎛ 1.6 × 10 −10 ) + log ⎜ ⎟ = 9.73 = 0. Note: The Henderson-Hasselbalch equation can only be used to solve for the pH of buffer solutions.9 × 10−6) = 5. C5H5NH+ ⇌ H+ + C5H5N Ka = Kw 1.4 × 10 −5 ) + log ⎜ ⎟ = 4.36 ⎝ 0. this is the same answer we calculated solving the equilibrium problem using the Ka reaction. 28.880 ⎠ Within round-off error. If the assumption is not valid.25 ! 0.00 = 5.9 × 10−6 Kb 1. this will almost always be true for useful buffer solutions.00 L.935 ⎠ [ NH 3 ] + 29.096 = 9.19 + [C 5 H 5 NH ] [C 5 H 5 N ] = 10−0.935 M 53.23 = 0. The Henderson-Hasselbalch equation will be valid when an assumption of the type 1. the solution will have such a low buffering capacity that it will be of no use to control the pH.31 that we just made in this problem is valid. From a practical standpoint.50 = 5.0 × 10 −14 = = 5.23 + log log [C 5 H 5 N ] [C 5 H 5 NH + ] b.23 [C 5 H 5 NH + ] [C 5 H 5 N ] = 10−0. pH = pKa + log [C 5 H 5 N ] [base] .0 g NH4Cl × 1 mol NH 4 Cl = 0. [NH4+] = 0.75 ⎞ = !log(5.23 We will use the Henderson-Hasselbalch equation to calculate the concentration ratio necessary for each buffer.31 + x ≈ 1. 4.23 + log [acid] [C 5 H 5 NH + ] a.59 + [C 5 H 5 NH ] .31 ⎞ pH = !log(6.49 g NH 4 Cl Using the Henderson Hasselbalch equation to solve for the pH of this buffer solution: pH = pKa + log ⎛ 0.15 [ NH 4 ] ⎝ 0.173 = 4. 5. 50.23 + log log [C 5 H 5 N ] [C 5 H 5 NH + ] [C 5 H 5 N ] = −0.19 + 0.935 mol NH4Cl added to 1.73 [C 5 H 5 NH + ] [C 5 H 5 N ] = −0. pH = 5.7 × 10 −9 pKa = −log(5.

6[C2H3O2−] = 2. Summarizing for each solution: [C2H3O2−] + [HC2H3O] = 2.18[HC2H3O2] or [HC2H3O2] = 5. Added OH− converts HC2H3O2 into C2H3O2−: HC2H3O2 + OH− → C2H3O2− + H2O From this reaction.0 M: [C2H3O2−] = [HC2H3O2] = 1.0 = 1.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA [C 5 H 5 N ] [C 5 H 5 NH + ] d.00.0 L of the 2.0 mol of NaOH to 1.0 [C 5 H 5 NH + ] [C 5 H 5 N ] = 100.30 mol of NaOH to 1.0 M HC2H3O2 solution to produce 0.0 M and [C2H3O2−] produced = [OH−] added a.50 = 5. = 10−0.26 = 1.0 M C2H3O2− solution.8 [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] − − 1.3 M = [OH−] added We need to add 1.23 + log [C 5 H 5 N ] = 100. pH = pKa + log Therefore. 4. we need to add 1.6 We need to add 0. b. .0 and [C2H3O2−] = [HC2H3O2]. 5. The resulting solution will have pH = 4.18 [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] − − [C2H3O2−] = 0. [HC 2 H 3O 2 ] Because [C2H3O2−] + [HC2H3O2] = 2.27 = 1. log 2 3 2 =0 [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] − − − [C 2 H 3 O 2 ] = 1.56[C2H3O2−] = 2.23 + log [C 5 H 5 N ] [C 5 H 5 NH + ] 263 c.00. Also. 5. for pH = pKa.0 M HC2H3O2 to produce a solution with pH = 5. the moles of C2H3O2− produced equal the moles of OH− added.74. [C2H3O2−] = 2 .74 = 0.30 M = [OH−] added 6.30 M C2H3O2−.9 [C 5 H 5 NH + ] 30. 5.0 M HC2H3O2 solution.0 L of 2. The resulting solution will have pH = pKa = 4.0 M (assuming no volume change on addition of NaOH).6[C2H3O2−] Because [C2H3O2−] + [HC2H3O2] = 2.74 + log [C 2 H 3 O 2 ] [C 2 H 3 O 2 ] .8[HC2H3O2] = [C2H3O2−] or [HC2H3O2] = 0. = 100.0 M. [C 2 H 3 O 2 ] [C H O ] .0 M = [OH−] added To produce a 1.00 = 4.0 L of 2. [C2H3O2−] = 1.23 = 5.0 M: [C2H3O2−] + 5. the total concentration of acetic acid plus acetate ion must equal 2. c.0 M.56[C2H3O2−] 1.3 mol of NaOH to 1.0 = 0.00 = 4.74 + log [C 2 H 3 O 2 ] [C 2 H 3 O 2 ] .

it converts C2H3O2− into HC2H3O2: C2H3O2− + H+ → HC2H3O2. [HC 2 H 3O 2 ] Let x = volume of 1. 4.0 M (assuming no volume change).0 L of the initial solution to produce a solution with pH = pKa.00 M HC2H3O2 and y = volume of 1. [C2H3O2−] = [HC2H3O2].8[HC2H3O2]. x 1.00 ! 0. x = 1.74 + log 2 3 2 .78 M = [H+] added 0.00.18.8[HC2H3O2] + [HC2H3O2] = 1.29 [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] [C2H3O2−] = 0.00 M NaC2H3O2 to produce a buffer solution at pH = 4.18 or = 0. which means that 0.54 = 0. From this reaction. pH = pKa + log − − − [C 2 H 3 O 2 ] [C H O ] .36 M = [H+] added 0.00 − y We need 850 mL of 1. [HC 2 H 3O 2 ] − For this to be true.8 × 10 −5 ) + log 2 3 2 [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] − − [C 2 H 3 O 2 ] = 0.15 = 0. = 10 −0. − − [C H O ] [C 2 H 3 O 2 ] b. for pH = pKa.00 L.74 + log 2 3 2 .8 c. 32.0 M [HC2H3O2] = 0.15 L.0 M and [HC2H3O2] = [H+] added a.20 = 4. 5. y(1.00 = !log(1.00 mol/L) = mol NaC2H3O2 = mol C2H3O2− y y = 0. Thus: .29[HC2H3O2]. solving: y = 0.50 M = [H+] added. [C2H3O2−] = [HC2H3O2] = 0.264 31.00 – y x(1. pH = pKa + log [C 2 H 3 O 2 ] .00 M NaC2H3O2 x + y = 1.00.18. Summarizing for each solution: [C2H3O2−] + [HC2H3O2] = 1.78 mol of HCl must be added to produce a solution with pH = 4.00 mol/L) = mol HC2H3O2.85 L. the moles of HC2H3O2 produced must equal the moles of H+ added and the total concentration of acetate ion + acetic acid must equal 1. 1.50 mol of HCl must be added to 1. 4. 0. this is also equal to the mole ratio between C2H3O2− and HC2H3O2.36 mol of HCl must be added to produce a solution with pH = 5.29[HC2H3O2] + [HC2H3O2] = 1.00 = 4. so x = 1. [C H O ] [C 2 H 3 O 2 ] = 100.26 = 1. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA When H+ is added.20. [HC 2 H 3O 2 ] [HC 2 H 3O 2 ] [C2H3O2−] = 1.0 M [HC2H3O2] = 0.00 M HC2H3O2 and 150 mL of 1.

35.040 → 0 Reacts completely A buffer solution still exists.46 ⎞ .28) = 7.50 M +0.CHAPTER 8 33.100 mol − = 100.010 ⎞ = −log(5.5000 L × = 0. the concentration ratio of [C2H3O2−]/[HC2H3O2] will equal the mole ratio of mol C2H3O2−/mol HC2H3O2. 0. pKa = −log(1. 4.100 mol mol HC 2 H 3O 2 L − − 0.74 + log mol C 2 H 3O 2 0. pKb for C6H5NH2 = −log(3.040 M −0.2500 L NH3 0.42 = 4. C2H3O2− and HC2H3O2.46 ⎛ 0.00 − 9. pKa for C6H5NH3+ = 14. 0.73 [ NH 4 ] ⎝ 1.040 1. mol HC2H3O2 = 0. APPLICATIONS OF AQUEOUS EQUILIBRIA [C 2 H 3 O 2 ] .25 + (−1.040 0. Before Change After 0. are both in the same volume of water. 9.040 0.6 × 10−10) + log ⎜ ⎟ = 9.010 mol = 0.77). Using the HendersonHasselbalch equation: pH = pKa + log b. Solution b has the greatest capacity since it has the largest concentrations of weak acid and conjugate base.100 mol mol C 2 H 3O 2 0. Buffers with greater capacities will be able to absorb more added H+ or OH−.8. 5.040 M.040 0 → → NH4+ 0.50 M −0.050 M −0.03 g = 15 g NaC2H3O2 mol Mass NaC2H3O2 = 0.54 + 0.74 [HC 2 H 3O 2 ] − 265 pH = pKa + log Because the buffer components.010 + H+ 0. pH = pKa + log ⎛ 0. the added H+ reacts completely with NH3 to form NH4+. [H+] added = a.19 Reacts completely A buffer solution still exists after H+ reacts completely.58 pH = pKa + log [C 6 H 5 NH 2 ] [C 6 H 5 NH 3 ] + .15 M +0.26 = 1.200 mol .54 ⎠ [ NH 3 ] Note: The two buffers differ in their capacity and not their initial pH (both buffers had an initial pH = 8. mol C2H3O2− = 0.50 M [C 6 H 5 NH 3 ] + .26 = log mol C 2 H 3O 2 .00 = 4.25 + log ⎜ ⎟ = 8.58 + log 0.040 0.42.20 = 4.18 mol NaC2H3O2 × 34.8 × 10−5) = 4.8 × 10−10) = 9.19 ⎠ [ NH 3 ] + + H+ → NH4+ 1.97 [ NH 4 ] ⎝ 0.040 M −0. a. Before Change After NH3 0.18 mol 82.

58 L of 0.03 = 11.38 = log CHAPTER 8 0.50 − (0.266 −0.0 × 10−4) + log pH = pKa + log [HNO 2 ] [HNO 2 ] 3.00 − x = volume of NaNO2 solution needed to form this buffer solution.60 ⎞ A buffer solution exists.50) x L = 0.50 − (0. ⎛ 0.00 − 0. pH = pKa + log − [HCO 3 ] [HCO 3 ] [base] = 6. [OH−] = = 0.50 M +0.0 L + OH− → C6H5NH2 0.06 = 0.00 g mol NaOH 1 . [H 2 PO 4 ] [ HPO 4 ] 2− = 1 = 1. = 100. = = − − [H 2 CO 3 ] 11 [HCO 3 ] [HCO 3 ] b.50 M NaNO2 to form a pH = 3.10 M −0.37 + log .2 M b.00 − x) × 0.9. (1.1 0.9 .55 = −log(4.55 = 3.50 mol HNO 2 (0.42 = 0.2 × 10 ) + log 2− −8 [ HPO 4 ] [H 2 PO 4 ] − − 2− .10 mol OH−.58 + log ⎜ ⎟ = 4.091 = 101.32 ⎝ 1. 3.70)x = 0.15 = 1. [C6H5NH3+] = [C6H5NH3Cl] = 1. then 1.1 ≈ 1 0 . a. pH = 4.0 g NaOH × 1 mol NaOH 1 mol OH − 0.50 mol NaNO 2 0.42 L We need 0. 37. [ NO 2 ] = 1.40 = −log(4.60 + H2O C6H5NH3+ Before Change After 1.2 M −0. 4.4 [HNO 2 ] [HNO 2 ] − − Let x = volume (L) HNO2 solution needed.15 = −log(6.10 0.1 ⎠ − − [ NO 2 ] [ NO 2 ] . 7.20)x = 0.10 → 0 36.50) x x× L (0.50. x = 0.10 1.50)x .10 M 40.21 + log [HPO 4 ] [H 2 PO 4 ] − 2− [HPO 4 ] [H 2 PO 4 ] − = 10−0.42 L of 0.55 buffer solution.40 + log [ NO 2 ] [ NO 2 ] .50 M HNO2 and 1. 7.10 mol × = 0. 7.4 = [HNO 2 ] − (1.50 M [C 6 H 5 NH 3 ] + APPLICATIONS OF AQUEOUS EQUILIBRIA .15 = 7.3 × 10−7) + log [H 2 CO 3 ] [H 2 CO 3 ] [acid] − − [HCO 3 ] [H 2 CO 3 ] [CO 2 ] 1 = 0.

0. The reaction OH− + CH3NH3+ → CH3NH2 + H2O goes to completion for solutions a. a weak acid (HF) and its conjugate base (F−) are both present in solution in large quantities. A pH of 7. No.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 267 c. so it is not a buffer solution. this solution would not be effective in resisting pH changes. After the OH− reacts completely. No. no buffer) c.10 0. no buffer) d. At this high of pH.1 M CH3NH2 (two bases present. Because we have added two solutions together. a buffer solution results.10 → → HF 0 +0. Note that the concentrations are halved from the initial values. d. A best buffer has approximately equal concentrations of weak acid and conjugate base. 39. 0. 0.10 M HNO3 and 0.5 × 10−3) = 2. a. H+ reacts completely with F−. This is so because equal volumes of two solutions were added together.15 is too high for a H3PO4/H2PO4− buffer to be effective. 0. c. especially when strong base is added. and d (no reaction occurs between the species in solution b because both species are bases).20 M !0.05 M CH3NH2 and 0. which halves the concentrations. so pH ≈ pKa for a best buffer. two acids are present (HNO3 and HF).10 M !0.05 M CH3NH3+ (a buffer solution results) Only the combination in mixture d results in a buffer. the concentration of each reagent has changed. Let’s determine the millimoles of each reagent present by multiplying the volume in milliters by the molarity in units of mmol/mL. there would be so little H3PO4 present that we could hardly consider it a buffer. The pKa value for a H3PO4/H2PO4− buffer is −log(7.10 Reacts completely After H+ reacts completely.05 M CH3NH2 (too much OH− added. a strong acid (HNO3) and a strong base (NaOH) do not form buffer solutions.05 M CH3NH2 (no CH3NH3+ remains.12. They will neutralize each other to form H2O. No. . no buffer) b.20 M NaF. that is. 40. The important components of each solution (after the OH− reacts completely) is(are): a. no CH3NH3+ remains.10 0 + F− 0. b. a solution of a strong acid (HNO3) and its conjugate base (NO3−) is not generally considered a buffer solution.05 M OH− and 0. Since equal volumes are mixed.05 M OH− and 0. c. What hasn’t changed is the moles or millimoles of each reagent.10 0. 38. H+ Before Change After 0. there must be both CH3NH3+ and CH3NH2 in solution for it to be a buffer. the initial concentrations in the mixture are 0.

pH = pKa + log [acid] buffer).5 mmol / 200. [acid] [HOCl] Any OCl−/HOCl buffer in a concentration ratio of 0.3 of the text on the exact treatment of buffered solutions.5 =) 7.35 : 1 will have a pH = 7. 7. 100.7 × 10 [C 5 H 5 N ] [base] .268 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 100. we need to calculate the [base]/[acid] ratio. For a pH = 5. 43. After the reaction.0 mL × 0.5 mmol H+ converts 2.5 mmol HF and (10.7 × 10−9. The equation is: ⎛ [ H + ]2 − K w [H + ]⎜ [A − ]0 + ⎜ [H + ] ⎝ Ka = [ H + ]2 − K w [ HA]0 − [H + ] ⎞ ⎟ ⎟ ⎠ . 42.025 M = 2.00 buffer would be the weak acid with a pKa close to 7.0 mL × 0. To make this buffer.00 because the base to acid concentration ratio is 0.35 M and [HOCl] = 1.0 mL ⎞ [F− ] = 3. we need to use the equation derived in Section 8.0 mL of solution.00 = pKa + pKb.00 buffer. pKa = 7.62.0 mL ⎟ = 3. = 10−0.5 mmol HF.0 × 10 −14 [base] .0 − 5. 14.2 (Ka = 3.0 mmol NaF.59 : 1. The pH of this solution will be 5. a buffer solution results containing 2.00 = 7.5 mmol F− into 2. we want the base to have a pKb close to (14. The best acid choice for a pH = 7.100 M = 10. we want an acid with a pKa close to 5. Ka = w = = 5.5 mmol HCl H+ + F− → HF.9 × 10−6 −9 Kb [acid] 1.3 is pyridine (C5H5N) with Kb = 1. One possibility is [NaOCl] = 0. 2.0 or Ka ≈ 1 × 10−7.59 M and [C5H5NHCl] = 1. The best choice in Table 7. One possibility is a solution of [C5H5N] = 0. For a conjugate acid-base pair.59 + [acid] [C 5 H 5 NH ] 5. HOCl is the best choice in Table 7. ⎛ 7. Because [acid] [base] = pKa + 0 = pKa (pH ≈ pKa for a best = [base] for a best buffer.0 M.0 M.46 = 0. pH = pKa + log K 1.35 .23 = 0.9 × 10-6) + log There are many possibilities to make this buffer.0 =) 9. To solve for [KOCl].46).00.5 mmol F− in 200.14 + log ⎜ ⎜ 2. ⎟ [HF] ⎝ ⎠ A best buffer has large and equal quantities of weak acid and conjugate base.00 buffer. So for a pH = 5.00.5 mmol / 200.0 or a Kb close to 1 × 10−9. assumptions good.00 = −log(5.5 × 10−8.0 − 2. pH = pKa + log 41.46 + log [base] [OCl − ] = 10−0.

3 × 10 −8 ) 2 − (1.3 × 10 −8 ⎝ Ka = 3. B + H2O ⇌ BH+ + OH− Kb = [BH + ][OH − ] [B] The equation for the exact treatment of B/BHCl type buffers would be analogous to the equation for HA/NaA type buffers.5 × 10−8 = 6.0 × 10−5.57 × 10 −8 ) (1. The equation is: ⎛ [OH − ]2 − K w [OH − ]⎜ [BH + ]0 + ⎜ [OH − ] ⎝ Kb = [OH − ]2 − K w [B]0 − [OH − ] ⎞ ⎟ ⎟ ⎠ Solving the buffer problem using the regular procedures: HONH2 + H2O Initial ⇌ HONH3+ + OH− Kb = 1.0 × 10 −6 ) + (9.57 × 10−8). the problem reduced down to the expression: Kb = [HONH 3 ] 0 [OH − ] [HONH 2 ] 0 + .) + x = [OH−] = 1.) 3.1 × 10−7 M. In the regular procedure to solve the buffer problem.0 × 10 −5 + x) x (1.3 × 10 −8 ([OCl − ] − 9.57 × 10 −8 ) ⎞ ⎟ ⎟ ⎠ (Carrying extra sig.20 = 6.3 × 10 −8 ) 2 − (1.3 × 10 −8 3.0 × 10−5 + x x Kb = 1.0 × 10−7 M 44.0 × 10−4 − x 1. [OCl−] = [KOCl] = 7.0 × 10 −5 ) x = ≈ [HONH 2 ] (1. ⎛ (6.83 × 10−14 = 6.0 × 10−5 M ~0 1.0 × 10 − 4 (Assuming x << 1.3 × 10−8 M.3 × 10-8([OCl−] − 9.0 × 10 −14 ) 6. 1.1% of 1. [H+] = 10−7.3 × 10 −8 ⎜ [OCl − ] + ⎜ 6.1 × 10−8 1.0 × 10 −6 − 6.0 × 10−4 M x mol/L of HONH2 reacts with H2O to reach equilibrium +x +x Change −x Equil.1 × 10−8 = [HONH 3 ][OH − ] (1.0 × 10−5 is good (x is 1.0 × 10 −14 ) 1.20.0 × 10−5).0 × 10 − 4 − x) 1. assumption that x << 1. figs.5 × 10−8 = (6.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 269 Because pH = 7.

9 × 10−8 [OH − ] 1.1 × 10−7 .0 × 10 −7 − [H + ] ⎞ ⎟ ⎟ ⎠ Solving exactly requires solving a cubic equation.6 × 10 −7 ⎝ 1.0 × 10 −14 ) [H + ]⎜ 5. pH = pKa = −log(1.0 × 10 −7 − 1. However. Instead. Checking the neglected term using the [OH−] calculated above: [OH − ]2 − K w (1. ⎛ (1. 45. Now we want to know if we need to worry about the contribution of OH− from water.6 × 10 −7 ) 2 − (1.6 × 10−7 M (the value obtained using the regular procedures). if ([OH−]2 − Kw) / [OH−] is much less than [HONH3+]0 and [HONH2]0. Using regular procedures.6 × 10−7) = 6. So for this problem we would calculate the same [OH−] using the exact equation as we calculated using the regular procedures.6 × 10−7 = (1. which was assumed when solving using the regular procedures.0 × 10 −7 + ⎜ 1.0 × 10 −14 ) = = 1.9 × 10−8 is 0. ⎛ [ H + ]2 − K w [H + ]⎜ [ A − ]0 + ⎜ [H + ] ⎝ −7 Ka = 1.19% of 1.0 × 10−5). Another problem with this answer is that x (= [H+]) is not small as compared with [HA]0 and [A−]0 . the pH is very close to that of neutral water.6 × 10 = [ H + ]2 − K w [HA]0 − [H + ] ⎞ ⎟ ⎟ ⎠ = ⎛ [H + ]2 − (1. Because the concentrations of the buffer components are less than 10−6 M. we only need to use the exact equation when the buffering materials have a concentration of 10−6 M or less. In general. [H+] = 1. so maybe we need to consider the H+ contribution from water. we will use the method of successive approximations where our initial guess for [H+] = 1. let us use the expression for the exact treatment of buffers to solve.1 × 10 −7 This is indeed much smaller than [HONH3+]0 and [HONH2]0 (1.1 × 10 −7 ) 2 − (1. From the equation for the exact treatment of buffers.0 × 10 −14 ) 5.6 × 10 −7 ⎞ ⎟ ⎟ ⎠ .0 × 10 −14 ) [H + ]⎜ 5. then the exact equation reduces to: Kb = [OH − ][HONH 3 ]0 [ HONH 2 ]0 + This is the same expression we ended up with to solve the problem using the regular procedures.0 × 10 −7 + ⎜ [H + ] ⎝ [ H + ]2 − (1.270 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA This expression holds if x is negligible as compared to [HONH3+]0 and [HONH2]0 as it was in this problem.80 since [A−]0 = [HA]0 in this buffer solution.0 × 10 −14 ) 5.6 × 10 −7 ) 2 − (1.

CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 271 We continue the process using 1. HA is the dominant species present. After OH− is added.has been added to convert all the weak acid HA into its conjugate base A−.0 × 10−7 M. Initially before any OH− is added (point d). we included almost the entire buffer region. At this point. . so [HA] = [A−] and pH = pKa.3 × 10−7) = 6. both HA and A− are present. At the equivalence point (points a and e). excess OH− is present. Past the equivalence point (region f). This gives [H+] = 1. For the answer to part b. After three more iterations. Acid-Base Titrations 46. the answer comes out to [H+] = 1. we converge on [H+] = 1.89 Note that if we were to solve this problem exactly (using the quadratic formula) while ignoring the H+ contribution from water. We get a significantly different answer when we consider the H+ contribution from H2O. and a buffer solution results (region b). Solving for the pH: pH = −log(1. A best buffer has about equal concentrations of weak acid and conjugate base present. The maximum buffer region (or the region which is the best buffer solution) is around the halfway point to equivalence (point c). We continue the process until we get a self consistent answer. enough OH− has been added to convert exactly one-half of the weak acid present initially into its conjugate base. Added OH− from the strong base converts the weak acid HA into its conjugate base A−. exactly enough OH. (f) all points after stoichiometric point (a) and (e) pH (c) (d) (b) mL base HA + OH− → A− + H2O.3 × 10−7 M.1 × 10−7 as our estimate for [H+].5 × 10−7.

Major species before reaction: H+. before any H+ is added (point d). See Fig. c. From 0. and a buffered solution results (region b). determine the [H+] in solution after the strong acid has completely dissociated. where [B] = [BH+]. we first determine how much of the H+ is neutralized by the OH−. b. a. 48. B is the dominant species present. Na+.1 to 99. After some strong base has been added. Na+.0 mL NaOH added). Initially. Here. NO3−. The example used was the titration of 50.100 M NaOH. Initially. For our example. and H2O.9 mL NaOH added. Here. excess H+ is present. both H+ and OH− have run out (this is the definition of the equivalence point). At the equivalence point (points a and e). NO3−. The equivalence point (100. Then we determine the excess [H+] and take the –log of this quantity to determine pH. In this region. and H2O. All we have in . As is always the case when something strong reacts. before any strong base has been added. Here are the important points. NO3−. Past the equivalence point (region f). as we always do for strong acid problems. and H2O.0 mL of 0. up to the equilivance point. Major species before any reaction: H+.00 mL NaOH added up to just before 100. which is a characteristic of a best buffer. we have added just enough OH− to neutralize all of the H+ from the strong acid (moles OH− added = moles H+ present). Let’s review the strong acid-strong base titration using the example (case study) covered in Section 8. the excess H+ from the strong acid determines the pH. After H+ is added. After the stoichiometry reaction (H+ + OH− → H2O). we included almost the entire buffer region. Major species: H+.5 of the text. OH−. Major species after reaction: H+. and H2O: To determine the pH of the solution. both B and BH+ are present. this is from just after 0. To determine the pH. pH = pKa .200 M HNO3 titrated by 0. and H2O. Na+ and NO3− have no acidic or basic properties. (d) CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA (c) (b) pH (a) and (e) (f) all points after stoichiometric point mL acid B + H+ → BH+. NO3−.1 for the titration curve. NO3−. we assume the reaction goes to completion. Major species after reaction: Na+. the OH− from the strong base reacts with some of the H+ from the strong acid to produce water (H+ + OH− → H2O).0 mL NaOH added. 8. For the answer to b. The maximum buffer region is around the halfway point to equivalence (point c).272 47. exactly enough H+ has been added to convert all the weak base present initially into its conjugate acid BH+. Na+. added H+ from the strong acid converts the weak base B into its conjugate acid BH+. OH−.

NO3−. We determine the excess [OH−] and convert this into the pH. and H2O. at the halfway point to equivalence. and past the equivalence point. at the equivalence point. . 8. pH = 10.2 × 10 −4 ) = 3. After the equivalence point. moles acid = moles base (MAVA = MBVB).00 because we have added just enough H+ from the strong acid to react with all the OH− from the strong base (moles of base present = moles of acid added).0 mL titrant added to reach equivalence point). pH = 7.1 and 8. The stoichiometry problem is still the same. Na+. Past the equivalence point (volume of NaOH added > 100. The pH increases as NaOH is added. 8. pH = 7. pH = pKa for HF = !log(7. but what is in excess after this reaction goes to completion is the reverse of the strong acid-strong base titration. then.0) because the only important major species present is a weak base (the conjugate base of the weak acid). Because Kb = 4. but the curves are the reverse of each other before and after the equivalence point.00 at the equivalence point. Past the equivalence point the pH becomes more acidic as excess HCl is added.4 × 10 −4 for CH3NH2. The pH is very acidic until just before the equivalence point. the pH is determined by the excess H+ present. the pH becomes more basic as excess NaOH is added. at the equivalence point. The pH starts off acidic. As can be seen from Figs.3 × 10 −11 and pKa = 10. The pH up to just before the equivalence point is determined by the excess OH− present. Titration iv is a weak acid titrated by a strong base. All require the same volume of titrant to reach the equivalence point. then at the halfway point to equivalence. Here the pH is very basic until just before the equivalence point. Na+. Past the equivalence point. OH−.2 for a titration curve of a strong base by a strong acid. 49. the pH will not be as basic as in titration ii. pH = pKa. Because all the molarities and volumes are the same in the titrations. then at the equivalence point. At the equivalence point for all these titrations. Titration iii is a weak base titrated by a strong acid. Major species after reaction: OH−. After the stoichiometry reaction goes to completion (H+ + OH− → H2O). CH3NH3+ has Ka = Kw/Kb = 2. and past the equivalence the pH is very basic.00. the pH is basic (pH > 7. both strong by strong titrations have pH = 7. Titration ii is a strong base titrated by a strong acid.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 273 solution are some ions with no acidic or basic properties (NO3− and Na+ in H2O).64. the volume of titrant will be the same (50. So. Titration i is a strong acid titrated by a strong base. where a strong base is titrated. a. pH = 7. H+ + OH− → H2O. Major species before reaction H+. The pH continues to increase past the halfway point.00. The pH drops as HCl is added. Past the equivalence point. and H2O.00) because the only important major species present is a weak acid (the conjugate acid of the weak base). the excess OH− from the strong base determines the pH.14. we have excess OH− present.64. at the halfway point to equivalence for this weak base-strong acid titration. At the equivalence point. See Fig. but not nearly as acidic as the strong acid titration (i). The pH continues to drop as HCl is added.00 at the equivalence point of a strong acid-strong base titration. The pH starts out basic because a weak base is present.2. d. the pH is very acidic.0 mL). NO3−. However. then at the equivalence point the pH is acidic (pH < 7. The pH = 7.

Equivalence point pH: iii < ii = i < iv.3) = !0. the strong-by-strong titrations have pH = 7.3 mmol 13. For the weak acid titration.7 × 10 −9 From the pKa values. it takes 25.2 mmol / VT [A − ] .3 mmol / V [HA] T ⎝ ⎞ ⎟ ⎟ ⎠ Because the log term will be negative [log(1. The only different answer when the weak acid and weak base are changed would be for part c.80 C5H5NH+. This is for the halfway point to equivalence.14.6 × 10 −10 ) = 9. HOC6H5. pH = pKa = 3.0 mL(0. and the strong base titration has the highest halfway point pH. 50.100 M NaOH to reach the equivalence point where mmol HA = mmol OH− = 25. pH = pKa + log ⎛ 1. The weak base titration has an acidic pH at the equivalence point.2 mmol → HA 0 +1. some HCl is added. pKa = 5. At the equivalence point.50 mmol. i < iv < iii < ii. The H+ from the strong acid reacts to completion with the best base present. . the correct ordering at the halfway point to equivalence would be i < iii < iv < ii. where pH = pKa.6 × 10 −10 . and a weak acid titration has a basic equivalence point pH.100 M) = 2.5 mmol !1. H+ Before Change After + A− 2.0 × 10 −14 = 5. pH = pKa = 10.7 = pKa + log ⎜ ⎜ 1. 4. the pH is acidic at the halfway point to equivalence. the pKa value of the acid must be greater than 4.3 mmol 1. the weak acid titration is next.0 mL × 0.2/1. d. followed by the weak base titration. A−.3 mmol 0 A buffer solution is present after the H+ has reacted completely. Note that for the weak base-strong acid titration using C5H5N.100 M !1. This is fine.00 at the equivalence point. and for the weak base titration.0 mL of 0.64. pKa = !log(1.7. with the strong base titration having the highest pH.9 × 10 −6 . this will always happen when the weak base titrated has a Kb < 1 × 10 −7 (so Ka of the conjugate acid is greater than 1 × 10−7) and when the weak acid titrated has a Ka < 1 × 10 −7 (so Kb of the conjugate base is greater than 1 × 10−7). c. Increasing initial pH: i < iv < iii < ii. Ka = 1. Ka = Kw K b . whereas the weak acid-strong base titration using HOC6H5 is basic at the halfway point to equivalence. HA + OH− → A− + H2O.23 1.3 mmol 1.274 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA b. the strong acid titration has the lowest pH at the halfway point to equivalence.035)]. C5 H 5 N = 1. the strong acid titration has the lowest pH.

Here. c. The weakest base has the strongest conjugate acid so its pH will be lowest (most acidic) at the equivalence point. the strong base has the highest pH (most basic). the pH curve with the highest pH at 0 mL of NaOH added will correspond to the titration of the weakest acid. so the acid titrated in this pH curve (plot d) has Ka ≈ 1 × 10−6. This is curve f. This is a strong acid (HClO4) titrated by a strong base (KOH).00. whereas the weakest base has the lowest pH (least basic).0. Added OH− from the strong base will react completely with the H+ present from the strong acid to produce H2O. The pH curve. The weak bases titrated have acidic pH’s because the conjugate acids of the weak bases titrated are the major species present. The pH curve with the lowest pH at 0 mL of NaOH added will correspond to the titration of the strongest acid. At the equivalence point (100. The equivalence point.00.0 mL HCl added) because [weak base] = [conjugate acid] at this point. If the pH = 7.0 Kb = 10-5 Kb = 10-10 Volume HCl added (mL) 53. The best point to look at to differentiate a strong acid from a weak acid titration (if initial concentrations are not known) is the equivalence point pH. pH = pKa at the halfway point to equivalence (50. if the pH is greater than 7. the pH at the halfway point to equivalence is equal to the pKa value. the acid titrated is a strong acid. This is pH curve a. Plot d has a pH ≈ 6. so the halfway point is 25 mL.CHAPTER 8 51.0 at the halfway point to equivalence. For the initial pH.0 at the halfway point. the pH at the halfway point to equivalence. For a weak acid-strong base titration. For all the weak bases titrated.0 mL HCl added). b. The three key points to emphasize in your sketch are the initial pH. . so pH = 9. Because all acids are the same initial concentration. occurs at 50 mL NaOH added. and the pH at the equivalence point. 52. strong base pH 7. the weak base with Kb = 1 × 10 −5 has a conjugate acid with Ka = 1 × 10−9.0 × 10−6. The weak base with Kb = 1 × 10 −10 has a pH = 4. from the plots. which represents the titration of an acid with Ka = 1. the strong base titration has pH = 7. will have a pH = −log(1 × 10−6) = 6. APPLICATIONS OF AQUEOUS EQUILIBRIA 275 a. the acid titrated is a weak acid.0 at the halfway point.0 at 25 mL of NaOH added.

0 mmol 2. pOH = 1.100 mmol OH − = 1.0 mmol → H2O Past the equivalence point.100 M = 8.0) mL This is a strong base.276 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA a.00 mmol OHb.00 mmol 0 4.0 + 40.00 mmol 4.00 at the equivalence point because only neutral species are present (K+.00 mmol −1. titrated by a strong acid. [H+] = 0. The units for molarity are moles per liter but are also equal to millimoles per milliliter.00 mmol + OH− 1.85.0) mL d. pH = 7. ClO4−.00 mmol −1.00 mmol + OH− → H2O 4.0 mL The excess H+ determines the pH.0 + 100.00 mmol 7.0 mmol OH− H+ Before After 8. H2O). The added strong acid will neutralize the OH− from the strong base.140 M 40.699 0.00 mmol OH− H+ Before After [H+]excess = 8.0 mmol = 0. Only strong acid present.100 M = 10. pH = 1.00 mmol OH−.0 mL × 0. mmol OH− added = 40. the pH is determined by the excess OH. .0 mmol H+ mL Note: The units millimoles are usually easier numbers to work with. pH = 12.0500 M. Ba(OH)2.100 M = 4.added = 80. mmol OH.200 M.854 c. e.to react with all the acid present.15 (40.0 mL × mL mmol H+ present = 40. mmol OH− added = 10. this is the equivalence point because we have added just enough OH.200 mmol H + = 8. mmol OH− added = 100. [H+]excess = pH = −log(0. 2.00 mmol H + = 0.present. [OH−]excess = 54. HCl. the reaction is assumed to go to completion.301 (40.0 mL × 0.0 mL × 0. As is always the case when a strong acid and/or strong base reacts.0 mL × 0.00 mmol = 0.014 M.140) = 0.00 mmol 0 + OH− 10. For a strong acid-strong base titration.00 mmol 0 → H2O Reacts completely 7.0 mL + 10. pH = 0. H+ Before Change After 8.

all we have in solution is Ba2+.0 mL × 0. 16.100 M. pOH = 0. mmol OH− present = 80. pH = 12. Cl−.0 mmol H + = 0.56 (80.0 mmol + 0.0 mmol 16.400 M = 32.000 (80. e.0 mmol H+ OH− Before After [H+]excess = 55. so pH = 7.0 mmol → H2O 16.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 277 a.10.0 mmol −8. All are neutral species.00 mmol H+ mL H+ 8.301 b. Only weak acid is present. Because the H+ will exactly neutralize the OH− from the strong base.0 mmol OH − = 0. pH = 13.0 mmol + H+ 12. a. pH = 12.0 mmol OH− mmol H+ added = 20. pOH = 1.0 mmol 0 → H2O 4.0 + 80. [OH−] = 2 × 0.0 + 30.0 mL × 0.90 80. but it breaks up into two moles of OH− ions for every mole of Ba(OH)2.00 mmol 0 → H2O Reacts completely [OH−]excess = 8.0 mL c. Solving the weak acid problem: .0 mmol OH − = 0. Only a strong base is present. mmol H+ added = 40. pH = 1.0 mL × 0.0 mmol 0 + H+ 32.400 M = 16. mmol H+ added = 80.400 mmol H + = 8.699.0 mL × OH− Before Change After 16.036 M.0 mL + 20.00.0 mmol H+.080 M.0 mmol 4.100 mmol Ba (OH) 2 2 mmol OH − × mL mmol Ba (OH) 2 = 16.400 M = 12. pOH = 1.0) mL This is a weak acid (HC2H3O2) titrated by a strong base (KOH).44.100 M = 0.0) mL d.00 mmol −8.0 mmol H+ OH− Before After [OH−]excess = 16.200 M. and H2O. this is the equivalence point.0 mL × 0.00 mmol 8. mmol H+ added = 30.

0 mmol 10.0 mmol + OH− 10.9 × 10−3 M 0.74 + (-0. For the [base]/[acid] term. HC2H3O2.72. assumptions good.0 ⎠ Note that the total volume cancels in the Henderson-Hasselbalch equation.00 mmol OH− mL OH− → C2H3O2− + H2O Reacts completely 5.00 mmol 5. c. we have a buffer solution containing a weak acid (HC2H3O2) and its conjugate base (C2H3O2−).00 mmol → 0 0 +5.00 mmol/VT [C 2 H 3 O 2 ] = −log (1.8 × 10−5) + log ⎜ ⎜ 15. x = [H+] = 1.0 mmol −5.200 M ~0 0 x mol/L HC2H3O2 dissociates to reach equilibrium −x → +x +x x x 0.0 mmol OH−.00 mmol 15.200 Ka = 1.0 mmol .00 mmol −5. let the OH− react to completion.200 − x x2 x2 ≈ .0 mmol HC2H3O2 mL 0.00 ⎞ pH = 4.0 mmol/V [HC 2 H 3O 2 ] T ⎝ ⎞ ⎟.74 + log ⎜ ⎟ = 4. then see what is remaining in solution after this reaction.0 mmol + 0.8 × 10−5 = pH = 2.0 mmol) of HC2H3O2 is present as before (it doesn’t change). HC2H3O2 Before After 20.278 CHAPTER 8 HC2H3O2 Initial Change Equil.0 mmol 0 → C2H3O2− + H2O 0 10.100 mmol OH − = 5.200 − x 0.26 ⎝ 15.200 mmol HC 2 H 3O 2 = 20. pH = pKa + log − ⎛ 5. the same amount (20. We will use the Henderson-Hasselbalch equation to solve for the pH. The added OH− will react completely with the best acid present.477) = 4. the mole ratio equals the concentration ratio because the components of the buffer are always in the same volume of solution.0 mL × mmol OH− added = 50.00 mmol After reaction of all the strong base. mmol OH− added = 100.0 mL × HC2H3O2 Before Change After 20.0 mL × (0. mmol HC2H3O2 present = 100. As before. b. where VT = ⎟ ⎠ total volume ⎛ 5. APPLICATIONS OF AQUEOUS EQUILIBRIA H+ + C2H3O2− ⇌ 0.100 mmol OH−/mL) = 10.

pH = 8.0 mmol This is the equivalence point. HC2H3O2 Before After 20.00 mL × 0.0 × 10 −14 C2H3O2− + H2O ⇌ HC2H3O2 + OH− Kb = w = Kb 1.100 M = 20.21.1 × 10−6 M 0.0667 − x x x x2 x2 ≈ . x = [OH−] = 6.74 + log ⎜ ⎜ 5. pH = −log(1.0 mmol OH−. .6 × 10−10 = pOH = 5. let the added OH− react to completion with the weak acid. assumptions good. pH = pKa.0 mL × 0.48 = 5. Enough OH− has been added to exactly neutralize all the weak acid present initially. then see what is in solution after this reaction. Added OH− reacts completely with the weak acid.6 × 10−9 x mol/L C2H3O2 reacts with H2O to reach equilibrium −x → +x +x 0.0 mmol/300. This is a weak base equilibrium problem.0 mmol/total volume.74 d. This is always true at the halfway point to equivalence for a weak acid-strong base titration. pH = pKa.100 M = 15. as before. mmol OH− added = 150.0667 − x 0.0 mmol + OH− 15.74 + log − ⎛ 15.8 × 10 −5 Initial Change Equil.0 mmol 0 → C2H3O2− + H2O 0 15.74 + 0.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 279 A buffer solution results after reaction. Because [C2H3O2−] = [HC2H3O2] = 10. K 1.0 mL 0 0 Kb = 5.0667 Kb = 5.0 mmol We have a buffer solution after all the OH− reacts to completion.0 mmol OH−. Using the HendersonHasselbalch equation: pH = 4. mmol OH− added = 200.0 mmol 5.79. 20. HC2H3O2 Before After 20.0 mmol 0 → C2H3O2− + H2O 0 20. All that remains that affects the pH at the equivalence point is the conjugate base of the weak acid (C2H3O2−).8 × 10−5) = 4.22 e.0 mmol [C 2 H 3 O 2 ] = 4.0 mmol 0 + OH− 20.0 mmol [HC 2 H 3O 2 ] ⎝ ⎞ ⎟ ⎟ ⎠ pH = 4.

we have a solution containing excess OH− and a weak base C2H3O2−. let the strong acid react completely with the weak base present.0 mmol + 0. To calculate the pH at the various points. x = [OH−] = 5.15 100.100 pOH = 3.100 mmol H 2 NNH 2 = 10. pOH = 1.74. Solving using the HendersonHasselbalch equation: pH = pKa + log K 1.00 mmol 0 → → H2NNH3+ 0 +4. assumptions good.5 × 10−4 M 0.0 × 10 −14 [base] = 3.0 mmol → C2H3O2− + 0 20.x ⇌ H2NNH3+ + OH− 0 x ~0 x Kb = 3.00 mmol −4. Ka = w = Kb [acid] 3.0 mmol −4. then see what is in solution. pH = 10. pH = 12. assume that the amount of OH− added from the weak base will be minimal.00 mmol Reacts completely A buffer solution results after the titration reaction. [OH−]excess = 56.0 × 10 −6 .0 mL × 0.26.0 mL + 250. mmol H2NNH2 present = 100. 5.00 mmol H+ mL H+ 4.0 mmol 5.0 mmol 0 + OH− 25. Only a weak base is present. When a strong base and a weak base are both present.014 M.100 M 0.0 mL × mmol H+ added = 20.00 mmol 4. the pH past the equivalence point is determined by the amount of excess strong base. a.100 M = 25. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA mmol OH− added = 250. 0.280 f. H2NNH2 + H2O Initial Equil.00 mmol 6.100 . Solve the weak base equilibrium problem.0 × 10−6 = x2 x2 ≈ .0 mmol OH− HC2H3O2 Before After 20.3 × 10−9 .85. that is.0 mmol H2O After the titration reaction.0 mmol H2NNH2 mL 0.100 − x 0.200 mmol H + = 4. b.0 mL This is a weak base (H2NNH2) titrated by a strong acid (HNO3).0 mmol = 0.0 mL × H2NNH2 Before Change After 10.

00 mmol This is the halfway point to equivalence where [H2NNH3+] = [H2NNH2]. which ⎟ ⎠ cancels. pH = −log(3.200 M = 10. ⇌ H+ 0 x + H2NNH2 0 x 10.0 mmol + H+ 5.00 mmol 0 → H2NNH3+ 0 8. pH = 8.3 × 10−9 = x2 x2 ≈ . At this point. assumptions good.3 × 10−9) = 8.0 mmol 2.00 mmol A buffer solution results.5 × 10−5 M 0.0667 − x 0.0 mmol / VT pH = −log(3. mmol H+ added = 50.3 × 10−9) + log ⎜ ⎜ 4.0 mmol H+ H2NNH2 Before After 10.82.200 M = 5.0 mL 0.0 mmol 0 + H+ 10. pH = pKa + log ⎛ 2.00 mmol H+ H2NNH2 Before After 10.0 mmol 0 → H2NNH3+ 0 10. x = [H+] = 1.0 mL × 0.00 mmol H+ H2NNH2 Before After 10. mmol H+ added = 40. Solving the weak acid equilibrium problem: H2NNH3+ Initial Equil.0 mmol As is always the case in a weak base-strong acid titration.48 + log(1. where VT = total volume.5) = 8.88 ⎟ ⎠ e.48 + log ⎜ ⎜ 8.0 mmol / VT [base] = 8. pH = pKa (which is characteristic of the halfway point for any weak base-strong acid titration). the pH at the equivalence point is acidic because only a weak acid (H2NNH3+) is present.0 mL × 0.00 mmol / V T ⎝ 281 ⎞ ⎟.60) = 7.0667 pH = 4.00 mmol / V [acid] T ⎝ ⎞ ⎟ = 8.0 mmol/150.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA ⎛ 6.18 = 8.48 + (-0.0 mmol 5. .00 mmol 0 → H2NNH3+ 0 5.48 d. mmol H+ added = 25.0667 − x Ka = 3.0 mL × 0.200 M = 8.66 c.0 mmol + H+ 8.48 + 0.

86 = 1. 10.4 × 10−4 0.0 mmol 10.100 − x 0.100 mmol = 0. but the excess H+ will determine the pH of the solution since H2NNH3+ is a weak acid.0 mmol 100.100 M ~0 0 x mol/L HLac dissociates to reach equilibrium −x → +x +x x x 0.40 = 2. 1.86: . only the weak acid HC3H5O3 is present.0 mmol 0 + H+ 20.200 M = 20.100 mmol = 2.0500 M.100 Up to the stoichiometric point.43. At the beginning of the titration. Using the Henderson-Hasselbalch equation where pKa = 3. pH = 1. mmol Lac− produced = 0.301 We will do sample calculations for the various parts of the titration.0 mL × mmol OH− added = 4.40 mmol HLac to 0.0 mmol H+ H2NNH2 Before After 10. For example. The 0.0 mL = 0. Let HLac = HC3H5O3 and Lac− = C3H5O3−.0 mmol → H2NNH3+ 0 10. [H+]excess = 57.40 mmol We have a buffer solution.0 mL × 0.100 − x x2 x2 ≈ . mmol HLac remaining = 2.7 × 10−3 M. x = [H+] = 3.0 mL + 100. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA mmol H+ added = 100.1 at the end of Exercise 60.10 mmol.40 mmol OH− mL Note: The units millimoles are usually easier numbers to work with. 0. The units for molarity are moles per liter but are also equal to millimoles per milliliter.50 mmol HLac mL 0.40 mmol Lac− according to the equation: HLac + OH− → Lac− + H2O Reacts completely.0 mL × 0. HLac Initial Change Equil.0 mmol Two acids are present past the equivalence point. All results are summarized in Table 8. assumptions good.4 × 10−4 = ⇌ H+ + Lac− Ka = 10−3.282 f. we calculate the pH using the Henderson-Hasselbalch equation.40 mmol of added OH− converts 0. pH = 2. at 4.50 − 0.0 mL of NaOH added: initial mmol HLac present = 25. This is the buffer region.

40) = 3.0 mL Lac− + H2O Initial Change Equil.50 mmol = 0. All that is present is a weak base.1 mL: OH− added = 25.7.72 = 3.100 mmol = 2.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA [Lac − ] (0. pOH = 3.0 mL OH− added). At the stoichiometric point (25.1) mL All results are listed in Table 8. Perform a stoichiometry problem first.) pH = 3. pOH = 5. pH = 8. The remainder is excess OH−.1 × 10−11 0.86 − 0.9 mL OH− added.50 mmol) into its conjugate base (Lac−).72. An example of this calculation follows. we perform a weak base calculation.28.0500 x = [OH−] = 1. assumptions good. At 25.0 × 10 −14 = 7.50 = 0.1 at the end of the solution to Exercise 60.10) 283 pH = pKa + log (Total volume cancels. The buffer region includes all points up to 24. The pH will be determined by the excess OH. pH = 10.01 mmol OH− [OH−]excess = 0.1 × 10−11 1. we have a weak acid problem: . [Lac−]0 = 2. we have added enough OH−to convert all of the HLac (2.ion present.0500 M 0 0 x mol/L Lac− reacts with H2O to reach equilibrium −x → +x +x 0.50 mmol of NaOH.4 × 10 − 4 0. Kb = ⇌ HLac + OH− Kb = 1.9 × 10−6 M. so we can use use the ratio of moles or millimoles.0 mL + 25.51 − 2. Past the stoichiometric point.1 mL × 0.50 mmol OH− neutralizes all the weak acid present. Excess OH− = 2.3 (25.0 + 25.14 Other points in the buffer region are calculated in a similar fashion.0500 − x 0.1 at the end of the solution to Exercise 60. Results for all points are summarized in Table 8.0500 M 25. we have added more than 2. To determine the pH. 58.51 mmol OH− mL 2.01 mmol = 2 × 10−4 M. At the beginning of the titration. followed by a buffer problem.86 + log [HLac] (2.0500 − x x x x2 x2 ≈ = 7.

9 mL are calculated this way. so we can use the ⎝ 0.100 [HOPr] x = [H+] = 1.284 CHAPTER 8 HOPr Initial Change Equil.96. assumptions good.89 + log [acid] [HOPr] ⎛ 2.1 × 10−3 M.40 mmol A buffer solution results.0 mL to 24.40 0.0 to 24.89 + log ⎜ ⎟ = 4.= C3H5O2− ⇌ 0. We will do a sample calculation at 24.100 mmol = 2.27 (Volume cancels.10 mmol + OH− → OPr- + H2O Reacts completely 2.0 mL × 0.89 + 1. Initial mmol HOPr present = 25.100 M ~0 0 x mol/L HOPr acid dissociates to reach equilibrium −x → +x +x 0.50 mmol −2.40 2.40 mmol OH− mL The added strong base converts HOPr into OPr−.3 × 10−5 = ≈ 0.3 × 10−5) = 4.100 mmol = 2. only a weak base (OPr−) is present: .40 → 0 0 +2. The buffer region is from 4.40 ⎞ pH = 4.9 mL of OH− added. At the stoichiometric point.100 − x 0. Using the Henderson-Hasselbalch equation where pKa = −log(1.40 mmol −2.) All points in the buffer region 4.50 mmol HOPr mL 0.89: pH = pKa + log [base] [OPr − ] = 4.38 = 6. APPLICATIONS OF AQUEOUS EQUILIBRIA H+ + OPrHOPr = HC3H5O2 OPr. pH = 2. See Table 8.1 at the end of Exercise 60 for all the results.0 mL OH− added.0 mL × mmol OH− added = 24. HOPr Before Change After 2.100 − x x x Ka = x2 x2 [H + ][OPr − ] = 1.10 ⎠ millimole ratio in the log term.

70. pH = 9.8 × 10 [ NH 4 ] We must determine the amounts of NH3 and NH4+ present after the added H+ reacts completely with the NH3.100 mmol = 2. only the weak base NH3 is present. Kb = 0.11.0 − 24.9 mL). As always. after 8.60 mmol − 2.8 × 10−5 0.79. we can use the Henderson-Hasselbalch equation: Ka = [ NH 3 ] 1. pOH = 2. For example.1). In the buffer region (4.100 − x 0.0 mL × 0.6 × 10−10. pOH = 2. 2. pH = 11.21.7 H 10−10 = ≈ Ka 0.50 mmol = 2.100 M 0. Beyond the stoichiometric point.0 × 10−3 M.2 × 10−6 M = [OH−].0500 M 50.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA OPr+ H2O 285 ⇌ OH− + HOPr Initial Change Equil.50 mmol 0 0 = 0.0 × 10 −14 = 5.100 x = [OH−] = 1.30 (25. pKa = 9.25. assumptions good.3 × 10−3 M. solve for the pH using the Kb reaction for NH3.8 × 10−5 x2 x2 ≈ = 1. For example at 26. pH = 8. Kb = 2.0500 − x x x [OH − ][HOPr] K w x2 x2 = = 7.89. the pH is determined by the excess strong base added. pOH = 5. The results are the same as those in Exercise 57 (see Table 8. pH = 11.50 mmol NH3 mL . assumptions good.100 − x ⇌ NH4+ 0 x + OH− ~0 x Kb = 1.0 + 26.0 mL NaOH added: [OH−] = 59. NH3 + H2O Initial Equil.0500 − x 0.0500 [OPr − ] x = 6.0 mL x mol/L OPr− reacts with H2O to reach equilibrium −x → +x +x 0.25 + log −5 + 1.0 mL HCl added: initial mmol NH3 present = 25.0) mL At beginning of the titration.

0 mL = 0. pH = 9.286 CHAPTER 8 mmol H+ added = 8.30 mmol excess H+ [H+]excess = 0.80 mmol H+ mL Excess H+ = 2.0 + 28. 0.80 (Mole ratios can be used since the total volume cancels. assumptions 0.50 mmol/50.) Other points in the buffer region are calculated in similar fashion.50 − 0.0500 .80 mmol pH = 9.100 − x 0.24 (25. 60. just enough HCl has been added to convert all the weak base (NH3) into its conjugate acid (NH4+).0 mL × APPLICATIONS OF AQUEOUS EQUILIBRIA 0.6 × 10−10 5.100 mmol = 2. assumptions good.80 mmol − 2.58 0. For example. pOH = 4.1.x ⇌ H+ + 0 x NH3 0 x Ka = 5. a weak base problem: py Initial Equil. At the stoichiometric point (25. Kb = + H2O ⇌ Hpy+ 0 x + OH− ~0 x py is pyridine.0500 M NH4+ Initial Equil.25 + log 1.3 × 10−5 M.28.80 mmol H+ mL Added H+ reacts with NH3 to completion: NH3 + H+ → NH4+ mmol NH3 remaining = 2.100 mmol = 0. Initially.0 mL H+ added).50 mmol = 0. [NH4+]0 = 2. the pH is determined by the excess H+.80 = 1.7 × 10−9 [py] 0.3 × 10−6 M.0500 M 0.0 mL × 0.0500 − x 0.7 × 10−3 M.70 = 9.1 at the end of Exercise 60. at 28. 0. pH = 2.0500 good.100 M 0. pH = 5.6 × 10−10 = x2 x2 ≈ .0 mL of H+ added: H+ added = 28.0) mL All results are summarized in Table 8. x = [H+] = 5. Results are summarized in Table 8.70 mmol.100 x = [OH−] = 1.11. mmol NH4+ produced = 0. Beyond the stoichiometric point.100 − x [Hpy + ][OH − ] x2 x2 = ≈ ≈ 1. . Perform a weak acid calculation.89.30 mmol = 5.

this is a weak acid problem since just enough H+ has been added to convert all the weak base into its conjugate acid.3 11. which follows this problem.11 5.0 × 10 −14 [py] = = 5.0 Exercise 57 2.0 28.6 6. Table 8. Hpy+ Initial Equil.28 3. Determine the moles (or millimoles) of py and Hpy+ after reaction.14 3.56 5.0 24.0500 M 0.9 5.29 11. See Exercise 59 for a similar sample calculation. pKa = 5.11 9.1. asumptions 0.9 × 10−6 x2 x2 ≈ .56 4.6 7.0500 − x ⇌ py 0 x + H+ 0 x Ka = 5.7 2. then use the HendersonHasselbalch equation to solve for the pH.23 + log −9 Kb 1.65 7.27.0500 − x 0.97 9.30 11.04 .59 for an example.6 6.27 2. 5.0 30.1 Summary of pH Results for Exercises 57 − 60 (Graph follows) Titrant mL 0. x = [H+] = 5.96 Exercise 58 2.71 2.5 3.86 4. At the stoichiometric point (25. pH = 3.49 6.24 2. Ka = Kw 1.53 3.95 5.89 5.17 4. The initial concentration of [Hpy+] = 0. See Exercise 8.3 11.58 9.9 × 10−6.43 3.3 8.23 4.9 × 10−6 = 0. Beyond the equivalence point.5 mL): Added H+ reacts completely with py: py + H+ → Hpy+.9 25.87 7.0 mL H+ added). the pH determination is made by calculating the concentration of excess H+.5 20.0500 M.0500 good.0 − 24.46 5.04 Exercise 60___ 9.96 Exercise 59 11. pH = 5.71 2.23.25 8.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 287 Buffer region (4.28 10.1.85 3.96 4.1 26.75 11.75 11. All results are summarized in Table 8.3 8.24 5.27 6.5 24.0 12.63 3.4 × 10−4 M.7 × 10 [Hpy + ] Results in the buffer region are summarized in Table 8.0 8.25 2.0 24.79 10.0 25.0 4.

mmol of C7H5O2−. b.0 × 102 mL = 2. 10. The volume of OH− added to reach the equivalence point is: 10.6 × 10−10 6.19 mmol HC7H5O2 present = 100. so pH = pKa (always for a weak acid-strong base titration).0 × 10 −14 = 1.55. [weak acid] = [conjugate base]. pH = −log(6. .050 − x 0. The total volume of the solution is 100. 10.45.288 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 61. mmol HC7H5O2. mmol/2. For the equivalence point. At the halfway point to equivalence. assumptions good.0 × 102 mL Equil. This is a weak base. 0.4 × 10 −5 Initial 10. mmol of OH− to produce 10. x = [OH−] = 2.0 mL + 1.4 × 10−5) = 4.050 − x Kb = 1. Solving the weak base equilibrium problem: C7H5O2− + H2O ⇌ HC7H5O2 + OH− Kb = 0 x 0 x 1. This is a weak acid-strong base titration.8 × 10−6 M 0.0 × 102 mL. At the halfway point to equivalence for a weak base-strong acid titration. pH = pKa because [weak base] = [conjugate acid]. mmol OH− H 1 mL 0.0 mL × 0. mmol of OH− must be added. pH = 8.6 × 10−10 = x2 x2 ≈ . mmol of HC7H5O2 is neutralized by 10.050 pOH = 5. a.10 M = 10.10 mmol OH − = 1.0 × 102 mL OH− At the equivalence point.

0 × 102 mL OH− 0.0 × 10 −14 = = 1. assumptions good.067 M Equil.067 − x Ka = 1.067 − x 0.067 pH = 5.25 mmol OH− → H2O 25 mmol 0 25 mmol = 0.0 + 1.50 M = 50. x = [H+] = 1.0 mL × 0. Cl−. mmol 25 mmol + 1 mL = 1. mmol/(100.20 mmol H + = 50. Therefore.0 mmol OH− added mL mL The added strong base reacts to completion with the weak acid to form the conjugate base of the weak acid and H2O. 75.0 mL × 0.0 × 10 2 ) mL At the equivalence point of a strong acid-strong base titration.8 × 10−11. mmol H+ × 1 mL 0.6 × 10 289 For the equivalence point (mmol acid added = mmol base present): mmol C2H5NH2 present = 100.10 mmol 0. so the pH = 7.0 + 50. mmol C2H5NH2 mL H+ added = 10.8 × 10−11 = ⇌ H+ + 0 x C2H5NH2 0 x x2 x2 ≈ .5 mmol HA.10 M = 10. c.10 mmol = 7. at the equivalence point. only neutral species are present (Na+. mmol H+ mL OH− added = 25 mmol OH− × H+ Before After [H+]excess = 50.74 −4 Kb 5. the halfway point has no special significance other than that exactly one-half of the original amount of acid present has been neutralized.00. [C2H5NH3+]0 = 10. and H2O). 30. mL H+ The strong acid added completely converts the weak base into its conjugate acid. pH = 0.89 (100.067 M. .8 × 10−11) = 10.CHAPTER 8 Ka = APPLICATIONS OF AQUEOUS EQUILIBRIA Kw 1.) mL = 0. pH = pKa = −log(1. 62. In a strong acid-strong base titration.0 mL × 0.1 × 10−6 M 0.96. Solving the weak acid equilibrium problem: C2H5NH3+ Initial 0. 0.0 mL × = 3. mmol H+ present = 100.13 M.

and the color of the solution is the color due to the HIn form. This drives the indicator equilibrium to the right.00 L × 0.0/4.5) = 5. In a very basic solution.0 mL of HCl added represents the halfway point to equivalence.0 mmol 0 0 3.10 L HA Initial Equil. The reason there is a color change with indicators is that the HIn form has one color associated with it. In very basic solutions.50 ! log(3.0909 x = 9. which drives the indicator equilibrium to the left. and the In− form dominates.00 and Ka = 1. H+ has been removed from solution. 500. g/mol 0.00 g = 100. The HIn form dominates.0909 M 1.100 mol HCl added to reach stoichiometric point. whereas the In− form has a different color associated with it. 0.0909 − x 0. pH = 3. 5.0 × 10−5 = x2 x2 ≈ 0. the solution takes on the color of the In− form. The 10.5 × 10−4 M = [H+]. Using the Henderson-Hasselbalch equation: ⎛ 3.18) = 5.0 × 10−5 Ka = 1. a. there are lots of H+ ions present. there is a range of pH values where the solution has significant amounts of both the HIn and In− forms present.68 = 2.0 mmol A buffer results after the OH− reacts to completion.0 mmol ⎞ [A − ] pH = pKa + log .5 mmol 3.290 HA Before After CHAPTER 8 + OH− APPLICATIONS OF AQUEOUS EQUILIBRIA A− + H2O → 7.1 × 10 −6 63. assumptions good.50 – (!0.0 mmol ⎟ ⎟ [HA] ⎝ ⎠ pKa = 5. 10.100 mol of NaA.00-g sample must have contained 0. 1. The related quilibrium is HIn ⇌ H+ + In−.x ⇌ H+ 0 x + A− 0 x Ka = 1.0 × 10−5. We abbreviate the acid form of an indicator as HIn and the conjugate base form as In−. 64. At the equivalence point. enough H+ has been added to convert all the A− present initially into HA. Ka = 10 −5.0 mmol / 105. In between very acidic and very basic solutions. An acid-base indicator marks the end point of a titration by changing color.100 mol b. This is . Thus pH = pKa = 5.50 = pKa + log ⎜ ⎜ 4.02. The concentration of HA at the equivalence point is: [HA]0 = 0.0909 . Acid-base indicators are weak acids themselves.5 mmol 4.100 mol = 0.5 mmol / 105.100 mol/L = 0. Which form dominates in solution and dictates the color is determined by the pH of the solution.0909 M 0. In a very acidic solution.68.

0 mL OH− added). Equivalence point: when enough titrant has been added to react exactly with the substance in the solution being titrated.01 pH units since.0 × 10 −9 = ⎜ ⎟ [H+]. at the equivalence point. [In−]/[HIn] = 7.8.0 × 10−3 [HIn] At 7. and the In2− form has the blue color associated with it. both colors are present.0 at color − 1 [In ] ⎝ 10 ⎠ change c. the HIn form dominates. and we want this pH to be close to the stoichiometric point of the titration. Ka = 1. HIn ⇌ In− + H+ Ka = [In − ][H + ] = 1. The pH at which the color change occurs is determined by the Ka of the indicator. Thymol blue cannot be monoprotic.89 [HIn] 93. We want the indicator to tell us when we have reached the equivalence point.00/93. so the solution will be yellow. b. . The HIn form has one color and the In− form has another color. The two forms of an indicator are different colors. Ka = 1. pH = 1. the pH is changing very rapidly with added titrant. thymol blue must be a diprotic acid. Endpoint: when the indicator changes color. [H+] = 1 × 10 −8 M.0 × 10 −3 = [ In − ] 7. When the ratio of the two forms is less than 10.00 = 1.00% conversion of HIn into In−.00. so the solution is very basic and the In− form of the indicator dominates. [H+] = 1. 10 [HIn] ⎛1⎞ = . yellow. that form must be in an approximately tenfold excess or greater over the other form. From Figure 8. thymol blue has three colors associated with it: orange. 66. To go from [HIn]/[In−] = 10 to [HIn]/[In−] = 0.89. The solution will be blue.00 The color of the base form will start to show when the pH is increased to 1.1 requires a change of 2 pH units (a 100-fold decrease in [H+]) as the indicator changes from the HIn color to the In− color. 65. HIn ⇌ In− + H+ Ka = [In − ][H + ] = 10 −3. The range over which an indicator changes color only needs to be close to the pH of the equivalence point. and blue. monoprotic indicators only have two colors associated with them (either the HIn color or the In− color). The H2In form has the orange color. To see only one color.00 × [H + ] = × [H + ].0 × 10 −9 [HIn] a. We can detect the endpoint visually and assume that it is the equivalence point for doing stoichiometric calculations. This is way past the equivalence point (100. In order for this to happen. the HIn− form has the yellow color.3 × 10 −2 M. In a very acid solution. pH = 8.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 291 where the color change occurs. The color change occurs when the concentration of the more dominant form is approximately ten times as great as the less dominant form of the indicator. They don’t have to be as close as 0.

8. pH < 8 for thymol blue to be yellow. Pt. When choosing an indicator. blue 69. the color change would be from yellow to yellowish orange at pH ≈ 6. Therefore. 68.79 3. For bromcresol green. Exercise 57 59 72. From results of the 74. Pt. Only a weak base-strong acid titration would have an acidic pH at the equivalence point. so the color would change from red to reddish orange at pH ≈ 4.3. Since the pH generally changes very rapidly at the equivalence point. and the color of the solution is the color of HIn (red).3 ± 1.00 8.4-dinitrophenol 70. The pH break at the equivalence point is too small. Note that at pH < 4. we want the color change of the indicator to occur approximately at the pH of the equivalence point.3. This is especially true for strong acid-strong base titrations.28 pH at Eq. In titrating a weak acid with base.3 (yellow). 7.3. 73. yellow b. This occurs when pH ≈ pKa of the indicator. .292 67. Exercise 58 60 The titration in Exercise 60 will be very difficult to mark the equivalence point.form of the indicator dominates. At pH > 6. The following are some indicators where the color change occurs at about the pH of the equivalence point.82 pH at Eq. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA pH > 5 for bromcresol green to be blue. Exercise 54 56 71. Pt.3.79 pH at Eq. and the color of the solution is the color of In− (yellow). the HIn form of the indicator dominates. a. the resulting green color indicates that both HIn and In− are present in significant amounts. 8. In titrating a weak base with acid. so only in this type of titration would the color change of methyl red indicate the approximate endpoint. Exercise 53 55 pH at Eq. 7. we don’t have to be exact. the useful pH range of methyl red where it changes color would be about 4. yellow c.28 5. Pt. we start off with an acidic solution with pH < 4. The pH is between 5 and 8.27 Indicator bromthymol blue or phenol red o-cresolphthalein or phenolphthalein Indicator bromthymol blue or phenol red bromcresol green Indicator o-cresolphthalein or phenolphthalein bromcresol green Indicator o-cresolphthalein or phenolphthalein 2.00 4.3. green (Both yellow and blue forms are present.3 (red) to 6. The color of the indicator will change over the approximate range of pH = pKa ± 1 = 5.) d. the In.

This is the first halfway point to equivalence.00909 + x) .0500 Using the quadratic formula: x2 + (1. assumption poor.0364 M 0.0 mL × 0. Because K a1 >> K a 2 >> K a 3 . HX ⇌ H+ + X−.0364 − x ⇌ H+ ~0 x + H2X− 0. assumptions good (5% error). x = 2.1 × 10−3.0 × 10−3 = x(0.00 mmol H2X− after OH− reacts completely with H3X.0 × 10−3 = x2 x2 ≈ . Solving the buffer problem: H3X Initial Equil. figs. x = 7. 0. . 0. 1. 0. Note that the results of the first two indicators are inconclusive.0364 − x Using the quadratic formula and carrying extra sig.00909 + x K a1 = 1.8 × 10−3 M = [H+].6 × 10−3 M = [H+].50 mmol OH− added results in 2. pH ≈ 5.01 × 10−2)x − 3. H3X Initial Equil.00 mmol H2X− are in a total volume of 110.55 c. This is the first stoichiometric point.18 b.0 mL. assumption that x is small does not work here. 5. pH = 2. 2.0500 M = 5. pH initially is determined by H3X equilibrium reaction.00 mmol H3X and 1.01 M Ka = 75. x = 6.00 mmol H3X initially a.0500 − x 0.00.01 100.00 mmol OH− added results in 5. 0. pH = 2. 4.50 mmol H3X and 2.0 × 10−5 = 0.0500 M 0. After this reaction goes to completion.50 mmol H2X− after OH− reacts completely with H3X.0500 − x ⇌ H+ ~0 x + H2X− 0 x K a1 = 1.00909 M 0. d. pH = p K a1 = 3.0.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 293 bromcresol green indicator. from the typical weak acid setup: [H+] = [X−] ≈ 1 × 10−5 M and [HX] ≈ 0.64 × 10−5 = 0.0 × 10−3)x − 5.00 mmol OH− added converts H3X into H2X−. [H + ][X − ] (1 × 10 −5 ) 2 = = 1 × 10−8 [HX] 0. x2 + (1.

50 mmol KOH added results in 2.00 = 9. 12.1 × 10−2)x − 1.5 mmol X3− after OH− reacts completely with H3X first. We must solve for the pH exactly.00 = 5.0 mmol HX2− after OH− reacts completely. using the quadratic formula: 0. Usually pH = pK a 3 but normal assumptions don't hold. This is the second stoichiometric point.00 − log(1.0 × 10−2 = x(0.00 mmol H2X− and 1. pH = 11.1 × 10−4 = 0. assumptions good. then H2X−.011 + x) .40.5 mmol HX2− and 2. x = 4.0 mmol OH− added results in 5. pH = pK a 2 = 7. 6.0 mL 0.020 − x .00 mmol HX2− after OH− reacts completely with H3X and then reacts completely with H2X−.3 × 10−3 M = OH−.5 mmol OH− added results in 2.00. This is the second halfway point to equivalence.00) = 6.011 − x ⇌ HX2− 0. This is the third stoichiometric point. 10. X3− Initial Equil. 7.011 + x + OH− 0 x Kb = Kw = 1.5 mmol/225.0 mmol = 0. pH = pK a 2 + pK a 3 2 = 7. 15.50 mmol H2X− and 2.0 × 10−2 K a3 5.00 mmol OH−added results in 4.00 + 7. [X3−-] = [HX2−] = 2. This is the third halfway point to equivalence.50 2 h.294 pH = CHAPTER 8 pK a1 + pK a 2 2 APPLICATIONS OF AQUEOUS EQUILIBRIA = 3. and finally HX2-.00/4.0 mmol X3− after OH− reacts completely.011 M 0.50 mmol HX2− after OH− reacts completely.00 2 e.020 M 250. Using the H2X− ⇌ H+ + HX2− reaction: [HX 2 − ] = 7.0 mL = 1.1 × 10−2 M X3− + H2O Initial Equil. assumptions good. [H 2 X − ] pH = pK a 2 + log f. + H2O ⇌ HX2− 0 x + OH− 0 x Kb = Kw = 1.0 mmol OH− added results in 5.011 − x x2 + (2.0 × 10−2 K a3 Kb = 1. 0. g.00 + 12.011 M 0.63 i.

0 mmol H3A.3 × 10−3) = 2.100 − x 0.0 × 10−2 ≈ .41. pH = 12. [X3−] = [OH−] = 5.0 × 10−2 M. x = 3.00 M = 10.0 mL × 1. H3A Initial Equil.0 mL × 0.0 mmol X3− and 5. Began with 100.020 − x 0.7 × 10−2)x − 1.3 × 10−3 M [OH−] = (1. pH = 12. ⇌ OH− + HX2− 0 x 1. Consider only the first dissociation. the initial pH is determined by H3A.2 × 10−2 M. b.100 [H+] = 3.9 × 10−3 [H 3 A] 0.7 × 10−2 M 1.0 mmol NaOH.0 × 10−2 = Using the quadratic formula: x2 + (2. 0. assumption poor. 10.52 = 5.0 × 10−4 = 0 x = [OH−] = 1. 1.100 M = 10.0 mmol = 1. Because K a1 >> K a 2 >> K a13 .CHAPTER 8 Kb = APPLICATIONS OF AQUEOUS EQUILIBRIA x2 x2 . pH = 2.7 × 10 −2 + x) x (1.34 76.7 × 10−2 + x Kb = 1.0 × 10−2)x − 2.7 × 10−2) + x = (1. pH = pK a1 + pK a 2 2 = 3. Because Kb for X3− is fairly large for a weak base.100 M 0.4 × 10−2. a.7 × 10−2 − x (1.7 × 10−2 M 1.7 × 10−2 M 300.0 mmol OH− excess after OH− reacts completely. This takes us to the first stoichiometric point where the amphoteric H2A− is the major species present.5 × 10−4 ≈ .67 2 . x = 5. 20.0 mmol OH− added results in 5. Added OH− converts H3A into H2A−.7 × 10−4 = 0. we have to worry about the OH− contribution from X3−.0 mL + H2O X3− Initial Equil.020 295 Using the quadratic formula: x2 + (1.7 × 10−2) + (5.00 j. K a1 = 0.9 × 10−3 M. assumptions good.100 − x ⇌ H+ ~0 x + H2A− 0 x [H + ][H 2 A − ] x2 x2 = = 1.82 + 7.7 × 10 − 2 − x) 1. x = 1.

19 = 3.2 mL of OH− are necessary to reach the first stoichiometric point.525 mmol OH− added.212 mmol H3A (carrying extra sig.00 = 6. The pH at 59.212 × 10−3 mol = 1.525 = 0.95 mmol OH− added H3A After 0 H2A− Before 1. It will require 60.8 × 10−7) Second stoichiometric point: pH = −10 pKa 2 + pKa 3 2 . 77.212 − 0. 59. 0.53 0 → → → H2A− + H2O 0 1. figs.00 M = 25.0 mL × 1.44 ( K a 3 = 3.82) ⎝ 60. After OH− reacts completely.687 − 10 −3.5 × 10−4 ( pK = 3. H3A + OH− → H2A− + H2O.6 × 10 ) b.) 165.0500 M OH − )(VOH − ) .0 mmol NaOH added.0 mmol HA2− and 5.74 OH− 1.0 mmol A3−.212 After 0.212 mmol H3A = (0. c. (10.50 K a1 = a1 0. assumptions good.200 g = 1.30 2− [HA ] This is the third halfway point to equivalence.73 )⎜ + 10 −3. 25.53 + OH− 0.212 A3− 0 0. 8.687 mmol H3A remains after OH− reacts completely and 0.56 ( K a 2 = 2.68 mmol + + OH− 1. Solving the buffer problem using the K a1 reaction gives: ⎞ ⎛ 0.0500 M OH− = 2. 1.212 mmol 2.0 g/mol a.95 mmol .74 0.50 First stoichiometric point: pH = pKa1 + pKa 2 2 = 5.0500 M) = 0.212 HA2− + H2O 0 1.212 After 0 HA2− Before 1. where pH = pK a 3 = 9.44.525 mmol H2A− formed.56 + pK a 3 2 pK a 3 = 9.296 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA c.525 (10 −3.82 + pK a 2 2 pK a 2 = 6. 1.0 mL of 0. K a3 = [H + ][A 3− ] . VOH − = 24.2 mL.5 mL to reach the third halfway point to equivalence. 24. because [A3−] = [HA2−]. [H+] = K a 3 . pH = pK a 3 = 11.73 ⎟ ⎠ = 1.44.50 mL)(0.73 60.53 mmol + H2O Before 1.0 mL of NaOH added should be a little lower than 9. the mixture contains 5.

the first equivalence point). Cl−.0 mmol H2A initially mL To reach the first equivalence point. Na+ F. CO2 (H2CO3).00.0 × 10−10 a. H2O. ⎛ 0. 5.70 = 2.10 mmol H 2 A = 5.0 mL of 0. Cl−. Cl−. CO2 (H2CO3).6 × 10 = ⎝ ⎛ 0. pH = 9. H+ (excess).00.70 + pK a 2 2 = 8.34 K a 3 = 3. K a1 = 10−6. CO 2− = 3 x [HCO 3 ][OH − ] [CO 3 ] 2− x = x2 x2 ≈ 0. K a 2 = 10−9. 0. HCO3−.100 M Equil. A.100 − x Kb = 2. Addition of 25. Na+ is present in all solutions.6 × 10−10 M.00. pH = 11.66. The major species present at the various points after H+ reacts completely follow. Solving for the Ka values: pK a1 = 6. making the normal assumptions. Na+ C.0 mL of 0. At the first equivalence point for a diprotic acid.70.53 mmol ⎞ + ⎜ ⎜ 109 mL ⎟ [H ] ⎟ ⎠ −10 .CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 297 Use the K a 3 reaction to solve for the [H+]. Point A (initially): CO32− + H2O Initial 0. H2O. CO32−. Cl−. 50.0 × 10−7 pK a1 + pK a 2 2 79.30. pH = ( pK a1 + pK a 2 )/2 = 8.0 mmol OH− must be added.8 × 10 −11 Kb = 2. [H+] = 4.100 − x 0.0 × 10 −14 = Ka2 4. Na+ b. The added H+ from HCl reacts completely with CO32− to convert it into HCO3−. 78. Na+ Kw 1.1 × 10−4 ⇌ HCO3− + OH− 0 ~0 K b . H2O.30 = 5.10 M NaOH. H2O. HCO3−.1 × 10−4 = − B. This occurs after addition of 50. CO32−.68 mmol ⎞ ⎜ ⎜ 109 mL ⎟ ⎟ ⎝ ⎠ Assumptions good.10 M NaOH will be the first halfway point to equivalence. CO2 (H2CO3). Point E represents the second equivalence point. H2O. After all CO32− is reacted (after point C.6 × 10−3 M = [OH−]. assumptions good. H2O.0 mL × 0. Cl− . H+ then reacts completely with the next best base present. Na+ E. = 8. . HCO3−.100 x = 4. 6. pK a 2 = 9. Na+ D.70. where [H2A] = [HA−] and pH = pK a1 = 6. HCO3−.

143 M.37.0 mmol HCl.0333 − x 0.92.00 mmol/mL × V.32.32 = 8.100 M HCl added).8 × 10−11) = 10.0 mmol A2− into HA. pK a1 = −log(4. assumptions good.35 2 Point D: The second halfway point where [HCO3−] = [H2CO3].by adding 10.0 mmol = 1. 0.3 × 10−7 = ⇌ H+ + 0 x HCO3− 0 x K a1 = 4.0333 x = [H+] = 1. We need to convert 10.0 mL = 0. The amphoteric Point C: HCO3− is the major acid-base species present. 80. pH = pK a 2 = 8.0333 − x K a1 = 4.298 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA Point B: The first halfway point where [CO32−] = [HCO3−]. 10. [H2A]0 = 20.00 mL of 0.00. The titration reaction is A2− + H+ → HA− (goes to completion).0 mL of 1. HA− ⇌ H+ + A2Ka = 1 × 10−8. [H2CO3] = 2.200 mmol/mL = 20. pH = pK a 2 = −log(4. which is 40. pH = pK a1 = 6.50 mmol/75. pH = 3.2 × 10−4 M. Begin with 100. 50.00 M HCl. This requires 40. assumptions good. because K a1 >> K a 2 . This will produce a solution where [HA−] = [A2−] and pH = pK a 2 = 8.3 × 10−7) = 6. where all of the CO32− present initially has been converted into H2CO3 by the added strong acid.0 mL HCl b.0 mmol = 0. assumptions good. First equivalence point (25. pH = pK a1 + pK a 2 2 .37 pH = 6. H2A is the major source of H+.00.0 mL HCl added.3 × 10−7 x2 x2 ≈ 0.0 mmol A2−. when [HA−] = [A2−].0333 M Equil.37 + 10.0 mmol H+. a. all A2− is converted into H2A. V = 10.0333 M H2CO3 Initial 0. Point E: This is the second equivalence point.0 mL .0 mL × 0. 140. At the second stoichiometric point.

CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA H2A 299 ⇌ H+ 0 x + HA− 0 x Initial Equil.143 M 0.3 × 10−5 mol/L 9.0 H 10−3 ≈ . s = solubility in mol/L.143 − x 0. Ag3PO4(s) ⇌ 3 Ag+(aq) + PO43−(aq) 0 0 s mol/L of Ag3PO4(s) dissolves to reach equilibrium −s → +3s +s 3s s Ksp = 1.3 × 10−3 g/L L mol .1 g × = 9. Initial Change Equil.4%.143 − x x2 x2 . s = 9.7 × 10−20)1/4 = 1.012 M.7 g Ag 3 PO 4 × = 6.012 × 100 = 8.6 × 10−5 mol/L = molar solubility 1. 1.7 × 10−3 g/L L mol Ag 3 PO 4 b.7 × 10−9 = [Ca2+][CO32−] = s2. can't neglect x.). we do not need to worry about their initial or equilibrium amounts.8 × 10−18 = [Ag+]3[PO43−] = (3s)3(s) = 27s4 27s4 = 1. CaCO3(s) ⇌ Ca2+(aq) 0 s + CO32−(aq) 0 s s = solubility (mol/L) Ksp = 8. figs. x = 0.143 x = 0.3 × 10 −5 mol 100.0115 M and pH = 1. check assumptions: 0. Using successive approximations: 0.0115 (carrying extra sig. [H+] = 0.6 × 10 −5 mol Ag 3 PO 4 418. In our setups. K a1 = 0.94 Solubility Equilibria 81. s = (6. Initial Equil.143 0.8 × 10−18. Because solids do not appear in the Ksp expression. a.

CdCO3(s) ⇌ Cd2+(aq) 0 s + CO32−(aq) 0 s s = solubility (mol/L) Ksp = 5. In our setup. we do not need to worry about their initial and equilibrium amounts. CaC2O4(s) ⇌ Ca2+(aq) + C2O42−(aq) 0 0 s mol/L of CaC2O4(s) dissolves to reach equilibrium !s → +s +s s s 6.8 × 10 −5 )2 = 2. a. This is defined as the maximum amount of a salt that can dissolve.300 c. s = solubility of the ionic solid in mol/L.1 g × = 3.4 × 10−8/4)1/3 = 1. a.3 × 10 −9 . PbI2(s) ⇌ Pb2+(aq) 0 s + 2 I−(aq) 0 2s s = solubility (mol/L) Ksp = 1.1 × 10−4 g/L L mol 82. L 128. s = 2 × 10−7 mol/L 83. Initial Equil.1 × 10−18 = [Hg22+][Cl−]2 = (s)(2s)2 = 4s3. Initial Equil. Sr3(PO4)2(s) ⇌ 3 Sr2+(aq) 0 3s + 2 PO43−(aq) 0 2s s = solubility (mol/L) Ksp = 1 × 10−31 = [Sr2+]3[PO43−]2 = (3s)3(2s)2 = 108s5.2 × 10−12 = [Cd2+][CO32−] = s2. Ksp = (4. CHAPTER 8 Hg2Cl2(s) APPLICATIONS OF AQUEOUS EQUILIBRIA Hg22+(aq) 0 s + 2 Cl−(aq) 0 2s ⇌ s = solubility (mol/L) Ksp = 1. Initial Equil.1 × 10 −3 g 1 mol CaC 2 O 4 × = 4. s = 2. s = Ksp = [Ca2+][C2O42−] = (s)(s) = s2.5 × 10 −7 mol 472. Initial Equil. s = 6.5 × 10−7 mol/L 6. Initial Change Equil.3 × 10−6 mol/L c.8 × 10 −5 mol/L. Because solids do not appear in the Ksp expression.10 g From the problem.4 × 10−8 = [Pb2+][I−]2 = s(2s)2 = 4s3 s = (1.5 × 10−3 mol/L = molar solubility b.

Initial Change Equil.CHAPTER 8 b. Ksp = 4(2. Initial Equil. So: Ksp = [Pb2+][Br−]2 = s(2s)2 = 4s3.20 × 10 −19 84.14 × 10 −2 M.25 × 10 −9 )5 = 3. M2X3(s) ⇌ 2 M3+(aq) + 3 X2−(aq) Ksp = [M3+]2[X2−]3 s = solubility (mol/L) 0 0 s mol/L of M2X3(s) dissolves to reach equilibrium !s +2s +3s 2s 3s 3. Ksp = 27(1.3 × 10 −12 86. Initial Change Equil. APPLICATIONS OF AQUEOUS EQUILIBRIA BiI3(s) 301 ⇌ Bi3+(aq) + 3 I-(aq) Initial Change Equil.1 × 10 −4 )3 = 5. Because the Ksp for CaF2 is the smallest.14 × 10 −2 )3 = 3.2 × 10 −4 M. s = [Pb2+] = 2. .1 × 10 −4 M Ksp = [Ag+]2[C2O42−] = (2s)2(s) = 4s3 = 4(1. [Ag+] = 2s = 2. s = 1. Ag2C2O4(s) ⇌ 2 Ag+(aq) 0 2s + C2O42−(aq) 0 s s = solubility (mol/L) From problem.25 × 10 −9 mol/L L 288 g Ksp = (2s)2(3s)3 = 108s5 . we can compare values of Ksp to determine relative solubility.32 × 10 −5 )4 = 8.30 × 10 −43 87.92 × 10 −5 85. Because both solids dissolve to produce three ions in solution. 0 0 s mol/L of BiI3(s) dissolves to reach equilibrium !s → +s +3s s 3s Ksp = [Bi3+][I−]3 = (s)(3s)3 = 27s4. PbBr2(s) ⇌ Pb2+(aq) + 2 Br-(aq) 0 0 s mol/L of PbBr2(s) dissolves to reach equilibrium !s → +s +2s s 2s From the problem. a.60 × 10 −7 g 1 mol M 2 X 3 × = 1. CaF2(s) has the smallest molar solubility. s = Ksp = 108(1.

2 × 10−5 = [Ag+]2[SO42−] = (2s)2s = 4s3.3 × 10−32 s = solubility (mol/L) Ksp = [Ca2+]3[PO43−]2 = (3s)3(2s)2 = 108s5. Initial Fe(OH)3(s) ⇌ Fe3+ + 3 OH− pH = 7. Ag2SO4(s) ⇌ 2 Ag+(aq) + 0 2s SO42−(aq) 0 s s = solubility (mol/L) Ksp = 1.0 × 10−22 s = solubility (mol/L) Ksp = [Fe3+][PO43−] = s2. s = (1.302 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA b.0 × 10 −22 = 1. Note: Comparing the solubilities in parts b and c to part a illustrates that the solubility of a salt decreases when a common ion is present.20 + s) ≈ 4s2(0. c.10)2(s).10 + 2s)2(s) ≈ (0.4 × 10−2 mol/L b.3 × 10−32/108)1/5 = 1. a. s = 1. a.10 + 2s SO42−(aq) 0 s s = solubility (mol/L) Ksp = 1.20). s = 3. Initial Equil Ag2SO4(s) ⇌ 2 Ag+(aq) + 0 2s SO42−(aq) 0. Ca3(PO4)2(s) Initial Equil.2 × 10−5 = (0.20 M 0. Ag2SO4(s) ⇌ 2 Ag+(aq) + 0.2 × 10−3 mol/L.0 × 10−11 mol/L FePO4 has the smallest molar solubility. s = 1.0.10 M 0.2 × 10−5 = (2s)2(0. .20 + s s = solubility (mol/L) 1. ⇌ 3 Ca2+(aq) + 2 PO43−(aq) 0 3s 0 2s Ksp = 1. We must calculate molar solubilities because each salt yields a different number of ions when it dissolves. Initial Equil. assumption good. s = 1.6 × 10−7 mol/L FePO4(s) Initial Equil. Initial Equil. assumption good.9 × 10−3 mol/L. 89. [OH−] = 1 × 10−7 M 0 1 × 10−7 M s mol/L of Fe(OH)3(s) dissolves to reach equilibrium = molar solubility → +s +3s Change −s s 1 × 10−7 + 3s Equil. 88. ⇌ Fe3+(aq) 0 s + PO43−(aq) 0 s Ksp = 1.

3000 L × 5.001 M s mol/L dissolves to reach equilibrium −s → +s − s 0. s = 4 × 10−11 mol/L = molar solubility c. solubility decreases.0 × 10 −21 mol ZnS 97. Initial Equil. assumption good (3s << 1 × 10−7). Fe(OH)3(s) ⇌ Fe3+ + 3 OH− pH = 11. Initial Change Equil.20 + 3s s = solubility (mol/L) Ksp = [Ce3+][IO3−]3 = s(0.0.050)s. 90.5 × 10−10 91.050 M 0. s = 5.0 × 10 −21 mol/L.45 g ZnS × = 1. b.20 M 0. Initial Equil. Fe(OH)3(s) ⇌ Fe3+ + 3 OH− pH = 5.4 × 10−8 mol/L. [OH− ] = 1 × 10−3 M (Buffered) (Assume no pH change) 0 0. Mass ZnS that dissolves = 0. s = 4 × 10−29 mol/L = molar solubility Note: As [OH− ] increases. s = 4.050 + s)(s) ≈ (0. Ce(IO3)3(s) ⇌ Ce3+(aq) 0 s + 3 IO3−(aq) 0.20 + 3(4.001 Ksp = 4 × 10−38 = [Fe3+][OH− ]3 = (s)(0. solving for Ksp: Ksp = (4. OH− = 1 × 10−9 M 0 1 × 10−9 M (Buffered) s mol/L dissolves to reach equilibrium −s → +s ⎯ (Assume no pH change in buffer) s 1 × 10−9 Ksp = 4 × 10−38 = [Fe3+][OH−]3 = (s)(1 × 10−9)3.050 + s Ksp = 2.4 × 10−8) × [0. Initial Change Equil.20 + 3s)3 From the problem.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 303 Ksp = 4 × 10−38 = [Fe3+][OH−]3 = (s)(1 × 10−7 + 3s)3 ≈ s(1 × 10−7)3 s = 4 × 10−17 mol/L.001)3.5 × 10 −22 = (0. ZnS(s) ⇌ Zn2+ + S2− 0 s Ksp = [Zn2+][S2−] s = solubility (mol/L) 0.5 × 10 −19 g L mol .0.4 × 10−8)]3 = 3. assumption good. This is the common ion effect.

304 92.052 M). solid Ag2CrO4 is formed. Thus equilibrium is shifted to the left (first reaction above). lowering the concentration of Ag+(aq).9 × 10 −12 = [Mg2+][OH−]2 = [0. fig. 93.01(0.9 × 10 −12 8. calculate the [OH−] required to reach this reduced [Mg2+]. 99% of the Mg2+ in seawater will be removed as Mg(OH)2(s). CaCO3. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA For 99% of the Mg2+ to be removed.01(0. leaving some Ag+(aq) and CrO42−(aq) in solution. pH = 10. we need. and the red solid disappears. at equilibrium. As more CrO42−(aq) goes into solution.3 × 10−4 M . The relevant reactions are: 2 Ag+(aq) + CrO42−(aq) excess H + 3 Sr2+ + 2 H3PO4 ⇌ Ag2CrO4(s). Ag2CrO4(s) Initial Change Equil. CdCO3 and Sr3(PO4)2. Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH−(aq) Ksp = 8. As Cl−(aq) is added. the AgCl solid forms.11.0 × 10−12. (red) Ag+(aq) + Cl−(aq) ⇌ AgCl(s) (white) In the first reaction. Using the Ksp equilibrium constant. ⇌ 2 Ag+(aq) + CrO42−(aq) 0 +2s 2s 0 +s s (2s)2(s) = Ksp = 9. which we can verify using Ksp values. then the solubility of the salt will increase as the solution becomes more acidic.) pOH = !log(1. the solution turns yellow. Hg2Cl2 and PbI2 do not have any pH dependence because Cl− and I− are terrible bases (the conjugate bases of a strong acids). Added H+ will react with the base. Ag3PO4(s) + H (aq) → 3 Ag (aq) + HPO4 (aq) CaCO3(s) + H → Ca + HCO3 + 2+ + 2+ − + + 2− excess H + 3 Ag+(aq) + H3PO4(aq) excess H + Ca2+ + H2CO3 [H2O(l) + CO2(g)] Cd2+ + H2CO3 [H2O(l) + CO2(g)] excess H + CdCO3(s) + H → Cd + HCO3− Sr3(PO4)2(s) + 2 H+ → 3 Sr2+ + 2 HPO42− 94. As the basic anion is removed. The yellow color is due to the presence of CrO42−(aq). [Mg2+] = 0. The salts with basic anions are Ag3PO4. If the anion in the salt can act as a base in water. s = 1. [OH−] = 1. This means that Ag2CrO4(s) is more soluble than AgCl(s).3 × 10 −4 M (extra sig.3 × 10 −4 ) = 3. forming the conjugate acid.052 M)] [OH−]2. more of the salt will dissolve to replenish the basic anion. at a pH = 10.89.1.

[SO42−] = 0. mL Q = [Ba2+]0[SO42−]0 = (7.5 × 10−2 M 200.5 × 10−2) = 1.6 × 10−8 mol/L.020 mmol mL = 7. 97.0075 mol/L Ba2+ react with SO42− to completion because Ksp << 1. therefore. 95.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA AgCl(s) 305 ⇌ Ag+(aq) + Cl−(aq) 0 +s s 0 +s s Initial Change Equil.0 × 10−5 M 0.9 × 10−4 > Ksp (1. mL 96.0175) s = 8. [BaBr2]0 = 0.250 L .0075 −0.0175 New initial (carry extra sig. The anions of the other choices are conjugate bases of strong acids. BaSO4(s) Before ⇌ Ba2+ + SO42− 0.5 × 10−3 M 200.6 × 10−8 M.025 M 0.5 × 10−3)(2. [Ba ]0 = 2+ [SO42−]0 = 125 mL × 0.018 M. Ni(CN)2 All these salts have anions that are bases. fig. assumption good. s2 = Ksp = 1. Pb(OH)2 c.) s mol/L BaSO4 dissolves to reach equilibrium Change −s → +s +s s 0.0175 + s) ≈ s(0. They have no basic properties in water and.040 mmol mL = 2.0175 + s Equil. [Ba2+] = 8. do not have solubilities that depend on pH. AgF b.150 L(1.5 × 10−9 = [Ba2+][SO42−] = (s)(0. Ksp = 1. a. 75.0 × 10 −4 mol / L) = 6.5 × 10−9) A precipitate of BaSO4(s) will form. s = 1. Change ← −0.3 × 10−5 M Thus Ag2CrO4(s) is more soluble than AgCl(s).0075 M Let 0.6 × 10−10.0 mL × 0.0075 Reacts completely After 0 0. Sr(NO2)2 d.

0 × 10−5)(2.8 × 10−18. precipitation will occur.0 × 10−5 M. Ag3PO4(s) ⇌ 3 Ag+(aq) + PO43−(aq).0 × 10 −5 ⎟ ⎝ ⎠ 1/ 3 .0 × 10−5 M) ⎛ 1. [C2O42−] = 2.4 × 10−4) = 1. Q = 1. 50. Q > Ksp. assumption good. 1. Now let some of the PbCl2(s) re-dissolve to establish equilibrium PbCl2(s) Initial ⇌ Pb2+(aq) + 2 Cl−(aq) 0 40. [Br-] = 1. 0.6 × 10−5 M. s 0.0 × 10−4 mol/L and [Cl−] = 0. 50.40 + 2s. Ksp for NiCO3 = 1.40 + 2s)2 ≈ s(0.0 mL × 0. BaC2O4(s) will not precipitate. The final concentration of ions will be: [Ba2+] = 6.8 × 10−18 = [Ag+]03[PO43−]0 = [Ag+]03(1. which leaves 40. In this problem.0 mmol Pb2+. For this solution.5. For CuCO3(s).0 × 10−5 M.0 mL × 1.0 mmol Pb2+ requires 10. Any [Ag+]0 greater than this calculated number will cause precipitation of Ag3PO4(s).5 × 10−10.6 × 10−5 = s(0.40 + 2s Ksp = [Pb2+][Cl−]2.40)2 s = 1.5 × 10−8 M Because Q < Ksp. precipitation begins when: .10 M = 5. At equilibrium: [Pb2+] = s = 1.0 mmol/100. when Q is greater than Ksp.0 × 10 −4 mol / L) = 2. CuCO3 will precipitate first because it has the smaller Ksp value and will be least soluble. Ag3PO4(s) will precipitate. Assume precipitation of PbCl2(s) is complete. From Table 8.100 L(6.40 M 99.8 × 10 −18 ⎞ ⎟ [Ag+]0 = ⎜ ⎜ 1.0 mL s mol/L of PbCl2(s) dissolves to reach equilibrium Equil. We will calculate the [Ag+]0 necessary for Q = Ksp. mmol of Cl− for complete precipitation. 100. [PO43−]0 = [Na3PO4]o = 1. From the Ksp values.0 × 10−4) = 0.306 [K2C2O4]0 = CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 0.2 × 10−4 M [K+] = 4. 5.6 × 10−5 M When [Ag+]0 = [AgNO3]0 is greater than 5.0 × 10−4 mol/L. [Ag+]0 = 5. mmol Cl−.0 M = 50. Ksp = 1.4 × 10−4 M 98. mmol Cl− in excess.8 × 10−4 M. so PbCl2 precipitates.40 + 2(1.250 L Q = [Ba2+]0[C2O42−]0 = (6.4 × 10−7 and Ksp for CuCO3 = 2.4 × 10−4 M 0.

NiCO3 [ Ni 2 + ] = 1. Cu + 2+ 2+ NaCl(aq) AgCl(s) Mg .25 M Determining the [Cu2+] when NiCO3(s) begins to precipitate: [Cu2+] = K sp . a.18% Cu2+ 0.6 × 10 −7 M For successful separation. Cu2 2+ + NH3(aq) .5 × 10 −10 = 1. 1% Cu2+ or less of the initial amount of Cu2+ (0.5 × 10 −10 = 4.4 × 10 −7 = 5. CuCO3 [Cu 2 + ] = 2.contains OH 2+ - Mg(OH) 2(s) Cu(NH3) 4 (aq) H2S(aq) CuS(s) . Mg . The percent of Cu2+ present when NiCO3(s) begins to precipitate is: 4.25 M Because less than 1% Cu2+ remains of the initial amount.25 M 307 [CO32−] = For NiCO3(s) to precipitate: [CO32−] = K sp . Ag . 101.0 × 10−9 M CO32− 0.6 × 10−7 M CO32− 0.5 × 10−4 M Cu2+ 5.5 × 10 −4 M × 100 = 0.25 M) must be present before NiCO3(s) begins to precipitate.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA K sp . the metals can be separated through slow addition of Na2CO3(aq). CuCO 3 [CO 3 ] 2− = 2.

C a . Pb . Bi3 + + Na2SO4(aq) or H2SO4(aq) PbSO4(s) Bi3 + H2S(aq) .308 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA b. AgBr(s). Fe 2+ 2+ 2+ NaCl(aq) PbCl2 (s) Ca .make basic Bi2S3(s) . Pb2 .make basic FeS(s) c. Br . F e 2+ 2+ Na2SO 4 (aq) or H 2SO 4(aq) CaSO 4(s) Fe 2+ H2 S(aq) . AgI(s) NH3(aq) AgBr(s) + AgI(s) Na2S2O3 AgI(s) Ag(S2O3)23 (aq) + Ag(NH3)2 (aq) + + Cl (aq) - Br (aq) - d. I - - - AgNO3(aq) AgCl(s). Cl .

010 −0. HgI2(s) + 2 I−(aq) → HgI42−(aq) Soluble complex ion Ag+(aq) + Cl−(aq) ⇌ AgCl(s).78 M KI 0. The order of formation constants is Kf [Ag(S2O3)23−] > Kf [Ag(NH3)2+] because addition of S2O32− causes the AgBr(s) precipitate to dissolve.010) . The order of Ksp values is Ksp (AgCl) > Ksp (AgBr) > Ksp (AgI).78 M 0 −0. 105. we will let the Hg2+ and I− ions present initially react to completion and then solve an equilibrium problem to determine the Hg2+ concentration.0 × 1030 0. 4 ( x)(0.0 × 1030 = = (0.010 Reacts completely (K large) 0 0.040 → +0. white ppt. ⇌ HgI42− K = 1.2 × 105 Hg2+(aq) + 2 I−(aq) → HgI2(s). AgCl(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl−(aq) Ag(NH3)2+(aq) + Br−(aq) ⇌ AgBr(s) + 2 NH3(aq).010 − x [HgI 4 ] [Hg ][I ] 2+ − 4 2− K = 1.010 M 0.3 × 10−32 M . assumptions good. but the presence of NH3 was unable to prevent AgBr(s) from forming.0 × 1030 ≈ (0. 104.0 g KI The formation constant for HgI42− is an extremely large number.010 − x) .500 L 166.74 0. = AgBr(s) AgBr(s) + 2 S2O32−(aq) ⇌ Ag(S2O3)23−(aq) + Br−(aq) Ag(S2O3)23−(aq) + I−(aq) ⇌ AgI(s) + 2 S2O32−(aq). K1 = 7. pale yellow ppt. x = [Hg2+] = 3. 65 g KI 1 mol KI × = 0. orange ppt. making usual assumptions: ( x)(0. The most soluble salt (largest Ksp value) must be AgCl because it forms initially but never re-forms. Hg2+ Before Change After Change Equil.9 × 101 ____________________________________________________________ Mn2+(aq) + 2 C2O42−(aq) ⇌ Mn(C2O4)22−(aq) Kf = K1K2 = 6.. + 4 I− 103. yellow ppt.9 × 103 Mn2+ + C2O42− ⇌ MnC2O4 2− 2MnC2O4 + C2O4 ⇌ Mn(C2O4)2 K2 = 7.74) .74 + 4x 0.74 + 4 x) 4 1. Because of this. = AgI(s) The least soluble salt (smallest Ksp value) must be AgI because it forms in the presence of Cl−and Br−.010 New initial x mol/L HgI42− dissociates to reach equilibrium +x +4x ← −x x 0.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 309 Complex Ion Equilibria 102. This assumes concentrations are about equal.

5 × 10 −5 M .15 M 3− x mol/L Fe(CN)6 dissociates to reach equilibrium +6x ← −x +x x 2.15 − x [Fe(CN ) 6 ] (0.0 + 6x 0. + 2 2 [Ag ][ NH 3 ] x (1.20 M 0 x + 2 NH3 2.20 [AgNH 3 ](1.2 × 103 = ⇌ + Ag(NH3)2+ + K2 = 8. AgNH3+ + NH3 8.15 − x) 0. 0.0 M 1. [Fe(CN)63−] = 0. It is very reasonable to approach the equilibrium in two steps. Ag+ + NH3 ⇌ AgNH3+ K1 = 2. Let the reaction go to completion since K is large.6) 2 assumptions good.20 = ≈ .20 ! x K = 1.0 M 0.20 0. Ag+ Before After Equil. Initial Change Equil. [NH3] = 1.6 M.2 × 103 __________________________________________________ K = K1K2 = 1.6 × 10 −9 M. assumptions good.0) 6 [Fe ][CN ] 3− K = 1 × 1042 = x = [Fe3+] = 2 × 10−45 M.7 × 107 Ag+ + 2 NH3 ⇌ Ag(NH3)2+ The initial concentrations are halved because equal volumes of the two solutions are mixed.7 × 107 = [Ag( NH 3 ) 2 ] 0.0 + 6 x) x(2. 106.090 mol/0. [Ag+] = x = 4.20 − x 0. [Ag(NH3)2+] = 0.6 + 2x + 107.6 × 10 −9 M.6 + 2 x) x (1.15 M.310 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA Note: 3. 1 × 1042 ≈ 6 3+ − 6 ( x)(2.60 L = 0.15 = .2 × 103 0.20 M Use either the K1 or K2 equilibrium expression to calculate [AgNH3+]. The reaction does essentially go to completion. then solve an equilibrium problem. ⇌ Ag(NH3)2+ 0 0. [AgNH3+] = 1.1 × 103 + + AgNH3 + NH3 ⇌ Ag(NH3)2 K2 = 8.15 M − x = 0.6) + [ Ag( NH 3 ) 2 ] [AgNH 3 ][ NH 3 ] = .3 × 10−32 mol/L corresponds to one Hg2+ ion per 5 × 107 L. x = 4.6 1. Fe3+ + 6 CN− ⇌ Fe(CN)63− K = 1 × 1042 0 2.

s = 4. ⇌ Cu(NH3)42+ + 2 OH− K = 1. taking the square root: [ NH 3 ]2 (1.0095 + 2s) 2 = [ NH 3 ]4 (5. APPLICATIONS OF AQUEOUS EQUILIBRIA 311 AgCl(s) ⇌ Ag+ + Cl− Ksp = 1.6 × 10−6 = s (0.0 – 2s −3 K = 2.0 − 2 s In pure water.0 − 4s) 4 2+ If s is small: 1.0 ) 4 Assumptions are not good.0 M 0 0.0 − 4 sguess ) 4 (0.7 × 10 −3 )1/2 = 5.0 M 0 0 s mol/L of AgCl(s) dissolves to reach equilibrium = molar solubility s s 1. We will solve the problem by successive approximations.6 × 10−6 = [Cu ( NH 3 ) 4 ][OH − ]2 s (0. mol/L (5.6 × 10−19 Cu2+ + 4 NH3 ⇌ Cu(NH3)42+ Kf = 1. ⇌ Ag(NH3)2+ + Cl− 1.0 × 1013 ____________________________________________________________________ K = KspKf = 1.6 × 10 −6 (5.7 × 10 −3 AgCl(s) + 2 NH3 ⇌ Ag(NH3)2+(aq) + Cl−(aq) AgCl(s) + 2NH3 Initial Equil.0 − 2s ) 2 + s = (2.3 × 10 −5 mol/L.6 × 10−6 Cu(OH)2(s) + 4 NH3(aq) ⇌ Cu(NH3)42+(aq) + 2 OH−(aq) Cu(OH)2(s) + 4 NH3 Initial b.2 × 10 −2 .6 × 10 −10 )1/2 = 1.6 × 10 −10 Ag+ + 2 NH3 ⇌ Ag(NH3)2+ Kf = 1. Cu(OH)2 ⇌ Cu2+ + 2 OH− Ksp = 1. 109. 5.7 × 10 −2 mol/L 1 . the solubility of AgCl(s) is (1. the results from six trials are: . s = 11.0095 + 2 sguess ) 2 . Notice how the presence of NH3 increases the solubility of AgCl(s) by over a factor of 3500.0 − 4s s 0. scalc = 1.CHAPTER 8 108.6 × 10-6 5.0095 M s mol/L Cu(OH)2 dissolves to reach equilibrium Equil. a.7 × 107 ________________________________________________________________ K = Ksp × Kf = 2.0095 + 2s K = 1.0095) 2 .7 × 10 [Ag( NH 3 ) 2 ][Cl − ] s2 = = .

taking the square root of both sides: (0. s = 1. K= + 2 S2O32− (Carry extra sig.050.500 − 2s ) 2 .056 mol/L in 5.) ⇌ Ag(S2O3)23− + Br− 0 +s s 0. 0.500 − 2s s s2 = 14.5 AgBr(s) Initial Change Equil.1 × 10−3 mol/L b. Cu+ forms the complex ion CuCl2. 0.6 × 10−2. figs.10)s = s 0.9 × 1013 Ag+ + 2 S2O32. 0.10)s = 1.056 1.055.in the presence of Cl-.0 × 10−13 Kf = 2. 0.500 M 0 s mol/L AgBr(s) dissolves to reach equilibrium −s −2s → +s 0.2 × 10−6 Kf = 8. s = 9. a.5.0 × 10−2 − (0. 110.0 M NH3.10 − s (1.10 = [CuCl 2 ] [Cl ] − − K = Ksp × Kf = 0.⇌ Ag(S2O3)23− _____________________________________________________ AgBr(s) + 2 S2O32− ⇌ Ag(S2O3)23− + Br− K = Ksp × Kf = 14.060.058.10 − s = ⇌ s .071.10. K = 0. 0. 1.10 CuCl2− 0 s where s = solubility of CuCl(s) in mol/L + Cl− 0. Initial Equil. CuCl(s) ⇌ Cu+ 0 s + Cl− 0 s s = solubility (mol/L) Ksp = 1.0 × 10−2. CuCl(s) ⇌ Cu+(aq) + Cl−(aq) Ksp = 1.2 × 10−6 = [Cu+][Cl−] = s2.10 M 0. 0.312 sguess: scalc: CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 0. We will consider both the Ksp reaction and the complex ion reaction at the same time.7 × 104 Cu+(aq) + 2 Cl−(aq) ⇌ CuCl2−(aq) ___________________________________________________________________________________________ CuCl(s) + Cl−(aq) ⇌ CuCl2−(aq) CuCl(s) Initial Equil.1 × 10−3 mol/L 111.049.056 Thus the solubility of Cu(OH)2 is 0. 0. AgBr(s) ⇌ Ag+ + Br− Ksp = 5. 0.

0.5 × 10−16 Kf = 1.0 − 2 s) (3.62)s.7 × 107 K = Ksp × Kf = 2. When enough NH3 is added.91 − (7.222 mol/L 0. to form NH4+.5 × 10−16 = s2. Test tube 3: Added H+ reacts with the weak base.0) Assumption good. The equations are Ag(NH3)2+(aq) + 2 H+(aq) → Ag+(aq) + 2 NH4+(aq). AgI(s) Ag+ + 2 NH3 AgI(s) + 2 NH3(aq) AgI(s) Initial Equil.0 M 0 0 s mol/L of AgI(s) dissolves to reach equilibrium = molar solubility 3. The presence of NH3 increases the solubility of AgI. As NH3 is removed from the Ag(NH3)2+ complex ion. s = 0.00 L × 112. Ag(NH3)2+. more AgI(s) will dissolve to replenish the Ag+ concentration.8 g AgBr × = 41. Test tube 2: Added NH3 reacts with Ag+ ions to form a soluble complex ion.0 − 2s s s + [Ag( NH 3 ) 2 ][I − ] s2 s2 = .500 − 2 s 1. Test tube 1: Added Cl− reacts with Ag+ to form a silver chloride precipitate. K= ⇌ ⇌ ⇌ + Ag+ + I− Ag(NH3)2+ Ag(NH3)2+(aq) + I−(aq) Ksp = 1. Ag+ ions are released to solution and can then react with Cl− to re-form AgCl(s). Added NH3 removes Ag+ from solution by forming the complex ion. The equation is AgCl(s) + 2 NH3(aq) → Ag(NH3)2+(aq) + Cl−(aq). all the silver chloride precipitate will dissolve. which causes the AgCl(s) to dissolve.222 mol AgBr 187. c.6 × 10−9 ≈ . Ksp = 1. 2.5 × 10−4 mol/L 2 2 2 [ NH 3 ] (3.2 × 10−8 mol/L b. a.81. As Ag+ is removed.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 313 s = 3. Ag(NH3)2+. and Ag+(aq) + Cl−(aq) → AgCl(s). 113. The net ionic equation is Ag+(aq) + Cl-(aq) → AgCl(s). Ag+ is removed from the solution. NH3. s = 1. s = 1. As this complex ion forms. s = 1.5 × 10−16 Initial s = solubility (mol/L) Equil.7 g AgBr = 42 g AgBr L mol AgBr AgI(s) ⇌ Ag+(aq) + 0 s I−(aq) 0 s Ksp = [Ag+][I−] = 1.6 × 10−9 + I− 2 NH3 ⇌ Ag(NH3)2+ 3. .

no precipitate forms. At this pH a buffer will have equal neutralization capacity for both added acid and base.0 × 107 = x = [Cd2+] = 1. Ka = Kw/Kb = 8. We will first calculate the equilibrium Cd2+ concentration using the complex ion equilibrium.0 − y 5 . Q: Q = [Cd2+][OH−]2 = (1.0 + 4x 0.4 × 10−17 < Ksp (5.0010 − x (0. a. and then determine if this Cd2+ concentration is large enough to cause precipitation of Cd(OH)2(s).9 × 10−15). 115. the optimal buffer pH is about 8. assumptions good.010 − x) (0. therefore.0 mL × 1.6 × 10−13 M.0 good.19 × 10−6.40 × 10−9) = 8.314 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA Additional Exercises 114. This is the maximum [Cd2+] possible. We now calculate the value of the solubility quotient. In 5.0 × 10−3 New initial x mol/L Cd(NH3)42+ dissociates to reach equilibrium +x +4x ← −x x 5.0 + 4 x) ( x)(5. The optimum pH for a buffer is when pH = pKa.010) ≈ 4 ( x)(5.0 × 107 1. Now we will determine if Cd(OH)2(s) forms at this concentration of Cd2+.0 1.0 × 10−3 −4.1. y = [OH−] = 9.1.8 × 10−5 = + ⇌ NH4+ + OH− 0 y ~0 y Kb = 1.996 ≈ 5.5 × 10−3)2 Q = 1.0) 4 Kf = 1.076 . assumptions = [ NH 3 ] 5.0 M Equil.0 M NH3 we can calculate the pH: NH3 + H2O Initial 5.40 × 10−9. As shown next. + 4 NH3 ⇌ Cd(NH3)42+ Kf = 1.6 × 10−13)(9.0 × 10−3 M 5.0 mmol Cd2+ added to the ammonia solution mL Thus [Cd2+]0 = 1. 1. pKa = −log(8. because the pKa for TRISH+ is 8.0 M 0 −1.8 × 10−5 y2 y2 [ NH 4 ][OH − ] ≈ . 5.0 − y Kb = 1.0 × 10−3 mol/L. Kb = 1.0 × 10−3 Reacts completely 0 4.5 × 10−3 M.0 × 10−3 → +1. Cd2+ Before Change After Change Equil.0 mmol = 1.

083 (at pH = 7.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA [TRIS] [TRIS] .08 + (0.60 g pH = pKa + log [TRIS] (0. ⎛ 0.0 × 10−3 mol H+ The H+ from HCl will convert TRIS into TRISH+. there are no examples of this type of salt in Table 8.030 0.0 × 10 −3 = 0.21 M = [TRIS] 2.21) [TRISH ] The amount of H+ added from HCl is: (0. 50. and Ag2SO4.24 ⎠ 116. This is the result when you have a salt that breaks up into three ions. Some examples are SrF2. either two cations and one anion or one cation and two anions. ii.5).0 g TRISHCl 1 mol × = 0.076 + log = 8.24 Reacts completely 6.5). either three cations and one anion (Ag3PO4) or one cation and three anions (ignoring the hydroxides.00 = 8. SrSO4.92 = 8.14 g 65. iii. Examples of these salts (but not all) include AgCl.030 M 0.0 L 121.21) = 8.076 + log ⎜ ⎟ = 7.21 M −0.3 (at pH = 9. pH = pKa + log [TRIS] = 10-1.50 × 10−3 L) × 12 mol/L = 6. The reaction is: TRIS Before Change After 0.030 0.076 + log + [TRISH ] [TRISH + ] 315 b.18 ⎞ pH = 8.030 → 0 Now use the Henderson-Hasselbalch equation to solve this buffer problem.206 M = 0.076 + log [TRIS] [TRIS] . = 100.0 L 157. i. This is the result when you have a salt that breaks up into two ions.2005 −0.00 = 8. This is the result when you have a salt that breaks up into five ions.21 M = [TRISHCl] = [TRISH+] 2 . 7. and ZnCO3.08 = 0. iv.00) + [TRISH ] 9.206 M = 0.0 g TRIS 1 mol × = 0. BaCrO4. .21 M +0.18 + H+ → TRISH+ 0.95 ⎝ 0.00) + [TRISH ] [TRISH + ] c. Hg2I2. This is the result when you have a salt that breaks up into four ions. either three cations and two anions [Sr3(PO4)2] or two cations and three anions (no examples of this type of salt are in Table 8.

0 buffers.080 + x + OH− 0 x Kw 1. Bz− Initial 0.0.37. pH = 4.316 117. assumptions good. 0. This mixture would yield a buffer consisting of HOCl (pKa = 7.46) and OCl−.080 + x)( x) (0. NH4C2H3O2 is commercially available. NH4+ is a weak acid (Ka = 5. d.19 + log = 4. these solutions have about equal concentrations of weak acid and conjugate base. HOCl and NaOH: This is the best choice to produce a conjugate acid-base pair with pH = 7.4 × 10−5) = 4. A mixture of the two will give a buffer at pH = 7. pH = 4.63.). CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA A best buffer is when pH ≈ pKa.080)( x) = ≈ = −5 Ka (0. Benzoic acid + NaOH will yield a buffer consisting of benzoic acid (pKa = 4.120 M and [HBz] will decrease to 0. and C2H3O2− is a weak base (Kb = 5.080 M 0. c. Therefore. fig.120 − x Kb = (0.0 buffer is an equimolar mixture of ammonium chloride and sodium acetate. 118.34 × 10−10 M (carrying extra sig. Potassium fluoride + HCl will yield a buffer consisting of HF (pKa = 3.120 M Equil.37 .080) [HBz] + H2O ⇌ HBz 0.19) and benzoate anion. assumptions good.0 buffer since acetic acid has a pKa value closest to 5. pH = pKa + log c.0.0 × 10 −14 (0.6 × 10−10). Actually. and its solutions are used for pH = 7. choose combinations that yield a buffer where pH ≈ pKa. [Bz−] will increase to 0. Sodium acetate + acetic acid (pKa = 4. the best choice for a pH = 7.74) is the best choice for pH = 5. that is.120 − x) 0.0 because the weak acid and weak base are the same strengths (Ka for NH4+ = Kb for C2H3O2−).120) [Bz − ] . Ammonium chloride + NaOH will yield a buffer consisting of NH4+ (pKa = 9. pOH = 9. The Henderson-Hasselbalch equation is derived from the Ka dissociation reaction.19 since [HBz] = [Bz-].120 6. where HBz = C6H5CO2H and [Bz-] = C6H5CO2−.4 × 10 x = [OH−] = 2. b.26) and NH3. b. a. a.080 M after OH− reacts completely with HBz.6 × 10−10). pH = pKa = −log(6. e. look for acids whose pKa is closest to the pH. (0.14) and F−.

We get the same answer. The equivalence point will be at pH = 7. mL 0 4. 8. Bromthymol blue would be the best indicator since it changes color at pH ≈ 7 (from base color to acid color). As can be seen from the plot.073 0.20 0. The results are summarized and plotted below. See Fig. P2− is the major species.22 mmol NaOH mL mmol HCl NaOH reacted with aspirin = 25.0 30. a strong base is titrated by a strong acid.3 11.46 5.18 0.0 12.0 24.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 317 d. so all constants are interrelated.53 3.28 10.5 20. benzoic acid and benzoate anion.5 24.96 |ΔpH/ΔmL| − 0.500 mmol = 25.14 3.23 0.5% 1.7 2 20 20 1 0.29 11.9 25. Kb is related to Ka by Kw and [OH−] is related to [H+] by Kw.427 g Here. NaOH added = 50. P2− is a weak base in water because it is the conjugate base of a weak acid.0.0 mL NaOH added: 2. . pH 2.0 mmol NaOH mL NaOH left unreacted = 31.8 mmol NaOH × Purity = 1 mmol aspirin 180.86 4.098 0.75 11.24 5. 120.22 = 15.3 8.0 121.42 g aspirin 2 mmol NaOH mmol 1.0 24. Both equilibria must hold true.14 ΔpH = = 0.6 6.8 mmol NaOH 15.8 of the text.0 25. At 4.1 26.0 − 9.0 mL × 0.43 − 3.92 mL HCl × 0.18 ΔmL 0 − 4 .289 mmol 1 mmol NaOH × = 9.0 8.0 The other points are calculated in a similar fashion. 119.2 mg × = 1420 mg = 1.11 At the equivalence point.0 28. the advantage of this approach is that it is much easier to accurately determine the location of the equivalence point.43 3.080 0. Both equilibria involve the two major species.42 g × 100 = 99.

024 P 2− 10 −5. Initial Equil.0 × 10 −14 .0 × 10−6 (0.049 + x 0.1 L 204.10 (Buffered solution) 1.1. a.) 0 .0 × 10−7 + 2s s = solubility (mol/L) Ksp = 1.0010 M 0.318 P2− Initial Equil.0010 −0. Kb = CHAPTER 8 + H2O APPLICATIONS OF AQUEOUS EQUILIBRIA ⇌ HP− 0 x + OH− ~0 x (carry extra sig. s 0.8 × 10−6 M.2 × 10−13 M .10 M pH = 13. fig. x = [Cr3+] = 2.0010 − x) (1.10)2. assumptions good.049 0.2 g 0.0010 1. x(0.2 H 10−9 = ≈ = w = Ka 0.050 M 0 1.0 × 10−6 M −0.0 × 10−7 + 2s)2 ≈ s(2s2) = 4s3 s = [Pb2+] = 6. s = [Pb2+] = 1. Phenolphthalein would be the best indicator for this titration because it changes color at pH ≈ 9 (from acid color to base color).10 M s mol/L Pb(OH)2(s) dissolves to reach equilibrium Equil.5 g 1 mol × = 0. 122. [OH−] = 0. b. assumptions good.0 × 1023 ≈ 123.024 − x K x2 x2 [HP − ][OH − ] 1. 3. assumption is good by the 5% rule.9.2 × 10−15 = [Pb2+][OH−]2 = s(1.7 × 10−6 M.049) Pb(OH)2(s) ⇌ Pb2+ 0 s + 2 OH− 1.0 × 10 −6 ) 2 [CrEDTA − ][H + ] 2 = (x)(0.024 − x 0.51 x = [OH−] = 8. pOH = 5. (0.0 × 10−7 M from water 1.0010 No change 0 0.0010) (1.2 × 10−15 = (s)(0.0 × 10 −12 ) .0 × 10−6 x mol/L CrEDTA− dissociates to reach equilibrium +x +x ← −x − x 0.00.049 + x) [Cr 3+ ][H 2 EDTA 2− ] (Buffer) Kf = 1. Cr3+ + H2EDTA2− ⇌ CrEDTA− + 2 H+ (Buffer) Reacts completely New initial 0.0 × 10−37 M. Initial Pb(OH)2(s) ⇌ Pb2+ + 2 OH− 0 0.0 × 1023 = 1.0010 − x 1.0010 → +0. pH = 8. Before Change After Change Equil.024 M 0.

s = 0. Ksp = 5.040) 1. pH = 12.2 × 10 −4 Ksp = 3.85.010 New initial x mol/L PbEDTA2− dissociates to reach equilibrium x 0.11 mol/L.07. Pb2+ Before Change After Equil. pH = 12.9 × 10 −3 ) = 1.3 × 10−19)(0.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 319 c.040 0.010 ≈ . 124.10 M since we have a solution buffered at pH = 13.043 mol/L.93 Ca(OH)2(s) Equil.043) = 0.040 + x) x(0.15 . + EDTA4− ⇌ PbEDTA2− K = 1. The concentration of OH− is 0.010 mol/L Pb2+ reacts completely (large K) −0. assumptions good.9 × 10 −3 mol/L. ( x)(0. pOH = 0.11) = 0.010 M 0.34 Sr(OH)2(s) Equil.3 × 10−19 M. Since K is large for the formation of PbEDTA2−.4 × 10 −2 mol/L. pOH = 1. assumption good. ⇌ Ca2+(aq) + 2 OH−(aq) s 2s Ksp = [Ca2+][OH−]2 = 1.010 − x) 0.010 −0. and then solve an equilibrium problem to get the Pb2+ concentration.3 × 10−21 < Ksp (1. Q = [Pb2+]0[OH−]02 = (2.050 M 0 0. pOH = 1.00. assumption good.2 × 10−15) Pb(OH)2(s) will not form since Q is less than Ksp. asssumption good.1 × 1018 0. s = 6. ⇌ Sr2+(aq) + 2 OH−(aq) s 2s Ksp = [Sr2+][OH−]2 = 3. pH = 13. let the reaction go to completion. We need to calculate the Pb2+ concentration in equilibrium with EDTA4-. [OH−] = 2s = 2(0.3 × 10 −6 = 4s3. [OH−] = 2(6.086 M.22 mol/L.10)2 = 2.3 × 10 −6 Ksp = 1. Ba(OH)2(s) ⇌ Ba2+(aq) + 2 OH−(aq) Ksp = [Ba2+][OH−]2 = 5.1 × 1018 = Now calculate the solubility quotient for Pb(OH)2 to see if precipitation occurs.040 + x 0.010 Reacts completely 0 0.010 → +0.66. [OH−] = 2(0.0 × 10 −3 = s(2s)2 = 4s3. x = [Pb2+] = 2.0 × 10 −3 0 s ~0 2s Initial s = solubility (mol/L) Equil. s = 0.2 × 10 −4 = 4s3.010 − x (0.

mmol HCl Amount of HCl that reacts with NaOH = 1.0 mL × 0.68 = 2.267 Kb 1.1 × 10 −3 mmol final mmol H + 100. (2.00 mmol NaOH initially At pH = 10. 5. − (1.1 × 10−3 M Beginning mmol HCl = 500. Ka = 0.400 × VNH3 mol NH 4 = = 0.3 mmol HC2H3O2 Need 6.267 M total volume 1. − 0. 50. C0 = 0.8 × 10−5 = [H + ][C 2 H 3O 2 ] [ H + ]2 = [ HC 2 H 3O 2 ] C 0 − [H + ] − [H+] = 10−2.36 × 103 mL = 4.400 mol/L × VNH3 = mol NH3 = mol NH4+ after reaction with HCl at the equivalence point.36 L = 4. pOH = 3.4 L NaOH 127.50 = 3.0 mL × 0.50 × 10−2)V. [OH−] = 10−3.50 × VNH3 ⇌ H+ 0 x + NH3 0 x Kw x2 x2 1.0150 V = = mL total volume 500.6 V = 4. 0. CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA HC2H3O2 ⇌ H+ + C2H3O2−.1 × 10 −3 ) 2 .2 × 10−4 mmol/mL × 73. 1.267 − x 0.0 mL × 0.100 M = 5.25 mmol/mL = 6.2 × 10−4 M mmol OH− remaining = 3. assumptions good.8 × 10−5 = ( 2.2 × 10−5 M.200 mmol/mL = 100.3 mmol KOH = VKOH × 0. pH = 4.92.320 125.6 × 10−10 = 0.0975 mmol/mL.50.267 M 0.0 + V 3.1 × 10−3)V = 100.0 × 10 −14 ≈ = . let C0 = initial concentration of HC2H3O2 From normal weak acid setup: Ka = 1.50 × 10−2 mmol/mL × V 7. At the equivalence point: [NH4+]0 = NH4+ Initial Equil.1 × 10−3 M.8 × 10 −5 x = [H+] = 1. − 3. VKOH = 65 mL 126.25 M C 0 − ( 2. 128.6 + (7.50. In the final solution: [H+] = 10−2.15 = 7.75 mL = 2.21 × 10−2)V = 100.4 × 10−2 mmol .1 × 10 −3 ) 25.267 − x + 0.

130.0 × 10−3 M 0 x + 3 X− ⇌ CuX32− K = K1K2K3 = 1. we have 13. 23. K= 1. equal milliliters of HA and A− are present.00)3 x(5.985 mmol Reacts completely 6.00 5.48 = 3.0 × 10 −3 − x) .0 × 10−3 M since equal volumes of each reagent are mixed.00 − 3(10−3) = 5.024 = 4.44 mL × A− Before Change After 13. Ka = 10−3. where pH = pKa (assuming HA is a weak acid).0 × 10−3 1.985 mmol −6. assume that the reaction goes completely to CuX32−.0.985 → 0 We have back titrated this solution to the halfway point to equivalence.98 mmol = 0. 4. x = [Cu+] = 8.98 mmol HA.97 mmol −6.produced from the neutralization reaction. then pH = pKa = 3.0 × 10−3 (1.97 × 10 −3 mol HA To determine the Ka value.00 M and [Cu+]0 = 1.98 mmol Because the weak acid is monoprotic. [X−]0 = 5.985 6. then solve an equilibrium problem. Cu+ Before After Equil. x(5.00 .36 mL OH− × Molar mass of HA = 0.5106 mmol OH − 1 mmol HA × = 13. [HA]0 = 129. 1.985 mmol H+ mL H+ → HA 0 +6. where HA = acetylsalicylic acid mmol HA present = 27. g/mol 13.0 × 109 ≈ . which only occurs at the halfway point to equivalence.0 × 109 5.97 mmol HA mL OH − mmol OH − 2. A− will react completely with the added H+ and re-form acetylsalicylic acid HA.97 mmol of A. mmol H+ added = 15.0 × 10−3 − x assumptions good. Because the K values are large.75 mL of the weak acid solution contains 4.4524 mmol H + = 6.0 × 10−15 M.985 6. This is true because after H+ reacts completely.00 + 3 x) 3 .48.210 M 23.3 × 10−4. After complete neutralization of acetylsalicylic acid by OH−.51 g HA = 180. Assuming acetylsalicylic acid is a weak acid. 1.00 M 5.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 321 mmol OH− that reacted = 5. use the pH data.985 mmol + 0.75 mL HA + OH− → A− + H2O.00 + 3x 0 1.

00-mL volume corresponded to the titration of adipic acid. (answer a) (answer b) (answer c) K a 3 is so small (4.8 × 10−13) that a break is not seen at the third stoichiometric point.95 + 0.0 mL Note: Because the buffer components are in the same volume of solution.0 × 10−3 − 8. giving us only one break.3 × 10−5) + log = 4. The stoichiometric points will occur when 1 mol of H+ is added per mole of salicylic acid present and when 2 mol of H+ is added per mole of adipic acid present. Challenge Problems 133.95 pH = pKa + log 33.89 + log = −log(1. and the added OH− will convert HC3H5O2 into C3H5O2−.8 mmol HC3H5O2 mL 0. Thus the 25.8 mmol [HC3 H 5 O 2 ] 33. For adipic acid the Ka values are fairly close to each other.0 × 10−3 M [CuX2−] = 2.8 100.700 mmol = 38.0 × 10−3 M K3 = [CuX3 ] [CuX2 ][X ] − − 2− . the pH will increase. mmol HC3H5O2 present initially = 45.0 × 10−15 M 131.00) − . When NaOH is added. so the resulting pH is: 4.322 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA [CuX32−] = 1. The pH after addition of OH− increases by 2.750 mmol = 33. we can use the mole (or millimole) ratio in the Henderson-Hasselbalch equation to solve for pH instead of using the concentration ratio of [C3H5O2−]/[HC3H5O2]. The total volume always cancels for buffer solutions.0 × 103 = (1.0 × 10−15 = 1.5 100.07 .0 × 10−3 ) [CuX2 ](5.0 mL × 0.0 × 10−7 M [Cu2+] = 8.0 mL = 4.5 mmol C3H5O2− mL mmol C3H5O2− present initially = 55. and the 50.025(4. [CuX2−] = 2. 132.0 × 10−7 M Summarizing: [CuX32−] = 1.00-mL volume corresponded to the titration of salicylic acid.5%. We will see only the first stoichiometric point in the titration of salicylic acid because K a 2 is so small.95) = 5. 1. Both protons will be titrated almost simultaneously.5 mmol − [C 3 H 5 O 2 ] 38.0 mL × The initial pH of the buffer is: 38.

a buffer solution still exists.07. and the millimole ratio between C3H5O2− and HC3H5O2 is: pH = pKa + log mmol C3 H 5 O 2 mmol C3 H 5 O 2 . The K a 2 reaction for H3PO4 is: H2PO4− ⇌ HPO42− + H+ The pH of the final solution will equal 7. so we assume the reactions go to completion.0 mmol CN−.9 mmol OH− added mmol HC3 H 5 O 2 33.89 + log mmol HC3 H 5 O 2 mmol HC3 H 5 O 2 − − − mmol C3 H 5 O 2 = 100.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 323 At this pH. Let’s see what is in solution after we let the best acid and best base react. Major species: PO43−.5 + x = 1. H2O PO43− and CN− are weak bases. something strong is reacting.21].9 mmol NaOH × 1 mL = 49 mL 0. 5. H+.10 M NaOH must be added to increase the pH by 2. the setup to the problem using millimoles is: HC3H5O2 Before Change After 33. Cl−.00 mmol 5. x = 4. 5. In each of the following reactions. Because OH− will essentially react to completion with HC3H5O2. Na+.00 mmol 15.5(33.5 = . .18 = 1. 1.8 mmol −x 33.8 − x) = 38.8 − x The volume of NaOH necessary to raise the pH by 2.21 when we have a buffer solution with [H2PO4− ] = [HPO42−].5 + x mmol C3 H 5 O 2 38.5 + x.50 mmol K+.5%.5 mmol HC3 H 5 O 2 Let x = mmol OH− added to increase pH to 5.07 = 4. 7.8 − x − + OH− x mmol −x 0 → → C3H5O2− 38.2 × 10−8) = 7. The first reaction to run to completion is H+ + OH− → H2O.6 × 10−5 One of the keys to this problem is to recognize that pK a 2 for H3PO4 = 7. PO43− + H2O CN− + H2O ⇌ ⇌ HPO42− + OH− HCN + OH− Kb = Kw/ K a 3 = 2. OH−. 134.1 × 10−2 Kb = Kw/Ka = 1.5 mmol +x Reacts completely 38.21 [−log(6.5% is: 4.10 mmol NaOH 49 mL of 0.

21.0 mmol After 5. we would need to add another 2.5 mmol → → HCN 5.0 mmol After 10.0 mmol After 2.00 mmol The next best base present is CN−. with Ka = 6.0 mmol + CHAPTER 8 OH− 5.5 mmol HCN (a very weak acid with Ka = 6. H+ Before 5. we are left with [HPO42−] = [H2PO4−] so that pH = pK a 2 = 7. is too weak of an acid to interfere with the H2PO4−/ HPO42− buffer. HX .324 H+ Before 15.5 mmol After 0 + + CN− 2.2 × 10−10).0 mmol We need to add 2.5 mmol 0 HPO42− 5.0 mmol After 0 + CN− 7.5 mmol After 5.5 mmol H+ in order to convert one-half the HPO42− present into its conjugate acid so that [HPO42−] = [H2PO4−] and pH = pK a 2 = 7. H+ Before 10. Volume HNO3 = 5.5 mmol H+ Before 2.5 mmol H+ to convert all the CN− into HCN.0 mmol + PO43− 5.50 mmol 2.00 mmol HPO42− and 7. 1 mL = 50. From here.100 mmol HNO3 a. so the dominate equilibrium is: NH4+ + X− ⇌ NH3 + HX Keq = [ NH3 ][HX] [ NH4 ][X − ] + = K a . Note that HCN.0 mmol H+ (HNO3) is added to the original mixture.21.0 mmol H+ to the original solution: H+ Before 5.00 mmol 0 → HPO42− 0 5. Best acid will react with the best base present.5 mmol → HCN 0 5. NH + 4 K a . mL HNO3 0. then all that remains is 5.0 mmol 7.5 mmol H2PO4− 0 2.00 mmol 0 APPLICATIONS OF AQUEOUS EQUILIBRIA → H2O The next best base present is PO43−.00 mmol 2.0 mmol HNO3 × 135. Adding 5.2 × 10−10.

8 × 10−5. Ammonium formate = NH4(HCO2) K a .37 pH = 9. pKa = 3. HX . HX = [HX]2 [X − ]2 [H + ] [H + ][X − ] [HX] = . NH + + pK a . HC 2 H 3O 2 = 1.8 × 10−4. pKa = 6.74 pH = 9.00 2 Ammonium bicarbonate = NH4(HCO3). NH4+(aq) + OH−(aq) → NH3(aq) + H2O(l). NH + 4 The Ka expression for HX is: K a . K a . or taking the −log of both sides: pH = pK a . HX = Substituting into the Keq expression: Keq = Rearranging: [H+]2 = K a .25. K a . HCO2 H 2 = 9. HSO4− is the best acid.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 325 Because initially [NH4+]0 = [X−]0 and [NH3]0 = [HX]0 = 0. HX [HX] [X − ] K a .25 + 6. HX [X ] ⎝ ⎞ ⎟ ⎟ ⎠ 2 4 + × K a .25 + 4.74 = 7. pKa = 9. at equilibrium [NH4+] = [X−] and [NH3] = [HX]. HX 4 2 b. Therefore: Keq = K a .37 = 7. a. and H2O. with H2O as the best base. NH 4 + = 1. K a . H 2 CO3 = 4. C2H3O2−(aq) + H+(aq) → HC2H3O2(aq) 136.6 × 10−10. NH + 4 K a . NH K a . HSO4−.74 = 6. . H2C6H6O6.0 × 10 −14 1.8 × 10 −5 = 5. K a . Major species: H+.50 2 Ammonium acetate = NH4(C2H3O2).74 pH = pK a . pKa = 4.25 + 3. HX [HX]2 ⎛ [H + ] = − 2 =⎜ ⎜ K a . HCO 2 H = 1. NH4 + + pK a .3 × 10−7.81 2 c.

mmol React OH− to completion.6 × 10−3 (0.5 × 10−3 M. and the best base remaining is SO42−. H+ Before 5. H 2SO 4 SO42− 5. mmol 10.9 × 10−5 = [H + ][HC6 H 6O6 ] [H + ] (0.050 − x) x = 8.050 − x APPLICATIONS OF AQUEOUS EQUILIBRIA + SO42− 0 +x x ⇌ H+ 0.0037) − [H+] = 2. H2C6H6O6 + Initial 20.050 + x)( x) = 1. [H+] = 0./200. pH = 2. ⇌ HC6H6O6− + HSO4− 0 +x x 0 +x x x2 = 6. Use either K a1 for H2C6H6O6 or K a 2 for H2SO4 to calculate [H+]. Na+. React the best base with the best acid. we must use the quadratic equation.10 − x)(0. H 2 C 6 H 6 O 6 K a 2 . 7.0037) = [H 2 C6 H 6 O 6 ] (0.23 b.6 × 10−3.2 × 10−2.10 – x K= K a1 . React these two together.326 CHAPTER 8 HSO4− Initial Change Equil.0 mmol HSO4−.050 M −x 0. pH = 1.025 – x = 6. OH−. 0. mL –x 0.1 × 10−3 M.0 mmol H2C6H6O6. x = 3.050 M +x 0. 0.025 − x) Using the quadratic equation. H2O 20.68 .050 + (8. Change –x Equil. 5. For example.0 mmol/200.0 After 0 + OH− → H2O 10. (0.5 × 10−3) = 5. the best acid remaining is H2C6H6O6. Major species: H+. 5.10 − 0.85 × 10−2 M.0 mmol After we have let OH− react to completion.7 × 10−3 M.050 + x (0. 5 – – HSO4− + OH− → H2O + SO42− Before 5.0 After 0 5 0 – – 0 5.

Major species: H+. React the best acid with the best base. 5. HSO4−.0 mmol 5. Na+. H2O. H+ + OH− → H2O Before 5.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA H2C6H6O6. H2O – – + SO42− 0 5. 0 ⇌ After we let all of the OH− react completely. H2C6H6O6 + OH− Before 20. After 0 20. mmol SO42−.0 mmol 20. React the best acid with the best base. Na+ 5. 20. H+ + OH− → Before 5. Na+.95 2 OH−. OH−. mmol 327 c.0 mmol 5. mmol 30. 5.0 mmol React OH− to completion first. – – HSO4− + OH− → Before 5.0 After 0 50. . HSO4−. 45 45 40. Dominant reaction: HC6H6O6− + HC6H6O6− pH = ⇌ H2C6H6O6 + C6H6O62− pK a 1 + pK a 2 2 = 4.0 mmol HC6H6O6− is the best acid as well as the best base present (amphoteric species).0 After 0 25 20. – – 0 20. mmol d. 25 – – H2O + SO42− – – 0 5.0 After 0 Before 5. the major species are: HC6H6O6−.10 + 11.0 HC6H6O6− + H2O 0 20. 0 40. H2O 50. mmol React OH− first to completion.0 – – HSO4− + OH− → H2O H2C6H6O6 + OH− → H2O + HC6H6O6− Before After 20. 20. H2C6H6O6.80 = 7. Major species: H+.0 After 0 30. H2O 20.

33 M Let y mol/L of Cu(CN)32− react to reach equilibrium. Now solve the back equilibrium problem. a.033 − x Kw x2 = 6. assume that enough CuBr(s) dissolves to completely use up the 1.0 M 0 0 x mol/L of CuBr(s) dissolves to react completely with 1. Kb = + H2O ⇌ HC6H6O6− 0 +x x + OH− 0 +x x 20.6 × 10−3 M. mmol/600. y = 1.33 − y ) 2 (0.328 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA HC6H6O6− + OH− → C6H6O62− + H2O Before After 20.33) 2 ≈ .0 M CN−. then solve the back equilibrium problem to determine the equilibrium concentrations. mmol After all the OH− reacts completely.33 − y 0.0 × 106 = .33 mol/L.08 137.0 M CN− −x −3x → +x +x 0 1. ⇌ Cu(CN)32− + Br− 0 0. assumptions good. so we can ignore it).3 × 10−3 = 0.0 × 10−5 Kf = 1. CuBr(s) + 3 CN− Before Change After ⇌ Cu(CN)32− + Br− x 1.033 − x Ka 2 Using the quadratic equation: x = [OH−] = 1.0 − 3x x x For reaction to go to completion. we have a solution of the weak base C6H6O62− (SO42− is a much weaker base than C6H6O62−.0 × 1011 Cu+ + 3 CN− ⇌ Cu(CN)32− ________________________________________________ CuBr(s) + 3 CN ⇌ Cu(CN)32− + Br− K = 1. CuBr(s) + 3 CN− Initial Change Equil. 1. 0 0 20. 0 20. pH = 12. mL −x 0.0 − 3x = 0 and x = 0. pOH = 1.0 × 106 Because K is large. CuBr(s) ⇌ Cu+ + Br− Ksp = 1. (3y) 3 27 y 3 K = 1.92.33 − y (0. +3y ← −y −y 3y 0. C6H6O62− Initial Change Equil.33 M 0. Solving the weak base problem.2 × 10−2 M.

only 3(1. [HSO4−]0 = [H+]0 = 0.2 × 10−2) × (6.0 M CN−.10 M −0.33 mol/L. Only 1. This amount.10 0. [Br−] = 0.6 × 10−3) = 4. the reaction essentially goes to completion. 0. this will produce 0. Indeed. assumptions good.20 − x 0.20 + 1.33 − 1. x = 1. Ba2+ will react with the SO42− produced from Ka reaction for HSO4−.20 M −x 0.20 +x 0.0 M NaCN.10 mol BaSO4(s) is produced. and H2O. 0.3 × 10−7 mol of this dissolves to reach equilibrium.20 M From the initial reaction essentially going to completion.10 mol BaSO4 × 139.10 0. Ba2+.8 × 10−3 M is present at equilibrium.3 × 10−7 = 0.20 − x New initial K = 8.10 mol HSO4−/L) = 0. Major species: H+.20 + x) x 0.70 [Ba2+] = 0. is the solubility of CuBr(s) in 1. Because H2SO4 is a strong acid.33 − y = 0. enough CuBr(s) did dissolve to essentially remove the initial 1. 1.10 M.0 × 106 = 0.20 − 1.10 mol HSO4− reacted. HSO4− Ba2+ + BaSO4(s) K = 1/Ksp = 1/(1. [CN−] = 3y = 3(1. pH = 0.20 ≈ . b. a.8 × 10−3 M 138. s 2s [Sr2+][F−]2 = Ksp = 7.3 × 10−7 = 0. 0. so 0. HSO4−.3 × 10−7 M.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 329 Of the initial 1.10 mol BaSO4(s). (0. s = 5. Initial SrF2(s) 233.5 × 10−9) = 6.20 M.8 × 10−4 mol/L in pure water .9 × 10−10 = 4s3.10 → 0 +x ← x 0.20( x) [H+] = 0.20 + x ⇌ 2− SO4 ⇌ H+ + SO42− K a 2 = 1. NO3−.0 L(0.4 g BaSO 4 = 23 g BaSO4 produced mol ⇌ Sr2+(aq) + 2 F−(aq) 0 0 s mol/L SrF2 dissolves to reach equilibrium Equil.6 × 10−3) = 4.7 × 108 _________________________________________________________________ Ba2+ + HSO4− ⇌ H+ + BaSO4(s) Koverall = (1.2 × 10−2 ⇌ H+ + BaSO4(s) 0.7 × 108) = 8. Ba2+ + HSO4− Before Change After Change Equil.33 M c.6 × 10−3 = 0.0 × 106 Because Koverall is so large.30 M −0.0 M CN−.10 M +0.

[H2S] = 0.00 buffer) [HF] [HF] [F − ] . forcing more SrF2 to dissolve. Solving: [HF] [Sr2+] = s.10) = = 1 × 10 −21 M [ H + ]2 (1 × 10 −3 ) 2 ⇌ Ni2+(aq) + S2−(aq) Ksp = 3. SrF2(s) ⇌ Sr2+ + 2 F− Ksp = 7.4 × 10−11 K a .0 × 10-7 H2S ⇌ H+ + HS− HS− ⇌ H+ + S2K a 2 = 1 × 10 −19 _________________________________________ [H + ] 2 [S 2 − ] H2S ⇌ 2 H+ + S2− K = K a1 × K a 2 = 1 × 10 −26 = [H 2 S] Because K is very small. [F−] = 2s/15 Ksp = 7. 2s = 15[F−].0 × 10 −21 Precipitation of NiS will occur when Q > Ksp.9 × 10 140.9 × 10−10 = [Sr2+][F−]2 Let s = solubility = [Sr2+].2 × 10−2 = [H + ][F − ] 1.0 × 10 −21 . some of the F− is converted into HF. Since F− is a weak base. We will calculate [Ni2+] for Q = Ksp. Therefore: total F− concentration = 2s = [F−] + [HF] HF ⇌ H+ + F− Ka = 7. because some of the F− would react with water: F− + H2O ⇌ HF + OH− Kb = Kw = 1. s = 3. Greater. c. [Ni2+] = 3.2 × 10−4 = 7. Q = Ksp = [Ni2+][S2−] = 3.0 × 10 −21 = 3M 1 × 10 − 21 .00 solution ⎝ 15 ⎠ 2+ − 2 2 Ksp = [Ni2+][S2−] = 3 × 10 −21 K a1 = 1. [HF] = 14[F−]. only a tiny fraction of the H2S will react. 2s = [F−] + [HF] = [F−] + 14[F−]. −10 ⎛ 2s ⎞ = [Sr ][F ] = (s) ⎜ ⎟ . [S2−] = NiS(s) K[H 2S] (1 × 10 −26 )(0. HF This lowers the concentration of F−. then 2s = total F− concentration.0 × 10 −2 [F − ] = (since pH = 2.10 M and [H+] = 1 × 10 −3 .5 × 10−3 mol/L in pH = 2.330 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA b. At equilibrium.

40 −1.0 × 10−6 4.0 [H + ]3 (2 × 10 −32 ) 40.0 7.0 5.2 × 10−7 4.0 10.0 × 10−2 4.0 × 10 −14 ) 4.40 −4. Kw = 1. Solubility in pure water: CaC2O4(s) ⇌ Ca2+ + C2O42− 0 s 0 s Ksp = 2 × 10−9 Initial s = solubility (mol/L) Equil.0 11. because [OH−]3 = (Kw/[H+])3 − Kw KK w [Al(OH) 4 ] = K.0 × 10 −13 + = [H+]3(2 × 1010) + (1.0 −1.0 × 10−14. K = 40. Ksp = s2 = 2 × 10−9.40 As expected.47 × 10−5 = 4 × 10−5 mol/L Solubility in 1.0 9. [OH−] = . [Al(OH)4−] = K[OH−] = + − [H ] [H + ] [OH ] S = [Al3+] + [Al(OH)4−] = [H+]3Ksp/Kw3 + KKw/[H+] b. Ksp = 2 × 10−32. Al(OH)3(s) ⇌ Al3+ + 3 OH−.7 −4.0 × 10−5 4.0 12. the solubility of Al(OH)3(s) is increased by very acidic solutions and by very basic solutions.0 6. mol/L) 2 × 10−2 2 × 10−5 4.0 (1.CHAPTER 8 141.0 8.0 × 10−4 4. APPLICATIONS OF AQUEOUS EQUILIBRIA 331 a.40 −2.40 −3.⇌ Al(OH)4− S = solubility = total Al3+ concentration = [Al3+] + [Al(OH)4−] [Al3+] = K sp [OH ] − 3 = Ksp × [H + ]3 Kw 3 .0 × 10−1 log S S= _________________________________________________ pH 4. s = solubility = 4.0 × 10 −14 ) 3 [H + ] [H + ] solubility (S.40 −0. 142.7 −6.0 M H+: .0 × 10−3 4. Al(OH)3(s) + OH.38 −5.

5 [HOCl] [HOCl] [HOCl] 1. a.10 M H + 2 × 10 −3 = = 50 Solubility in pure water 4 × 10 −5 CaC2O4(s) is 50 times more soluble in 0. H2O cannot be ignored as a source of H+. V = 3.10 – 2s s s 5 × 10−4 = s2 s .0500 mol HOCl initially. From Section 7.54 = 3.039 mol Need to add 0. This will be a buffer solution because the pH is close to the pKa value.9 of text. For HOCl.46. s = 2 × 10 −3 mol / L 2 0. try: [H+] = (Ka[HA]0 + Kw)1/2 = 2. pH = pKa + log [OCl − ] [OCl − ] [OCl − ] . 0.00 L × 0.10 − 2 s (0. = 100.46 + log . [HA]0 = 1.5) nHOCl (4. Ka = 3. The total moles of OCl− and HOCl must equal 0. Added OH− converts HOCl into OCl−.5)nHOCl = 0.5 × 10−8) = 7. 143.9 L NaOH Note: Normal buffer assumptions hold.00 = 7.0500 mol. pH = 6. 8. = (5 × 10 − 4 )1/ 2 .10 M 0 0 s mol/L of CaC2O4(s) dissolves to reach equilibrium Equil. This increase in solubility is due to the weak base properties of C2O42−. nHOCl = 0.011 mol.0100 M. HA ⇌ H+ + A− Ka = 5. 0.039 mol NaOH to produce 0.039 mol OCl−.5 × 10−8 and pKa = −log(3.332 CHAPTER 8 CaC2O4(s) C2O42− + H+ HC2O4− + H+ APPLICATIONS OF AQUEOUS EQUILIBRIA Ksp = 2 × 10−9 K = 1/ K a 2 = 1.039 mol = V × 0. nOCl − = 0.6 × 104 K = 1/ K a1 = 15 Koverall = 5 × 10−4 ___________________________________________________________________________________ ⇌ ⇌ ⇌ Ca2+ + C2O42− HC2O4− H2C2O4 CaC2O4(s) + 2 H+ Initial ⇌ Ca2+ + H2C2O4 0.0500.10 − 2s ) Solubility in 0.0500 M = 0.00 × 10−4 M Because this is a dilute solution of a very weak acid. Solving where n = moles: nOCl − + nHOCl = 0.0 × 10−10.10 M H+ than in pure water.62 Check assumption: . 144.0500 and nOCl − = (3.4 × 10−7 M.

000 mmol HCl/mL = 135.0 × 10−5 = x2 x2 ≈ . figs.4 × 10−5 M = [OH−] pOH = 4.47.09 × 10−5 − x Kb = 2.76 × 10−5 + x Kb = 2. assumption poor. a.00 × 10−3 mmol A− are in 105.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA [ H + ]2 − K w = 2. figs.0 mL × 0.0 mL 9.08 c. x = 3.0 mmol HCl 100.0 × 10−-4.0 mL = 4.0100 mmol = 9. 145.00 × 10−4 mmol/mL) = 1. let OH− react completely with HA. pH = 9.2 × 10−5 M. all the HA is converted into A−. 5.00 × 10−3 mmol NaOH added. assumption good.0 mL × 1.0 × 10−5 4. After reaction.00 mL × (1.52 × 10−10 = 0 x = [OH−] = 1.0 × 10−5 0.09 × 10 − x) 9. 4.76 × 10 −5 + x) x .0 mL × (1. 200.09 × 10−5 M 110.3 × 10−5.53 Assumption to ignore H2O contribution to OH− is good.250 mmol Na3PO4/mL = 50. A− Initial Equil.00 × 10−2 mmol HA 5. + H2O ⇌ HA 0 x + OH− 0 x Kb = 2.76 × 10−5)x − 9.0 × 10−5 = (4. pOH = 4. pH = 6.76 × 10−5 M 4. x will not be small compared to 4.76 × 10−5 M A− + H2O Initial Equil.76 × 10−5.0 × 10−3 mmol HA and 5. −5 −5 (9. [A−]0 = [HA]0 = 5.0 × 10−5)x − (1. 100.0 mmol Na3PO4 135.00 × 10−3 mmol/mL) = 5. At the stoichiometric point.0 × 10−7 << 1.0 mL × 0.62 + [H ] 333 b.0 mL.0 mmol NaCN .82 × 10−9) = 0.09 × 10 Using the quadratic formula and carrying extra sig.76 × 10−5 M 4. x = 4.100 mmol NaCN/mL = 10. (4.: x2 + (6.76 × 10−5 − x ⇌ HA + OH− 0 x Kb = Kw/Ka = 2. pH = 9.: x2 + (2.00 × 10−3 mmol/105.76 × 10 −5 − x) Using the quadratic formula and carrying extra sig.92.

0 mmol of HCl reacts to convert all CN− to HCN and all PO43− to H2PO4−. HCN dissociation will be minimal.30 × 10−2 M.00 − 1. Here. resulting in a solution with 1. ⇌ H+ 0 x + H2PO4− 25. The final solution contains 25. At this point 10.0/435.0575 + x K a1 = 7. converting 25. pH = 7.00 mmol OH−. OH− will then react with the next best acid (HOCl).0 mmol H3PO4.0650)x − 4. 435.5 × 10−8 M. . HCN (Ka = 6.0 mL × 0. We have a buffer solution composed of HOCl and OCl−.0 mmol H2PO4−.0 mL × 0.00 mmol NaOH.0 mmol H2PO4−.0575 + x) . The remaining HCl reacts completely with H2PO4−.: x2 + (0.100 M = 5.0 mmol HCl are in solution. react the strongest base first and so on.5 × 10−3) or H2PO4− ( K a 2 = 6. HSO4−.2 × 10−8). and 25. (50. pH = 2.31 × 10−4 = 0. 50.50 mmol OCl−. let the best base (PO43−) react with the best acid (H+). so ignore it.0 mL 0. 10. normal assumptions don't hold here.0061 M = [H+].0 − 25. and H2O plus cations that don't affect pH.0575 − x Using the quadratic formula and carrying extra sig.00 mmol SO42− OH− still remains after reacting completely with H2SO4.00 mmol H2O + 5.50 mmol OCl− and (3.0 0. The remaining 1. SO42−. Assume the reaction goes to completion because H+ is reacting. SO42− is an extremely weak base (Kb = 8.46.0 mmol/435.5 × 10−3 = x(0. 10. OCl−. we've added 11.3 × 10−13).2 × 10−10) is a much weaker acid than either H3PO4 ( K a1 = 7.0 mL × 0.00 mmol H2SO4. figs.0 mL 50.50 mmol HOCl into 1.21 b.100 M = 3. H+. Because [HOCl] = [OCl−]: [H+] = Ka = 3.50 mmol Ba(OH)2 = 5.334 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA Let H+ from the HCl react to completion with the bases in solution. We have a buffer solution. 110.0 mL × 0.50 =) 1. In general. 147.5 × 10−3 25. [HCN] = 146.50 mmol OH− total.0575 − x K a1 = 7. 30. 0. 10.100 M = 2.0 =) 25.00 mmol H2SO4 → 10.200 M = 5. x = 0.0 mmol = 2. Principal equilibrium reaction is: H3PO4 Initial Equil. Major species PO43−. and Na+.0 mmol HCN.50 mmol HOCl. and 10. The major species at this point are HOCl.0 mL × 0. assumptions good.00 mmol HOCl 25. H2O.0 mmol HCN.0 mmol to H3PO4. Note that the concentrations are halved when equal volumes of the two reagents are mixed.00 mmol OH− + 5. Let OH− react completely with the best acid present (H2SO4).150 M = 1.50 mmol KOH 25.50 mmol OH− will convert 1.

mL – ⇌ HPO42− + OH− 0 +x x 0 +x x Kb = Kw 1.25 M After 0.66. At third equivalence point. react the best base (PO43−) with the best acid (HSO4−). pH = pK a 3 = −log(4. HPO42−. At the third halfway point. assume the reaction goes to completion. because the best base present (PO43−) and best acid present (HPO42−) are conjugate acidbase pairs. pOH = 1.022 M. 10.0 × 10 −14 = K a3 4.15 M 0. HSO4−.021). using quadratic equation: 0.050 M Major species: PO43−.100 M 0 0.34 148.15 − x x = [OH−] = 0.15 M −x 0. b.100 M +x 0. and Na+.021 Kb = 0. K a . HPO42−.32. 0.1 × 10−2 . HSO − 4 PO43− + HSO4− → HPO42− + SO42− K= = 2. Because Kb for PO43− is a relatively large value (Kb = K w /K a.8 × 10−13) = 12. Because K for this reaction is very large. mmol 400.8 × 10 −13 −x 0. the usual assumptions that the amount of base that reacts to each 4 equilibrium is negligible compared with the initial concentration of base will not hold. H2O.050 M 335 Before 0.021 = (0.20 M 0. and Na+. HPO 2− = 0. a buffer solution exists.025 − x Kb = 2. SO42− (a very weak base with Kb = 8.15 − x H2O ⇌ → HPO42− 0. the reaction is: PO43− + H2O Initial Change Equil. pH = 12.100 + x)( x) . H2O.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA PO43− + H+ → HPO42− 0 0.050 M 0 Major species: PO43−.050 M 0 0. HPO 2− 4 Before 0.100 + x + OH− 0 +x x Kb = 0.20 M After 0.050 M 0.3 × 10−13). a.5 × 1010 K a . Solving using the Kb reaction for PO43−: PO43− + Initial Change Equil.

30.1 × 10−2.014 + x)( x) (0.1 × 10−2 (0.82. The [OH−] in solution is not negligible compared to 0. The usual buffer assumptions don’t hold in very acidic or very basic solutions. Therefore. so the usual assumptions don’t hold here. pH = 11. ⇌ HPO42− + OH− PO43− + H2O 0.8 × 10−13 M This looks fine. In part a we assumed that x was negligible: HPO42− + H2O Initial Change Equil.014)( x) ≈ .025 − x x = 1.014 − x – – – ⇌ HPO42− + OH− 0. using the quadratic equation: (0. 149.0/350.50 2 . The pH at the third halfway point must be more acidic (lower pH) than the pH at the third equivalence point. +x 0.18 c.014) x = 4.0 mmol/350.0 × 10−3 M.014 M.70 The pH at the second stoichiometric point is: pH = pK a 2 + pK a 3 2 = 7.00.014 M −x 0.14 − x) x = [OH−] = 7.15.014 M +x 0. pH = 12. pOH = 2.8 × 10−13 5. H3A: pK a1 = 3.5 × 10−2 M = [OH−]. In this very basic solution.336 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA x2 = 2. using the quadratic equation: 0.014 + x (0.70 = 9.18).85 This pH answer makes more sense because it is below the pH at the third equivalence point calculated in part b of this problem (pH = 12. Initial Change Equil. mL −x 0. pOH = 1.32.30 + 11.14 + x)( x) = 2.1 × 10−2. (0.014 + x 0 +x x Kb = 2. pK a 3 = 11. pK a 2 = 7. we must use the Kb reaction and the quadratic equation: PO43− + H2O d. but this is a situation where we must use the Kb reaction for the weak base PO43− to solve for the pH.014 − x ⇌ PO43− + H3O+ 0 +x x K a 3 = 4. 5. the pH at the third halfway point cannot equal 12.014 − x) (0.

00 mmol/mL × VNaOH.00) and the first pK a1 + pK a 2 stoichiometric point (pH = = 5. pH = −log(5.55 mmol We need to add 4.0 mL (to reach pH = 9.7.7.0 mmol (mole balance) .00 mmol OH− added This is the first halfway point to equivalence. = 10+0. where [H3A] = [H2A−] and pH = pK a1 .0 mL × 0. we need 10. 8.0 mL × 0. To reach the second stoichiometric point. the mole ratio also equals 10.0 mmol OH− = 1.00) Note: Normal buffer assumptions are good.67 = 8.67 = 4.00 is between the first halfway point to equivalence (pH = pK a1 = 3. so the mole ratio also equals 4. Let n = mmol: nHA 2− nH 2A − = 4. Since pK a 2 = 8. 4. assumptions good.00 mmol H3A initially.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 337 Thus to reach a pH of 9.50. pH = pK a1 + log [H 2 A − ] [H A − ] [H 2 A − ] .00 mmol/mL × VNaOH.00.0 mL × 0.00 = 3.100 M = 10. VNaOH = 4. Let n = mmol: nH 2A − nH 3 A = 10.00 mmol (mole balance) 11nH 3A = 5.00 + log [HA 2 − ] [HA 2 − ] . 150. Solving for VNaOH: VNaOH = 10.55 mmol H2A− from the original H3A present.00.0500 mmol/mL = 5. and nH 2A − + nH 3A = 5.30. 4. a buffer mixture of H2A− and HA2− can produce a pH = 8. we must go to the second stoichiometric point.55 mmol = 1.15).45 mmol. 100.7)nH 2A − .0 × 10− 4) = 3. nHA 2− = (4.7 [H 2 A − ] [H 2 A − ] Both species are in the same volume.0500 M = 5. 100. nH 2A − = 4.55 mL of NaOH (to reach pH = 4. nHA 2− + nH 2A − = 10. [H 3 A] [H 3 A] [H 3 A] Because both species are in the same volume.67 solution. 100. 2 This is the buffer region controlled by H3A ⇌ H2A− + H+. = 10.00 + log 2 .0 mmol H3A initially a.55 mmol OH− to get 4. b.50) pH = 4. n H 3A = 0.

01 mg NaHCO3/mmol = 1. 3.99 mg/mmol = 2. nHA 2− = 8.0500 M × V.89 mmol H+.7 mL = 3.7)nH 2A − CHAPTER 8 = 10. 0.9% NaHCO3 0. V1 corresponds to two titration reactions: OH− + H+ → H2O and CO32− + H+ → HCO3−.2 mmol = 0. a. Because the first stoichiometric point only involves the titration of Na2CO3 by H+.2 mmol NaOH.2 mmol H2Ainto 8.78 mmol NaHCO3 × 84. 1. The second stoichiometric point involves the titration of HCO3− by H+.9 mL = 1.338 (5.89 mmol NaHCO3 came from the first stoichiometric point of the Na2CO3 titration. 151.150 g NaHCO3 Mass % Na2CO3 = Mass % NaHCO3 = 0. c.8 mmol. 18. which is titrated in the V1 region.67 mmol H+ = 3.2 mmol HA2− . we must add a total of 18.200 + 0.8 mmol H2A−. V2 corresponds to just one titration reaction: HCO3− + H+ → H2CO3.0 mmol. V2 corresponds to the titration reaction of HCO3− + H+ → H2CO3.89 mmol Na2CO3 × 105.89 = 1. 1.150) g 0. there are two sources of HCO3−: NaHCO3 and the titration of Na2CO3. V1 corresponds to the titration reaction of CO32− + H+ → HCO3−.2 mmol OH− converts 8.67 − 1.150 g × 100 = 42. V = 364 mL NaOH Note: Normal buffer assumptions are good.67 mmol HCO3− mL 1. The next 8. so V2 > V1. 0.100 mmol HCl/mL × 18.200 g Na2CO3.350 g .0 mmol OH− converts all of the 10.1% Na2CO3 (0. Here.0 mmol H3A into H2A-.00 × 102 mg = 0.50 × 102 mg NaHCO3 = 0. V1 > V2 due to the presence of OH− . nH 2A − APPLICATIONS OF AQUEOUS EQUILIBRIA = 1. b.200 g × 100 = 57. The sample contains 1. Here.100 mmol H + × 36.89 mmol of CO32− has been converted into HCO3−.2 mmol To reach this point. leaving 1.78 mmol HCO3− came from NaHCO3 in the original mixture. 10.

90 × 10−2 [H2A]0 = initial concentration K a1 = 5. s = 6. the total volume of solution is: 250. assumptions good. Because K a1 >> K a 2 . The millimoles of A2− present at the equivalence point equal the millimoles of H2A present initially (2.3 × 10−6 = [Ca2+][OH−]2 s = solubility (mol/L) Ksp = 1.7 × 10−3 M H+. The volume of Ca(OH)2 required to deliver 5.5 mmol).0 × 10 −2 mol H 2 A = 2.0 mmol OH− × 1 mmol Ca (OH) 2 2 mmol OH − × 1 mL 6. The [H+] donated by the K a1 reaction is 10−2.06 = 8.3 × 10−6 = (s)(2s)2 = 4s3.0 mmol OH−added. the added OH− has converted all the H2A into A2−.90 × 10−2 = x2 (8. ⇌ Ca2+ 0 s + 2 OH− ~0 2s Ksp = 1.0 × 10−2 M = [H 2 A ]0 − x [H 2 A]0 − 8.250 L × Molar mass H2A = 0. and the millimoles of OH− added to reach the second equivalence point are 2(2. The only information we need now in order to calculate the K a 2 value is the volume of Ca(OH)2 added in order to reach the second equivalent point.0 mmol OH− (the amount of OH− necessary to reach the second equivalence point) is: 5. H2A + 2 OH− → A2− + H2O. a. [H2A]0 [H2A]0 − x ⇌ H+ ~0 x + HA− 0 x K a1 = 5.7 × 10 −3 1. We will use the Ksp value for Ca(OH)2 to help solve for the volume of Ca(OH)2 added. so A2− is the major species present that determines the pH. g/mol 2. mL + 360 mL = 610 mL .7 × 10 −3 ) 2 . at the second equivalence point. Ca(OH)2(s) Initial Equil. the amount of H+ contributed by the K a 2 reaction will be negligible.9 × 10−3 M Ca(OH)2.5 mmol) = 5.CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 339 Marathon Problem 152.5 × 10−3 mol H2A L Mol H2A present initially = 0.5 × 10 −3 mol H 2 A b. H2A Initial Equil.9 × 10 −3 mmol Ca (OH) 2 = 362 mL = 360 mL Ca(OH)2 At the second equivalence point. [H2A]0 = 1.225 g H 2 A = 90.

1 × 10 −3 − x From the problem: pH = 7. Using the equation derived in Exercise 7.5 mmol 610 mmol 4. the setup to the problem requires the Kb reaction for A2−.1 × 10−3 M − x 0 x 0 x 1.0 at the second equivalence point.0 × 10 −14 x2 = Ka2 4.0 × 10 −14 (9. because the pH is less than 8. .1 × 10−7 M = x Kb = 1.340 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA Now we can solve for K a 2 using the pH data at the second equivalence point.135.1 × 10 −3 ) − (9. we get the same K a 2 value as calculated above by ignoring the OH− contribution from H2O. K a 2 = 5. In addition.04 = 9.1 × 10 −7 ) 2 = = 2. so [OH−] = 10−6.1 × 10 −7 ) Note: The amount of OH− donated by the weak base HA− will be negligible because the Kb value for A2− is more than a 1000 times the Kb value for HA−.0 × 10 Ka2 Ka2 Initial Equil.0 × 10−5 Ka2 (4.0 × 10−10. −14 K A2− + H2O ⇌ HA− + OH− Kb = w = 1. Kb = 2. Because the only species present that has any effect on pH is the weak base A2−.96. the amount of OH− added by H2O may need to be considered.

energy flows into the system as heat to increase the potential energy of the system. the products have higher potential energy (weaker bonds on average) than the reactants. etc. only step 4 does PV work (step 3 has a constant volume of 10. AND THERMOCHEMISTRY The Nature of Energy 15. Some state functions for an airplane trip from Chicago to Denver would be longitude change. All of B's energy is kinetic energy at this point. latitude change. In pathway I (steps 1 + 2). State functions are path independent. Ball A: PE = mgz = 2. The net result is that the quantity of energy Δ(PE) is transferred to the surroundings as heat when reactants are converted to products. 341 . In an exothermic process. ENTHALPY. the sum of the total energy will equal 196 J.00 kg × 9. Etotal = KE = 196 J. the bonds in the product molecules are stronger (on average) than those in the reactant molecules. In an endothermic process. time traveling.81 m × 3. At point II. At point II: PE = mgz = 4. 18. In pathway II (steps 3 + 4). elevation change.0 L).CHAPTER 9 ENERGY. and overall time zone change.00 kg × 9.00 m = 118 J s2 KE = Etotal − PE = 196 J − 118 J = 78 J 16.0 m = = 196 J s2 s2 At point I: All this energy is transferred to ball B. Only when there is a volume change can PV work be done. they only depend on the initial and final states. 17. only the first step does PV work (step 2 has a constant volume of 30. Plot a represents an exothermic reaction. Some path-dependent quantities are miles traveled. fuel consumption of the airplane. One can fly directly from Chicago to Denver or one could fly from Chicago to Atlanta to Los Angeles and then to Denver.81 m 196 kg m 2 × 10. Path-dependent functions for a trip from Chicago to Denver are those quantities that depend on the route taken.0 L). For an endothermic process (plot b). airplane snacks eaten.

38 L atm = − 650.9 kJ 101. ENTHALPY.0 L) = !20. q = w = −950.38 L atm of work done by the gases 101.0 L. J 20. both pathways have the same initial and final states. atm × (Vf − 0. q = −40. 19. J = 77 J b. AND THERMOCHEMISTRY 101.0 L 760 23.040 L).80 L ! 8. Step 1: ΔE1 = q + w = 72 J + 35 J = 107 J.4 kJ) = 18. Because w depends on the pathway.900 J C mol = 30.0 − 0.30 L) = 10.0 L atm × Pathway II: w = !PΔV = !1.3 J = 1060 J L atm 101.00 atm × (998 L − 876 L) = −122 L atm × L atm ΔE = q + w = 30.0)°C = 30.4 kJ w = −PΔV = −1.8 J × 39. work cannot be a state function.400 J = −12.66 kJ. −9.3 J = −12. step 2: ΔE2 = 35 J − 72 J = −37 J ΔEoverall = ΔE1 + ΔE2 = 107 J − 37 J = 70. J + 1060 = 1410 J c. w = !PΔV = !1.5 L atm × ΔE = q + w = 350. In this problem.9 kJ + (−12.342 CHAPTER 9 ENERGY.00 atm(29.90 atm(2. Vf − 0. J. −950. a. w = −PΔV .00 atm(30. Vf = 11.2 L) = !17.3 J L atm = !2. J × 1 L atm = −9.5 kJ o 101.3 J w = −PΔV.0 L) = -40. ΔE = q + w = !23 J + 100. We get different values of work for the two pathways.0 L atm × Note: The sign is minus (!) because the system is doing work on the surroundings (an expansion).05 × 103 J 101.040 = 11.1 mol × (38. w = !PΔV = !1.3 J = !1810 J L atm 22. H2O(g) → H2O(l).1 L ! 11. ΔE = q + w.0 L ! 10.0 L ! 10.3 J L atm = !4.00 atm(30. q = molar heat capacity × mol × ΔT = 20.9 L atm × ΔE = q + w = 1037 J ! 1810 J = !770 J 21.03 × 103 J Pathway I: w = !PΔV = !2.

and the heat flow by a system at constant volume equals ΔE. the heat flow by a system at constant pressure equals ΔH. . heat must be absorbed.5 J = 52.6 L) = 30.0 J × 1 L atm = !1. When the system cannot do PV work. so this is an exothermic process.530 L atm = !0. !102. then ΔH ≠ ΔE.66 kJ + 3.56 kJ 24. 4 Fe(s) + 3 O2(g) → 2 Fe2O3(s) ΔH = -1652 kJ. note that 1652 kJ of heat is released when 4 mol Fe reacts with 3 mol O2 to produce 2 mol Fe2O3. The H2SO4(aq) will get very hot and possibly boil unless cooling is provided.06 L = 58.10 kJ ΔE = q + w = −40.10 kJ = −37. This is an endothermic reaction. 28.02 g 1 cm 3 × = 18.000 mol H2O(l) × w = −PΔV = −1.10 × 103 J L atm = 3. H2O(g) → H2O(l).3 J w = !PΔV. The combustion of gasoline releases heat.1 cm3 = 18.9 L = initial volume Properties of Enthalpy 25. Heat must be added (absorbed) in order to break a bond. a.0181 L − 30. b. An important way to differentiate ΔH from ΔE is to concentrate on q. then ΔH = ΔE at constant pressure.CHAPTER 9 ENERGY. so this is an endothermic process. d. ΔE = q + w. ΔV = 3. so this is an exothermic process.500 atm × ΔV.6 L atm × 101.530 L atm 101.0 L ! Vi. 27. One should try to cool the reaction mixture or provide some means of removing heat since the reaction is very exothermic (heat is released). The high-temperature environment of internal combustion engines provides the heat.00 atm × (0. so heat must be absorbed in order to convert reactants into products. Thus when a system at constant P can do pressurevolume work. 3. the heat flow. !1. To convert a solid to a gas.3 J = 3. the difference between ΔH and ΔE at constant P is the quantity PΔV. from the definition of enthalpy.5 J + w. 26. ΔH = ΔE + PΔV at constant P. c. w = !155. heat is released when water vaper condenses. ENTHALPY.06 L ΔV = Vf – Vi.996 g 343 Volume of 1 mol H2O(l) = 1.1 mL mol 0. Vi = 54. so this is an endothermic process. AND THERMOCHEMISTRY 18. 29.

32.00 mol Fe2O3 × c.33 mole ratio. 2.86. Because the heat transfer process is only 60. J Mass C3H8 = 2. − 1652 kJ = !34. Concentrate on the moles of gaseous products versus the moles of gaseous reactants to predict ΔV for a reaction. AND THERMOCHEMISTRY − 1652 kJ = !1650 kJ. O2 is limiting since the actual mole Fe/mole O2 ratio is greater than the required mole ratio. q = 1.09 g C3 H 8 × = 4. ΔH < ΔE when ΔV < 0.00 mol Fe × ENERGY.3 × 108 J × 60. from this equation.179 mol Fe/0. 1. 826 kJ of heat released 2 mol Fe 2 O 3 b. c. the total energy required is: 1.1. 7. 1650 kJ of heat released 4 mol Fe − 1652 kJ = !826 kJ.2 × 108 J × 1 mol C3 H 8 44. so ΔV < 0 and ΔH < ΔE. a. There are 4 moles of gaseous reactants converting to 2 moles of gaseous products. and ΔH = ΔE when ΔV = 0. The 2. Consider the constant volume process first.0625 mol O2 = 2. 4.0 g Fe × 1 mol Fe − 1652 kJ × = !7.4 kJ of heat released 3 mol O 2 From Example 9. The Thermodynamics of Ideal Gases 33. ΔH = ΔE + PΔV. There are 9 moles of gaseous reactants converting to 10 moles of gaseous products. so ΔV = 0. . ENTHALPY. J = 2.4 × 103 g C3H8 3 mol C3 H 8 2221 × 10 J 31.4 kJ.2 × 108 J efficient.00 g Fe × d.344 CHAPTER 9 a. ΔH = ΔE.179 mol Fe. 34.39 kJ.0625 mol O2 55.0625 mol O2 × 30. 0. 10. so ΔV > 0 and ΔH > ΔE. There are 2 moles of gaseous reactants converting to 2 moles of gaseous products. ΔH > ΔE when ΔV > 0.00 g O2 × = 0. For this reaction.3 × 108 J.39 kJ of heat released 55. b. 1.% 100.85 g 32.5 kJ/mol quantity is the work done by the vaporization process in pushing back the atmosphere. When a liquid is converted into gas.00 g 0. the balanced equation requires a 4 mol Fe/3 mol O2 = 1. there is an increase in volume.85 g 4 mol Fe 1 mol O 2 1 mol Fe = 0.

0 − 25.3 mol)(52.00 atm.70 J °C−1 mol−1)(55°C − 165°C) ΔH = −8510 J = −8.3 kJ 74.0 L) w = −PΔV = −(3.1 kJ 0 88.8 kJ = 88.3 kJ + (33.1 kJ − 13.00 × 103 g × ΔE = nCvΔT = (33.300 J = 74. qp = ΔH = nCpΔT = (33.0°C) = 74.3145 J K−1 mol−1)(50.00 mol)(8.800 J = −13. L atm .83 kJ ΔE = q + w = −8.00 mol)(38.1 kJ −13.3 kJ ΔH = ΔE + ΔPV = ΔE + nRΔT ΔH = 74.60 J °C−1 mol−1)(75.8 kJ ΔE = q + w = 88.0 g N2O × 74.00 atm.3 mol)(8.00 mol.3 mol)(8.1 kJ Now consider the constant pressure process.00 mol N2O 44. 88.51 kJ + 1.0 K)(1 kJ/1000 J) ΔH = 74.00 atm)(55. Cv = = o 30.8 kJ = 74. ENTHALPY.0 L) = −120. 3. ΔE = qv = 74. ΔH = nCpΔT = (2.0 L) → (5.1 kJ = ΔH w = −PΔV = −nRΔT = −(33.3 kJ ΔE = q + w.60 J 44.02 g N 2 O At constant pressure. 3.3145 J K−1 mol−1)(−110. 15.1 kJ 74. w = 0.0 K) qp = 88.3 kJ + 13.00 mol. since ΔV = 0. AND THERMOCHEMISTRY 1 mol 44.07 g K mol C mol 345 n = 1.0 K) = −13. qp = ΔH. Pathway I: Step 1: (5.3 kJ 88.0 − 15.60 J = 33.8 kJ 1 mol N 2 O = 2.3 mol C2H6.3 mol)(44.CHAPTER 9 ENERGY. 55.92 J K−1 mol−1)(50.51 kJ = qp w = −PΔV = −nRΔT = −(2.3 kJ Summary Constant V Constant P q ΔE ΔH w 34.100 J = 88.68 kJ 35.3145 J K−1 mol−1)(50. K) = 1830 J = 1.3 kJ 88.83 kJ = −6.

2 kJ Step 2: (5.00 mol. Δ(PV) = (P2V2 − P1V1) nR R 5 5 ⎛ 5 ⎞ Δ( PV ) R.00 mol.3 J 1 kJ × = 30.4 = −11 kJ L atm 1000 J ΔH = −113 L atm × w = −PextΔV = −(6.4 kJ L atm 1000 J ΔH = qp = 300.5 L atm × ⎛ 5 ⎞ ⎛ Δ (PV ) ⎞ 5 ΔH = nCpΔT = n ⎜ R ⎟ ⎜ ⎟ = ΔPV ⎝ 2 ⎠ ⎝ nR ⎠ 2 ΔH = 5 (−45 L atm) = −113 L atm (Carry an extra significant figure.00 atm.) 2 101.3 kJ L atm 1000 J ΔE = q + w. 6.) 2 101.5 L atm (Carry an extra significant figure.8 kJ = q + 21. ΔH = ⎜ R ⎟ = Δ (PV ) 2 2 ⎝2 ⎠ R ΔH = qp = nCpΔT = nCp × For an ideal monatomic gas: Cp = ΔH = qp = 5 5 Δ(PV) = (165 − 45. 3.1 kJ .00 atm)(20.00 atm.3 kJ.0) L = 210. L atm H ENERGY.4 kJ − 12. L atm × 101.0 L) → (5. ENTHALPY. AND THERMOCHEMISTRY 101. L atm w = 210. q = −28.2 kJ = 18.0 − 55. L atm 2 2 101.0) L atm = 300. 55.3 J 1 kJ × = −12. −6. L atm × ΔE = q + w = 30.2 kJ L atm 1000 J C Δ (PV ) Δ (PV ) = p .0 L) ⎛ 3 ⎞ ⎛ Δ (PV ) ⎞ 3 ΔE = nCvΔT = n ⎜ R ⎟ ⎜ ⎟ = ΔPV ⎝ 2 ⎠ ⎝ nR ⎠ 2 ΔE = 3 (120.8 kJ L atm 1000 J ΔE = −67.3 J 1 kJ × = 21. − 165) L atm = −67.3 J 1 kJ × = −11. 20.346 CHAPTER 9 w = −120.3 J 1 kJ × = −6.

3 kJ −6.3 J 1 kJ × = 6.0) L atm = 67.0 kJ L atm 1000 J ΔE = q + w = 7. 15. 6.40 kJ 7.00 atm.8 kJ −11 kJ 2.6 kJ Summary: Path II Step 3 Step 4 Total q w ΔE ΔH 6.5 L atm × w = −PΔV = 0 because ΔV = 0 ΔH = ΔE + Δ(PV) = 67.00 atm.4 kJ −3. 15.00 atm)(20.4 kJ −28.2 kJ 30.3 kJ 9.00 mol.0 kJ = 4.6 kJ 14.0 kJ 11. ENTHALPY.1 kJ 11. 3.0 L atm = 112. .84 kJ 11.84 kJ L atm 1000 J ΔE = qv = 67.40 kJ Step 4: (5.0 L) → (5.84 kJ 0 6.90.3 J 1 kJ × = −3. L atm w = −30.4 kJ 19.0 − 15.0 L) ⎛ 5 ⎞ ⎛ Δ (PV ) ⎞ 5 ΔH = qp = nCpΔT = ⎜ R ⎟ ⎜ ⎟ = ΔPV ⎝ 2 ⎠ ⎝ nR ⎠ 2 ΔH = 5 (120. 20.0 − 45.00 mol.3 J 1 kJ × = 7.0 L) → (5. 6.6 kJ 7. 15.0 kJ 4.00 mol.5 L atm 2 2 101.CHAPTER 9 ENERGY.1 kJ 21.4 kJ 19 kJ Step 3: (5.6 kJ L atm 1000 J w = −PΔV = − (6.0) L atm = 75 L atm 2 ΔH = qp = 75 L atm × 101.4 kJ −12.0) L = −30.00 atm.5 L atm + 45.00 mol.6 kJ − 3.0 L) ΔE = qv = 3 5 Δ(PV) = (90. L atm × 101. 6.5 L atm = 11. AND THERMOCHEMISTRY Path I Step 1 Step 2 Total 347 Summary: q w ΔE ΔH Pathway II: 30.2 kJ 18.0 kJ .00 atm.6 kJ −3.

10.00 mol. hence ΔH and ΔE are state functions.3 J L−1 atm−1 = −12.00 mol.) w = −PΔV = −(10.0 − 5.5 kJ 60.3 − 40. For a monoatomic gas.0 atm. 20. hence q and w are path functions. − 100) = 1.0 × 103 L atm = 101.0 L) → (2. In this problem.5 kJ ΔE = q + w = 101. 36. 5. ENTHALPY. Cv = (3/2)R and Cp = (5/2)R.0 L) → (2.0 L) → (2.0 L) ΔH = qp = 5 5 Δ(PV) = (500.) = −125 L atm × 101.6 kJ Step 2: (2. 10.348 CHAPTER 9 ENERGY.3 kJ 2 2 w = −PΔV = −(20.0 atm. AND THERMOCHEMISTRY State functions are independent of the particular pathway taken between two states.0 atm.1 kJ −7.6 kJ. Step 1: (2. − 100. 20.7 kJ Step 3: (2.0 atm. 20. 5.0 atm.3 kJ .8 kJ 101.6 kJ 12.7 kJ 5. w = 0 since ΔV = 0 2 2 ΔH = ΔE + Δ(PV) = 75 L atm + 50. L atm = −40.7 kJ 101. L atm = 125 L atm = 12.7 kJ 2 (We will carry all calculations to 0.0 atm)(5.6 kJ −12.1 = −7.2 kJ −35.0 L) ΔE = qv = nCvΔT = 3 3 Δ(PV) = (100 − 50. L atm = 5.6 kJ 0 7.3 kJ 96. 10.8 kJ 101. the overall values of ΔH and ΔE for the two pathways are the same.00 mol.5 = 60.7 + 5.00 mol. 10.8 kJ Summary: q w ΔE ΔH Step 1 Step 2 Step 3 Total −12.0 L) ⎛ 5 ⎞ ⎛ Δ (PV ) ⎞ 5 ΔH = qp = nCpΔT = n ⎜ R ⎟ ⎜ ⎟ = ΔPV ⎝ 2 ⎠ ⎝ nR ⎠ 2 ΔH = qp = 5 (50. path functions are dependent on the particular pathway.0 − 10.00 mol.1 kJ ΔE = q + w = −12.) = 75 L atm = 7. 25. 5.0 atm)(25.00 mol. The overall values of q and w for the two pathways are different.0 atm.0) L = 50.1 kJ. 5.0) L = −400.7 kJ 7.4 kJ 60.3 kJ −40.

7 kJ × energy kJ = 140°C ΔT = = 0. To determine heat flow. qsurr can be calculated and then equated to qsys (!qsurr = qsys). we need to know the heat capacity of the surroundings. Therefore.18 J × 25. For an endothermic reaction. a. the surroundings (the calorimeter contents) donates heat to the system. a coffee-cup calorimeter is at constant (atmospheric) pressure.24 J 0. the system donates heat to the surroundings (the calorimeter). 0. m = = 1. ENTHALPY.24 J 1250 × m × (15. the mass of the surroundings that accepts/donates the heat. so temperature increases.2 Cg Specific heat capacity is defined as the amount of heat necessary to raise the temperature of one gram of substance by one degree Celsius. and the change in temperature. The heat released or gained at constant volume is ΔE. qP = ΔH.24 J 107. In calorimetry.0 g × (298 K − 273 K) = 9. s = specific heat capacity = 0.30 × 103 J o Cg The largest temperature change when a certain amount of energy is added to a certain mass of substance will occur for the substance with the smallest specific heat capacity.0 × 102 J Kg b. what happens to the surroundings is the exact opposite of what happens to the system. The amount of heat for H2O(l) is: energy = s × m × ΔT = 4. This is Hg(l).24 J × 150. 38. o Kg Cg Energy = s × m × ΔT = 0. qV = ΔE. AND THERMOCHEMISTRY 349 Calorimetry and Heat Capacity 37.0 g × (37. and the temperature change for this process is: 1000 J 10.0°C − 15. 1250 J = 39. The heat released or gained at constant pressure is ΔH. where s = specific heat capacity. g o Cg 40.0°C). Molar heat capacity = 0. heat flow is determined into or out of the surroundings.14 J s×m × 550. ΔEsys = !ΔEsurr.24 × 3. This is accompanied by a decrease in temperature of the surroundings. .0°C) = 2. Because ΔEuniv = 0 by the first law of thermodynamics.2°C − 12. A bomb calorimeter is at constant volume. Heat gain by water = heat loss by metal = s × m × ΔT. For an exothermic reaction. If we know these quantities.6 × 103 g Ag o 0. H2O(l) with the largest heat capacity value requires the largest amount of heat for this process.24 J = since ΔT(K) = ΔT(°C).9 g Ag × = o mol Ag Cg o 26 J C mol c.CHAPTER 9 ENERGY.

0 − Tf) + 4.0 g × (23.00 g Fe × (100.0 o C = 75.18 J × mhot × (55. keeping all quantities positive to avoid sign error: 0.18 J × 150.5)Tf + 450 − (4.00 × 10 mol 1000 J .3°C .15. 450 − (4.0 g × (75.18 J = o × 97.350 Heat gain = CHAPTER 9 ENERGY.0 g × 15. So q = −330 J and ΔH (heat per mol AgCl formed) is negative with a value of: ΔH = − 330 J 1 kJ × = −66 kJ/mol −3 5. Heat loss = 2100 J = s × 150.5(100.3°C).0 g = 0. Heat lost by chemicals = heat gained by solution Heat gain = 4.18 J × 100.45 J × 5.00 × 10−3 mol of both AgNO3 and HCl are reacted.0 − Tf) = 407(Tf − 22.0 g × (37.25 J °C−1 g−1 o 41.5)Tf = 407Tf − 8950 416Tf = 9850.100 mol/L = 5.0 − Tf) o Cg Cg 4. ENTHALPY.00 g Al × (100. Heat loss by hot water = heat gain by cold water.0°C) = 2100 J o Cg A common error in calorimetry problems is sign errors. Tf = 23.0°C − Tf) + o × 10. Keeping all quantities positive helps to eliminate sign errors. AND THERMOCHEMISTRY 4.0°C − 18. Thus 5.60)°C = 330 J o Cg Heat loss = 330 J.0°C) Cg 4. this is the heat evolved (exothermic reaction) when 5.0 × 10−3 L × 0.0 o C 42.00 × 10−3 mol of AgCl is produced. Heat loss by Al + heat loss by Fe = heat gain by water.7°C 43.0°C) = o × 90.0°C ! 37.0°C) o Cg Cg mhot = 90.0 g hot water needed 18.40 − 22. s = 2100 J 56.0 °C ! 22.00 × 10−3 mol of AgCl will be produced because there is a 1 : 1 mole ratio between reactants.3 g H2O × (Tf − 22. keeping all quantities positive to avoid sign errors: 4.89 J 0. 50.0).0 g × (18.7 C × 150.18 J 4.5(100.

0.0) g × (Tf − 25.5 kJ × = 8.0°C) o Cg 8.0°C = 39. so this is an endothermic process (ΔH is positive).08 kJ 110.76°C = Tf − Ti = Tf − 25. 80. AND THERMOCHEMISTRY 351 Note: Sign errors are common with calorimetry problems.18 J × 76.60 g = 76.0 g CaCl2 × 1 mol CaCl 2 81.60 g NH 4 NO 3 mol NH 4 NO 3 1000 J Because ΔH is exothermic. HCl is the limiting reactant. then the reaction is endothermic because the reaction absorbed heat from the water.0300 mol Ba(OH)2 is present.2°C 4.2°C.18 J × 400. then the reaction is exothermic because heat was released.0°C. Heat lost by solution = 4.00 × 10−2 mol HCl × ΔT = 1.95 × 103 J = o Cg 5.95 kJ of heat is evolved by reaction 2 mol HCl 4. For calorimetry problems.6 kJ/mol NH4NO3 dissolving 1. ENTHALPY. heat is absorbed as NH4NO3 dissolves.00 × 10−2/2 = 2.00 × 10−2 mol HCl L 0.50 × 10−2 mol Ba(OH)2 is required.500 mol HCl = 5. if ΔT of the solution increases. NH4NO3(s) → NH4+(aq) + NO3−(aq) ΔH = ?. Tf = 14. 5. the correct sign for ΔH can be determined easily from the ΔT data. the temperature of the solution will increase as CaCl2(s) dissolves. and if ΔT of the solution decreases.18 × 136 46.34)°C = 532 J = heat gained as o Cg NH NO dissolves 4 3 ΔH = 45. mass of solution = 75. To help eliminate sign errors.98 g CaCl 2 mol CaCl 2 heat gained by solution = 8.300 L × To react with all the HCl present. 44.0 g + 1.05 g NH 4 NO 3 532 J 1 kJ × × = 26.18 J × (125 + 11.00 × 10−2 mol Ba(OH)2 L 0. This will help eliminate sign errors. However. Because 0.08 × 103 = 14.08 × 103 J = Tf − 25.8°C . Keeping all quantities positive: heat loss as CaCl2 dissolves = 11. Here. keep all quantities positive until the end of the calculation and then decide the sign for ΔH. because temperature decreases as NH4NO3 dissolves.2°C + 25.100 mol Ba (OH) 2 = 3. i.100 L × 0. Tf = 26.0 g × ΔT Heat gained by solution = 2. 118 kJ = 2.e.0°C = 4.6 g Heat lost by solution = heat gained as NH4NO3 dissolves.6 g × (25. we will keep all quantities positive (q and ΔT) and then deduce the correct sign for ΔH at the end of the problem..CHAPTER 9 ENERGY.00 − 23.

so heat released = qv = ΔE: ΔE = − 24. which is the heat evolved (exothermic reaction) by the combustion of 0. AND THERMOCHEMISTRY 1. 0. ENTHALPY. 50. because pressure is constant: ΔE = qp + w = ΔH + w = 30.46 g mol c.00 kJ 342.0 kJ.04 g × = !1.1964 g ΔEcomb = − 25 kJ 108. A bomb calorimeter is at constant volume. ΔEcomb = 48. 5 kJ = 532 kJ o C − 532 kJ 26.8 kJ Hess’s Law 51. + 273 K) = −2940 J. where Δn = moles of gaseous products – moles of gaseous reactants.1964 g of quinone.7 kJ + (−2. so ΔH = ΔE = −5630 kJ/mol.79 g CH4 × 340.09 g × = −2700 kJ/mol g mol 1 mol CH 4 802 kJ × 16. kJ = 31. ΔH = ΔE + Δ(PV) = ΔE + Δ(nRT) = ΔE + ΔnRT.kJ) 2 CO2 + H2O → C2H2 + 5/2 O2 ________________________________________________ ΔH = 226 kJ 2 C(s) + H2(g) → C2H2(g) .94 kJ) = 27.2°C = 5. A(l) → A(g) ΔHvap = 30.5 kJ/°C 10. ΔH = 2(−394 kJ) 2 C + 2 O2 → 2 CO2 ΔH = −286 kJ H2 + 1/2 O2 → H2O ΔH = − (−1300.0 kJ = heat loss by quinone o C Heat loss = 5.0 kJ = −25 kJ/g.8 o C Heat capacity of calorimeter = b. For this reaction.30 g = −5630 kJ/mol C12H22O11 × 1.56 kJ × 3.3145 J K−1 mol−1)(80.10 × 103 kJ/mol 12. C12H22O11(s) + 12 O2(g) → 12 CO2(g) + 11 H2O(l) b. Heat gain by calorimeter = heat loss by CH4 = 6. kJ a.7 kJ w = −PΔV = −ΔnRT.6 g C 2 H 2 mol C 2 H 2 a. CHAPTER 9 Heat gain by calorimeter = ENERGY.9°C × ΔEcomb = 49 31. Heat loss by C2H2 = heat gain by calorimeter = 16. Δn = 12 −12 = 0. where Δn = nproducts − nreactants = 1 − 0 = 1 w = −(1 mol)(8. − 5. Because we are at constant volume.352 47.04 g mol = 340. qv = ΔE.

______________________________________________________________________________________________ CaC2(s) + 2 H2O(l) → Ca(OH)2(aq) + C2H2(g) 54. the combustion reaction refers to 1 mole of that quantity reacting with O2(g).4 kJ) 1/2 Cl2O + 3/2 F2O → ClF3 + O2 ΔH = 1/2 (!43.1 kJ ΔH = !(!1300. ΔH = 1/2 (167.CHAPTER 9 ENERGY.5 kJ) ΔH = !713 kJ 53. C4H4(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l) C4H8(g) + 6 O2(g) → 4 CO2(g) + 4 H2O(l) H2(g) + 1/2 O2(g) → H2O(l) ΔHcomb = −2341 kJ ΔHcomb = −2755 kJ ΔHcomb = −286 kJ By convention. kJ) ΔH = !635.8 kJ) ΔH = !653.4 kJ) F2 + 1/2 O2 → F2O ____________________________________________________________ ΔH = !108. H2O(l) is produced when enthalpies of combustion are given. Using Hess’s Law to solve: ΔH1 = −2341 kJ C4H4(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l) 4 CO2(g) + 4 H2O(l) → C4H8(g) + 6 O2(g) ΔH2 = − (−2755 kJ) ΔH3 = 2(−286 kJ) 2 H2(g) + O2(g) → 2 H2O(l) ___________________________________________________________________ ΔH = ΔH1 + ΔH2 + ΔH3 = −158 kJ C4H4(g) + 2 H2(g) → C4H8(g) .4 kJ) ClF + 1/2 O2 → 1/2 Cl2O + 1/2 F2O ΔH = !1/2 (341. and because per mole quantities are given. AND THERMOCHEMISTRY 353 Note: The enthalpy change for a reaction that is reversed is the negative quantity of the enthalpy change for the original reaction.7 kJ ClF(g) + F2(g) → ClF3(g) CaC2 → CaO + H2O → 2 CO2 + H2O → Ca + 1/2 O2 → 2 C + 2 O2 → Ca + 2 C Ca(OH)2 C2H2 + 5/2 O2 CaO 2 CO2 ΔH = !(!62. let's first calculate ΔH for the reaction: 6 FeO(s) + 6 CO(g) → 6 Fe(s) + 6 CO2(g) ΔH = −2(18 kJ) 6 FeO + 2 CO2 → 2 Fe3O4 + 2 CO 2 Fe3O4 + CO2 → 3 Fe2O3 + CO ΔH = − (−39 kJ) ΔH = 3(-23 kJ) 3 Fe2O3 + 9 CO → 6 Fe + 9 CO2 ____________________________________________________ 6 FeO(s) + 6 CO(g) → 6 Fe(s) + 6 CO2(g) ΔH = −66 kJ So for: FeO(s) + CO(g) → Fe(s) + CO2(g) ΔH = − 66 kJ = −11 kJ 6 55.5 kJ ΔH = 2(!393. If the coefficients in a balanced reaction are multiplied by an integer. To avoid fractions. ENTHALPY. then the value of ΔH is multiplied by the same integer. 52.

4 kJ C6H4(OH)2 → C6H4O2 + H2 H2O2 → H2 + O2 ΔH = −(−191. ENTHALPY.8 kJ) 2 H2O(g) → 2 H2O(l) ________________________________________________________________ C6H4(OH)2(aq) + H2O2(aq) → C6H4O2(aq) + 2 H2O(l) ΔH = −202. The change in enthalpy that accompanies the formation of one mole of a compound from its elements.1 kJ ΔH = −4(46 kJ) 2 N2(g) + 6 H2(g) → 4 NH3(g) ΔH = −3(-484 kJ) 6 H2O(g) → 6 H2(g) + 3 O2(g) __________________________________________________ 2 N2(g) + 6 H2O(g) → 3 O2(g) + 4 NH3(g) ΔH = 1268 kJ No.6 kJ _______________________________________________________ P4O10(s) + 6 PCl5(g) → 10 Cl3PO(g) ΔH = −610. products f − ∑ n r ΔH o reactants . Pb(s) + S(s) + 2 O2(g) → PbSO4(s) 61.7 kJ) 10 PCl3 + 5 O2 → 10 Cl3PO ΔH = −6(−84. The balanced equation is: 2 NH3(g) + 3 O2(g) + 2 CH4(g) → 2 HCN(g) + 6 H2O(g) . In general: ΔH° = ∑ n p ΔH o. H2(g) + 1/2 O2(g) → H2O(l) 6 C(graphite. CHAPTER 9 ENERGY. with all substances in their standard states. The reactions that refer to ΔH o are: f Na(s) + 1/2 Cl2(g) → NaCl(s).2 kJ) 6 PCl5 → 6 PCl3 + 6 Cl2 P4 + 6 Cl2 → 4 PCl3 ΔH = −1225.2 kJ) ΔH = 2(−241. it would not be a practical way of making ammonia because of the high energy costs required. is the standard enthalpy of formation for a compound. 57. Standard Enthalpies of Formation 60.3 kJ) ΔH = 10(−285.354 56.8 kJ) 2 H2 + O2 → 2 H2O(g) ΔH = 2(−43. because the reaction is very endothermic (requires a lot of heat to react). and all elements in their standard f. AND THERMOCHEMISTRY NO + O3 → NO2 + O2 ΔH = −199 kJ ΔH = −1/2 (−427 kJ) 3/2 O2 → O3 ΔH = −1/2 (495 kJ) O → 1/2 O2 ______________________________________________________ NO(g) + O(g) → NO2(g) ΔH = −233 kJ ΔH = 177.6 kJ P4O10 → P4 + 5 O2 ΔH = −(−2967. s) + 6 H2(g) + 3 O2(g) → C6H12O6(s). f a. state have ΔH o = 0 by definition. 59. 58.

H 2O ) f f − (2 mol NH3 × ΔH o. f HCl ) ⎡ ⎡ ⎛ − 314 kJ ⎞⎤ ⎛ − 46 kJ ⎞ ⎛ − 92 kJ ⎞⎤ ΔH° = ⎢1 mol ⎜ ⎟⎥ − ⎢1 mol ⎜ ⎟ + 1 mol ⎜ ⎟⎥ ⎝ mol ⎠⎦ ⎝ mol ⎠ ⎝ mol ⎠⎦ ⎣ ⎣ ΔH° = −314 kJ + 138 kJ = −176 kJ d. The balanced equation is: C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(g) ⎡ ⎡ ⎛ − 242 kJ ⎞ ⎤ ⎛ − 278 kJ ⎞⎤ ⎛ − 393. kJ . AND THERMOCHEMISTRY 355 ΔH° = (2 mol HCN × ΔH o. Ca3(PO4)2(s) + 3 H2SO4(l) → 3 CaSO4(s) + 2 H3PO4(l) ⎡ ⎛ − 1433 kJ ⎞ ⎛ − 1267 kJ ⎞⎤ ΔH° = ⎢3 mol CaSO 4 (s)⎜ ⎟ + 2 mol H 3 PO 4 (l)⎜ ⎟⎥ ⎝ mol ⎠ ⎝ mol ⎠⎦ ⎣ ⎡ ⎛ − 814 kJ ⎞⎤ ⎛ − 4126 kJ ⎞ − ⎢1 mol Ca 3 (PO 4 ) 2 (s)⎜ ⎟⎥ ⎟ + 3 mol H 2SO 4 (l)⎜ ⎝ mol ⎠⎦ ⎝ mol ⎠ ⎣ ΔH° = −6833 kJ − (-6568 kJ) = −265 kJ c. CH 4 ) f ΔH° = [2(135. ΔH o = 0 .5 kJ ⎞ ΔH° = ⎢2 mol ⎜ ⎟ ⎥ − ⎢1 mol ⎜ ⎟⎥ ⎟ + 3 mol ⎜ ⎝ mol ⎠ ⎦ ⎝ mol ⎠⎦ ⎝ mol ⎠ ⎣ ⎣ ΔH° = −1513 kJ − (−278 kJ) = −1235 kJ e. kJ b.CHAPTER 9 ENERGY. f NH 3 + 1 mol HCl × ΔH o. NH3(g) + HCl(g) → NH4Cl(s) ΔH° = (1 mol NH4Cl × ΔH o. f ⎡ ⎛ − 167 kJ ⎞ ⎛ − 911 kJ ⎞ ⎤ ΔH° = ⎢4 mol ⎜ ⎟ + 1 mol ⎜ ⎟⎥ ⎝ mol ⎠ ⎝ mol ⎠ ⎦ ⎣ ⎡ ⎛ − 687 kJ ⎞ ⎛ − 286 kJ ⎞ ⎤ − ⎢1 mol ⎜ ⎟ + 2 mol ⎜ ⎟⎥ ⎝ mol ⎠ ⎝ mol ⎠ ⎦ ⎣ ΔH° = −1579 kJ − (−1259 kJ) = −320. SiCl4(l) + 2 H2O(l) → SiO2(s) + 4 HCl(aq) Because HCl(aq) is H+(aq) + Cl−(aq).1) + 6(−242)] − [2(−46) + 2(−75)] = −940. f NH 3 + 2 mol CH4 × ΔH o. HCN + 6 mol H2O(g) H ΔH o. f NH 4 Cl ) − (1 mol NH3 × ΔH o. ENTHALPY.167 = -167 kJ/mol.

f b.356 f. kJ ⎞⎤ ΔH° = ⎢2 mol ⎜ ⎟ + 1 mol ⎜ ⎟⎥ ⎝ mol ⎠ ⎝ mol ⎠⎦ ⎣ ⎡ ⎛ 34 kJ ⎞ ⎛ − 286 kJ ⎞ ⎤ − ⎢3 mol ⎜ ⎟ + 1 mol ⎜ ⎟ ⎥ = −140. kJ ⎞ ⎤ ⎡ ⎛ − 286 kJ ⎞⎤ ΔH° = ⎢2 mol ⎜ ⎟ ⎥ − ⎢2 mol ⎜ ⎟⎥ = −368 kJ ⎝ mol ⎠ ⎦ ⎣ ⎝ mol ⎠⎦ ⎣ . CHAPTER 9 ENERGY. AND THERMOCHEMISTRY MgO(s) + H2O(l) → Mg(OH)2(s) ⎡ ⎛ − 925 kJ ⎞ ⎤ ⎡ ⎛ − 286 kJ ⎞ ⎤ ⎛ − 602 kJ ⎞ ΔH° = ⎢1 mol ⎜ ⎟ ⎥ − ⎢1 mol ⎜ ⎟⎥ ⎟ + 1 mol ⎜ ⎝ mol ⎠ ⎦ ⎣ ⎝ mol ⎠ ⎦ ⎝ mol ⎠ ⎣ ΔH° = −925 kJ − (−888 kJ) = −37 kJ 62. ENTHALPY. ⎛ − 416 kJ ⎞ 4 Na(s) + O2(g) → 2 Na2O(s). ΔH° = ∑ n p ΔH o. 63. kJ ⎞⎤ ΔH° = ⎢2 mol ⎜ ⎟ ⎥ − ⎢2 mol ⎜ ⎟⎥ = −112 kJ ⎝ mol ⎠ ⎦ ⎣ ⎝ mol ⎠⎦ ⎣ 3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g) ⎡ ⎛ − 207 kJ ⎞ ⎛ 90. a. ⎡ ⎛ − 46 kJ ⎞⎤ ⎛ − 242 kJ ⎞ ⎤ ⎡ ⎛ 90. 12 NH3(g) + 15 O2(g) → 12 NO(g) + 18 H2O(g) 12 NO(g) + 6 O2(g) → 12 NO2(g) 12 NO2(g) + 4 H2O(l) → 8 HNO3(aq) + 4 NO(g) 4 H2O(g) → 4 H2O(l) _________________________________________________ 12 NH3(g) + 21 O2(g) → 8 HNO3(aq) + 4 NO(g) + 14 H2O(g) The overall reaction is exothermic since each step is exothermic. kJ ⎞ ΔH° = ⎢4 mol ⎜ ⎟⎥ = −908 kJ ⎟ ⎥ − ⎢4 mol ⎜ ⎟ + 6 mol ⎜ ⎝ mol ⎠⎦ ⎝ mol ⎠ ⎦ ⎣ ⎝ mol ⎠ ⎣ 2 NO(g) + O2(g) → 2 NO2(g) ⎡ ⎛ 34 kJ ⎞ ⎤ ⎡ ⎛ 90. products − ∑ n r ΔH o reactants f f. ΔH° = 2 mol ⎜ ⎟ = −832 kJ ⎝ mol ⎠ 2 Na(s) + 2 H2O(l) → 2 NaOH(aq) + H2(g) ⎡ ⎛ − 470. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g). kJ ⎝ mol ⎠ ⎝ mol ⎠ ⎦ ⎣ Note: All ΔH o values are assumed ± 1 kJ.

02 g ⎞ ⎛ 46.000 × 103 g × − 2677 kJ = −6177 kJ 433. kJ ⎞ ⎛ 54 kJ ⎞ ⎤ − ⎢5 mol ⎜ ⎟ + 4 mol ⎜ ⎟ ⎥ = −4594 kJ ⎝ mol ⎠ ⎝ mol ⎠ ⎦ ⎣ 66." Both reactions are exothermic and each reaction produces a flammable gas. a mixture of 3 mol Al and 3 mol NH4ClO4 yields 2677 kJ of energy.000 kg of fuel: 1. The mass of the stoichiometric reactant mixture is: 26.000 × 103 g × − 4594 kJ = −7129 kJ 644.49 g ⎞ ⎛ ⎜ 3 mol × ⎟ + ⎜ 3 mol × ⎟ = 433.98 g ⎞ ⎛ 117.41 g mol ⎠ ⎝ mol ⎠ ⎝ For 1. .5 kJ ⎞⎤ ⎛ − 242 kJ ⎞ ΔH° = ⎢12 mol ⎜ ⎟⎥ ⎟ + 4 mol ⎜ mol ⎠ ⎝ mol ⎠⎦ ⎝ ⎣ ⎡ ⎛ − 20.42 kJ mol ⎠ ⎝ mol ⎠ ⎝ For 1. kJ ⎞ ΔH° = ⎢6 mol ⎜ ⎟⎥ ⎟ + 1 mol ⎜ ⎟ + 3 mol ⎜ ⎟ + 1 mol ⎜ ⎝ mol ⎠⎦ ⎝ mol ⎠ ⎝ mol ⎠ ⎝ mol ⎠ ⎣ ⎡ ⎛ − 295 kJ ⎞ ⎤ − ⎢3 mol ⎜ ⎟ ⎥ = −2677 kJ ⎝ mol ⎠ ⎦ ⎣ 65. H2 and CO. 5 N2O4(l) + 4 N2H3CH3(l) → 12 H2O(g) + 9 N2(g) + 4 CO2(g) ⎡ ⎛ − 393. For Exercise 64.08 g ⎞ ⎛ mass is: ⎜ 5 mol × ⎟ + ⎜ 4 mol × ⎟ = 644. sodium metal reacts with the "extinguishing agent.5 kJ ⎞⎤ ⎡ ⎛ − 416 kJ ⎞ ΔH° = ⎢1 mol ⎜ ⎟⎥ = −133 kJ ⎟⎥ − ⎢1 mol ⎜ ⎟ + 1 mol ⎜ ⎝ mol ⎠⎦ ⎝ mol ⎠⎦ ⎣ ⎝ mol ⎠ ⎣ In reactions 2 and 3. respectively.000 kg of fuel: 1. we get 4594 kJ of energy from 5 mol of N2O4 and 4 mol of N2H3CH3. The 92.5 kJ ⎞⎤ ⎛ − 110.42 g Thus we get more energy per kilogram from the N2O4/N2H3CH3 mixture.41 g In Exercise 65.CHAPTER 9 ENERGY. ENTHALPY. AND THERMOCHEMISTRY 357 2Na(s) + CO2(g) → Na2O(s) + CO(g) ⎡ ⎛ − 393. 64. 3 Al(s) + 3 NH4ClO4(s) → Al2O3(s) + AlCl3(s) + 3 NO(g) + 6 H2O(g) ⎡ ⎛ − 1676 kJ ⎞⎤ ⎛ − 704 kJ ⎞ ⎛ − 242 kJ ⎞ ⎛ 90.

2 ClF3(g) + 2 NH3(g) → N2(g) + 6 HF(g) + Cl2(g) ΔH° = (6 ΔH o. ΔH f . The energy required is: 1. more than this quantity of energy is needed since heat is always lost in any transfer of energy.) kJ = −112 kJ ΔH° = −1196 kJ 69.0% efficient) process. AND THERMOCHEMISTRY a. C 2 H 4 . ΔH f . J = 1. SO3(g) + H2O(l) → H2SO4(aq) d. kJ + 143 kJ) = −199 kJ ΔH° = −909 kJ − [−396 kJ + (-286 kJ)] = −227 kJ ΔH° = 2(34) kJ − 2(90. Mass of H2O = 1.8) kJ − ΔH f . f f f NH 3 ) ⎛ − 271 kJ ⎞ ⎛ − 46 kJ ⎞ o −1196 kJ = 6 mol ⎜ ⎟ − 2 ΔH f . ΔH° = 3 mol(227 kJ/mol) − 1 mol(49 kJ/mol) = 632 kJ b. ClF3 + 92 kJ.358 67.00 gal × 3. 2 NO(g) + O2(g) → 2 NO2(g) ΔH° = −166 kJ − (143 kJ + 52 kJ) = −361 kJ ΔH° = 34 kJ − (90.18 J × 3790 g × 10.98 × 105 J × 1 mol C 2 H 2 26. ClF3 + 2ΔH o.5 kJ/mol Energy Consumption and Sources 71. HF ) − (2 ΔH o.98 × 105 J 80 . a.1 kJ = −1358.58 × 105 J × 100 .785 L 1000 mL 1. ENTHALPY. C 2 H 4 o o −1411. O3(g) + NO(g) → NO2(g) + O2(g) c. C2H4(g) + 3 O2(g) → 2 CO2(g) + 2 H2O(l) ΔH° = −1411 kJ o ΔH° = −1411.5) kJ + 2(−285. CHAPTER 9 ENERGY. C 2 H 4 = 52.1 kJ = 2(−393.0 °C = 1. × 10 J .58 × 105 J o Cg Energy required (theoretical) = s × m × ΔT = For an actual (80.0 J Mass of C2H2 = 1.6 kJ − ΔH f . Because 3 C2H2(g) is higher in energy than C6H6(l). ClF3 = (−1626 + 92 + 1196) kJ − 169 kJ = 2 mol mol 70.04 g C 2 H 2 × = 3. ClF3 − 2 mol ⎜ ⎟ ⎝ mol ⎠ ⎝ mol ⎠ o o −1196 kJ = −1626 kJ − 2 ΔH f . C2H4(g) + O3(g) → CH3CHO(g) + O2(g) b.97 g C2H2 3 mol C 2 H 2 1300. 68.00 g × × = 3790 g H2O gal L mL 4. acetylene will release more energy per gram when burned in air.

CH3OH(l) + 3/2 O2(g) → CO2(g) + 2 H2O(l) ΔH° = [!393.67 kJ/g mol 46. J + w.3145 J K−1 mol−1)(298 K)(1 mol) = ΔH − 2480 J ΔH° = −242 kJ/mol − (−286 kJ/mol) = 44 kJ/mol ΔE = 44 kJ − 2. ΔEoverall = ΔEstep 1 + ΔEstep 2.CHAPTER 9 72. J) = 35 J ΔEstep 2 = −ΔEstep 1 = −35 J = q + w.04 g Ethanol has a higher fuel value than methanol. and there are extra safety hazards associated with using high-pressure compressed-gas tanks. The boiling point of propane is -42°C.7 kJ/g for octane (Example 9. −35 J = −60.096 g g The two fuel values are very close. Thus it is more difficult to store propane.] ΔE = ΔH − (8. C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) ΔH° = [3(−393. ENTHALPY.48 kJ. ENERGY. [H2O(l) is a liquid. this is a cyclic process. Δ(PV) = Δ(nRT) = RTΔn at constant T We go from n = 0 to n = 1.068 g 73. Because ΔE is a state function. ΔEoverall = 0 and ΔEstep 1 = −ΔEstep 2.52 kJ = 42 kJ . Additional Exercises 75.8) × mol 44. An advantage of propane is that it burns more cleanly. 74.37 kJ = versus −47. ΔEstep 1 = q + w = 45 J + (−10. w = 25 J 76. thus Δn = 1.7 kJ/g versus !29.5 kJ + 2(!286 kJ)] ! (!239 kJ) = !727 kJ/mol CH3OH 1 mol − 727 kJ × = !22. AND THERMOCHEMISTRY 359 C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(l) ΔH° = [2(−393.5 kJ) + 3(−286 kJ)] − (−278 kJ) = −1367 kJ/mol ethanol − 1367 kJ 1 mol × = −29. which means that the overall initial state and final state are the same.67 kJ/g for ethanol mol 32. H = E + PV. ΔE = 41. ΔE = ΔH − Δ(PV) Assume that H2O(g) is ideal.5 kJ) + 4(−286 kJ)] − (−104 kJ) = −2221 kJ/mol C3H8 − 2221 kJ 1 mol − 50. ΔH = ΔE + Δ(PV).

79)ΔT.90 kJ = heat gain by water and calorimeter ⎛ 4.8 kJ ΔE° = ΔH° − PΔV = ΔH° − ΔnRT ⎛ 1 kJ ⎞ ΔE° = 285.056 g × 26.18 kJ ⎞ ⎛ 6. which is equal to 4.54 cm 1m ⎞ 1 kg ⎞ 9.8 kJ − (1.18 kJ/°C o C kg This is the portion of the heat capacity that can be attributed to H2O.66)ΔT = (10.91°C 81. ΔT = 2.42 kJ/g = 27.1 kJ 4.8 kJ H2O(l) → H2(g) + 1/2 O2(g) ΔH° = 285.205 lb ⎠ s ⎝ ⎝ ⎠ 200 J of energy is needed to climb one step.90 = (4. Na2SO4(aq) + Ba(NO3)2(aq) → BaSO4(s) + 2 NaNO3(aq) ΔH = ? .66 kJ ⎞ ⎟ Heat gain = 27.18 = 6.18 kJ = 4.8 kJ − 3. so: 1.3145 J K−1 mol−1)(298 K) ⎜ ⎜ 1000 J ⎟ ⎟ ⎝ ⎠ ΔE° = 285.84 − 4.13 + 6. Total heat capacity = Ccal + C H 2O .81 m ⎛ ⎟× ⎟ = 160 J ≈ 200 J PE = mgz = ⎜180 lb × × ⎜ 8 in × × 2 ⎜ ⎟ ⎜ m 100 cm ⎟ 2.18 kJ °C−1 kg−1 We have 1. Tf = 25.586°C 2.00 kg of H2O.72 kJ = 282.90 kJ = ⎜ o ⎜ C kg × 0.18 kJ = 1.00 kg × 4. ENTHALPY. 80.50 − 0 mol)(8. Ccal = 10. f −285.586°C = Tf − 23. The total number of steps to climb are: 2 × 106 J × 79. AND THERMOCHEMISTRY H 2O ( l) = H2(g) + 1/2 O2(g) → H2O(l) ΔH° = ΔH o.360 77. CHAPTER 9 ENERGY.66 kJ/°C Heat released = 1.32°C. 1 step = 1 × 104 steps 200 J The specific heat of water is 4.67 × 103 kJ ≈ 2 × 103 kJ kcal 78.987 kg × ΔT ⎟ + ⎜ o C × ΔT ⎟ ⎠ ⎝ ⎠ ⎝ 27.18 J °C−1 g−1. 400 kcal × ⎛ 2.

0)EC = 4. COCl2(g) → CO(g) + Cl2(g). w = −PΔV.00 mol 0.06 × 105 J/mol = !306 kJ/mol 1.50 × 10 −2 mol NaOH × 84.00 × 103 g 1L mL 6. w is negative (w < 0).59 × 105 J Cg Mass of solution = 3.CHAPTER 9 1. N2(g) + O2(g) → 2 NO(g). However. − 4. c.50 mol Ba(NO3)2 L L 361 The balanced equation requires a 1 : 1 mole ratio between Na2SO4 and Ba(NO3)2.0 ! 30.00 × 103 g × (42.37 J Heat gain by solution = o × 6. w is positive (w > 0). 4.2000 L × 0.50 mol BaSO 4 |qsurr| = |qsolution + qcal|. b.59 × 105 J for the reaction. Because we have fewer moles of Ba(NO3)2 present. because the volume did not change (ΔV = 0).2 kJ of heat is released. 7.00 L × Because the solution gained heat.00 mol Na2SO4. ΔH = 82.59 × 105 J = !3. it is limiting and 1. the reaction is exothermic.50 × 10 −2 mol NaOH L Because the balanced reaction requires a 1 : 1 mole ratio between HCl and NaOH. − 56 kJ = !4. HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq) ΔH = !56 kJ 0.00 L × = 1. 0. mol NaOH a. if the calorimeter has a nonzero heat capacity.2 kJ.750 mol = 2. and because fewer moles of NaOH are actually present as compared with HCl.00 × 10 −2 mol HCl L 83. then qsurr is too small. Heat gain by solution = heat loss by reaction 1000 mL 2. . If we ignore qcal.500 mol NaOH = 7. because the volume of the piston apparatus decreased as reactants were converted to products (ΔV < 0). no PV work is done (w = 0). because the volume increased (ΔV > 0).50 mol BaSO4 will be produced [there is a 1 : 1 mole ratio between Ba(NO3)2 and BaSO4].1500 L × 0. NaOH is the limiting reagent. giving a calculated ΔH value that is less positive (smaller) than it should be.400 mol HCl = 8. 2. ENTHALPY. we normally assume that qcal is zero (no heat gain/loss by the calorimeter).00 g × = 6. then some of the heat absorbed by the endothermic reaction came from the calorimeter. AND THERMOCHEMISTRY 2. 2 SO2(g) + O2(g) → 2 SO3(g).00 L × ENERGY. q = !4.

Only gases can do PV work (we ignore solids and liquids). Challenge Problems 88. Δn = moles of gaseous products − moles of gaseous reactants. Δn = 2 − 0 = 2 moles. and this reaction would do expansion work against the surroundings. NH4Br(s) → NH4+(aq) + Br-(aq) 87. AND THERMOCHEMISTRY In order to predict the sign of w for a reaction. C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(l) c. 2 Al(s) + 3/2 O2(g) → Al2O3(s) b. 86. When ΔV < 0 (Δn < 0). reaction b. Ba(OH)2(aq) + 2 HCl(aq) → 2 H2O(l) + BaCl2(aq) d. e. e. ENTHALPY. When a balanced reaction has more moles of product gases than moles of reactant gases (as in b). the reaction will expand in volume (ΔV positive).. and the surroundings will do compression work on the system.79 J K−1 mol−1 2 2 . 2 C(graphite.g. keeping the mass of the amplifier down. then w < 0. Using Al. The specific heat capacities are: 0.45 J °C−1 g−1 (Fe). s) + 3/2 H2(g) + 1/2 Cl2(g) → C2H3Cl(g) e. When a balanced reaction has a decrease in the moles of gas from reactants to products (Δn negative). and the system does work on the surroundings (c and e). the reaction will contract in volume (ΔV negative). aluminum oxide = Al2O3. a. C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l) Note: ΔHcomb values assume 1 mole of compound combusted. where Δn = 2 − 2 = 0. the reaction will expand in volume (ΔV positive). and the surroundings will do compression work on the system.89 J °C−1 g−1 (Al) and 0. and the surroundings do work on the system (a and d).. When a balanced reaction has a decrease in the moles of gas from reactants to products (as in a). If the gas is monoatomic: Cv = 3 5 R = 12. then w > 0. the same amount of heat could be dissipated by a smaller mass.47 J K−1 mol−1 and Cp = R = 20. When there is no change in the moles of gas from reactants to products. It has a higher heat capacity and a lower density than Fe. When there is no change in the moles of gas from reactants to products (as in c). w = −PΔV. and the system will do work on the surroundings.362 CHAPTER 9 ENERGY. compare the coefficients of all the product gases in the balanced equation to the coefficients of all the reactant gases. f. When ΔV = 0 (Δn = 0). ΔV = 0 and w = 0. 85. When ΔV > 0 (Δn > 0). in reaction c. ΔV = 0 and w = 0.g. For example. When a balanced reaction has more moles of product gases than moles of reactant gases (Δn positive). and the system does work on the surroundings. reaction a. Al would be the better choice. where Δn = 0 − 1 = −1. then w = 0 (b). the reaction will contract in volume (ΔV negative).

273. ΔHfus. J) = 1455 J (Gas expansion. AND THERMOCHEMISTRY 363 If the gas is behaving ideally.92% total energy per hour 3. 258.00 mol = 5. 273.13 kJ ΔHfus.563 kJ ΔH2 = 1 mol(5.2 K) H2O(l. Energy needed = 20. 273.2 K) H2O(s.0 K ) Cp − Cv = 29. 2 K) → H2O(l.2 K).9 kJ/2. 273. At constant volume: qv = 2079 J = nCvΔT Cv = 2079 J 2079 J = = 20. 89. H2O(s) → H2O(l) ΔH = ΔHfus.2 = ΔH1 + ΔH2 + ΔH3 ______________________________________________________________________________________________________________ ΔHfus. then Cp − Cv = R = 8.0 kJ = s m2 s m2 Energy from sun = 1.0 − 550.2 K) → H2O(s.5 J K−1 mol−1)(−15. so system does work on surroundings.0°C (or 258.2 K = 10.2 K) → H2O(l. × 103 g C12 H 22 O11 1 mol C12 H 22 O11 5640 kJ × × = 3.3 J K−1 mol−1)(15.3 J K−1 mol−1 = R The gas is behaving ideally since Cp − Cv = R.79 = 8.) Cp = qp nΔT = 1455 J = 29. 273. ENTHALPY.3145 J K−1 mol−1.0 K) = −563 J = −0.1 − 20.79 J K−1 mol−1 nΔT (1 mol)(400. 258.000 m2 × 1.2 K) H2O(s.2 = 6. 273. 258. for 1 mol of supercooled water at −15.3 × 105 kJ energy used per hour × 100 = × 100 = 0.0 − 300. the gas is not a monoatomic gas. ΔHfus.13 kJ.2 K) → H2O(l.45 kJ ΔH3 = 1 mol(75.3 × 105 kJ/h h 342.0 kW/m2 = 1000 W/m2 = 10.45 kJ/mol.0 K) = 1130 J = 1.3 g C12 H 22 O11 mol 1000 J 1.47 J.CHAPTER 9 ENERGY.6 × 10 7 kJ Percent efficiency = . 273.1 J K−1 mol−1 (1 mol)(600.45 kJ + 1. At constant pressure: qp = nCpΔT qp = ΔE − w = 1305 J − (−150.0 K ) Because Cv ≠ 3/2 R = 12.563 kJ + 5. Using Hess’s law and the equation ΔH = nCpΔT: H2O(s. 258.6 × 107 kJ/h 2 min h sm 3.02 kJ/mol 90.0 kJ 60 s 60 min × × = 3. 258.2 K) ΔH1 = 1 mol(37.2 = −0.45 kJ/mol) = 5.

9)(223)(1 kJ/1000 J) = 6.0 K)(1 kJ/1000 J) = 5. HCl ) − ( ΔH o.800 J = 10.4 × 105 kJ.13 × (2.37 J K−1 mol−1 Molar heat capacity of H2O(g) = 2.9 × 104 kJ/m2 2 min h sm Only 13% of the sunlight is converted into electricity: 0.2 K) → H2O(g. kJ h 3600 s × = 1. Using Hess's law and the equation ΔH = nCpΔT: ΔH1 = -83.1)(−223)(1/1000) = −6. 298.2 K) ΔH3 = 1 mol(36.73 kJ __________________________________________________________________________ H2O(l.3 kJ CH3Cl(248°C) + H2(248°C) → CH4(248°C) + HCl(248°C) CH3Cl(25°C) → CH3Cl(248°C) ΔH2 = 1 mol(48.44 kJ − 9.2 K) ΔH2 = 1 mol(40.0 h = 2.4 J K−1 mol−1 Using Hess’s law and the equation ΔH = nCpΔT: H2O(l.8 kJ ΔH3 = 1(28.2 K) ΔH1 = 1 mol(75. CH 3Cl = −85 kJ/mol f f 93.0 hours = 10.2 K) → H2O(l. CH 3Cl + 0). a. 373.44 kJ H2(25°C) → H2(248°C) CH4(248°C) → CH4(25°C) ΔH4 = 1(41. 373.4 J K−1 mol−1)(−75. 373.2 K) → H2O(g. CH 3Cl + ΔH o. 298.2 K) → H2O(g. H 2 ) f f f f −81.65 kJ H2O(l.5 J °C−1 mol−1)(223°C) = 10.66 kJ H2O(g.9 × 104 kJ/m2) × area = 1. Energy used in 8. 373.015 g/mol) = 36. ΔH° = (ΔH o.58 kJ/mol Using ΔH o values in Appendix 4 (which are determined at 25° C): f ΔH°vap = −242 kJ − (−286 kJ) = 44 kJ To two significant figures.0 K)(1 kJ/1000 J) = −2.21 kJ − 6.8 kJ + 6.37 J K−1 mol−1)(75.184 J K−1 g−1(18.2 K = ΔH1 + ΔH2 + ΔH3 = 43.3)(−223)(1/1000) = −9. ENTHALPY.49 kJ ____________________________________________________________________________ CH3Cl(25°C) + H2(25°C) → CH4(25°C) + HCl(25°C) ΔH° = ΔH1 + ΔH2 + ΔH3 + ΔH4 + ΔH5 ΔH° = −83.364 91. kWh = 40.66 kJ/mol) = 40. CH 4 + ΔH o. 92.0 hours = 40. the two calculated ΔHvap values agree (as they should). 298.015 g/mol) = 75.4 × 105 kJ s h Energy from the sun in 8. 298. 298.8 kJ b.3 kJ + 10. AND THERMOCHEMISTRY Molar heat capacity of H2O(l) = 4.2 K) ΔH vap.8 kJ = (−75 kJ − 92 kJ) − (ΔH o. kJ 60 s 60 min × × × 8. CHAPTER 9 ENERGY.21 kJ HCl(248°C) → HCl(25°C) ΔH5 = 1(29.02 J K−1 g−1(18. area = 37 m2 . ΔH o.49 kJ = −81.

AND THERMOCHEMISTRY 365 a.0-L bulb. We call this a free expansion of a gas. the gas will be evenly dispersed throughout the two bulbs. q required to convert 1 mol H2O(s) at 0EC into 1 mol H2O(l) at 0EC.4 mol(0. and w = 0. q = −w = −(−PexΔV).EC into 1 mol H2O(g) at 100. Eventually.5 atm Vf 24. use the specific heat capacity of H2O(s) 2. c. ΔH = 0.EC. q required to heat H2O(s) from !30. q required to convert 1 mol H2O(l) at 100. Pinitial = Pi = nRT 2.EC to H2O(g) at 140. If the expansion occurs against some nonzero constant external pressure.0 L Pi Vi 15 atm(4.0 L Pfinal = Pf = b. use the specific heat capacity of H2O(g) We will sum up the heat required for all five parts. . ΔH = 0. 95.CHAPTER 9 94. Because ΔE = q + w = 0.EC. For an isothermal (constant T) process involving the expansion or compression of a gas. use ΔHvaporization 5. q required to heat H2O(l) from 0EC to 100. The gas will flow out of the 4. Assuming the gas behaves ideally. ΔE = 0 and ΔH = 0. Work can only occur in the expansion of a gas when the gas expands against a certain nonzero external pressure. From ΔE = q + w = 0. which will be discussed in detail in Chapter 10.EC. The pressure will be the same inside both bulbs. then ΔE = 0. Because w = 0. The gas is expanding against a vacuum (Pex = 0). then ΔE = nCvΔT and ΔH = nCpΔT. ENERGY.EC to 0EC.0 L. This driving force is related to entropy.0 L) = = 2.0 L to 24. Here we have an expansion of a gas where w = −PexΔV. Instead. However. q = −w = PexΔV (if the gas expands or contracts against some constant pressure).EC to 140.00 mol of H2O(s) at !30. The moles of gas (n) and the temperature (T) are constant. ΔE = nCvΔT = 0 (ΔH is also zero). q required to heat H2O(g) from 100. ΔE = 0. We need to calculate: 1. use ΔHfusion 3. q = −w = 0. q = −w. as the gas expands from 4. There are five parts to this problem. 96. Because ΔT = 0. use the specific heat capacity of H2O(l) 4.08206 L atm K −1 mol −1 )(305 K ) = = 15 atm Vi 4. q = −w = PexΔV. q = 0.0 L bulb into the 20. w ≠ 0 and q ≠ 0. In this problem the gas mixed evenly throughout both bulbs is the most probable (likely) state to occur. The driving force is the natural tendency of processes to spontaneously proceed toward states that have the highest probability of existing. So if the expansion or compression occurs against some nonzero external pressure. ENTHALPY. For a free expansion of an ideal gas at a constant temperature.EC. so w = 0. and this will be the total amount of heat required to convert 1. the pressure will decrease.

00 mol X = 227 g − 132 g − 45.8 kJ Marathon Problems 97. 0. and 0.5 × 103 J qtotal = q1 + q2 + q3 + q4 + q5 = 5. and because only -189.50 mol H2O ⎜ ⎟ ⎝ mol ⎠ ⎝ mol ⎠ ⎛ 32. 2. – 100.00 °C)(1 kJ/1000 J) qrxn = −189.)EC = 1.1 kJ (carrying extra significant figsures) Because ΔH = −1893 kJ/mol for the decomposition reaction.250 mol H2O. AND THERMOCHEMISTRY q1 = 2. ENTHALPY.1 × 103 J q2 = 1. The total moles of gas produced can be determined from the gas law data provided in the problem.53 × 103 J q4 = 1. 189.52 .100 mol X From the problem.0 g ⎞ ⎛ 18.25 mol O2 ⎜ ⎟ + (mass of A) ⎝ mol ⎠ Mass of A in 1.300 mol CO2.0 g − 8.25. Therefore.0 g ⎞ + 0.1 kJ × (1 mol X/1893 kJ) = 0.00 mol × 6.50 mol H2O. 0. Because H2O(l) is a product.02 J °C−1 g−1 × 18. For the reaction at constant P (ΔH = q): − q H 2O = q rxn = -4. Molar mass of X = 22. the identity of A.0 g ⎞ 1.)]EC = 1.18 J °C−1 g−1 × 18.03 J EC−1 g−1 × 18.68 × 104 J = 56.02 g × (140.00 mol X contains 3. we need the moles of A produced. X → CO2(g) + H2O(l) + O2(g) + A(g) ΔH = −1893 kJ/mol (unbalanced) To determine X.25 mol O2. Ptotal = Pgases + PH 2O .366 CHAPTER 9 ENERGY.7 g X = 227 g/mol 0. 1. and 0. we need to subtract PH 2O from the total pressure.01 × 103 J q3 = 4. Pgases = 778 torr − 31 torr = 747 torr RT .000 × 104 g)(29.7 × 104 J/mol = 4.0 g = 42 g A To determine A. we must determine the moles of X reacted.184 J °C-1 g-1(1.02 g × (100. and the moles of A produced.02 g × [0 – (!30.00 mol CO2.01 × 103 J/mol = 6.00 mol × 40. ⎛ 44. – 0)EC = 7.00 mol CO2 ⎜ ⎟ + 2.1 kJ of heat was released for this reaction.07 × 104 J q5 = 2. ntotal = PV .100 mol X produced 0.025 mol O2.100 mol X were reacted.00 mol X = 227 g = 3.

⎛ 1 atm ⎞ b.50 mol A.150 mol A Because 0.3 L atm ⎟ ⎝ ⎠ ⎛ 8.100 mol X reacted.08206 L atm RT (302.25 kJ/0. for your information. V = (59. AND THERMOCHEMISTRY 367 ⎛ 1L ⎞ ⎟ V = height × area. N 2 ) − (ΔH o.25 kJ ⎟ ⎠ c.5 kJ/mol) = −1906 kJ/mol ΔH o for C3H5N3O9 can be estimated from standard enthalpies of formation data and assuming f ΔH rxn = ΔH o .100 mol = −12. which from a previous calculation represents 42 g A. ENTHALPY. w = −1.5ΔH o. C3H 5 N 3O9 = −2.50 mol A Because A is a gaseous element. For the balanced reaction given in part a. is nitroglycerine.5 N2(g). w = −PΔV = −778 torr ⎜ ⎜ 760 torr ⎟ (12. 1. H 2O + 0. where ΔH o = −1893 kJ: rxn rxn −1893 kJ = (3ΔH o. For a balanced reaction. C3H 5 N 3O9 ) f f f f f −1893 kJ = [3(−393.00 cm)2 ⎜ ⎜ 1000 cm 3 ⎟ = 12.67 K ) K mol Mol A = 0.0 L ⎝ ⎠ T = 273. Molar mass of A = 42 g A = 28 g/mol 1. Now we can determine the formula of X.5 kJ/mol ΔE = ΔH + w = −1893 kJ/mol + (−12.0 L) ⎟ PV ⎝ ⎠ ntotal = = = 0.08206 L atm K −1 mol −1 ⎝ ⎞ ⎟ = −1250 J = −1.5ΔH o. area = πr2.5 H2O(l) + 0.3145 J K −1 mol −1 −12.300 mol CO2 − 0.25ΔH o. a.67 K ⎛ 1 atm ⎞ 747 torr⎜ ⎜ 760 torr ⎟ (12.3 L atm ⎜ ⎜ 0.CHAPTER 9 ENERGY. where q = ΔH since at constant pressure.5(−286) kJ + 0 + 0] − ΔH o.025 mol O2 = 0. the only element that is a gas and has this molar mass is N2(g).5 kJ/mol = −3 kJ/mol f .15 + 29.8 cm)(π)(8.5) kJ + 2.00 mol X would contain 1. C3H 5 N 3O9 f ΔH o.25 kJ.0 L − 0) = −12. X → 3 CO2(g) + 2.25 O2(g) + 1.475 mol = mol CO2 + mol O2 + mol A 0. For 1 mol of X decomposed: w = −1. which.52 = 302. Thus A = N2(g). ΔE = q + w. X = C3H5N3O9.475 mol total − 0. CO 2 + 2. O 2 + 1.

00 ! a = mol H2O (assuming 1. CHAPTER 9 ENERGY.69 = y . ENTHALPY.5(3) ! 121(8) ! ΔH o 3H8 . AND THERMOCHEMISTRY ⎛ 2 x + y/2 ⎞ CxHy + ⎜ ⎟ Ο2 → x CO2 + y/2 H2O 2 ⎝ ⎠ [x(!393.5.1 g/mol 0.751 g/L = 1. Only C3H8 works.02 = 29.5)x ! 121y ! ΔH C x H y = !2044. the molar mass of CxHy must be less than the molar mass of Kr (83. along with other combinations.574 2 . !2044. mol H2O = 0. MM of CO2/H2O mixture = 29.5 = !393.80 g/mol).69)x = Thus: 0.368 98.5) + y/2 (!242)] ! ΔH o x H y = !2044.00 total moles of mixture) (44. multiply by three. solving: a = 0.00 atm × MM . ΔH o 3H8 = !104 kJ/mol C C . which gives y = 8.426 mol CO2 . !(393.574 mol y 0. x = 6 is possible. Because the hydrocarbon has a lower density than Kr.5 C dgas = P • MM .01)a + (1.00 ! a) × 18.426 x x For whole numbers. y = (2. x = 3. where MM = average molar mass of CO2/H2O mixture RT 0. 2.1. Note that y = 16.08206 L atm × 473 K K mol Let a = mol CO2 and 1.

2 kJ 1 kJ 0 kJ Etotal = AB AB AB 0 kJ 2 kJ 4 kJ B A 1 kJ A B 1 kJ B A 2 kJ A B 2 kJ 3 kJ 3 kJ B A A B The most likely total energy is 2 kJ. f. 15. We draw all the possible arrangements of the two particles in the three levels. The system is the portion of the universe in which we are interested. Processes c. b. ENTROPY. Entropy is how energy is distributed among energy levels in the “particles” that constitute a given system. and f require an external source of energy in order to occur since they are nonspontaneous. b. and g are spontaneous. 2 kJ 1 kJ 0 kJ Total E = x xx 0 kJ x x 1 kJ xx x 2 kJ 2 kJ 3 kJ x x xx __ __ 4 kJ The most likely total energy is 2 kJ. a. d. The universe is everything. universe = system + surroundings. 13. Entropy is closely associated with probability. AND FREE ENERGY Spontaneity and Entropy 12. The surroundings are everything else in the universe besides the system. A spontaneous process is one that occurs without any outside intervention. Processes a. c. d.CHAPTER 10 SPONTANEITY. 369 . 14. Positional probability is a type of probability that depends on the number of arrangements in space that yield a particular state. where the most probable arrangement (state) is the highest entropy state. e. e.

b. with solids having the smallest positional disorder (smallest entropy). a. All lead to an increase in positional probability. S = k ln 6 = 2. ENTROPY. Ω = 1. There is no change in volume and thus no change in the numbers of positions of the molecules. To change the probability. S = 1.370 16. The seven is not favored by energy. a. b. we would have to expend energy (do work). S = k ln 1 = 0 Ω = 4. e. N2. One die 1 2 3 4 5 6 1 2 3 4 5 6 7 2 3 4 5 6 7 8 3 4 5 6 7 8 9 4 5 6 7 8 9 5 6 7 8 9 6 7 8 9 10 Sum of the two dice 10 11 10 11 12 There are six ways to get a seven. S = k ln 4 = (1. Positional probability decreases because the volume decreases (P and V are inversely related). c. H2O(l) has greater positional probability than H2O(s). H2 at 100°C and 0. Thus a. 18. rather. There are more ways to roll a seven. which increases disorder. CHAPTER 10 SPONTANEITY. c. it is favored by probability. Arrangement I: Arrangement II: Arrangement III: S = k ln Ω. there is a greater volume accessible to the randomly moving gas molecules. 17. followed by liquids. AND FREE ENERGY Of the three phases.47 × 10−23 J/K . and g involve an increase in entropy. gases have the greatest positional probability (greatest entropy).91 × 10−23 J/K Ω = 6. The positional probability doesn't change. N2 at STP has the greater volume. 19.38 × 10−23 J/K) ln 4. We can consider all the possible throws by constructing a table. higher temperature and lower pressure mean greater volume and hence greater positional probability. more than any other number.5 atm. Positional probability increases. 20. b. c.

7 L . 71.1 The remainder of the energy (PΔV = nRΔT) goes into expanding the gas against the constant pressure. = 1240 − (12.9 kJ.0 K) = 4. V3 = 28.74 L P1 c.20.31 = 52. the units on the heat capacities also could be J °C−1 mol−1.4)Tf. V2 = nRT = 12. and Entropy Changes Involving Ideal Gases and Physical Changes 21.014 g qv =ΔE = nCvΔT = 3.9 kJ. 100.5 J °C−1 mol−1)(Tf .00 × 103 g C2H6 × 1 mol = 33. K.570 mol(20. as calculated previously (ΔE is unchanged). It takes nCpΔT amount of energy to carry out this process.9 kJ At constant volume.8 J K−1 mol−1)(60. 1.4 nRT = 5. The volumes for each step are: a.3 mol(52. V1 = b. because ΔT in °C = ΔT in K.9 kJ of energy is required.3 kJ For the constant pressure process.8 L P2 1340 = 77.53 × 104 J = 85.46 × 103 J = 4.715 nC p ΔT Cp 29. AND FREE ENERGY 371 Energy. Enthalpy. At constant pressure (assuming ethane acts as an ideal gas): Cp = Cv + R = 44.60 J K−1 mol−1)(48.8 = v = = 0.00 atm. ENTROPY. (0. T = 350.60 + 8.00 mol.0 °C − Tf) (5. The internal energy of the system increases by nCvΔT.00)Tf − 100.3 mol(44.4 K) = 7.46 kJ 23.4 K) = 8.91 J K−1 mol−1)(48.7 J °C−1 mol−1)(100. P2 = 2. P1 = 5.600 mol)(20.91 J K−1 mol−1 Energy required = qp = ΔH = nCpΔT = 33.570 mol 28. Tf = 24.CHAPTER 10 SPONTANEITY.0 °C) = (0.0 °C 17. and ΔE = 71. n = 1.00 atm. ΔE = 71. So the fraction that goes into raising the internal energy is: nC v ΔT C 20.07 g qv = ΔE = nCvΔT = 33. 22.19 × 104 J = 71. P3 = 1. Heat gain by He = heat loss by N2.400 mol)(12.3 mol 30.24 atm.0 g N2 × 1 mol = 3.

00 atm)(28.0)(1. V1) → (P2.74 L) = −16 L atm (P2. P2 = P1V1 (5.3 J = −3200 J = total work L atm wrev = −nRT ln(P1/P2) = −(1. a.0 mol)(8.000 mol)(28. ⎛V ⎞ ⎛ 20.27 J K−1 mol−1) ln(350.00) = -4680 J 25. qv =ΔE = nCvΔT = (1. V2) w = 0 (P3.51 × 103 J = 1.64 J/K + 5.8 L) = −15.00 mol)(8.94 × 103 J = 1.27)(350. V3) w = −(1.000 atm . w = −PΔV = −1.0 L ⎞ a.0) = = 2.0 − 298. 27. AND FREE ENERGY The process can be carried out in the following steps: (P1. ΔS = S350 − S298 = nCp ln(T2/T1) S350 − 213. −32 L atm × 101.0/298.3 J L−1 atm−1 = −1250 J ΔE = 0 for isothermal expansion. V1) → (P2.24 atm)(12. V2) → (P3.94 kJ b.7 − 12.51 kJ qp = ΔH = nCpΔT = (1.23 atm(20. V1) w = −PΔV = 0 (constant volume process) (P2.8 − 5. wrev = −nRT ln ⎜ 2 ⎟ = −(1. P1V1 = P2V2 since n and T are constant. so qrev = −wrev = nRT ln(V2/V1).95 J K−1 mol−1)(350.0 K) qv = 1.00/1.0) = 1. so qrev = -wrev = 1720 J b. V2) w = −(2.3145 J K−1 mol−1)(298 K) ln ⎜ ⎜ 10. so q = 1250 J.9 L atm wtotal = −16 − 15.000 mol)(37.3 L atm −12.63 J/K = molar entropy at 350.0 L − 10. w = 0.9 = −32 L atm.0 − 298.0 L ⎟ = −1720 J ⎟ ⎜V ⎟ ⎝ ⎠ ⎝ 1⎠ For isothermal expansion: ΔE = 0. K) ln(5. ΔE = 0.0) Gas expands isothermally against no pressure.0 K and 1. V2) → (P3.0/1.64 J/K = (1.0) = 350 J 26.0 L) = −12.3 L atm × 101.5 atm V2 (2. so ΔE = 0.994 J/K = 219.3145 J K−1 mol−1)(350. T = PV = 61 K nR qrev = (1.3145 J K−1 mol−1)(61 K) ln(2.372 CHAPTER 10 SPONTANEITY.00 mol)(8. and q = 0.000)(37.0) S350 = 213. ENTROPY.

174) = 218.3145 J K−1 mol−1) ln(1.0 L ⎞ Sf − 378 J/K = (3.1 J K−1 mol−1) = 378 J/K nRT = V1 = P1 3.174) − S(350. 1.174 atm) 1. 0. AND FREE ENERGY 373 c. 75°C): ΔS = nCp ln(T2/T1) = 1. 5. ΔS for this process is the sum of ΔS for each of the three steps.0 J K−1 mol−1) ln(348 K/398 K) = −10.8 J/K For a phase change. 25°C. 75°C) → A(g.50 × 104 J .11 J/K The sum of the three step gives A(l. 25°C. 25°C. 0.1 J K−1 mol−1) = 12. ΔS = nR ln(P1/P2) = S(350. 125°C) → A(g.0 J K−1 mol−1) ln(398 K/428 K) = −2.2 J/K b.125°C): ΔS = nCp ln(T2/T1) = 1.100 mol.6 J/K ⎟ ⎝ ⎠ Sf = 378 + 92.08206 L atm × 298 K K mol = 2. 25°C.63 J/K = (1.8 J/K) = 2.593 J/K = 13. 125°C) → A(l.00 mol(75. 28. 155°C) → A(g.4 L ⎟ = 92.00 mol(126.100 mol)(8.00 atm ⎛ 3000.100 mol. Si = 3.334 J/K = S(350.45 L 1.1 + 75. 155°C): ΔS = 75.000 mol)(8.45 L) Sf = 12.0 J K−1 mol−1 For A(g.6 J/K + 0. 1. He(g.11 = 62. He(3.00 atm) → He(3.00 atm) → He(g.100 mol(126. 1. 125°C).CHAPTER 10 SPONTANEITY.08206 L atm × 298 K K mol = 73.00 mol.100 mol × 0.30 J K−1 mol−1 a.00 mol.3145 J K−1 mol−1) ln ⎜ ⎜ 73.174) ΔS = −1. 3000. ΔS = −10.00 L) ΔS = nR ln(V2/V1) = Sfinal − Sinitial. 1. ENTROPY. 1. At 125°C: ΔHvap = TΔS = 398 K(62.6 J/K = (0.174) − 219.3145 J K−1 mol−1) ln(5. − 219.0 L) ΔS = nR ln(V2/V1) = Sfinal − Sinitial.6 = 471 J/K 29.6 J/K 0.00 mol × 0. S(350. ΔS = nR ln(V2/V1).0 − 2.00 mol)(8.00 mol(29.00 L/2. For A(l. 1. ΔS = ΔH/T.1 J/K For A(l. Si = 0.63.000 atm/1.00 atm nRT = V1 = P1 Sf − 12.000) ΔS = S(350.4 L 1. V = nRT/P.

800 J = 56.2 K ⎟ ⎝ ⎠ 101.2 K ) = 33.000 mol)(37.000 mol)(75.00 atm(30. q = (1.700 J + 1460 J = 56.2 K ⎞ 6010 J ΔS = (1.8 kJ At constant pressure: qp = ΔH = 56.6 L) w = −30.0°C to 140.5 J/K + 109 J/K + 3.00 atm(33.6 L 1.018 L) − 1.9 L atm.5 J K−1 mol−1) ln ⎜ ⎜ 243.8 kJ nRT = P 1.2 K ⎟ + 373.0 K) + 40.00 atm At 100.374 30. Keep all quantities positive to avoid sign errors.2 K ⎟ + 273.8 kJ.3 J K−1 mol−1)(100.2 K ⎟ ⎟ ⎝ ⎠ ΔS = 4.3 L atm = −33.43 kJ.08206 L atm × 372.4 J K−1 mol−1) ln ⎜ ⎜ 373.8 kJ − 3. AND FREE ENERGY Calculate q by breaking up the total process into several steps.700 J + (1. Calculate the final temperature by equating heat loss to heat gain.000 mol)(36. wtotal = −1.4 J K−1 mol−1)(40.2 K ⎟ ⎝ ⎠ ⎛ 413. −33.000 mol × 0.0°C: V = At 140.2 K ⎞ + (1. ΔH = 56. . ΔE = 53.4 kJ Calculate ΔS by breaking up the total process into several steps and using ΔS = nCp ln(T2/T1) or ΔS = ΔH/T (for phase changes) to calculate ΔS for each step.8 kJ.0 K) q = 1130 J + 6010 J + 7530 J + 40. w = −3.2 K ⎞ 40.000 mol)(37. and use the formula q = nCΔT or the ΔH values to calculate q for each step.43 kJ L atm ⎛ 373.700 J + (1.4 kJ.5 J K−1 mol−1)(30.2 K K mol = 30.0 J/K + 23.0°C. ⎛ 273.000 mol)(75.0°C: V = nR (413.6 L − 0.36 J/K + 22.43 kJ = 53.0 K) + 6010 J + (1.9 L atm × ΔE = q + w = 56.6 L atm − 3. CHAPTER 10 SPONTANEITY.30.71 J/K = 163 J/K Summary: q = 56.9 .3 J K−1 mol−1) ln ⎜ ⎜ 273. ENTROPY.9 L P Work is only done when vaporization occurs and when the vapor expands as T is increased from 100. ΔS = 163 J/K 31.3 J = −3430 J = −3. w = −PΔV.000 mol)( 36.

000 mol H2O Heat gained by the ice: (1.0 J/K Entropy and the Second Law of Thermodynamics: Free Energy 33.3 J K−1 mol−1) ln ⎜ ⎟ ⎝ 273. 54. Heat 3 mol H2O: ΔS1 = (3.0°C) + 6. ΔS = ΔH/T.2) = −29.00 mol)(75.01 × 103 J + (1.9 J/K ΔSwater = (3.000 mol)(75.02 g ice = 1.3 J K−1 mol−1) ln(327.000 mol(75.5 J °C−1 mol−1)(10.40 J/K + 22.8 .600 J − 226Tf Solving: Tf = 53.9 = 2.3)Tf = 22.0) Heat lost by H2O(l) = 3. for a phase change.000 mol)(75. For all processes combined.5 J K−1 mol−1) ln ⎜ ⎜ 263.05 g H2O = 3.2 K ⎟ + 273.16.2 K ⎞ 6010 J ΔSice = (1.0 J/K + 13. ⎛ 273.8°C Now calculate ΔS for the various changes using ΔS = nCp ln(T2/T1) or.000 mol)(75.0/373. 18.3 J °C−1 mol−1)(Tf − 0.9 = 7. .9 J/K ΔStotal = ΔSheat + ΔScool = 19.9 J/K 32.CHAPTER 10 SPONTANEITY.3 J °C−1 mol−1)(100. ENTROPY. Green plants use the energy from sunlight to produce glucose from carbon dioxide and water by photosynthesis.9 − 29.000 mol ice.000 mol)(37.0°C − Tf) Heat gain by ice = heat lost by H2O.5 J/K = 36. ΔSuniv must be greater than zero (second law).00 mol)(75.8 J/K Cool 1 mol H2O: ΔS2 = (1.3 J °C−1 mol−1)(Tf − 0°C) = (1.2 K ⎟ ⎝ ⎠ ⎛ 327.0 ⎞ + (1. Living organisms need an external source of energy to carry out these processes.00 mol)(75.00 mol)(75. AND FREE ENERGY 375 (3.2 ⎠ ΔSice = 1.000 mol)(37.9 J/K ΔStotal = ΔSice + ΔSwater = 36.3 J K−1 mol−1) ln(298/373) = −16.3 J °C−1 mol−1)(100. In the human body the energy released from the metabolism of glucose helps drive the synthesis of proteins.°C − Tf) Solving: Tf = 25°C = 298 K Now we can calculate ΔS for the various changes using ΔS = nCp ln (T2/T1). 375 J + 6010 J + (75.3 J K−1 mol−1) ln(298 K/273 K) = 19.

the entropy of the surroundings increases (ΔSsurr is positive). in turn. heat flows into the surroundings from the system. the gaseous state has a much larger volume associated with it and. This is an exothermic process.45 kJ/K = 7. In an endothermic reaction (ΔH > 0). the sign of ΔSsurr is negative. CO2(g). so the negative sign converts the negative ΔH value into a positive quantity. For an endothermic process where ΔH is positive. By the second law of thermodynamics. a. The magnitude of ΔSsurr also depends on the temperature. The negative sign in the ΔSsurr = !ΔH/T equation is necessary to get the signs correct. a. b.376 kJ/K = −376 J/K T 298 K b. To boil a liquid requires heat. Hence this is an endothermic process. Heat is released when gas molecules slow down enough to form the solid. The diamond form is a very ordered structure. a specific amount of heat exchange makes a larger percent change in the surroundings than the same amount of heat flow at a higher temperature. ΔSuniv must have increased even though it looks as if we have gone through a cyclic process. the gaseous state has a much larger volume associated with it and. In exothermic processes. more parts (electrons). heat is transferred from the surroundings into the system. a much greater positional probability. ΔSsurr = 38. ΔSsurr is primarily determined by heat flow. HCl(g). 36. greater positional probability. this increases ΔSsurr. a much greater positional probability.45 × 103 J/K T 298 K − ΔH − 112 kJ = = −0. AND FREE ENERGY It appears that the sum of the two processes has no net change. For an exothermic reaction where ΔH is negative. This is unfavorable. C2H5OH(g). e. 39.376 34. larger molecule. in turn. b. This is not so. All endothermic processes decrease the entropy of the surroundings (ΔSsurr is negative). d. greater positional probability. ΔSsurr = − ΔH − (−2221 kJ ) = = 7. c. This heat flow into or out of the surroundings comes from the heat flow out of or into the system. The heat flow into the surroundings increases the random motions in the surroundings and increases the entropy of the surroundings (ΔSsurr > 0). The relationship is inverse. N2O(g). Decrease in positional probability. at low temperatures. and the negative sign converts the positive ΔH value into a negative quantity. a. CHAPTER 10 SPONTANEITY. This heat flow out of the surroundings decreases the random motions in the surroundings and decreases the entropy of the surroundings (ΔSsurr < 0). more complicated molecule with more parts. 35. This is a favorable driving force for spontaneity. ENTROPY. a. 37. In an exothermic process (ΔH < 0). Cgraphite(s). graphite has the larger positional probability. ΔS°(−) .

2 H2S(g) + SO2(g) → 3 Srhombic(s) + 2 H2O(g). Decrease in positional probability (Δn < 0). HCl(g) has a greater positional probability due to the huge volume of gas. Decrease in positional probability (Δn < 0). Increase in positional probability. ENTROPY. ΔS° = o ∑ n pSo products − ∑ n r S reactants ΔS° = [3 mol Srhombic(s)(32 J K−1 mol−1) + 2 mol H2O(g)(189 J K−1 mol−1)] − [2 mol H2S(g)(206 J K−1 mol−1) + 1 mol SO2(g)(248 J K−1 mol−1)] ΔS° = 474 J/K − 660. ΔS° will be positive as positional probability increases when the moles of gas increase. ΔS° will be negative as positional probability decreases when the moles of gas decrease. 40. Fe2O3(s) + 3 H2(g) → 2 Fe(s) + 3 H2O(g). AND FREE ENERGY 377 b. because Δn of gases = 0 (Δn = 3 − 3). we can’t easily predict if ΔS° will be positive of negative. J K−1 mol−1) + 3 mol(131 J K−1 mol−1)] ΔS = 138 J/K 41. When Δn is negative. Let S o = SE for Fe(CO)5(l) and S o = SE for Fe(CO)5(g). J/K = −186 J/K b. SE = 198 J K−1 mol−1 for CO(g). d. So 4 = 262 J K−1 mol−1 CF CF 42. ΔS°(−) e. because there are more molecules of reactant gases as compared to product molecules of gas (Δn = 2 − 3 < 0). ΔS = 2 mol(27 J K−1 mol−1) + 3 mol(189 J K−1 mol−1) − [1 mol(90. ΔS°(−). g l . and e. When there are more gaseous product molecules than gaseous reactant molecules (Δn > 0). ΔS°(+) c.CHAPTER 10 SPONTANEITY. ΔS° = 2So 4 + So 2 − [ So 2 H 2 + 4So2 ] CF H C F − 358 J/K = (2 mol)So 4 + 131 J/K − [201 J/K + 4(203 J/K)]. Increase in positional probability. a. concentrate on the gaseous products and reactants. ΔS°(+) For c. From Appendix 4. 2 SO3(g) → 2 SO2(g) + O2(g). and SE = 27 J K−1 mol−1 for Fe(s). ΔS°(−) d. Because Δn of gases is positive (Δn = 3 − 2). f. ΔS = 2 mol(248 J K−1 mol−1) + 1 mol(205 J K−1 mol−1) − [2 mol(257 J K−1 mol−1)] = 187 J/K c. C2H2(g) + 4 F2(g) → 2 CF4(g) + H2(g). then ΔS° is negative. then ΔS° will be positive.

ΔG = 0. ΔG = 0 and ΔSuniv = 0.) = 110.7 × 103 J / mol − ΔH = = !110. C2H5OH(l) → C2H5OH(g). J K−1 mol−1) g S o = SE for Fe(CO)5(g) = 447 J K−1 mol−1 g 43. so T = 48. b. So 3 = 184 J K−1 mol−1 AlBr AlBr At the boiling point. a. at the boiling point. 44. J K−1 mol−1 T 351 K ΔSsys = !ΔSsurr = !(!110. NH3(s) → NH3(l). −144 J/K = (2 mol) So 3 − [2(28 J/K) + 3(152 J/K)]. ΔH 5650 J / mol = = 196 K. ΔS = ΔH 27.51 × 103 J / mol = = 629. ΔS 28. for ΔG to be negative only above a certain temperature.9 J K−1 mol−1) ΔG = 5650 J/mol − 5780 J/mol = −130 J/mol Yes. K(28. For the vaporization process.5 kJ / mol = = 8. ΔG = ΔH − TΔS.9 J K −1 mol −1 a. ΔSsurr = 38. T = ΔH 58. At the melting point. ΔG = 0. ΔG = ΔH − TΔS = 5650 J/mol − 200. Because ΔS is positive. To calculate ΔSsys. AND FREE ENERGY ΔSE = !677 J/K = 1 mol(S o ) – [1 mol(27 J K−1 mol−1) + 5 mol(198 J K−1 mol−1)] l S o = 340.93 × 10−2 kJ K−1 mol−1 = 89. then ΔH is positive and ΔS is positive (see Table 10. Srhombic is the more ordered crystalline structure (has the smaller positional probability associated with it). we will determine ΔSsurr from ΔH and the temperature. At the boiling point. Srhombic → Smonoclinic. . J K−1 mol−1 l ΔSE = 107 J/K = 1 mol(S o ) – 1 mol(340. so ΔH = TΔS. ENTROPY. then ΔSsys = !ΔSsurr for a system at equilibrium. whereas ΔH is a negative value. NH3 will melt because ΔG < 0 at this temperature. J K−1 mol−1 47.7 K ΔS 92.378 CHAPTER 10 SPONTANEITY. b.6 of text). ΔG = 0 so ΔH = TΔS.92 J K −1 mol −1 46. this phase transition is spontaneous (ΔG < 0) at temperatures above 95°C.3 J K−1 mol−1 T ( 273 + 35) K 45. ΔS is a positive value.

ENTROPY.7 K = !229. ΔSo = ∑ n pSo f f. We can use ΔG° = ΔH° − TΔS° (be careful of units): ΔG° = ΔH° − TΔS° = −803 × 103 J − (298 K)(−4 J/K) = −8. a. products − ∑ n r ΔH o reactants .5 kJ/mol −286 −1275 0 f S° 214 J K−1 mol−1 70. SPONTANEITY.5 −242 f ΔG o f −51 kJ/mol 0 −394 −229 (Appendix 4 data) S° 186 J K-1 mol-1 205 214 189 _____________________________________________________________________ o ΔH° = ∑ n p ΔH o.0 J K −l mol −1 Free Energy and Chemical Reactions 50. AND FREE ENERGY 379 Solid I → solid II.CHAPTER 10 49. T = ΔH/ΔS = − 743.018 × 105 J = −802 kJ or we can use ΔG o values. ΔG° = 2 mol(−229 kJ/mol) + 1 mol(−394 kJ/mol) − [1 mol(−51 kJ/mol)] ΔG° = −801 kJ (Answers are the same within round-off error.)] = −262 J/K ΔG° = 2802 kJ − (298 K)( −0.5 kJ/mol) − [1 mol(−75 kJ/mol)] = −803 kJ ΔS° = 2 mol(189 J K−1 mol−1) + 1 mol(214 J K−1 mol−1) − [1 mol(186 J K−1 mol−1) + 2 mol(205 J K−1 mol−1)] = −4 J/K There are two ways to get ΔG°. products − ∑ n r S reactants ΔH° = 2 mol(−242 kJ/mol) + 1 mol(−393.5)] = 2802 kJ ΔS° = 6(205) + 212 − [6(214) + 6(70. + 2 O2(g) → CO2(g) + 2 H2O(g) CH4(g) _____________________________________________________________________ ΔH o −75 kJ/mol 0 −393. ΔG = ΔH ! TΔS. where ΔG° = f ∑ n p ΔG o.1 J / mol = 43. 212 205 ______________________________________________________ ΔH° = −1275 − [6(−286) + 6(−393.) b. equilibrium occurs when ΔG = 0. 6 CO2(g) + 6 H2O(l) → C6H12O6(s) + 6 O2(g) _______________________________________________________ ΔH o −393.262 kJ/K) = 2880.5°C − 17. products − ∑ n r ΔG o reactants : f f. ΔH = TΔS. kJ .

and ΔSE.1766 kJ/K) = −5. CH2 O CH2(g) + HCN(g) CH2 CHCN(g) + H2O(l) . HCl(g) + NH3(g) → NH4Cl(s) ___________________________________________________________ ΔH o −92 −46 −314 f (kJ/mol) S° 187 193 96 (J K−1 mol−1) ___________________________________________________________ ΔH° = −314 − (−92 − 46) = −176 kJ. (J K−1 mol−1) _______________________________________________ ΔH° = 4 mol(−1279 kJ/mol) − [1 mol(−2984 kJ/mol) + 6 mol(−286 kJ/mol)] = −416 kJ ΔS° = 4(110. ENTROPY.6 K o − 0. However. We calculate ΔHE and ΔS° values for a reaction using Appendix 4 data.03 kJ = = 328. ΔS° = 96 − (187 + 193) = −284 J/K ΔG° = ΔH° − TΔS° = −176 kJ − (298 K)(−0. ΔG° = -58. C 4 H10 . AND FREE ENERGY P4O10(s) + 6 H2O(l) → 4 H3PO4(s) ______________________________________________ ΔH o −2984 −286 −1279 f (kJ/mol) S° 229 70.1766 kJ / K ΔS 53. ΔHE. The temperature is usually assumed to be 25EC. 52. −5490. T = ΔH o − 58. ΔGE has the greatest dependence on temperature.03 kJ − (298 K)(−0. kJ = 8(−394 kJ) + 10(−237 kJ) − 2 ΔG o. ΔG o. if other temperatures are used in a reaction.) − [229 + 6(70.284 kJ/K) = −91 kJ 51.380 c.)] = −209 J/K ΔG° = ΔH° − TΔS° = −416 kJ − (298 K)(−0. CHAPTER 10 SPONTANEITY. ΔG° is negative below 328.40 kJ ΔG° = 0 = ΔH° − TΔS°. where the favorable ΔH° term dominates. and then use the different temperature in the ΔG° = ΔHE ! TΔS° equation to determine (estimate) ΔG° at that different temperature. C 4 H10 = −16 kJ/mol f f Of the functions ΔGE. a. 110. 54.6 K. we can estimate ΔG° at that different temperature by assuming ΔH° and ΔS° are temperature independent (which is not always the best assumption).209 kJ/K) = −354 kJ d.

ΔS° = 161 − (219 + 189) = −247 J/K When ΔG° = 0. the favorable entropy term will dominate.0) − [4(20.°C = 343 K. Because ΔG° is positive. 56. this reaction is not spontaneous at standard conditions at 298 K. − 247 J/K ΔSo . ΔG° = 2(−270. ΔH° = ΔG° + TΔS° = 464 kJ + 298 K(0.1) = −183 kJ. J/K ΔG° = ΔH° − TΔS° = −183 kJ − 298 K(−0.)] = −1336 kJ ΔS° = 192 + 6(189) + 4(274) − [6(211) + 4(266. ΔG 973 = ΔH° − TΔS° = −1336 kJ − 973 K(0.9) + 6(90. ENTROPY.129 kJ/K) o ΔG 343 = −177 kJ + 44 kJ = −133 kJ c. At these temperatures.°C = 973 K. HC≡CH(g) + HCN(g) → CH2=CHCN(g) ΔH° = 185. kJ) − 2(−502 kJ) = 464 kJ b. ΔH° = TΔS°.0 − 286 − (−53 + 135. c. C2H4(g) + H2O(g) → CH3CH2OH(l) ΔH° = −278 − (52 − 242) = −88 kJ.1 + 227) = −177 kJ. − (242 + 202) = −100. AND FREE ENERGY 381 ΔH° = 185. 4 CH2=CHCH3(g) + 6 NO(g) → 4 CH2=CHCN(g) + 6 H2O(g) + N2(g) ΔH° = 6(−242) + 4(185. ΔG 343 = ΔH° − TΔS° = −177 kJ − 343 K(−0.179 kJ/K) = 517 kJ We need to solve for the temperature when ΔG° = 0: ΔG° = 0 = ΔH° − TΔS°. T = ΔH o 517 kJ = = 2890 K o 0.179 kJ/K ΔS This reaction will be spontaneous at standard conditions (ΔG° < 0) when T > 2890 K.CHAPTER 10 SPONTANEITY.088 kJ/K) o ΔG 973 = −1336 kJ − 86 kJ = −1422 kJ 55. a.9)] = 88 J/K o T = 700.100 kJ/K) = −153 kJ b. ΔS° = 274 − (202 + 201) = −129 J/K o T = 70. ΔG° = ΔH° − TΔS°.0 − (135. so T = ΔH o − 88 × 103 J = = 360 K. ΔS° = 274 + 70.

so ΔS must provide the driving force for the change.5 + 189) = −127 J/K This reaction can never be spontaneous at standard conditions because of the signs of ΔH° and ΔS°. so the original enzyme has the more ordered structure (has the smaller positional probability). a. J/K ΔG° = ΔH° − TΔS° = −16 kJ − (298 K)(−0. 57.5 + (−201)] = −173 kJ. kJ This reaction also has a favorable enthalpy and an unfavorable entropy term.7 − 242) = 49 kJ. 6 C(s) + 6 O2(g) → 6 CO2(g) ΔG° = 6(−394 kJ) ΔG° = 3(−237 kJ) 3 H2(g) + 3/2 O2(g) → 3 H2O(l) 6 CO2(g) + 3 H2O(l) → C6H6(l) + 15/2 O2(g) ΔG° = −1/2 (−6399 kJ) ____________________________________________________________________ ΔG° = 125 kJ 6 C(s) + 3 H2(g) → C6H6(l) Enthalpy is not favorable. This is not practical. CH4(g) + CO2(g) → CH3CO2H(l) ΔH° = −484 − [−75 + (−393. Thus ΔS is positive. There is an increase in positional probability. so the reaction will be spontaneous when ΔG° < 0. ΔS° = 131 + 161 − (229. Because there are more reactant molecules of gas than product molecules of gas (Δn < 0). − (186 + 214) = −240. Since the signs of ΔH° and ΔS° are both negative. This reaction is spontaneous at temperatures below T = ΔH°/ΔS° = 622 K (assuming standard concentrations).5)] = −16 kJ. this reaction will be spontaneous at temperatures below 360 K (where the favorable ΔH° term will dominate). ΔS° = 160. When a bond is formed. The reaction of CH3OH and CO will be preferred at standard conditions. ΔS° = 160. 59.278 kJ/K) = −90. this reaction is spontaneous only at temperatures below T = ΔH°/ΔS° = 67 K (where the favorable ΔH° term will dominate. Thus the reaction C2H4(g) + H2O(g) → C2H5OH(l) would be preferred at standard conditions. CH3OH(g) + CO(g) → CH3CO2H(l) ΔH° = −484 − [−110. ΔS will be negative. 58. energy is released. C2H6(g) + H2O(g) → CH3CH2OH(l) + H2(g) ΔH° = −278 − (−84. It is spontaneous at high enough temperatures that the rates of reaction should be reasonable.382 CHAPTER 10 SPONTANEITY. giving a negative ΔG° value). .) = −278 J/K ΔG° = −173 kJ − (298 K)(−0. ΔG = ΔG°. where ΔG = ΔG°. so ΔH is negative. 60.240 kJ/K) = 56 kJ At standard concentrations. Substances will be in condensed phases and rates will be very slow at this extremely low temperature. − (198 + 240. AND FREE ENERGY At standard concentrations. ENTROPY.

ΔG° = 63. ΔG° = 2(−371) − [2(−300. the forward reaction is spontaneous. As long as ΔG is a negative. At constant temperature and pressure. Because ΔG° is negative. At 10. the system cannot minimize its free energy anymore. the sign of ΔG (positive or negative) tells us which reaction is spontaneous (the forward or reverse reaction). note: ΔG = ΔG° when all gases are ⎟ ⎠ at 1. the purpose of the elevated temperature must be to increase the rate of the reaction. then the forward reaction is spontaneous and if ΔG > 0.0 atm: ΔG = −142 kJ + ⎛ (10. AND FREE ENERGY 383 b.0) ⎟ = −148 kJ 1000 J / kJ ⎝ ⎠ PN 2O 4 2 PNO 2 65. then the reaction is at equilibrium (neither the forward nor reverse reaction is spontaneous). The equilibrium position represents the lowest total free energy available to any particular reaction system. where the ΔH term dominates. products − ∑ n r ΔG o reactants . ΔG° gives the equilibrium position by deter-mining K for a reaction utilizing the equation ΔG° = !RT ln K. the favorable enthalpy term must dominate. kinetic reasons.0) 2 (10. i. then the reverse reaction is spontaneous.00 atm. ΔS will be positive. 2 ⎛ PSO 3 ⎜ ΔG = ΔG° + RT ln Q = −142 kJ + RT ln 2 ⎜ PSO × PO 2 2 ⎝ ∑ n p ΔG o. so ΔG = ΔG° since Q = 1 and ln Q = 0. These are standard conditions. for this reaction to be spontaneous (ΔG < 0). ENTROPY. Once equilibrium is reached. Free Energy: Pressure Dependence and Equilibrium 62. this reaction is spontaneous at all temperatures. ΔG = ΔH − TΔS.)] = −142 kJ ⎞ ⎟ . All reactions want to minimize their free energy. The reaction will be spontaneous at low temperatures. ΔG° can only be used to predict spontaneity when all reactants and products are present at standard pressures of 1 atm and/or standard concentrations of 1 M.3145 J K −1 mol −1 ⎟ (298 K ) ln⎜ ⎜ (10.CHAPTER 10 SPONTANEITY. Converting from reactants to products or products to reactants will increase the total free energy of the system. ΔG = ΔG° + RT ln Q = ΔG° + RT ln ΔG° = 1 mol(98 kJ/mol) − 2 mol(52 kJ/mol) = −6 kJ a.e. the process occurs.. which reactions do not want to do. Because there is no thermodynamic reason to do this. From the signs of ΔH and ΔS.0) 2 ⎞ 8. Because there are more product gas molecules than reactant gas molecules (Δn > 0). 61. The reaction shifts right to reach equilibrium. If ΔG = 0. 64. If ΔG < 0. It will cost money to heat the reaction mixture. This is the driving force for any process. f f. .

ΔG = −6 × 103 J + 8.72 ⎟ = exp⎜ = 9.) 3 ΔG = −34 kJ − 33 kJ = −67 kJ b.) 2 ln 1000 J / kJ ( 200.)] = −90. 66. ΔG° = 3(0) + 2(−229) − [2(−34) + 1(−300.3145 J K −1 mol −1 )(298 K ) (50. ΔG = −6 × 103 J + 8. o ΔH° = 2 ΔH f . AND FREE ENERGY 0.29) 2 ΔG = −6 × 103 J + 7.6 (0. kJ 67.030) 2 kJ ⎢ln ⎥ −4 2 1000 ⎣ (1.3145 J K −1 mol −1 )(298 K ) ⎟ = e RT ⎝ ⎠ Note: When determining exponents. we will round off after the calculation is complete.3145 J K−1 mol−1(298 K) ln 1.)(200. . Assume ΔH° and ΔS° are temperature independent. the reverse reaction is spontaneous.010) ⎦ ΔG = −90.3145 J K−1 mol−1(298 K) ln ΔG = −6 × 103 J + 6. kJ ΔG = ΔG° + RT ln 2 PH 2O 2 PH 2S × PSO 2 = −90.) 3 ΔG = −34 kJ − 34. This helps eliminate excessive round off error. kJ + ⎤ (8. ENTROPY.3145 J K −1 mol −1 )(298 K ) (200. c.0 × 10 ) (0. ΔG° = 2ΔG o.7 kJ = −50.3145)(298) ⎡ (0.3 × 103 J = 1. kJ + 39.50 (0.) 2 ln 1000 J / kJ (200. ΔG = −34 kJ + (8.)(600. so the reaction shifts to the left to reach equilibrium.000 J ) 13.1 × 105 ⎜ (8.0 × 103 J = 0 Since ΔG = 0.384 CHAPTER 10 SPONTANEITY. a.4 kJ = −68 kJ c. NH 3 = 2(−46) = −92 kJ. this reaction is at equilibrium (no shift). ΔG° = −RT ln K K= ⎛ ⎞ − ΔG o − (−34.3 × 103 J = 1 × 103 J Since ΔG is positive. ΔG = ΔG° + RT ln 2 PNH 3 3 PN 2 × PH 2 = −34 kJ + (8.21) 2 b. NH 3 = 2(−17) = −34 kJ f ΔS° = 2(193 J/K) − [192 J/K + 3(131 J/K)] = −199 J/K.

one needs to know ΔGE at that temperature.199 kJ/K) = 47 kJ 700 ΔG700 = 47 kJ + (10.3145 J K −1 mol −1 )(100.92 × 10−14) = 8. ΔG° = −RT ln K = − 8.9 kJ/mol K mol − 8. which occurs when ΔHE = TΔSE.)(200. K = 1 because ΔGE = 0.) 2 (8. we want ΔGE = 0.) 2 (8. We assume ΔHE and ΔSE are temperature-independent and use the equation ΔGE = ΔHE .) 3 ΔG700 = 47 kJ − 88 kJ = −41 kJ 68.11 × 104 J = 81. 70. K)(−0. −242 34 −174 −286 S° (J K−1 mol−1) 193 205 211 189 240. NH3(g) O2(g) NO(g) H2O(g) NO2(g) HNO3(l) H2O(l) ΔH o (kJ/mol) f −46 0 90.) 3 ΔG100 = −72 kJ − 13 kJ = −85 kJ d. AND FREE ENERGY 385 o o ΔG100 = ΔH° − TΔS°.) − [4(−46)] = −908 kJ . ΔG o = −92 kJ − (700. a. Again. At this temperature. assume ΔHE and ΔSE are temperature independent. and then solve for T (= ΔHE/ΔSE). 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g) ΔH° = 6(−242) + 4(90. To determine K at a temperature other than 25EC. 69. 156 70. K can never equal one. o ΔG 313 = −RT ln K = ΔGE = !RT ln K. When the signs are opposite. a.3145 J (313 K) ln(2. K ) ln 1000 J / kJ (50. For K = 1.3145 J K −1 mol −1 )(700.1 kJ/mol K mol b. K will always be greater than one (when ΔHE is negative and ΔSE is positive) or K will always be less than one (when ΔHE is positive and ΔSE is negative).99 × 104 J = 79.TΔSE to estimate ΔGE at the different temperature. K)(−0.3145 J (298 K) ln(1.199 kJ/K) = −72 kJ o ΔG100 = ΔG100 + RT ln Q = −72 kJ + (10. When the signs of ΔHE and ΔSE are opposite.CHAPTER 10 SPONTANEITY. ENTROPY. ΔG100 = −92 kJ − (100. This only works for reactions where the signs of ΔHE and ΔSE are the same (either both positive or both negative).)(200.00 × 10−14) = 7. K ) ln 1000 J / kJ (50.

3 × 1011 ⎥ = e −1 −1 RT 8. K= 2 PNF3 2 3 PN 2 × PF2 = (0. ENTROPY.3145 J K mol (1098 K ) ⎦ K = exp c. AND FREE ENERGY ΔS° = 4(211) + 6(189) − [4(193) + 5(205)] = 181 J/K ΔG° = −908 kJ − 298 K(0. Thus the purpose for the high temperature must be to increase the rate of the reaction.181 kJ/K) = −1107 kJ o ⎡ ⎤ − ΔG1098 − (−1.386 CHAPTER 10 SPONTANEITY.3145 J K mol (298 K ) ⎦ ⎣ Note: When determining exponents. we will round off after the calculation is complete. 3 NO2(g) + H2O(l) → 2 HNO3(l) + NO(g) ΔH° = 2(−174) + (90. ln K = − ΔG o − (−962 × 103 J ) = = 388 RT 8.107 × 10 6 J ) 121.) − [3(34) + (−286)] = −74 kJ ΔS° = 2(156) + (211) − [3(240.48) 2 = 4.4 −2 = exp ⎢ ⎥ = e = 9 × 10 −1 −1 RT ⎣ 8.4 × 104 0. K = 10168 (an extremely large value) 2 NO(g) + O2(g) → 2 NO2(g) ΔH° = 2(34) − [2(90. There is no thermodynamic reason for the elevated temperature since ΔH° is negative and ΔS° is positive.021(0.) + (70.303 log K.267 kJ/K) = 6 kJ K = exp ⎤ ⎡ − ΔG o − 6000 J −2. 71. ΔS° = 2(240.)] = −267 J/K ΔG° = −74 kJ − (298 K)(−0.258 = exp ⎢ = 4.) − [2(211) + (205)] = −147 J/K ΔG° = −112 kJ − (298 K)(−0.44 = exp ⎢ = 8. T = 825 + 273 = 1098 K. log K = 168. o ΔG1098 = ΔH° − TΔS° = −908 kJ − (1098 K)(0.147 kJ/K) = −68 kJ K = exp ⎤ ⎡ − ΔG o − (−68.063) 3 .000 J ) 27. ΔG° = −RT ln K.)] = −112 kJ.3145 J K −1 mol −1 × 298 K ln K = 2. We must determine ΔG° at 1098 K.589 × 1052 ⎥ = e −1 −1 RT ⎣ 8.3145 J K mol (298 K ) ⎦ b.181 kJ/K) = −962 kJ ΔG° = −RT ln K.

and PC = 0.22 × 10 ⎝ ⎠ b.100 + x = 0.3 mol ATP. Because there are more molecules of reactant gases than product gases.100 + x + 2 B(g) 0. the net change that occurs for this reaction to reach equilibrium is for products to convert to reactants. ΔG° = −RT ln K. AND FREE ENERGY 387 o ΔG 800 = −RT ln K = −8.1 kJ/mol 74. ΔG° = 2(−371 kJ) − [2(−300.100 + 2x ⇌ ← C(g) 0. PB = 0. K = exp ⎜ −1 −1 ⎜ 8.0) 2 . this reaction must be exothermic (ΔH° < 0).100 + 2(0. A(g) Initial Change Equil. the reaction will be spontaneous at relatively low temperatures.100 atm !x 0. where the favorable ΔH° term dominates. ln K = K = e57.3145 J K−1 mol−1(298 K) ln(5.311 RT 8. The equilibrium partial pressures are: PA = 0. Because the partial pressure of C(g) decreased. x = 0.100 – x.3 molecules ATP/molecule glucose mol glucose 30.100 ! x From the problem.220 atm.1 × 103 J/mol = !4.50) From the negative value of ΔG°.1 × 104 J/mol = −71 kJ/mol 72.060 atm.0 × 10−12 atm 2 PSO 2 × (0. PC = 0.4 × 104) = −7.2 0.2) = !4.040 atm = 0.060 = 0.311 = 7.76 × 1024 K = 7. this reaction is spontaneous at standard conditions.3145 J K −1 mol −1 (298 K ) = ( 2.160 atm.040 = 5.100 atm +x 0. ENTROPY.100 atm +2x 0. K= 0.000 J ) = = 57.CHAPTER 10 SPONTANEITY. 0. Therefore. 73. ΔS° will be negative (unfavorable).500 J ) 5 ⎟ a.76 × 1024 = 2 PSO 3 2 PSO 2 × PO 2 − ΔG o − ( −142.160(0.100 + 0. K) ln(4. 94. PSO 2 = 1. ⎛ ⎞ − (−30. When ΔH° and ΔS° are both negative.5 kJ . C6H12O6(s) + 6 O2(g) → 6 CO2(g) + 6 H2O(l) ΔG° = 6 mol(−394 kJ/mol) + 6 mol(−237 kJ/mol) − 1 mol(−911 kJ/mol) = −2875 kJ 2875 kJ 1 mol ATP × = 94.040 atm. 2 SO2(g) + O2(g) → 2 SO3(g).3145 J K−1 mol−1(800.220) 2 ΔGE = !RT ln K = !8.60) = 0. kJ)] = −142 kJ ΔG° = −RT ln K.3145 J K mol × 298 K ⎟ = 2.

000 J = = −5. 75.0°C: ΔG° = −58.86.166 = 8. = = −1. At 25.3145 J K −1 mol −1 )(298.388 CHAPTER 10 SPONTANEITY.03 × 103 J/mol − (298.65 = 3.2 K ) At 100. K = e6. HgbO2 → Hgb + O2 ΔG° = − (−70 kJ) Hgb + CO → HgbCO ΔG° = −80 kJ _________________________________________ HgbO2 + CO → HgbCO + O2 ΔG° = −10 kJ ⎛ − ΔG o ΔG° = −RT ln K.2 K)(−176. K = e−2. K = e2.540.3 × 104 K Δx 3. ln K = b.000 J ) = = 6.2 K)(−176.5 × 102 −1 −1 RT 8.540 = 0.5 × 10−3 −1 −1 RT (8. only 38 moles of ATP are produced by metabolism of 1 mole of glucose.6 J K−1 mol−1) = −5.37 × 103 J/mol ΔG° = −RT ln K. K = e−5. 1/T will yield a straight line with slope = m = −ΔH°/R and a y intercept = b = ΔS°/R.37 × 103 J / mol) = = 2. The assumption that all the free energy goes into this reaction is false.0 × 10 −3 K −1 − 0 .3145 J K −1 mol −1 )(298 K ) ⎟ = 60 ⎠ ⎝ ⎠ − ΔG o − 14. AND FREE ENERGY This is an overstatement.72 RT (8. a.88 × 103 J/mol ln K = − (7.03 × 103 J/mol − (373.166. From the plot: slope = Δy 0 − 40. K = exp ⎜ ⎜ RT ⎝ 76.5 = −17 kJ ln K = − ΔG o − (−17.0789 (8. ln K = − ΔG o − (−5. The equation ln K = − ΔH o ⎛ 1 ⎞ ΔSo is in the form of a straight line equation (y = mx + ⎜ ⎟+ R ⎝T⎠ R b). ENTROPY. ⎞ ⎛ ⎞ − (−10 × 103 J ) ⎟ = exp⎜ ⎟ ⎟ ⎜ (8.3145 J K −1 mol −1 )(373.5 kJ ___________________________________________________________________________ Glutamic acid + ATP + NH3 → Glutamine + ADP + H2PO4− ΔG° = 14 − 30.3145 J K mol (298 K ) 77.6 J K−1 mol−1) = 7.86 = 9.2 K ) 78.3145 J K mol )(298 K ) ΔG° = 14 kJ Glutamic acid + NH3 → Glutamine + H2O ATP + H2O → ADP + H2PO4− ΔG° = −30. Actually. A graph of ln K vs.88 × 10 3 J / mol) = −2.0°C: ΔG° = ΔH° − TΔS° = −58.65.

× 8. Assuming that ΔH° and ΔS° are temperature independent: .00 × 10−14 2. the slope of the ln K vs.66 3. 79.3145 J K−1 mol−1) = 5.78).09 × 8.91 × 103 K = R ΔH° = − (−6.09 ⎝T⎠ o − ΔH Slope = −6. ΔH° = 57. When ΔH° is negative. Temp (°C) 0 25 35 40.537 ⎛1⎞ The straight-line equation (from a calculator) is: ln K = −6. From part a. = ΔS°/R.92 × 10−14 5. 1/T plot is negative. a. AND FREE ENERGY 389 −1.14 × 10−15 1.19 3.1 × 105 J/mol y intercept = 40.91 × 103 K × 8.3145 J K−1 mol−1 = 330 J K−1 mol−1 As seen here. T(K) 273 298 308 313 323 1000/T (K−1) 3.3145 J K−1 mol−1 = 1.165 −30. ENTROPY.47 × 10−14 ln Kw −34. the slope of the ln K vs.3145 J K−1 mol−1 = −75.36 3.499 −31. ΔH° = 1.25 3.236 −31.5 kJ/mol and ΔS° = −75. ΔS° = −9.75 × 104 J/mol = 57. when ΔH° is positive.6 J K−1 mol−1. 1/T plot will be positive (slope = −ΔH°/R).3 × 104 K × 8.09 × 10−14 2.3 × 104 K = −ΔH°/R. A graph of ln K vs. 1/T will yield a straight line with slope equal to -ΔH°/R and y intercept equal to ΔS°/R (see Exercise 10.6 J K−1 mol−1 R b.91 × 103 ⎜ ⎟ − 9.408 −32.5 kJ/mol ΔSo y intercept = −9. 50. ΔS° = 40.09 = .CHAPTER 10 SPONTANEITY. as in an exothermic process.10 Kw 1.

25 × 10 −2 ⎞ ⎛ 1 ΔH o 1 ⎞ ⎟= ⎜ ⎟ − ln⎜ −1 −1 ⎜ ⎟ ⎜ 8.7 × 10 4 J / mol) + (8.61 = (5. ΔH° = −9. AND FREE ENERGY ΔG° = 57.124 × 105 J/mol = !112.84 8. 81.4 kJ/mol !14.00 then ΔG° = 0 since ln(1.400 J/mol = 106.84 at T = 25°C: ln(8. ln K = − ΔH o ΔSo + .84) = ΔSo − (−9. When K = 1.3145 J K −1 mol −1 ΔSo = −37.51 = ΔSE/R. ΔH° < 0 and ΔS° < 0.3145 J K−1 mol−1 RT R For two sets of K and T: − ΔH o ⎛ 1 ⎞ ΔSo − ΔH o ⎛ 1 ⎞ ΔSo ⎜ ⎟+ ⎜ ⎟+ ln K1 = . R = 8. ΔHE = !(8.78. Assuming that ΔH° and ΔS° do not depend on temperature: ΔH° = TΔS°. 1/T plot gives a straight line with slope = !ΔHE/R and y intercept = ΔSE/R.6 J K−1 mol−1) = 106.6 J K−1 mol−1 Note that the signs for ΔH° and ΔS° make sense. ΔS° = −310 J K−1 mol−1 8.3145 J K−1 mol−1) = !120.500 J/mol − 647 K(−75.352 × 104 K = !ΔHE/R.3145 We get the same value for ΔS° using K = 3. ENTROPY.00) = 0.3145 J K −1 mol −1 )(298 K ) 8.8 ×10−5 mol/J)(ΔH°).3145 J K−1 mol−1)(1.3145 J K mol ⎝ 298 K 348 K ⎟ ⎠ ⎠ ⎝ −5. ΔSE = (!14.4 kJ/mol 80. 1. ΔG° = 0 = ΔH° − TΔS°.51)(8. ΔG° = −RT ln K. When a bond forms. The ln K vs.352 × 104 K) ΔHE = !1. ln K 2 = R ⎜ T1 ⎟ R R ⎜ T2 ⎟ R ⎝ ⎠ ⎝ ⎠ Subtracting the first expression from the second: ln K2 − ln K1 = ΔH o ⎛ 1 1 ⎞ K ΔH o ⎛ 1 1 ⎞ ⎜ − ⎟ ⎜ − ⎟ or ln 2 = ⎜T T ⎟ ⎜T T ⎟ R ⎝ 1 K1 R ⎝ 1 2 ⎠ 2 ⎠ ⎛ 3. T = ΔH o − 9.390 CHAPTER 10 SPONTANEITY.7 × 10 4 J / mol = = 310 K ΔSo − 310 J K −1 mol −1 .25 × 10−2 at T = 348 K data.7 × 104 J/mol For K = 8. From Exercise 10.

q = 0 and ΔE = w = nCvΔT. We need to calculate n. V2 = (35.3145 J K−1 mol−1)(162 K − 298 K) = −346 J 83.08206 L atm K −1 mol −1 ) Note: we also could have used the formula T2/T1 = (V1/V2)(−1 to calculate T2. For a monoatomic ideal gas.00 atm⎜ ⎜ 12.00 L ⎞ = 298 K⎜ ⎜ 12.00 L = = 0.5 L ⎟ ⎟ ⎝ ⎠ 2/3 = 162 K 5/3 ⎛V ⎞ ⎛ 5.204 mol RT 0.204 mol(3/2)(8. Cp = Cv + R. n= PV 1.3145 J K−1 mol−1 = 28.5 J K−1 mol−1 + 8.50 atm(12. Cp = Cv + R = 20.84 × 103 J .40 Cv P2 20.1 L)1. Two equations derived in Section 10.CHAPTER 10 SPONTANEITY.1 L 1. where ( = Cp/Cv.5 nRT1 1.6)1/1. ENTROPY.08206 L atm K −1 mol −1 × 298 K ΔE = w = 0.75 mol (0.5 L ⎟ ⎟ ⎜V ⎟ ⎝ ⎠ ⎝ 2⎠ γ = 0.75 mol(20. T2 = 4.8 L) P2 V2 = = 401 K nR 1.40 = 35. so γ = 5/3 and γ − 1 = 2/3.50 atm P1 1. w = ΔE = nCVΔT = 1.217 atm Because we have an adiabatic process.8 . P1V1( = P2V2(. Cp = (5/2)R and Cv = (3/2)R.75 mol(0. AND FREE ENERGY 391 Adiabatic Processes 82. ⎛V ⎞ T2 = T1 ⎜ 1 ⎟ ⎜V ⎟ ⎝ 2⎠ γ −1 ⎛ 5.5 J K−1 mol−1)(401 K – 294 K) = 3.6. where ( = = = 1.00 atm × 5.14 for reversible adiabatic processes are T1V1γ-1 = T2V2γ−1 and P1V1γ = P2V2γ where γ = Cp/Cv. we need T2 in order to calculate ΔT.00 L ⎞ P2 = P1 ⎜ 1 ⎟ = 1. For an ideal gas. For reversible adaiabatic process.8 L 4.40 = To calculate w = ΔE = nCVΔT.08206 L atm K −1 mol−1 ) (294 K ) = = 28.50 atm (28.40 = 12.50 atm V1 = V21.8 J K−1 mol−1 V2( = Cp P1V1γ 28.

08206 L atm K −1 mol −1 ) 300. for a reversible adiabatic change (q = 0): ⎛V ⎞ ln⎜ 1 ⎟ ⎜V ⎟ Cv = ⎝ 2⎠ R ⎛T ⎞ ln⎜ 2 ⎟ ⎜T ⎟ ⎝ 1⎠ ⎛ T2 ⎞ ⎜ ⎟ ⎜T ⎟ ⎝ 1⎠ Cv = ⎜ ⎜ ⎛T ⎞ ⎛V ⎞ ⎛ V1 ⎞ ⎟ . w = −PexΔV. 84.01 × 103 J. AND FREE ENERGY Note that for the adiabatic reversible compression.392 CHAPTER 10 SPONTANEITY.14 of the text.0 kJ 85.9 J K−1 mol−1 ΔE = nCvΔT = 1.3 J L−1 atm−1 = −1. K ) = 24.99 × 103 J q = −w = 1. b.00 mol (0.3145 J K−-1 mol−1)(300.0 × 103 J = −3. a.3 kJ ΔH = ΔE + nRΔT = −2300 J + 1. K) ln(5.00 atm w = −(1.00) = −4.00/1.00 atm)(24. K = 4. V1 = 1. we need to determine the molar heat capacity of the ideal gas. Isothermal irreversible expansion against a constant external pressure of 1.00 atm Vf = 1. so ΔE increases. .01 × 103 J Since ΔE = 0. T increases. so ΔE = 0. ENTROPY.99 × 103 J As expected.00 mol(8.300 J = −2. ⎜T ⎟ ⎟ ⎜V ⎟ ⎝ 1⎠ ⎝ 2⎠ ⎝ V2 ⎠ R Since V2 = 2V1: Cv ln(1/2) = = 3. the internal energy of the system increases (ΔE = w).08206)(300.50 mol(26.24 R ln(239 K/296 K) Cv = (3. C v ln⎜ 2 ⎟ = R ln⎜ 1 ⎟.00 atm. we get more work from the reversible process. and q = −w.6 L 1.6 L – 4.9 J K−1 mol−1)(239 K − 296 K) = −2.24)(8. Isothermal reversible expansion: ΔT = 0 so ΔE = 0 w = −nRT ln(V2/V1) = −nRT ln(P1/P2) w = −1.3145 J K−-1 mol−1) = 26.92 L) × 101. To calculate ΔE and ΔH.00 mol (0. q = −w = 4. As derived in Section 10.50 mol(8. As work is added during the compression.92 L 5.3145 J K−1 mol−1)(239 K − 296 K) ΔH = −3.

AND FREE ENERGY 393 c.92 L)1. In order to calculate T2.00/1.00 mol(0.29 = 1 1 28.CHAPTER 10 SPONTANEITY.65 × 103 J As expected. a.00 mol(28. w.00 mol(8. ΔSsurr = ΔSsys = −13. we need to determine V2. Adiabatic reversible expansion: q = 0 so ΔE = w.6 L – 4.00 atm 1.6 L 1.3 J L−1 atm−1 = 1. 86.3145 J K−1 mol−1) ln(5.1 L) = = 208 K nR 1.92 L 5. From part b.1 = 1. so ΔE = 0.4 J/K (a state function).00 mol(0.8 J K−1 mol−1 Cp CV = P V1.3145 J K−1 mol−1 = 28. ΔSsys = q rev nRT ln(P1 / P2 ) = = nR ln(P1/P2) T T ΔSsys = 1.92 L.00 atm Vf = q = PexΔV = 1. we need Cv and ΔT to calculate ΔE and.8 P2 5.29 = 39. K) = −2.00 mol(0.92 L) × 101.0.4 J/K b.08206 L atm K −1 mol −1 ) (300. V21. V1 = 4. Isothermal reversible expansion: ΔSuniv = 0 (reversible process).99 × 103 J . K ) = 4.8 J K−1 mol−1)(208 K – 300. ΔE = nCvΔT. ΔT = 0. and qrev = – wrev = nRT ln(P1/P2). ΔE = 0 = q + w.08206) (300.29. V2 = 17.29 = T2 = P2 V2 1.00 atm (17.4 J/K ΔSuniv = 0 = ΔSsys + ΔSsurr.29 37.00) = 13. Cv = Cp – R = 37.08206 L atm K −1 mol −1 ) ΔE = w = nCvΔT = 1.00 atm(24. we do not get as much work in the adiabatic reversible process as when the gas expands isothermally and reversibly. ENTROPY.1 L 1. Isothermal irreversible expansion against a constant pressure: ΔSsys = 13. in turn. P1V1( = P2V2(. K ) = 24. For a gas behaving ideally: Cp = Cv + R.00 atm (4.1 J K−1 mol−1 – 8.00 atm V21. q = −w = PexΔV Vi = 1. where ( = Cp/Cv.

Adiabatic reversible expansion: ΔSuniv = 0 (reversible).ΔSsurr are both positive). ΔG = 1.63 J/K T 300. just as ΔSuniv goes in one direction. positional probability increases. so ΔSuniv is positive (as it must be when ΔSsys and . ΔSuniv cannot decrease. 90.7 × 10 −2 ) 2 0. this is an exothermic process. T T and since ΔSsys = 0. ΔG°= −RT ln K = −(8. so ΔG = ΔG = 1. AND FREE ENERGY − q actual − 1. b. the amount of useful work obtainable from a spontaneous process is always less than wmax.3145 J K−1 mol−1)(298 K) ln (2.99 × 103 J = = −6. K ΔSuniv = ΔSsys + ΔSsurr = 13. the magnitude of ΔG is equal to the minimum amount of work that must be expended to make the process spontaneous.8 × 104 J/mol a. wmax = ΔG. As any process occurs. the magnitude of ΔG is equal to the maximum possible useful work obtainable from the process (at constant T and P). When an ionic solid dissolves.77 J/K c.0 and ln Q = 0). ΔSsys = −ΔSsurr. HF(aq) ⇌ H+(aq) + F−(aq).8 × 104 J/mol (since Q = 1. when ΔG is negative. the dissolving process is spontaneous. so ΔSsys is positive. ENTROPY. ΔSsurr must equal zero. 91. Because ΔG° is positive. an amount of work greater than wmax must be applied to make the process spontaneous. Due to waste energy (heat) in any real process. Time also goes in one direction. Since temperature increased as the solid dissolved.2 × 10−4) = 1.63 J/K = 6. Additional Exercises 87.98 . Or one could say that because ΔSuniv = 0. Since the solid did dissolve. ΔG = ΔG° + RT ln [H + ][F − ] [ HF] 88. and for a nonspontaneous reaction. When ΔG is positive. 89.3145 J K−1 mol−1)(298 K) ln(7.394 ΔSsurr = CHAPTER 10 SPONTANEITY. ΔSsurr = − q actual − q rev = = 0. The purpose of redundant information is to provide a control to check the "correctness" of the transmitted information. The introduction of mistakes is an effect of entropy.4 J/K – 6. ΔSuniv will increase. the reaction shifts left to reach equilibrium. and ΔSsurr is positive (ΔSsurr = −ΔH/T). qrev = 0 so ΔSsys = qrev/T = 0.8 × 104 J/mol + (8. The concentrations are all at standard conditions.

8 kJ of work must be applied to transport 1 mol K+.52 d.47 × 10−10 atm The pressure of H2 decreased from 1.27) = 1. Therefore.8 × 104 + 8.0 × 10 −5 ) 2 = −1. For ΔG° to be negative. ΔG = RT ln ⎜ + m ⎜ [K ] b ⎝ ΔG = ⎞ ⎟ . Either anions must be transported into the cells.3145(298) ln (1.3145(298) ln at equilibrium e. ENTROPY.67) = 2 × 103 J/mol. ΔG = 8.29 mol ATP + 30.10 × 1013 molecules ⎜ ⎟⎜ ⎟ (298 K ) ⎟ ⎜ 6.8 × 104 J/mol = 0 Because ΔG = 0.15 ⎞ 3 (310. the ratio of the partial pressure of PCl5 (a product) to the partial pressure of PCl3 (a reactant) will decrease when T is raised.0050 ⎠ At least 8.022 × 10 23 molecules / mol ⎟ ⎜ mol K nRT ⎠ ⎝ ⎠⎝ = = = V 1.8 kJ/mol K mol ⎝ 0.00 atm since there is a 2:1 mole ratio between HBr and . At equilibrium: 94. shifts left 0.8 × 104 + 8.8 × 10 J/mol = 8. PHBr = 2. or cations (Na+) in the cell must be transported to the blood.47 × 10−10 atm.8 × 104 J/mol − 1. ΔG = 1.1 × 104 J/mol.2 × 10 −4 (0. 8. ΔG = 1. ΔG = wmax ⎟ ⎠ 8.8 × 104 + 8. K decreases as T increases because ΔG° becomes more positive (ΔG° = −RT ln K). ΔG = 1. shifts right 1.8 × 104 − 1. ΔS° will be negative because 2 moles of gaseous reactants forms 1 mole of gaseous product.27 1.8 × 104 = 0.3145(298) ln 92. The latter is what happens: [Na+] in blood is greater than [Na+] in cells as a result of this pumping. 0. K) ln ⎜ ⎟ .5 kJ mol K 93.3145 J ⎛ 0. Other ions will have to be transported in order to maintain electroneutrality.8 kJ 1 mol ATP × = 0.08206 L atm ⎞ 1. ⎛ [K + ] K+(blood) ⇌ K+(muscle) ΔG° = 0. Therefore.0 × 10 −3 (0.CHAPTER 10 SPONTANEITY.00 atm to 4. Essentially all the H2 and Br2 has reacted. c. PH 2 ⎛ ⎞ ⎛ 0. AND FREE ENERGY 395 ΔG = 1. For this sign combination of ΔH° and ΔS°.0 × 10 −5 7. ΔH must be negative (exothermic). the reaction is at equilibrium (no shift).00 L 4.

PH 2 × PBr2 ( 4. then we will have equal moles of H2 and Br2 at equilibrium. then ΔG becomes negative.3145 J K −1 mol −1 × 298 K .26 = 7. and ΔG is positive (not spontaneous). Looking at ΔG: ΔG = ΔG° + RT ln (PI2 / PI 2 ).10 atm.200 J = = !9. ΔH o − ΔG o − 103.73 × 10 −5 − ΔG o − 24. ENTROPY. Thus 2 I(g) will be favored at low pressure.767 RT 8. the logarithm term is negative. ln Ksp = Ksp = e−7.767 = 5. K= 2 PHBr (2.47 × 10 −10 ) 2 ΔG° = −RT ln K = −(8.47 × 10−10 atm. Therefore.00) 2 = = 2.26 RT 8.396 CHAPTER 10 SPONTANEITY. Ba(NO3)2(s) ⇌ Ba2+(aq) + 2 NO3−(aq) K = Ksp.000 J = = −7. If |RT ln Q| > ΔG°.0 × 10−4 − ΔG o − 18.00 × 1019) = −1.00 × 1019. AND FREE ENERGY H2 in the balanced equation. s = (40)1/2 = 6.800 J − (−1.3145 J K mol × 298 K ⎦ NaCl(s) ⇌ Na+(aq) + Cl−(aq) 0 s Ksp = 40 Initial s = solubility (mol/L) 0 Equil.200 J ΔGE = !RT ln K. s Ksp = 40 = s(s).10 × 105 J/mol ΔS° = 95. PH 2 = PBr2 = 4. ΔG° = −561 + 2(−109) − (−797) = 18 kJ ΔG° = −RT ln Ksp. ln(PI2 / PI 2 ) > 0 when PI = PI 2 = 10 atm. 96. But at PI = PI 2 = 0. and the reaction is spontaneous.3145 J K −1 mol −1 (298 K ) 97. NaCl(s) ⇌ Na+(aq) + Cl−(aq) K = Ksp = [Na+][Cl−] ΔGE = [(!262 kJ) + (!131 kJ)] – (!384 kJ) = !9 kJ = !9000 J ⎡ ⎤ − (−9000 J ) ΔGE = !RT ln Ksp. Since we began with equal moles of H2 and Br2.3 = 6 M = [Cl−] 98. ΔGE = ΔHE ! TΔSE = !28. assumptions good. Ksp = exp ⎢ ⎥ = 38 = 40 −1 −1 ⎣ 8.3145 J K−1 mol−1)(298 K) ln(2.10 × 105 J ) = = 20 J/K T 298 K Using Le Chatelier's principle: A decrease in pressure (volume increases) will favor the side with the greater number of particles. ln K = K = e −9.0 × 103 J – 298 K(!175 J/K) = 24.

.125 M !x 0. Vhex = = R(342 K) = 28. The rxn reason for the sign change in the Ka value between HF versus HCl. four particles are forming one. HX(aq) ⇌ H+(aq) + X−(aq) Ka reaction.CHAPTER 10 SPONTANEITY. S = k ln Ω. while the other hydrogen halide acids have Ka > 1. In the case of hexane and methane.572.00 mol(0. ΔGE = !RT ln K = ΔHE ! TΔSE.20 × 103 J / mol = .572 = 11.29 J K−1 mol−1 As the molar volume of a gas increases. R ln(Vhex/Vmet) = 9.2 = 11. the difference in molar volume accounts for 82% of the difference in the entropies.1 L P 1. which results in a smaller decrease in positional probability than for reaction 1. For hexane: ΔS = Vmet = nRT 1. 99.00 atm P ΔShex − ΔSmet = 84. The entropy of hydration strongly opposes HF dissociating in water. and k has units of J/K (k = 1. There is a high degree of ordering that occurs as the water molecules associate (hydrogen bond) with the small F− ions. the value of Ka for HF is less than one.2 J K−1 mol−1 T T 112 K 28. S has units of J K−1 mol−1.9 × 103 J / mol = 84. HBr.68 × 10 −3 M 0. 103.3 J K−1 mol−1.73 × 10 −5 Initial Change Equil. pH = 14. In terms of ΔGE. In reaction 2.5 J K−1 mol−1 342 K 102. ΔSvap also increases. ΔS is more favorable (less negative) for reaction 2 than for reaction 1. ΔS for the dissociation of HF is very large and negative.5 − 73. HF must have a positive ΔG o value. and HI is entropy. seven particles in solution are forming one particle in solution. resulting in K2 > K1.125 ! x 0 +x x ~0 +x x Kb = 5. x = [OH−] = 2. water molecules are also present. In reaction 1.19 L. ENTROPY. AND FREE ENERGY B + H2O 397 ⇌ BH+ + OH− K = Kb = 5. The hydrating water molecules must be in a highly ordered arrangement when surrounding these anions.000 – 2. 0.68 × 10 −3 ) = 2. making HF a weak acid. so much so that it overwhelms the favorable hydration energy.125 [B] pOH = !log(2.125 − x 0. 100.73 × 10 −5 = x2 x2 [BH + ][OH − ] = ≈ . ΔS = ΔH vap q rev 8. for methane: ΔS = = 73. 101. assumptions good. while the other H-X acids have ΔGrxn < 0.38 × 10−23 J/K).08206)(112 K ) nRT = = 9. There is an apparent increase in ordering (decrease in positional probability) when these ions are placed in water as compared to the separated state. Note that these substances are not in the solid state but are in the aqueous state.428.

6 × 106 H2O(l. J/K = 119 J/K H H Step 2: H2O(g. AND FREE ENERGY To make units match: S (J K−1 mol−1) = NAk ln Ω when NA = Avogadro's number 189 J K−1 mol−1 = 8. ΔH = nCpΔT. 298 K) → H2O(g. K)(−38. 24.8 J/K V1 ⎠ ⎝ ΔStotal = 119 + 30.00 L ⎞ ΔS = nR ln ⎜ 2 ⎟ = (1. L/mol). since Pext = 0. ΔE = 0 ΔE = q + w.31 J K−1 mol−1 ln Ωg −(70.5 L ⎟ = 30. a.00 mol)(8. not spontaneous 105. 298 K. V = nR (298) = 24. Isothermal: ΔH = 0 (assume ideal gas) ⎛V ⎞ ⎛ 1. 104.3145 J K−1 mol−1) ln ⎜ ⎟ ⎜ 24. 298 K) → H2O(g.3145 J/K) ln ⎜ ⎟ ⎜ 24.3145 J K−1 mol−1) ln ⎜ ⎟ ⎜ 100. ΔH = 0 . L ⎞ V2 = (1.5 L) 1.5 L ⎟ = 131 J/K ⎠ ⎝ ΔG = 44. J K−1 mol−1 = 8.02 × 103 J − 298 K(131 J/K) = 5. q = 0.00 mol)(8. 298 K) → H2O(g.3 J/K) = +11. 298 K.31 J K−1 mol−1(ln Ωg − ln Ωl) 14.00 atm ΔS = So 2O ( g ) − So 2O ( l ) = 189 J/K − 70.3 = 1.3 = ln(Ωg/Ωl). ΔE = nCvΔT.5 kJ 106.8 = 150. L) ΔS = nR ln ⎛ 1000. Break process into two steps: Step 1: H2O(l. 298 K.0 × 103 J.500 J = 11. V = 1000. Free expansion w = 0. V = 100. L/mol): ⎛ 100.02 × 103 J − 298 K(150.31 J K−1 mol−1 ln Ωl) __________________________________________________ Subtracting: 119 J K−1 mol−1 = 8.0 L ⎟ = −38. Ωg Ω1 = e14. L ⎞ ΔS = 119 J/K + (8. J/K) = −700 J. 298 K.398 CHAPTER 10 SPONTANEITY. spontaneous For H2O(l. 1000.5 L) → H2O(g. J/K ΔG = 44. ENTROPY. since ΔT = 0. since ΔT = 0.3 J/K ⎜V ⎟ ⎠ ⎝ ⎝ 1⎠ ΔG = ΔH − TΔS = 0 − (300.

62 − 4. ΔS = nR ln(P1/P2) = (1. (a) Free expansion 0 0 0 0 2.3 J L−1 atm−1) = −1500 J ΔE = 0 = q + w.00 mol)(8.00 atm) = 7.39 J/K −717 J a.62 J/K) = −2320 J w = −PΔV = −(2.00 atm (12.00 L) × (101. qrev = -wrev = 718 J Summary: q w ΔE ΔH ΔS ΔG 107.00 mol × 0. K) ln ⎜ ⎜ 30.39 J/K) = −717 J b. Isothermal: ΔE = 0 and ΔH = 0 if gas is ideal.62 J/K T= PV 5. ΔSuniv > 0 for spontaneous processes: ΔSuniv = ΔSsys + ΔSsurr = ΔSsys − ΔSuniv = 7.00 atm × 5.00 atm/2.00 atm)ΔV. ⎛V ⎞ ⎛ 40.08206 L atm K −1 mol −1 ΔG = ΔH − TΔS = 0 − (305 K)(7.0 L ⎟ = −718 J ⎟ ⎜V ⎟ ⎝ ⎠ ⎝ 1⎠ ΔE = 0 = q + w. these are state functions.CHAPTER 10 SPONTANEITY.00 mol)(8.00 L = = 305 K nR 1. Reversible expansion ΔE = 0. 305 K . ENTROPY.5 − 5.3145 J K−1 mol−1) ln(5.3145 J K−1 mol−1) ln ⎜ ⎟ ⎜ 30. AND FREE ENERGY 399 ⎛V ⎞ ⎛ 40.0 L ⎟ = 2.39 J/K. ΔS = 2. ΔG = −717 J.0 L ⎞ ΔS = nR ln ⎜ 2 ⎟ = (1. ΔH = 0. thus the process is spontaneous.39 J/K −717 J b) Reversible 718 J −718 J 0 0 2. where Vf = nRT = 12.39 J/K ⎜V ⎟ ⎠ ⎝ ⎝ 1⎠ ΔG = ΔH − TΔS = 0 − 300.0 L ⎞ wrev = −nRT ln ⎜ 2 ⎟ = −(1.5 L 2. q = 1500 J b.3145 J K−1 mol−1)(300. K(2.00 mol)(8.7 J/K.62 J/K − q actual T 1500 J = 7.9 = 2.00 atm w = −2. Second law.

1 L = = 226 K nR 2.00 atm = 2. Vf = nRT/5. From the ideal gas equation (see part a).1 L P2 1. Cp = (5/2)R and Cv = (3/2)R. V1 = 24.00 atm × 37.0 J/K w = −5. where γ = Cp/Cv. Using the ideal gas law: T2 = P2 V2 1.08206 L atm K −1 mol −1 b. P1V1γ = P2V2γ and T1V1γ−-1 = T2V2γ−1.5 L.9)T2 − 7430 .00) = −10. Because argon is a monoatomic gas.3 J L−1 atm−1) = 2370 J ΔE = 0 = q + w. V2 = (413)3/5 = 37.00 atm (24.00 atm For an adiabatic reversible process. ΔSsurr = 2370 J −q = = 19. w = −PΔV. a.4 J/K T 122 K ΔSuniv = ΔSsys + ΔSsurr = −10.08206 L atm K −1 mol −1 × 298 K = = 24.400 108.3 J ⎞ ⎛ 8. ΔH = 0.0 J/K) = 1220 J Challenge Problems 109.0 J/K + 19.00 mol × 0.4 J/K ΔG = ΔH − TΔS = 0 − (122 K)(−10.3145 J ⎞ 1.5 L P1 2.5 L) ⎜ ⎟ ⎟ ⎜ L atm ⎟ = 2. CHAPTER 10 SPONTANEITY.00 mol(3/2) ⎜ mol K ⎟(T2 − 298 K ) ⎜ ⎠ ⎠ ⎝ ⎝ We will ignore units from here.4 J/K = 9. For an expansion against a fixed external pressure.00 atm γ We can either use the ideal gas law or the T1Vγ−1 = T2V2γ−1 equation to calculate the final temperature.00 atm(V2 – 24.67 L)(101.00 mol)(8.00 atm(2.00 L ΔS = nR ln(P1/P2) = (1.5 L) 5 / 3 = = 413. Note that both sides of the equation are in units of J.3145 J K−1 mol−1) ln(1. ENTROPY. AND FREE ENERGY Isothermal: ΔE = 0.00 mol × 0. V2γ = P1V1 2. q = −2370 J. V1 = nRT1 2. w = −PΔV = nCvΔT ⎛ 101. ΔE = w = nCvΔT. so γ = 5/3. (−101)V2 + 2480 = (24. For an adiabatic process (q = 0).50/5.00 L − 6.

we need to find an expression for V2.08206)T2 = = (0. q = −w.3145)(305) ln ⎜ ⎟ = −2320 J ⎜V ⎟ ⎝ 12. Because pressure is not constant. then V2 = 12. P1 = 5. T2 = 239 K 110.0 atm(12..0 atm.0 L) = −15 L atm = −1520 J 2320 − 1520 = 2. If P2 = 2. so TΔS = qrev. qrev = nRT ln ⎜ 2 ⎟ = (1. ΔSuniv = rev T T T Since the processes are isothermal. V1 = 5. n = 1. . a.164 T2) + 2480 = (24.5)T2 = 9910. ΔG = +2320 J. and ΔSuniv = ΔS + ΔSsurr. ΔE = 0.5 L. ΔG = ΔH − TΔS.5 ⎠ ⎝ 1⎠ w = −P(ΔV) = 37. ΔH = 0. Using the ideal gas equation: V2 = nRT2 2. For the processes to be spontaneous. ΔSuniv > 0.CHAPTER 10 SPONTANEITY. ΔG cannot be used to predict spontaneity.9)T2 − 7430.6 J/K 305 q = 1520 J.3145)(305) ln ⎜ ⎟ = 2320 J ⎜V ⎟ ⎝ 5.0 mol. ΔG = −2320 J.0 ⎠ ⎝ 1⎠ w = −P(ΔV) = −2.164)T2.0 L.5 ⎞ qrev = nRT ln ⎜ 2 ⎟ = 1.5 L atm = 3800 J.00 −101(0.00 mol (0.0)(8.5 L − 5. ΔS = q rev . ⎛V ⎞ ⎛ 5. ΔH = 0 for both. ΔSuniv = Because ΔSuniv > 0. ⎛V ⎞ ⎛ 12. for the compression.9 J/K (ΔSuniv > 0) 305 c.0(8. q = −3800 J ΔSuniv = − 2320 − ( −3800) = 4. AND FREE ENERGY 401 To solve for T2. T For the expansion.0 ⎞ b. ENTROPY. ΔSsurr = . substituting: P2 1. giving T = 305 K from the ideal gas equation. ΔS = q rev q −q −q . (41. the process is spontaneous.0 atm.

87 J/K ΔSuniv. it is not true that the magnitude of qrev is always greater than the magnitude of qactual. ENTROPY. exp = − q actual − 855 J = = – 2. For the isothermal compression of an ideal gas.87 J/K = 0 ΔSsurr. ΔSsurr. overall = 0 + 2. T q 855 J Reversible expansion: qrev = 855 J. so q = −2(855) J.87 J/K – 2. Only when the compression is done reversibly does qactual = qrev. ΔSsurr = T T However. It is true that ΔS is related to qrev and ΔSsurr is related to qactual: ΔS = − q actual q rev .87 J/K = 2.87 J/K T 298 K For the compression. comp = − q actual − [−2(855) J ] = = 5. ΔS = CHAPTER 10 SPONTANEITY. the compression step is isothermal. Because the initial and overall final state are the same. ΔScomp = −ΔSexp = −2.87 J/K 112. AND FREE ENERGY q rev . overall = –2. ΔS = rev = = 2. overall + ΔSsurr.87 J/K T 298 K From the problem. ΔScomp = q rev − 855 J = = −2. so qrev = qactual (ΔS = ΔSsurr). overall = ΔSsys.402 111. overall ΔSsys. Also consider a sample of ice and water at 0°C and 1 atm.3 and specifically the compression experiments.87 J/K T 298 K b. isothermal: ΔT = 0 so ΔE = 0 and q = −w.74 J/K = 2. we go back to the initial state for the overall process (expansion then compression). ΔSoverall = 0 = ΔSexp + ΔScomp.74 J/K T 298 K ΔSsurr. all state functions like ΔS must equal zero. Reference Table 10. a. One cannot say that |ΔS| is always larger than |ΔSsurr| because |qrev| is not always greater than |qactual|. it still must have qrev = −855 J. overall = 2. The work done on the system is 2(855) J. Here this system is at equilibrium.87 J/K + 5. ΔSuniv. . the magnitude of qactual is always greater than qrev. so q = −w.87 J/K Note: Even though the compression step is not a reversible process.

5 torr.5 mol(75. Vessel 1: At 0°C. q = 0 so ΔSsurr = 0 = ΔSsys. 6. Kp = PCO 2 . The process is the cooling of the water from 90. AND FREE ENERGY 403 The system is the 1.00 × 103 mL × 1. Because the vessel is perfectly insulated. T2 = 110. The surroundings are the room (at 25°C) and everything else.72 × 105 J ) = = 913 J/K 298 K T ΔSsurr = ΔSuniv = ΔS + ΔSsurr = −825 J/K + 913 J/K = 88 J/K Not too surprising. the equation is: RT R ⎞ ⎟ ⎟ ⎠ ln Let T1 = 25°C = 298 K. ENTROPY. so ΔSuniv = 0 and ΔS = ΔSsurr. ΔSsys must be positive (ΔS > 0) in order for ΔSuniv to be positive. K2 = 7. Therefore. 114.78.5 mol(75. K2 = ? ln K2 79.72 × 105 J T − q actual − (−2. SPONTANEITY. ln K = K2 ΔH o = K1 R ⎛1 1 ⎜ ⎜T − T 2 ⎝ 1 ΔSo − ΔH o + .CHAPTER 10 113. the partial pressure of CO2 should be greater than 7. b. to prevent Ag2CO3 from decomposing.23 × 10 −3 K2 = e7.1 = 1.3 J K−1 mol−1) ln(298/363) = −825 J/K ΔSsurr = − q actual .23 × 10 −3 torr 8. this is a spontaneous process due to the favorable ΔSsurr term.3 J K−1 mol−1)(−65 K) = −2.1.23 × 10−3 torr.°C = 383 K. In vessel 2 the conversion of ice into water will be spontaneous at 0°C.14 × 103 J / mol = 6. . From Exercise 10.3145 J K −1 mol −1 ⎛ 1 1 ⎜ ⎜ 298 K − 383 K ⎝ ⎞ ⎟ ⎟ ⎠ ln K2 = 7. a.00-L sample of water. so ΔSuniv > 0.°C to 25°C. PCO 2 should be greater than Kp. ΔSsurr = 0. For two conditions of K and T.00 g 1 mol × = 55.5 torr −3 6. 115.5 mol H2O mL 18. qactual = nCpΔT = 55. K1 = 6. Vessel 2: The presence of salt in water lowers the freezing point of water to a temperature below 0°C.23 × 10 To prevent decomposition of Ag2CO3.2 × 103. this system is at equilibrium.02 g ΔS = nCp ln(T2/T1) = 55. Because the vessel is perfectly insulated. 1.

AND FREE ENERGY + X−(aq) 0 x (1. ΔH° = 286 × 103 J ln 7. Q > K and the reaction shifts left. 298 ⎠ 7. 3 O2(g) ln K = ⇌ 2 O3(g). K. From Exercise 10. K = e−131.22 × 10−58 −1 −1 RT (8. . But with only two ozone molecules in this huge volume.10 – x SPONTANEITY.5 × 10 −6 Ka = [H + ][X − ] [HX] ⇌ H+(aq) ~0 x From problem: x = [H+] = 10 −5.22 × 10 −58 286 × 103 ⎛ 1 1 ⎞ = − ⎜ ⎟ = 34.404 116.3145 J K mol ) (298 K ) − ΔH o ΔSo + RT R We need the value of K at 230.3 × 10 −11 0.10 − 1. CHAPTER 10 HX(aq) 0. T2 = 298. At these conditions. K230 = 1.8206 L atm K −1 mol−1 )(230.13 = 6.573 = 7.5 × 10 −6 ) 2 = 2.022 × 10 23 mol)(0. ΔH° = 2(143) = 286 kJ.3 × 10 −11 ) = 6. ENTROPY.1 × 104 J/mol = 61 kJ/mol 117.83 = 1.5 × 1017 L. it is extremely unlikely that they will collide with each other.5 × 1017 L − 41 P (3. When only two ozone molecules are in a volume of 9. T1 = 230.22 × 10 −58 = e34.573.3 × 10−41 atm The volume occupied by one molecule of ozone is: V= nRT (1 / 6.10 M 0. PO3 = 3.22 × 10−58. the concentration of ozone is not large enough to maintain equilibrium.3145 J K−1 mol−1(298 K) ln(2.5 × 10 −6 . ΔG° = 2(163) = 326 kJ − ΔG o − 326 × 103 J = = −131. Under these conditions. K1 = K230.3145 ⎝ 230.3 × 10 atm) Equilibrium is probably not maintained under these conditions. the reaction is not at equilibrium. K ) = . K.6 × 1014.78: ln K = For two sets of K and T: ln K2 ΔH o ⎛ 1 1 ⎞ ⎜ = ⎜T − T ⎟ ⎟ K1 R ⎝ 1 2 ⎠ Let K2 = 7. V = 9.1 × 10−72 K 230 K230 = 1. Initial Equil.0 × 10 −3 atm) 3 . Ka = ΔGE = !RT ln K = !8.1 × 10−72 = 2 PO3 3 PO 2 = 2 PO3 (1.13 K 230 8.

SPONTANEITY.333 + (0. ΔG = ΔH − Δ(TS) = ΔH − (T2S2 − T1S1) Since ΔS = 8.)(8. ENTROPY.43 J/K ⎜T ⎟ ⎝ 2 ⎠ ⎝ 200. ⎞ ΔS = nC p ln ⎜ 2 ⎟ = (1.00 + x ⇌ B(g) 1. a.3145)(298) ln(0. K) = 2080 J ΔE = nCvΔT =3/2 R(ΔT) = 3/2 (8. x = 0. A(g) Initial Equil. ⎠ ⎝ 1⎠ ΔS due to ΔV = nR ln ⎛T ⎞ V2 = nR ln ⎜ 2 ⎟ = 3.333.50 atm c.) .00 mol(8. − 200.00 > K.00 atm 1. K= 1.3145 J K−1 mol−1)(300.43 J/K.00 + 0.00 − x K = PB/PA 1.50 atm 1.333 ⎣ ⎦ ⎝ ⎠ b.333)x.50/1.00 − 0.00 atm 1.06 J/K ⎜V ⎟ ⎜ ⎟ ⎝ 2 ⎠ ⎝ T1 ⎠ ⎝ 1⎠ G = H − TS.50 atm.00 J/K. S°1 = 8.00 − x = 0. ΔG = ΔG° + RT ln Q = ΔG° + RT ln(PB/PA) ΔG = 2722 J + (8. K) = 1250 J w = −P(ΔV) = −(nR)(ΔT) = 1. figs.00 + x PB = 1. 1. Let x = atm of B(g) that reacts to reach equilibrium.)(16. so So = 16.3145 J K−1 mol−1)(300.50 = 0.43 J/K. − 200.43) − (200.00 − x = 0.50 = 1.3145 J K −1 mol −1 )(298 K ) ⎥ = 0. ΔG° = G o − G o = 11.718 − 8996 = 2722 J B A ⎛ − ΔG o ⎞ ⎡ ⎤ − 2722 J ⎟ K = exp⎜ ⎜ RT ⎟ = exp ⎢ (8. reaction shifts left.37 J/K ⎜T ⎟ V1 ⎝ 1⎠ ⎛V ⎞ ⎛3 ⎞ ⎛T ⎞ ΔS due to ΔT = nC V ln ⎜ 2 ⎟ = n ⎜ R ⎟ ln ⎜ 2 ⎟ = 5. Since Q = 1. AND FREE ENERGY 405 ΔH = nCpΔT = 5/2 R(ΔT) = 5/2 (8. PA = 1.CHAPTER 10 118.50) = 2722 J − 2722 J = 0 (carrying extra sig.00) ⎜ R ⎟ ln ⎜ ⎟ = 8. K) = 831 J q = nCPΔT = 5/2 RΔT = ΔH = 2080 J ⎛T ⎞ ⎛ 5 ⎞ ⎛ 300. 2 ΔG = 2080 J − [(300.3145 J K−1 mol−1)(100.00)] = −1250 J 119.

so ΔSuniv is positive. Since H2O(g) has a greater positional probability. figs. an equilibrium will be reached (physical equilibrium). ΔH = 0 ⎛ ⎞ nRT nRT 101. ENTROPY. Step 1: ΔE = 0 and ΔH = 0 since ΔT = 0 w = −PΔV = −(9.) w = −(9. we cannot identify the sign for ΔG (since it is not a constant pressure problem.00 mol(0.93 × 10 −3 − 9.93 × 10 −3 atm ⎟ = 5. ΔS is positive. it is spontaneous.87 × 10 −3 atm ⎞ ⎟ q = −w = 1240 J.45 × 10 −2 atm ⎞ ⎟ ΔS = 1. Since the vessel is insulated. Because the process occurs.3 J L−1 atm−1) = −1480 J ⎛P ⎞ ΔE = q + w = 0. ΔG does not tell us about spontaneity).406 120. CHAPTER 10 SPONTANEITY. ΔS = nR ln ⎜ ⎜ 4.00 mol(8. so ΔSsurr = 0.87 × 10−3 atm)(1480 L) = −14. ΔH is positive.56 J/K) = −2250 J Step 2: ΔE = 0.08206)(298 K) ⎜ ⎜ 9. thus ΔTwater will be negative.56 J/K ⎝ ⎠ ΔG = ΔH − TΔS = 0 − 298 K(7.6 L atm(101.87 × 10−3 atm)ΔV. The water will become cooler (the higher-energy water molecules leave). ΔS = 7. R = 0. AND FREE ENERGY The liquid water will evaporate at first.77 J/K ⎝ ⎠ ΔG = 0 − 298K(5. ΔS = nR ln ⎜ 1 ⎟ ⎜P ⎟ ⎝ 2⎠ ⎛ 2.93 × 10 −3 atm)⎜ ⎜ 4.08206 L atm K−1 mol−1 P ⎛ ⎞ 1 1 ⎟ ΔV = 1. q = −w = +1480 J. q = 0.45 × 10 − 2 atm ⎟ ⎝ ⎠ ΔV = 1480 L (we will carry all values to three sig. V = ⎛ 1 1⎞ ΔV = Vf − Vi = nRT ⎜ − ⎟ ⎟ ⎜P ⎝ f Pi ⎠ nRT .87 × 10 −3 atm ⎟ L × L atm = −1240 J ⎝ ⎠ ⎛ 9.3145 J K−1 mol−1) ln ⎜ ⎜ 9.87 × 10 −3 atm ⎟ . and eventually. • • • • • • Since evaporation is an endothermic process. 121.3 J ⎟ w = − (4.87 × 10 −3 atm − 2.77 J/K) = −1720 J . Since we don’t know the relative magnitudes of ΔH and ΔS.

1 J/K ⎝ 2⎠ ⎝ ⎠ ΔG = ΔH − TΔS = 0 − (298 K)(19.69 kJ c.3 J ⎟ w = −(2.45 × 10−3 atm) ⎜ ⎜ 2.1 J/K. AND FREE ENERGY 407 Step 3: ΔE = 0. ΔS = q rev .81 J/K ⎝ ⎠ ΔG = 0 − 298 K(5.45 × 10 −3 atm ⎟ = 5. ENTROPY.300 J = 22. ΔS = −19.14 J/K ΔH 0 0 0 0 ΔG −2250 J −1720 J −1730 J −5. ΔS = nR ln ⎜ ⎜ 2.1 J/K) = 5.3 J ⎟ w = −2. ΔS = 19.93 × 10 −3 ⎟ L × L atm = −1250 J ⎝ ⎠ ⎛ 4. ΔG = 5690 J a. ΔG = −5.69 kJ T ΔE = 0 = q + w.3145 J K−1 mol−-1) ln ⎜ ⎜P ⎟ ⎜ 2.3 kJ .69 × 103 J = −5.69 × 103 J = −5. Same as in part a since these are all state functions. ΔH = 0.3 J ⎟ w = −PΔV = − 2.45 × 10 −3 atm ⎟ = 19.45 × 10−2 atm ⎜ ⎜ 2.1 J/K) = −5. Isothermal: ΔE = 0.45 × 10 −3 − 2. R = 0. ΔH = 0 ⎛ ⎞ nRT nRT 101.69 × 103 J.69 × 103 J = 5.56 J/K 5.77 J/K 5.45 × 10 − 2 − 2.93 × 10 −3 atm ⎞ ⎟ q = −w = 1250 J. 1480 J 1240 J 1250 J 3970 J w −1480 J −1240 J −1250 J −3970 J ΔE 0 0 0 0 ΔS 7.45 × 10 −3atm⎜ ⎜ 2. PV = nRT.) (The signs are opposite those in part ⎛ ⎞ nRT nRT 101.45 × 10 −3 ⎟ L × L atm = 22. ΔH = 0.70 × 103 J a. ΔE = 0. wrev = −qrev = −5.81 J/K) = −1730 J q Step 1 Step 2 Step 3 Total 122.45 × 10 − 2 ⎟ L × L atm = −2230 J ⎠ ⎝ q = −w = 2230 J ⎛ 2. ΔH = 0.45 × 10 −2 atm ⎞ ⎛P ⎞ ⎟ ΔS = nR ln ⎜ 1 ⎟ = (1.81 J/K 19.69 kJ b.08206 L atm K−1 mol−1 ⎞ ⎛ nRT nRT 101.45 × 10 −3 − 4. qrev = TΔS = 298 K(19.CHAPTER 10 SPONTANEITY.00 mol)(8.3 kJ ⎝ ⎠ ΔE = q + w = 0.1 J/K. ΔE = 0. q = −22.

0 atm) → CO2(10. 227°C) ___________________________________________________________________________ o ΔH 500 = ΔH1 + ΔH2 + ΔH3 + ΔH4 2 SO2(g.0 atm) → 2 CO(1.00 atm) + O2(1. 25°C) ΔH3 = ΔH o = −198 kJ 298 ΔH4 = nCpΔT 2 SO3(g.0 atm) 124. c = 123.000 J ) 90 ⎟ ⎜ ⎟ K = exp ⎜ ⎜ RT ⎟ = exp⎜ (8. 227°C) + O2(g. ΔSsurr. K. 25°C) ΔH2 = nCpΔT 2 SO2(g. ENTROPY. b = −ΔS = −19.00 atm) → 2 CO2(1.24 × 10 ⎝ ⎠ ⎝ ⎠ b. 25°C) → 2 SO3(g.3145 J K −1 mol −1 ) (298 K ) ⎟ = 1.1 = −154 J/K 2 CO(10.0 atm) + O2(10.00 atm) ΔS = nR ln(P1/P2) = 19.45 x 10-3 V1 e.300 J = 74. ΔSsurr. a. CHAPTER 10 SPONTANEITY. ΔG° = 2 mol(−394 kJ/mol) − 2 mol(−137 kJ/mol) = −514 kJ ⎛ − ΔG o ⎞ ⎛ ⎞ − (−514.00 atm) ΔS° = −173 J/K 2 CO2(1.45 x 10-2 P (atm) (a) (b) 2. 227°C) .00 atm) O2(10. 25°C) → 2 SO3(g.0 atm) → O2(1. 2 SO2(g.3 J/K ΔS = nR ln(P1/P2) = 38.48 J/K T 298 K 22.0 atm) ΔS = nR ln(P1/P2) = −38.408 d. ΔSo = 2(257) − [205 + 2(248)] = −187 J/K 298 298 Set up a thermochemical cycle to convert to T = 227°C = 500. ΔSsurr = (c) V2 − q actual − 2230 J .3 J/K 2 CO(10. 227°C) → 2 SO2(g. 227°C) → 2 SO3(g. a = = −7. 227°C) → O2(g. O2(g) → 2 SO3(g) 2 SO2(g) + _________________________________________ ΔH o −297 kJ/mol 0 −396 f 205 257 S° 248 J K−1 mol−1 __________________________________________ ΔH o = 2(−396) − 2(−297) = −198 kJ. AND FREE ENERGY 2.8 J/K 298 K ΔSsurr. 25°C) ΔH1 = nCpΔT O2(g.1 J/K __________________________________________________________________________ ΔS = −173 + 19.1 J/K (reversible process). 25°C) + O2(g.00 atm) → 2 CO2(10. ΔS° = 2(214 J/K) − [2(198 J/K) + 205 J/K] = −173 J/K 2 CO(1.

8545 = a + 500.16 0.0 b + (400.4) ln(298/500.5 kJ = −199.16 J K−2 mol−1)(20.5 kJ = −200.0)2 c 29.7262 = a + 300./298) o ΔS500 = −41.0 b + (300.0)2 c 29.0 b + (500.2 J/K − 187 J/K + 52. 0 T(K) 73 93 113 133 173 213 243 263 273 Cp (J K−1 mol−1) 12 15 17 19 24 29 33 36 37 Cp/T (J K−2 mol−1) 0.15 0.7 × 202 1000 o ΔH 500 = −16. -60.14 0.14 Total area of Cp/T versus T plot = ΔS = I + II + III (See following plot. K) + (0.4 × (−202 K) + 1 × × (−202) − 198 kJ + 1000 J / kJ 1000 2× 409 o ΔH 500 = 2 mol × 50. -140.CHAPTER 10 SPONTANEITY. K) ΔS = 3. T(°C) −200.9 J K −1 mol −1 29.4 = 29 J K−1 mol−1 126.14 0. kJ For the same cycle but using the equation ΔS = nCp ln (T2/T1) and ΔSo : 298 o ΔS500 = 2(39.14 0. K) + 1/2 (0. -160.5 J/K = −191 J/K 125.2 + 25 + 0.7) ln(500.1 kJ − 5.14 J K−2 mol−1)(180.0)2 c . ENTROPY.) − 187 + 2(50.3 J/K − 15.14 0. AND FREE ENERGY 39.2937 = a + 400. -180.) ΔS = (0.02 J K−2 mol−1)(40. K) + 1(29. We can set up three equations in three unknowns: 28. -10. -100.14 0.94 kJ − 198 kJ + 20.16 0. -30.9) ln(298 K/500.

5°C) → C6H6(s.02 J K−1 mol−1 T2 ΔS = n T1 T2 ∫ C p dT T = n∫ T2 T1 T2 (a + bT + cT 2 ) dT .2 K) → C6H6(s.98. n = 1. 5. 5.7 K) C6H6(s. 283. we need ΔH at 10.59 kJ C6H6(l. 278. ENTROPY.000 ⎟ ⎜ b ⎟ = ⎜ 29. 278. we can calculate ΔSsys at the melting point (5.2 K) → C6H6(l.41 kJ − 9.0°C) → C6H6(s. Solving for ΔH at 5. 25. 25. 278.000 ⎞ ⎛ a ⎞ ⎛ 28. 5.2 K) ΔSsys = −34. T To calculate ΔSsurr. T 278.3 + 4.0°C) → C6H6(s.9 J/K 127.2 K): ΔS = −33.2 K) ΔS = nCp ln(T2/T1) = 1.04 kJ ΔH = nCpΔT/1000 = 2. 25.0 250.410 CHAPTER 10 SPONTANEITY.91 × 10−3. 5. 283.5°C).98 + 5. 278. K and T1 = 100.5°C (using a thermochemical cycle): C6H6(l.73 − 0. From the data in the problem. For a phase change.130 J/K C6H6(l.14 = 63.5°C) At the melting point.7 K) → C6H6(s. where ΔH is determined at the melting point (5. b = 5.3 J/K − ΔH ). One way involves setting up a matrix and solving with a calculator.2937 ⎟ ⎜1 500.41 × 103 J ΔH = = −33. 25.7 K) ΔS = nCp ln(T2/T1) = −2. ΔSsys = ΔH = −9.0 160.96 kJ __________________________________________________________ C6H6(l.91 × 10−3(900.0°C) ΔH = −10. To calculate ΔSsys at 10.8 J/K. such as: ⎛1 300.00 mol T T1 T2 ΔS = a dT ∫ T +b T1 ∫ dT + c ⎛T ⎞ c(T22 − T12 ) T dT = a ln ⎜ 2 ⎟ + b(T2 − T1 ) + ∫ ⎜T ⎟ 2 ⎝ 1⎠ T1 Solving using T2 = 900. K: Cp = 26. K: ΔS = 59.0°C) C6H6(s.0 90.8 J/K C6H6(l.7 K) → C6H6(s.5°C). AND FREE ENERGY These can be solved by several methods.0°C.608 J/K ___________________________________________________________________ C6H6(l.0°C (ΔSsurr = .) − 3.7262 ⎞ ⎜ ⎟⎜ ⎟ ⎜ ⎟ ⎜1 400. 283.)2 = 32. 283.0°C (283.5°C) ΔH = nCpΔT/1000 = −1. ΔSsys = qrev/T = ΔH/T.4 × 10−7 At 900.8545 ⎟ ⎝ ⎠⎝ ⎠ ⎝ ⎠ The solution is: a = 26. c = −3.4 × 10−7(900.5°C) → C6H6(l.7 K For the phase change at 10.000 ⎟ ⎜ c ⎟ ⎜ 29. we need a place to start.

55 kJ − ΔH − (−9.0°C) ΔSsurr = ΔH = −9. Ni(s) + 4 CO(g) ⇌ Ni(CO)4(g) ΔH° = −607 − 4(−110.55 × 103 J ) = = 33. 10. K o ΔG 500 = −165 kJ − (500. c. h.66. The temperature change causes the value of the equilibrium constant to change from a large value (greater than 1) favoring formation of Ni(CO)4 to a small value (less than 1) favoring the decomposition of Ni(CO)4 into pure Ni and CO.0°C) ΔH = −10.1 × 105 −1 −1 RT (8.3145) (500.)] = −405 J/K d.04 kJ ΔH = nCpΔT/1000 = 2.1 × 10−4 (8. − ΔG o − (−34. 25.7 J/K T 283. Since ΔS° is negative.0°C) ΔH = nCpΔT/1000 = −1. b. T = 50. K)(−0.51 kJ _____________________________________________________________ C6H6(l.00 kJ C6H6(l. a. 10. T = e.405 kJ/K) = 38 kJ ln K = − 38.) g. ΔS° will be negative since there is a decrease in the number of moles of gas.5) = −165 kJ.0°C) → C6H6(l.3145 J K mol ) (323 K ) T = 227°C + 273 = 500. K = e12.000 J ) = = 12. Ni(CO)4(l) ⇌ Ni(CO)4(g) Kp = PNi ( CO ) 4 .2 K Marathon Problems 128. 25.0°C) → C6H6(s. 25. 10. K = e−9. ΔSsurr is positive.14 = 1. 25. ΔG° = 0 = ΔH° − TΔS°.66 = 3.000 = −9. ENTROPY.0°C) → C6H6(s. ΔH° must be negative for the reaction to be spontaneous at some temperatures. AND FREE ENERGY 411 C6H6(l.0°C) → C6H6(s. Therefore. 10.14. This is exactly what is wanted in order to purify a nickel sample.0°C) C6H6(s.405 kJ/K) = −34 kJ ΔH o − 165 × 103 J = = 407 K or 134°C − 405 J / K ΔSo ln K = f.°C + 273 = 323 K o ΔG 323 = −165 kJ − (323 K)(−0. ΔS° = 417 − [4(198) + (30.CHAPTER 10 SPONTANEITY.

33 atm)(−1. ⎛ 101. (q = −202 J).3 J ⎞ w = −[(1. In an irreversible process.00 L)] × ⎜ ⎜ L atm ⎟ = 337 J ⎟ ⎝ ⎠ q = −337 J. ΔH = 0.3145 (425 K ) A maximum pressure of 17 atm can be attained before Ni(CO)4(g) will liquify. ΔE = 0. w = −nRT ln⎜ 2 ⎟ = ⎢− PV ln⎜ 2 ⎟⎥ ⎜V ⎟ ⎜ V ⎟ L atm = −281 J ⎝ 1⎠ ⎢ ⎝ 1 ⎠⎥ ⎦ ⎣ q = 281 J. a. the system and surroundings are unchanged. ⎛ V ⎞⎤ 101. w = −(2.1 J/K) = −10.412 CHAPTER 10 SPONTANEITY. AND FREE ENERGY At 42°C (the boiling point): ΔG° = 0 = ΔH° − TΔS° ΔS° = ΔH o 29.00 L)] × q = 236 J. ΔE = ΔH = 0 Note: Overall work for the one-step process = −203 + 405 = 202 J. ΔE = ΔH = 0 f.00 L) + (2. Kp = e2.86 = 17 atm 8.1 J/K T 315 K o At 152°C: ΔG152 = ΔH° − TΔS° = 29. ln Kp = 10.86. q = 203 J c.0 × 103 J − 425 K(92.00 L) × ⎜ ⎜ L atm ⎟ = 405 J ⎟ ⎝ ⎠ q = −405 J.00 L) + (1.0 × 103 J = = 92. ENTROPY.00 L)(101.100 J ΔG° = −RT ln Kp. 129. w = −[(1.3 J L−1 atm−1) = −203 J. Because ΔE = 0 = q + w. b. Overall work for the two-process = −236 + 337 = 101 J. .00 atm)(1.3 J d.3 J ⎞ e. q = −w. ΔE = ΔH = 0 g. ΔE = ΔH = 0 101. ΔE = ΔH = 0. ΔE = ΔH = 0 ⎛ 101.100 J = 2. (q = 0).00 atm)(−2.33 atm)(1. w = −(1.3 J ⎛V ⎞ ⎡ w = − nRT ln⎜ 2 ⎟ = ⎢− PV ln⎜ 2 ⎟⎥ ⎜V ⎟ ⎜ V ⎟ L atm = 281 J ⎝ 1⎠ ⎢ ⎝ 1 ⎠⎥ ⎦ ⎣ q = −281 J.3 J = −236 J L atm ⎛V ⎞ ⎡ ⎛ V ⎞⎤ 101. Thus in an overall reversible process (expansion + compression). (q = −101 J).00 atm)(−1.00 atm)(2. Overall work for the reversible process = w = −281 + 281 = 0. this is not the case.

Each H atom goes from the +1 to the 0 oxidation state by gaining one electron. In order to harness this reaction to do useful work. Hence two electrons are transferred in the balanced reaction. Magnesium is an alkaline earth metal. The oxidation state of hydrogen in HCl is +1. In a galvanic cell. To be reduced. a spontaneous redox reaction occurs that produces an electric current. This is accomplished by making a galvanic cell that separates the reduction reaction from the oxidation reaction in order to control the flow of electrons through a wire to produce a voltage. Mg will oxidize to Mg2+.CHAPTER 11 ELECTROCHEMISTRY Galvanic Cells. Cell Potentials. and Standard Reduction Potentials 15. The obvious choice for the hydrogen product is H2(g). Mg goes from the 0 to the +2 oxidation state by losing two electrons. electricity is used to force a nonspontaneous redox reaction to occur. The balanced reaction is Mg(s) + 2 HCl(aq) → MgCl2(aq) + H2(g). the oxidation state of H must decrease. Electrochemistry is the study of the interchange of chemical and electrical energy. Since there are two H atoms in the balanced equation. no work is obtained. e Salt bridge e Anode (oxidation) Cations Anions Cathode (reduction) 413 . a total of two electrons are gained by the H atoms. we must control the flow of electrons through a wire. When the electrons are transferred directly from Mg to H+. A typical galvanic cell diagram is: 16. 17. A redox (oxidation-reduction) reaction is a reaction in which one or more electrons are transferred. where hydrogen has a zero oxidation state. In an electrolytic cell.

43 V cell . a. Pt is the most common choice. Note that cations always flow into the cathode compartment and anions always flow into the anode compartment. and Cr2O72− in solution We need a nonreactive metal to use as the electrode in each case since all the reactants and products are in solution. and H2SO4 (H+ source) in solution Anode: Pt electrode.77 V (Fe2+ → Fe3+ + e−) × 5 a ___________________________________________________________________ 6 H+ + IO3− + 5 Fe2+ → 5 Fe3+ + 1/2 I2 + 3 H2O E o = 0.33 V 7 H2O + 2 Cr3+ → Cr2O72− + 14 H+ + 6 e− a ________________________________________________________________________ 7 H2O(l) + 2 Cr3+(aq) + 3 Cl2(g) → Cr2O72− (aq) + 6 Cl− (aq) + 14 H+(aq) E o = 0. Cu2+ + 2 e− → Cu E o = 0. Another possibility is graphite.36 V c − E o = −1. H+. Mg2+ in solution c. Cl2 bubbled into solution. Reference Table 11. in the Solutions Guide. Cu2+ in solution Anode: Mg electrode.0 atm.414 CHAPTER 11 ELECTROCHEMISTRY The diagram for all cells will look like this. (Cl2 + 2 e− → 2 Cl−) × 3 E o = 1. Cr3+. 5 e− + 6 H+ + IO3− → 1/2 I2 + 3 H2O E o = 1. b.0 M and partial pressures at 1.71 V Cu2+(aq) + Mg(s) → Cu(s) + Mg2+(aq) cell Cathode: Cu electrode. Also remember that standard potentials are not multia plied by the integer used to obtain the overall balanced equation. IO3−. The contents of each half-cell will be identified for each reaction. E o = 0. we will represent E°(cathode) as E o and c represent −E°(anode) as − E o .20 V c − E o = −0.03 V cell The contents of each compartment are: Cathode: Pt electrode.37 V Mg → Mg2+ + 2 e− a ______________________________________________________________ E o = 2. Cl− in solution Anode: Pt electrode.43 V cell or 12 H+(aq) + 2 IO3−(aq) + 10 Fe2+(aq) → 10 Fe3+(aq) + I2(s) + 6 H2O(l) Cathode: Pt electrode. Fe2+ and Fe3+ in solution Note: I2(s) would make a poor electrode since it sublimes. with all concentrations at 1.1 for standard reduction potentials. This is required to keep each compartment electrically neutral.34 V c − E o = 2. I2. Remember that E o = cell E°(cathode) − E°(anode).

with all solute concentrations at 1. spontaneous cell 19.97 V cell This reaction is spontaneous at standard conditions because E o > 0. (5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O) × 2 E o = 1. not spontaneous 2H2(g) → 2H+(aq) + 2 H−(aq) cell d.54 V (2 I− → I2 + 2 e−) × 5 a _______________________________________________________________________ 16 H+(aq) + 2 MnO4−(aq) + 10 I−(aq) → 5 I2(aq) + 2 Mn2+(aq) + 8 H2O(l) E o = 0.0 M and all gases at 1.e. a reaction with a positive overall standard cell potential. Zn2+ in solution 18.17 for a typical galvanic cell design.23 V. Au3+ + 3 e− → Au E o = 1. H2 → 2H+ + 2 e− E o = 0.80 V (Ag → Ag+ + e−) × 3 a _________________________________________________________________ Au3+(aq) + 3 Ag(s) → Au(s) + 3 Ag+(aq) E o = 0. .56 V cell Cathode: Ag electrode. Only this combination gives a spontaneous overall reaction.51 V c − E o = !2. and the half-reaction with the smallest reduction potential will be reversed to become the anode reaction.23 V H2 + 2 e− → 2H− a ___________________________________________ E o = !2.00 V c − E o = !2.CHAPTER 11 d.0 atm.50 V c − E o = −0. a. cell c. i. the half-reaction with the largest standard reduction potential will be the cathode reaction.70 V.80 V c 415 − E o = 0. (5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O) × 2 E o = 1.36 V cell This reaction is not spontaneous at standard conditions because E o < 0. Ag+ in solution Anode: Zn electrode. cell b. Reference Exercise 11. ELECTROCHEMISTRY (Ag+ + e− → Ag) × 2 E o = 0. For each pair of half-reactions.76 V Zn → Zn2+ + 2 e− a _________________________________________________ Zn(s) + 2 Ag+(aq) → 2 Ag(s) + Zn2+(aq) E o = 1.. The contents of each half-cell compartment are identified below.87 V (2 F− → F2 + 2 e−) × 5 a ________________________________________________________________________ 16 H+(aq) + 2 MnO4−(aq) + 10 F−(aq) → 5 F2(aq) + 2 Mn2+(aq) + 8 H2O(l) E o = −1.51 V c − E o = −0.

H2O2 + 2 H+ + 2 e− → 2 H2O E o = 1. Mn2+.27 V cell The contents of each compartment are: Cathode: Pt electrode. (2 e− + 2 H+ + IO4− → IO3− + H2O) × 5 E o = 1.036 V c − E o = 1.1. In all cases the anode compartment contains the species . Cl. IO3−. H2O2 and H+ in solution Anode: Pt electrode. and H2SO4 in solution c. (Fe3+ + 3 e− → Fe) × 2 E o = −0. and then figure which combination will give a positive standard cell potential.09 V 2 Br.51 V (4 H2O + Mn2+ → MnO4− + 8 H+ + 5 e−) × 2 a ________________________________________________________________________ 10 H+ + 5 IO4− + 8 H2O + 2 Mn2+ → 5 IO3− + 5 H2O + 2 MnO4− + 16 H+ E o = 0.78 V c − E o = −0. O2(g) bubbled in. Mn2+ in solution 20.416 a. and H2SO4 (as a source of H+) in solution Anode: Pt electrode.14 V cell Cathode: Fe electrode. H2O2 and H+ in solution d. Locate the pertinent half-reactions in Table 11. Br2 and Br.36 V c ELECTROCHEMISTRY − E o = −1.68 V H2O2 → O2 + 2 H+ + 2 e− a _______________________________________________________________________ 2 H2O2(aq) → 2 H2O(l) + O2(g) E o = 1.in solution Anode: Pt electrode.09 V cell This simplifies to: 3 H2O(l) + 5 IO4−(aq) + 2 Mn2+(aq) → 5 IO3−(aq) + 2 MnO4−(aq) + 6 H+(aq) E o = 0.in solution b.09 V cell Cathode: Pt electrode. MnO4−. IO4−. Anode: Mn electrode.10 V cell Cathode: Pt electrode. Cl2(g) bubbled in. Fe3+ in solution.60 V c − E o = −1.→ Br2 + 2 e− a _________________________________________________ Cl2(g) + 2 Br-(aq) → Br2(aq) + 2 Cl−(aq) E o = 0.18 V (Mn → Mn2+ + 2 e−) × 3 a ________________________________________________________________________ 2 Fe3+(aq) + 3 Mn(s) → 2 Fe(s) + 3 Mn2+(aq) E o = 1. Cl2 + 2 e− → 2 Cl− CHAPTER 11 E o = 1.

Fe3+ + e− → Fe2+ E° = 0. SCE is the cathode. 22. A double line separates the two compartments. the anode is listed first and the cathode is listed last. the copper compartment is the anode. deduce which combination will produce a positive overall cell potential. b. H+ (1.40 V cell 21.0 M).1 and the given SCE potential. . SCE is the anode.0 M).0 atm) | Cl− (1.0 M) | Pt Mn | Mn2+ (1.77 V Ecell = 0. and in part b. with all solutes and gases toward the middle.0.77 . A single line is used to indicate a phase change.0 M) | Pt Pt | H2O2 (1. Br2 (1.0 M) || Cl2 (1.0 M).0 M). 19d.CHAPTER 11 ELECTROCHEMISTRY 417 with the smallest standard reduction potential. a.22 = 0. H+ (1. By convention. 19a. The reduction half-reaction for the SCE is: Hg2Cl2 + 2 e− → 2 Hg + 2 Cl− ESCE = 0. H+ (1.22 V Ecell = 0.40 V Cd → Cd2+ + 2ea _____________________________________________________________________ 2 VO2+(aq) + 4 H+(aq) + Cd(s) → 2 VO2+(aq) + 2 H2O(l) + Cd2+(aq) E o = 1.50 V c – E o = −0.00 V c – E o = 0.0 M) | Fe 19c.34 V cell b. the cadmium compartment is the anode. c. Ecell must be positive. the electrodes are on the ends. H+ (1.0 M). In part a.0 M) | O2 (1.16 V (Cu+ → Cu2+ + e−) × 3 a __________________________________________________________ Au3+(aq) + 3 Cu+(aq) → Au(s) + 3 Cu2+(aq) E o = 1. (VO2+ + 2 H+ + e− → VO2+ + H2O) × 2 E o = 1.0 M). Pt | Br− (1.0. MnO4− (1. Cu2+ + 2 e− → Cu E° = 0.242 − 0.0 M) | Pt Pt | Mn2+ (1.10 V.0 atm) | | H2O2 (1. a.53 V.0 M).34 V Ecell = 0.0 M) | | IO4− (1. IO3− (1.242 = 0.0 M) | | Fe3+ (1.242 V For a spontaneous reaction to occur. 19b. In standard line notation. Using the standard reduction potentials in Table 11.34 . We also included all concentrations. Au3+ + 3 e− → Au E o = 1. SCE is the anode. AgCl + e− → Ag + Cl− E° = 0.242 = 0.02 V.

H2 → 2 H+ + 2 e− −E° = 0. The ordering from worst to best reducing agents is: !E°(V) F− < H2O !2.77 − 0.00 V.20 25. Good reducing agents are easily oxidized.92 E° = 0. Ag+ + e− → Ag E° = 0. cell cell d. SCE is the cathode.e.23 V Ecell = 0. Cr3+ + e− → Cr2+ E° = −0. 2 I− → I2 + 2 e− −E° = -0. yes.→ Na E° = 1.47 V.13 V E° = −2.1. Of the species available. cell c.34 V E o = −0. e.16 < H− < 2.66 V CHAPTER 11 ELECTROCHEMISTRY Ecell = 0. Al3+ + 3 e− → Al E° = −1. the best reducing agents have the most positive !E° value. a. Oxidizing agents are on the left side of the reduction half-reactions listed in Table 11. 2 H+ + 2 e− → H2 E° = 0. Cl2 + 2 e− → 2 Cl− Pb2+ + 2 e− → Pb Na+ + e.50 − 0.77 V. We look for the largest. SCE is the cathode.418 d. cell conditions.80 V. Ni2++ 2 e− → Ni E° = −0.83 < Cd2+ −0.242 + 0. Cu → Cu2+ + 2 e− −E° = -0. The reducing agents are on the right side of the reduction half-reactions listed in Table 11. H2 can reduce Ag+ to Ag at standard conditions ( E o > 0).92 −1. The best reducing agents have the most negative standard reduction potentials (E°). Fe2+ cannot reduce Cr3+ to Cr2+ at standard Good oxidizing agents are easily reduced.77 V.23 = 0.99 < IO3− 1. no.1.23 K 2.90 V.54 = 0. Ag+ would be the best oxidizing agent since it has the most positive E° value. Fe3+ can oxidize I− to I2.92 −0.71 V Ag+ + e− → Ag Zn2+ + 2 e− → Zn a.54 V E o = 0.00 V.23 < I2 < Cu+ −1.50 V E o = −0. Fe3+ + e− → Fe2+ E° = 0. 23.27 V.36 V E° = −0.. no. i. Fe2+ → Fe3+ + e− −E° = -0. .66 = 1. The ordering from worst to best oxidizing agents is: E°(V) K+ < H2O −2.76 V 26.40 < I2 < AuCl4− 0.54 0. cell cell b.20 −0. H+ cannot oxidize Cu to Cu2+ at standard conditions ( E o < 0). most positive standard reduction potentials to correspond to the best oxidizing agents.23 V.80 V E o = 0.80 V E° = −0. yes.242 + 1. 24. Oxidizing agents (species reduced) are on the left side of the above reduction halfreactions.34 V.77 = −1.

23 V. 2 Br.is coupled with these reagents. Zn would be the best reducing agent since it has the most positive −E° value. Ag. the reducing agent must have a − E o value between −0. E o > 1. Cu2+ + e− → Cu+ E o = 0. which have a − E o value between −0.23 V > E c > −1. E o > 0. VO2+. Cr3+.20 V. H2O2.34 a and −0.34 and −0. MnO2. PbSO4.90 V c − E o = 0. ClO2−. The reducing agents cell (species oxidized) are on the right side of the half-reactions in Table 11. Cd . cell b. Of the species available.36 V to not oxidize Cl . and H2O will be able to oxidize Mn but not oxidize Ni (assuming standard conditions). they give E o > cell 0. ClO− + H2O + 2 e− → 2 OH− + Cl− 30. Hg22+. 2 Cl− → Cl2 + 2 e− − E o = −1. NO. to reduce Cu2+ to Cu c c but not reduce Cu2+ to Cu+.1. a. cell 27. Cu2+ + 2 e− → Cu E o = 0. cell cell 29. Cr2O7 .1: .09 V a a c 2− − − o to oxidize Br . I2 + 2 e− → 2 I− E o = 0.36 V. The reagents at standard conditions.16 V. Fe2+.0 M Cl−). Consider the strongest oxidizing agent combined with the strongest reducing agent from Table 11.09 V. E o is positive. SO42− + 4 H+ + 2 e− → H2SO3 + H2O E o = 0.16 V.10 V 2 NH3 + 2 OH− → N2H4 + 2 H2O + 2 e− a __________________________________________________________ ClO−(aq) + 2 NH3(aq) → Cl−(aq) + N2H4(aq) + H2O(l) E o = 1.00 V cell Because E o is positive for this reaction.54 V. E c < 1.66 V. E o = 0. any oxidizing a a 2+ o agent with −0. and MnO4− are all capable at standard conditions of reducing Br2 to Br− but not reducing I2 to I−. 28. Al → Al3+ + 3 e− − E o = 1. Zn2+. Fe2+. O2. and when coupled with Cl−. Hg.1.→ Br2 + 2 e− − E o = −1. When these reagents are coupled with Br2.18 V. c c Au (in 1. Mn → Mn2+ + 2 e− − E o = 1. they give E o < 0 (assuming standard conditions). SO42− can oxidize Pb and Zn at c standard conditions. at standard conditions ClO− can spontaneously cell oxidize NH3 to the somewhat toxic N2H4. are Ag (in a 1. b. Ni → Ni2+ + 2 e− − E o = 0.16 V (so E o is positive only for the Cu2+-to-Cu reduction). Al can oxidize Ag+ and Zn2+ at standard conditions a since E o > 0. from Table 11.34 V. Br2 + 2 e− → 2 Br− E o = 1.CHAPTER 11 ELECTROCHEMISTRY 419 b. and IO3− are all possible because when all these oxidizing agents are coupled with Br−. cell d. and when coupled with I2. c. a. Reducing agents (species oxidized) are on the right side of the reduction half-reactions.0 M Cl−) and H2SO3. E o < 0.09 V. When SO42.18 V will work.

Fe2+ + 2 e− → Fe E° = !0. Free Energy. Fe2+ + 0) . Round-off error explains the f f 1-kJ discrepancy. Fe3+ = !11 kJ/mol Fe → Fe3+ + 3 e− f Or consider: Fe3+ + 3 e− → Fe E° = !0. Because the cells are at standard conditions. wmax = ΔG = ΔG° = − nFE o .420 F2 + 2 e− → 2 F− CHAPTER 11 E o = 2.485 C/mol e-)(0.036 J/C) = 10.44 J/C 32. kJ/mol.036 V ΔG° = !(3 mol e−)(96. See Exercise cell 11.485 C/mol e−)(1.70 × 105 J = −270.87 V c − E o = 3. cell 20a.20 for the balanced overall equations and E o .88 × 105 J = −388 kJ wmax = −(2 mol e−)(96.485 C/mol e−)(!0.400 J ≈ 10.92 V cell ELECTROCHEMISTRY The claim is impossible.44 V = !0. This is not the case for cell potentials. 20b.77 V ΔG° = !(1 mol e)(96. The free energy change for a reaction depends on whether 1 mole of product is produced or 2 moles of product are produced or 1 million moles of product are produced. ΔG° = !nFE° = !(2 mol e−)(96. Fe3+ + 0) . kJ 10. wmax = −(3 mol e−)(96. It is the n term that converts the intensive property E into the extensive property ΔG.300 J = !74 kJ ΔG° = 74 kJ Fe2+ → Fe3+ + e− 2+ − ΔG° = !85 kJ Fe → Fe + 2 e ___________________________________________________ ΔG° = !11 kJ.34 J/C) = −3. ΔG o.485 C/mol e−)(!0.05 V (Li → Li+ + e−) × 2 a _______________________________________________ F2(g) + 2 Li(s) → 2 Li+(aq) + 2 F−(aq) E o = 5.40 J/C) = −2. The strongest oxidizing agent and reducing agent when combined only give E o of about 6 V. kJ = 0 ! (ΔG o. kJ . ΔG o. and Equilibrium 31. n is the number of moles of electrons transferred in the balanced reaction that ΔG is associated with. 33.77 J/C) = !74. Fe3+ = !10. Consider: Fe3+ + e− → Fe2+ f E° = 0. The equation that relates ΔG to E is ΔG = !nFE. ΔG o.44 J/C)(1 kJ/1000 J) = 85 kJ 85 kJ = 0 ! (ΔG o. An extensive property is one that depends directly on the amount of substance. Fe2+ = !85 kJ f f We can get ΔG o. cell Cell Potential. which do not depend on the amount of substance.485 C/mol e−)(1. Fe3+ two ways.

Cl2(aq) + 2 Br-(aq) → Br2(aq) + 2 Cl−(aq) E o = 0.485 C/mol e−)(0. balanced reactions are necessary to determine n.0591 log K.54 V − 1.0591 0. no cell d. Only O2 in the presence of H+ has a large enough standard reduction potential to oxidize Fe2+ to Fe3+ (resulting in E o > 0).82 J/C) = −1. including the cell possible reduction of Fe2+. K = 109.46 V. c. Fe2+ can be oxidized or reduced.46) = 31.2 × 104 J = −52 kJ cell Eo = cell 0.6 × 1027 n 0. 19a.3 × 1031 0.82 V.82) 0.27 J/C) = −5. this reaction is not spontaneous at standard concell ditions since E o < 0. Reference Exercise 11. H2O.27) log K. the moles of electrons transferred. All other combinations. The other species present are H+. log K = = = 9.82 J/C cell ΔG° = − nFE o = −(2 mol e−)(96.46 J/C)(1 kJ/1000 J) = −180 kJ cell log K = 4(0. and O2 from air. K = 1027.0591 nE o 2(0. log K = = = 27.75 = 5.0591 The 35. SO42−. cell Cl2(g) + 2 I−(aq) → I2(s) + 2 Cl−(aq) E o = 0.27 J/C.14. Possible reaction: I2(s) + 2 Cl− (aq) → 2 I−(aq) + Cl2(g) E o = 0.0.0591 .36 V = −0. E o = −0.19 for the balanced reactions and standard cell potentials. Possible reaction: 2 Ag(s) + Cu2+(aq) → Cu(s) + 2 Ag+(aq) reaction occurs.0591 Note: When determining exponents. K = 1.75.485 C/mol e−)(0.CHAPTER 11 34. ELECTROCHEMISTRY 421 a. The reaction will occur.82 V = 0.27 V = 0. cell b. The spontaneous reaction is: 4 Fe2+(aq) + 4 H+(aq) + O2(g) → 4 Fe3+(aq) + 2 H2O(l) E o = 1.82 V.77 = 0. this reaction is cell spontaneous at standard conditions since E o > 0. n = 2 mol e− cell ΔG° = − nFE o = −(2 mol e−)(96.46 V cell ΔG° = − nFE o = −(4 mol e−)(96. Possible reaction: Cl2(g) + 2 I−(aq) → I2(s) + 2 Cl−(aq) E o = 0. we will round off to the correct number of significant figures after the calculation is complete in order to help eliminate excessive round-off errors.485 C/mol e−)(0.4 × 109 n 0.13. give negative cell potentials.14 = 1. No reaction occurs.6 × 105 J = −160 kJ cell E° = nE o 2(0.0591 0.23 .

485 C/mol e−)(0. K = 1013.14) = 115.9 × 104 J)/(8. K = 5.36 V c − − o − E a = −0.0591 19c. (H2O + ClO2 → ClO3− + 2 H+ + e−) × 5 5 e + 4 H+ + ClO2 → Cl− + 2 H2O ________________________________________________ 3 H2O(l) + 6 ClO2(g) → 5 ClO3−(aq) + Cl−(aq) + 6 H+(aq) − 37. E o = 1. a.485 C/mol e−)(1.2 = 2 × 1015 0.10 J/C) = −2. kJ log K = 6(1.68 × 1037 0. 19b.09) = 15. ΔG° = −(2 mol e−)(96.0591 0.954 V (ClO2 → ClO2 + e ) × 2 ____________________________________________________________ 2 ClO2−(aq) + Cl2(g) → 2 ClO2(aq) + 2 Cl−(aq) E o = 0. ΔG° = −(6 mol e−)(96. K = 1.0591 19d.18 V (Mn → Mn2+ + 2 e−) × 3 a _______________________________________________________________________ 3 Mn(s) + 8 H+(aq) + 2 NO3−(aq) → 2 NO(g) + 4 H2O(l) + 3 Mn2+(aq) E o = 2.91 × 104 J = −79 kJ cell ΔG° = −RT ln K. ΔG° = −(10 mol e−)(96. K = 1015.12 × 105 J = −212 kJ log K = 2(1.4 × 1013 0.225.2.736. so K = exp(−ΔG°/RT) K = exp[(7. we will round off to the correct number of significant figures after the calculation is complete in order to help eliminate excessive round-off errors.422 CHAPTER 11 ELECTROCHEMISTRY Note: When determining exponents.09 J/C) = −9 × 104 J = −90 kJ log K = 10(0.0 × 1013 or log K = nE o 2(0.60 × 105 J = −660.41) = = 13.0591 Cl2 + 2 e− → 2 Cl− b.41 V = 0.41 J/C) = −7. a.87 = 7.485 C/mol e−)(1.87.14 J/C) = −6. E o = 0.0591 36.14 V cell (4 H+ + NO3− + 3 e− → NO + 2 H2O) × 2 .41 J/C cell ΔG° = − nFE o = −(2 mol e−)(96.3145 J K−1 mol−1)(298 K)] = 7.10) = 37.96 V c − E o = 1.485 C/mol e−)(0.45 × 10115 0.

10(0. K = 1015. Eo = cell 0. E° will have a small temperature dependence when ΔS° is close to zero. we should get a straight line (y = mx + b).0591 2 H2(g) + O2(g) → 2 H2O(l). E o = 1. 40.2 = 2 × 1015 0. Because ΔS is negative.0591 0. a. Because the value of ΔG° is negative.24 × 106 J = cell −1240 kJ o nE 6(2.75 × 105 J = −475 kJ cell b.0591 Periodate oxidation (see part a for E o ): cell ΔG° = −(10 mol e−)(96.14 J/C) = −1.09 V cell b.09) = 15. products − ∑ n r ΔG o. From the equation above. Because two moles of O appear in the balanced reaction. Therefore.23 V cell n 4 ΔG° = − nFE o = −(4 mol e−)(96. Because moles of gas decrease as reactants are converted into products. ΔH° must be negative (ΔG° = ΔH° − TΔS°). oxygen goes from the zero oxidation state to the -2 oxidation state in H2O.485 C/mol e−)(0.485 C/mol e−)(1. Nitric acid oxidation (see part a for E o ): cell ΔG° = − nFE o = −(6 mol e−)(96. ΔS° will be negative (unfavorable). ΔG° = !nFE° = ΔH° ! TΔS°. reactants = 2(−237) + (−394) − (−166) = −702 kJ f f . CH3OH(l) + 3/2 O2(g) → CO2(g) + 2 H2O(l) ΔG° = ∑ n p ΔG o.0591 log K = log(1.23 J/C) = −4.28 × 1083).60 V c − E o = −1. The slope (m) of the line is equal to ΔS°/nF.14) log K = = = 217.2. ΔG = wmax = ΔH − TΔS.51 V 2 × (Mn2+ + 4 H2O → MnO4− + 8 H+ + 5 e−) a ________________________________________________________________________ 5 IO4−(aq) + 2 Mn2+(aq) + 3 H2O(l) → 5 IO3−(aq) + 2 MnO4−(aq) + 6 H+(aq) E o = 0. E° = TΔSo ΔH o − nF nF If we graph E° versus T.09 J/C)(1 kJ/1000 J) = −90 kJ log K = 38. and the y intercept is equal to -ΔH°/nF. ΔG becomes more positive (closer to zero). wmax will decrease as T increases. n = 2(2) = 4 mol electrons transferred. c.CHAPTER 11 ELECTROCHEMISTRY 5 × (2 e− + 2 H+ + IO4− → IO3− + H2O) 423 E o = 1. as T increases. 39.0591 0. K ≈ 10217 0.485 C/mol e−)(2.

485 C / mol e − ) For this reaction: ΔS° = 2(70. ΔG° = −nFE°.0591 0.0591 b.16 V a ____________________________________________________________ E o = 0.44 J/C) = !84. . nE o 2(0.485 C/mol e−)(0. E° will decrease with an increase in temperature.485 C/mol e−)(0.44 V.) + 214 − [127 + 3/2 (205)] = −81 J/K From Exercise 11. E° = TΔSo ΔH o − .36) 0.77 V a _____________________________________________________________ E o = !1. The reaction that occurs is Ag+ reacting with Zn. not spontaneous 3 Fe2+(aq) → 2 Fe3+(aq) + Fe(s) cell c.44) = = 14. Cu+ + e− → Cu E o = 0. a.900 J = !85 kJ cell log K = 42. nF nF Because ΔS° is negative.44 V c (Fe2+ → Fe3+ + e−) × 2 − E o = !0.2 × 106 n 0.36 J/C) = !34.21 V nF (6 mol e − ) (96.09 = 1.09. K = 106.700 J = -35 kJ cell Eo = cell nE o 1(0. Fe2+ + 2 e− → Fe E o = !0.000 J ) = = 1. K = 7. log K = = = 6.0591 NO3− is a spectator ion.424 The balanced half-reactions are: CHAPTER 11 ELECTROCHEMISTRY H2O + CH3OH → CO2 + 6 H+ + 6 e− and O2 + 4 H+ + 4 e− → 2 H2O For 3/2 mol O2. 41.39.65 V c HClO2 + H2O → ClO3− + 3 H+ + 2 e− − E o = !1.0591 0. E° = − ΔG o − (−702. spontaneous 2 Cu+(aq) → Cu2+(aq) + Cu(s) cell ΔG° = − nFE o = !(1 mol e−)(96.36 V.0591 log K.89.52 V c Cu+ → Cu2+ + e− − E o = !0.21 V a ______________________________________________________________________ 2 HClO2(aq) → ClO3−(aq) + H+(aq) + HClO(aq) E o = 0.8 × 1014 0. 6 moles of electrons will be transferred (n = 6).21 J/C = 1. HClO2 + 2 H+ + 2 e− → HClO + H2O E o = 1.21 V. spontaneous cell ΔG° = − nFE o = !(2 mol e−)(96.

1 × 10−12: Eo = cell 0.56 V cell log K = 43. nE 2(1.76 V Zn → Zn + 2 e a _________________________________________ 2 Ag+ + Zn → 2 Ag + Zn2+ E o = 1.81 = 6.44 V a ____________________________________________ E o = !0. Ksp = 10 −19.0591 0. Manipulate the given equations so that when they are added together.792 = 6.56) = . CuI + e− → Cu + I− Eo = ? CuI Cu → Cu+ + e− − E o = −0.41) = = 20.71 V = E o − 0. K = Ksp = 1. we get the Ksp reaction.52 V cell CuI For this overall reaction.01 V c Fe → Fe2+ + 2 e− − E o = 0. K = Ksp.0591 45.80 V c 2+ − ! E o = 0. Then we can use the value of E o for the reaction to determine Ksp. The Ksp reaction is FeS(s) ⇌ Fe2+(aq) + S2−(aq).41 V cell log K = nE o 3(0.0591 0.0591 log Ksp = log(1.71 V n 1 E o = −0.0591 Al3+ + 3 e− → Al E o = −1. K = 1052.5 × 1020 0.29.19 V cell CuI CuI .52 V a _________________________________________________ CuI(s) → Cu+(aq) + I−(aq) E o = E o − 0.57 V Fe(s) → Fe2+(aq) + S2−(aq) cell log Ksp = nE o 2(−0.66 V c − E o = 2.29 = 5.07 V Al + 6 F− → AlF63− + 3 e− a ___________________________________________________ Al3+(aq) + 6 F−(aq) → AlF63−(aq) K=? E o = 0.CHAPTER 11 ELECTROCHEMISTRY 425 (Ag+ + e− → Ag) × 2 E o = 0. cell FeS + 2 e− → Fe + S2− E o = !1.1 × 10 −20 0.0591 0. E o = −0.57) = = !19.0591 44.52. K = 1020.81.19 × 1052 0.0591 0.1 × 10−12) = −0.

05 [H + ]14 47.84 − log 3 3 [Au 3+ ] 1.33 V c 3+ − (Al → Al + 3 e ) × 2 − E o = 1.0591 0. At 25°C.84 V cell b.426 CHAPTER 11 ELECTROCHEMISTRY Galvanic Cells: Concentration Dependence 46.66 V a _________________________________________________________ E o = 2.0591 log K = log(2. ΔG° = − nFE o = −(3 mol e−)(96.15) 2 . a.0 × 10 − 2 Ecell = 1.20) = 2.84 − (−0.0591 [Tl + ]3 0.0591 log Q. (Cr2+ → Cr3+ + e−) × 2 Co + 2 e− → Co _____________________________________ 2 Cr2+(aq) + Co2+(aq) → 2 Cr3+(aq) + Co(s) 2+ Eo = cell 0.0 = 0.0591 [Al3+ ]2 [Cr 3+ ]2 log Q .401.0591 (0.84 V − 0.79 × 107) = 0. E = 2.52 × 1093 0.99 V Cr2O72− + 14 H+ + 2 Al → 2 Al3+ + 2 Cr3+ + 7 H2O cell E = EE ! 0.0591 0. K = 1093.7 × 10 −3 ⎞ − 6(0.0591 [Tl + ]3 (1. pH = -log(0.9 M.99 V ! log 2− n 6 [Cr2 O 7 ][H + ]14 0.99 ! ⎛ 3.04 V 48.9) = 0.55)[H + ]14 3.0591 0.485 C/mol e−)(1. [H+]14 = 0.0 × 10 −4 ) 3 log = 1. where Q = .01.37.34 V a _________________________________________________ Au3+(aq) + 3 Tl(s) → Au(s) + 3 Tl+(aq) E o = 1.220 V n 2 . Cr2O72− + 14 H+ + 6 e− → 2 Cr3+ + 7 H2O E o = 1.93 = 0.84) = = 93. log n (0.84 J/C) = −5.0591 ⎠ ⎝ 3. Au3+ + 3 e− → Au E o = 1. n [Au 3+ ] c.7 × 10 −3 = 10 −2.01 = 2.02) ⎟ = log ⎜ ⎜ [ H + ]14 ⎟ 0.50 V c (Tl → Tl+ + e−) × 3 − E o = 0.401 = 2. [H+] = 0.30) 2 (0. Ecell = E o − cell Ecell = 1.0591 0.33 × 105 J = −533 kJ cell log K = nE o 3(1.

E = E° − RT 0.12 = 0.0) = 0.51 − e.60) 2 0.34 V − E° = 0.53 V − [Al3+ ]2 (1.0591 [Cr 3+ ]2 ( 2 .51 V − 0. E = E° − log Q.53 V − 0.0 × 10 −3 )8 [MnO 4 ][H ] 0.220 V − log = 0.083 = 1.22 V 2 E° = 1.0591 (0.34 − 0.0591 = 1.43 V 8⎥ 5 ⎣ (0. E = 1.10) 3 (Pb2+ + 2 e− → Pb) × 3 Ecell = 1.60 mol/L) = 0.34 V − (−8.27 V = 1. or at 25°C.9 × 10−3 V) = 0.0591 (23) = 1.10) = 0. nF n For Cu2+(aq) + 2 e− → Cu(s) E = 0.34 − 0. E = 0.485 C/mol e−)(0.51 V c.0591 log = 0.0591 0.1 kJ 49.60 mol/L (Al3+ is a product in the spontaneous reaction).0 ) 2 0.10) (0.010) ⎤ 0.0591 0.151 J/C) = −2.0591 log ⎢ = 1.51 − 0.51 − ⎡ (0. a.010) log = 1.10) (1.31 V 2 b.10) ⎦ .50 V 50.34 − d.34 V. E = E° − 0.90 M. Ecell = 1.0591 log(1/1.20) 427 ΔG = −nFE = −(2 mol e−)(96. E = 0. 5 e− + 8 H+(aq) + MnO4− (aq) → Mn2+(aq) + 4 H2O(l) E = E° − [Mn 2 + ] 0.35 V 2 0.91 × 104 J = −29.30) 2 (0.51 V − log − + 8 5 5 (0.24 V 5 E = 1.0591 ln Q.53 − log log 6 6 [Pb 2 + ]3 (0.34 V − 0. when the [Al3+] has increased by 0.CHAPTER 11 E = E° − ELECTROCHEMISTRY 0.66 V a ________________________________________________________ 3 Pb2+(aq) + 2 Al(s) → 3 Pb(s) + 2 Al3+(aq) E o = 1.0591 log(1/2. then the Pb2+ concentration has decreased by 3/2 (0.0591 log(1/0.0591 log(1/[Cu2+]) n 0. E o = −0.53 V cell From the balanced reaction.151 V n 2 [Cr 2+ ]2 [Co 2 + ] (0.030 V = 0.034 V = 1.13 V c (Al → Al3+ + 3 e−) × 2 − E o = 1.0 × 10−4) = 0.

98 V − (−0. ΔG = −nFEcell = −2(96.0591 log log ⎜ + 2 2 ⎜ [H ] [HSO − ]2 ⎟ 2 2 (4. 52. oil becomes more viscous at lower temperatures.446 V ESCE = 0.485)(0.504 V = 0.077 V) = 2.98 V nF (2 mol e − )(96. The combination of these two factors results in batteries failing more often on cold days than on warm days.5) (4.05 V d.204 − d.242 V SCE will be the oxidation half-reaction with Ecell = 0.12 V b. We can calculate ΔG° from ΔG° = ΔH° − TΔS° and then E° from ΔG° = −nFE°. 0.4 kJ b.concentrations.0591 0.485 C / mol e − ) c.98 J/C = 1. Ecell = 0.04 V − 0.5) 2 = 2.98 V − ln + 2 − nF nF [H ] [ HSO 4 ]2 (8. n = 2 for this reaction (lead goes from Pb → Pb2+ in PbSO4).5) (4. To calculate Ecell at nonstandard CrO42.204 V − (0.98 V − RT 1 RT ln Q = 1.0591 ⎟ = 2.066 V) − − 2 (2 mol e )(96.0591/2) log[CrO42−] log[CrO42−] = −10.204 V − log[CrO42−] 2 2 0.0.152. CHAPTER 11 a.3145 J K −1 mol −1 )(253 K ) 1 ln = 1. E − 20 = E o 20 − − E−20 = 1.204 V.0591 log[CrO42−] = 0.352 V 2 c. Therefore. we use the following equation.04 V − (−0. o Ecell = Ecell − 0. the cell potential decreases.428 51. Also.204)J = −3. which adds to the difficulty of starting an engine on a cold day. we assume all concentrations are constant.485 C / mol e ) (4. or we can use the equation derived in Exercise 11.148 V) = 0. [CrO42−] = 10−10. Ag2CrO4(s) + 2 e− → 2 Ag(s) + CrO42−(aq) Hg2Cl2 + 2 e− → 2 Hg + 2 Cl− E° = 0.5) 2 4 ⎝ ⎠ 2.9 × 103 J = = 1.152 = 7.5 J / K ) + 315.0591 log(1.00 × 10−5) = 0. only CrO42− appears in the Q expression. In SCE. and it will appear in the numerator since CrO42− is produced in the reduction half-reaction.204 V − (−0. E = Eo − cell ELECTROCHEMISTRY ⎛ ⎞ 1 1 0.05 × 10−11 M . As the temperature decreases.446 . E o − 20 = TΔS o − ΔH o (253 K )(263.39.242 = 0. a.94 × 104 J = −39.

and the lower ion concentration is always at the anode. which causes an increase in the cell potential. the cell potential increases.35 V ) ( 2) = −11. and we use the Nernst equation to calculate the [Ag+] at the anode.80 V _________________________________________________________________ Ag2CrO4(s) → 2 Ag+(aq) + CrO4−(aq) Eo = −0.446 V c o 429 Ag2CrO4 + 2 e− → 2 Ag + CrO42− (Ag → Ag+ + e−) × 2 − Ea = -0. Thus. This can be accomplished by decreasing the ion concentration at the anode and/or by increasing the ion concentration at the cathode. ELECTROCHEMISTRY Eo = 0. y M) and the Nernst equation is: E = EE − 0. The net reaction in a concentration cell is: Ma+(cathode. 0.0591 log a + . Equilibrium for a concentration cell is reached (E = 0) when the ion concentrations in the two compartments are equal. All concentration cells have E o = 0 because both compartcell ments contain the same contents. the more negative is the log Q term. log Ksp = n 0. and the more positive is the cell potential. Eo = 0 cell To register a potential (E > 0). Adding Cl− lowers the Ag+ concentration. The cell produces a voltage as long as the ion concentrations are different. The magnitude of the cell potential depends on the magnitude of the differences in ion concentrations between the anode and cathode. Ag+ reacts with Cl− to form AgCl(s). .84. and the smaller ion concentration is always in the anode compartment. [Cl−] is given. As is the case for all concentration cells. To determine Ksp for AgCl (Ksp = [Ag+][Cl−]). The driving force for the cell is the different ion concentrations at the anode and cathode. 54.4 × 10−12 log Ksp. Ecell = 0. K = Ksp = ? cell Eo = cell 53. x M) → Ma+(anode.0591 [M a + (anode)] 0. This occurs when Ma+(cathode) > Ma+(anode). The higher ion concentration is always at the cathode. The general Nernst equation for the Ni | Ni2+ (x M) | | Ni2+(y M) | Ni concentration cell is: o 55. as the difference in ion concentrations between the anode and cathode compartments increases.0591 (−0.84 = 1. Ksp = 10−11.0591 Concentration cell: a galvanic cell in which both compartments contain the same components but at different concentrations. The larger the difference in ion concentrations.35 V. the log Q term must be a negative value.CHAPTER 11 e. When NaCl is added to the anode compartment. log Q = − n a [M (cathode)] where a is the number of electrons transferred. Here. we must know the equilibrium Ag+ and Cl− concentrations.

0 log = = 8. electrons flow to the left in the diagram.0 [ Ni ]cathode o c. [M2+] = [SO42−] at equilibrium.0591 − 0.0 M Ni2+. Ecell = [ Ni 2+ ]anode − 0.44 = − log log 2 2 1 .0 × 10 −5 − 0.10 log = 0. Because both compartments are at standard conditions ([Ni2+] = 1.0 e.00 V − Eo = 0.3 × 10−15)2 = 1. Cu2+(aq) + H2(g) → 2 H+(aq) + Cu(s) Eo = 0. electron flow is always from the anode to the cathode.13 V log 2 1. electrons flow to the left in the diagram. Cathode = 2.0 M). Cathode = 1.9 × 10−3 V log 2+ 2 2 2 . Ecell = − 0. Ksp = [M2+][SO42−] = (1.0 M Ni2+.0591 0.430 o Ecell = Ecell − CHAPTER 11 [ Ni 2+ ]anode 0.3 × 10−15 M 0.5/2. No electron flow occurs.80 V Anode: M(s) → M2+ + 2e− ______________________________________________________ M2+(cathode) → M2+(anode) Ecell = 0.89.0591 Because we started with equal numbers of moles of SO42− and M2+. 56. Since both concentrations are equal.34 V and n = 2 cell .0 × 10−5 M Ni2+.5) = log(1.030 V 2 1.0 d. Ecell = Ecell = 0 V. anode = 1.34 V − 0.44) = −14.10 M Ni2+. 0. so electrons flow to the right in the diagram. Cathode: M2+ + 2e− → M(s) Eo = 0.0591 0. Ecell = 4. [M2+]anode = 1. No electron flow occurs.0 M Ni2+.0591 = 0.0) = 0.80 V c o − Ea = −0. log(2. anode = 4.00V = 0.0 [M 2+ ]cathode log [M2+]anode = − 2(0.00 V cell [M 2+ ]anode [M 2 + ]anode 0. anode = 0. Cathode = 1.0591 0.0 M Ni2+.0591 log Q = log n 2 [ Ni 2 + ]cathode ELECTROCHEMISTRY a.0591 . and Ecell = 0.7 × 10−30 57. b.0591 1 .44 V = 0.

A graph of Ecell versus log[Cu2+] will yield a straight line with slope equal to 0. so: [Cu2+] = Ecell = Eo − cell 1 0. Ecell = Ecell − (0.0) 3 log [Al3+]2 = −39.0591 [Al3+ ]2 log log . .34 V − 0. log = 4. [Cu2+] = 10−4.6 × 10 −19 = 1.0 M: Ecell = Ecell − a.34 − = 0. c. Ksp = (1.91 2+ 2 [Cu ] [Cu 2+ ] = 1.0591 log 2 [Cu 2+ ] 431 o Since PH 2 = 1. d. 58. Cu(OH)2(s) ⇌ Cu2+(aq) + 2 OH−(aq) Ksp = 1.2 × 10−5 M Note: When determining exponents.59. from the problem.23 V 2 2.10) From the problem.0296 log [Cu2+].6 × 10−19 = [Cu2+][OH−]2 1.0 × 10−4 M.23 V + 1. 0.11 V = 0.0591 log = 0.34 V − 0.6 × 10 −17 = −0. for the silver concentration cell.91.50 log 2+ 2 2 [Cu ] 1. Ag+(x M.0591 [Al3+ ]2 0.0591/2) log (1/[Cu2+]) = Ecell + 0. a.0591 1 0. [OH−] = 1.195 V = 0. Ecell = 0. we will carry extra significant figures.10 M.16 V for the reverse reaction.59. 1.00 (as is always the case for concentration cells) and n = 1. The cell reaction is 2 H+(aq) + Cu(s) → Cu2+(aq) + H2(g).43 V. o 3 Ni2+(aq) + 2 Al(s) → 2 Al3+(aq) + 3 Ni(s) Ecell = −0.6 × 10−17 M 2 (0. and Ecell = 0. EE = 0.5 × 10 − 4 b.0591 1 1 log .0591 1 log = 0.34 V − 0.6 mV. this equation is in the form of a straight-line equation.6 × 10−32 59.0 atm and [H+] = 1. anode) → Ag+(0. but the reverse reaction is spontaneous.34 − 0.16 V Because Ecell < 0.CHAPTER 11 ELECTROCHEMISTRY 1 0.82 V = 1.66 V = 1.0 × 10−4)3 = 1. y = mx + b.10 M. [Al3+]2 = 10−39. the forward reaction is not spontaneous. [OH−] = 0. The Cu electrode becomes the anode. cathode). Use the Ksp expression to calculate the Cu2+ concentration in the cell.43 V − n 6 [ Ni 2 + ]3 (1.6 × 10−20)(1.6 × 10−20 M Al(OH)3(s) ⇌ Al3+(aq) + 3 OH−(aq) Ksp = [Al3+] [OH−]3. n = 6 o o Ecell = Eo − cell 0.0296 V or 29. [Al3+] = 1.

485 C 1s × × × = 1.8 g I 2 × × = 71 g I2 − 96. 15 A = 15 C 60 s 60 min × × = 5.0 g Ni × 1 mol 2 mol e − 96. a.485 C 1s × × × = 33 s − 58.76 = -0.485 C 6 mol e − mol Cr .7 g mol Ni 100.0 C mol e = 3.0 × 103 g × 1 mol Al 3 mol e − 96. 3 mol e− is needed to produce 1 mol Al from Al3+. 5.050) 2 Electrolysis 60.9 g Cr 96. Cr is in the +6 oxidation state in CrO3. Al3+ + 3 e− → Al.0 mol Ag × 61.4 × 104 C × 1 mol e − 1 mol Cr 52.10 b.4 × 10 −14 (0.432 E = 0. 2 I− → I2 + 2e−.0 C mol e c.0 g mol Al 100.485 C 2 mol e − mol 1 mol e − 1 mol Hf 178.0 × 101 hours b.3 hours − mol Ag 100.5 g × × = 25 g Hf 96.9 g × × = 16 g Co 96. 5. Ag+(aq) + 2 S2O32−(aq) K= [Ag(S2 O 3 ) 2 ] [Ag + ][S2 O 3 ]2 2− 3− ⇌ Ag(S2O3)23−(aq) = 1.07 × 105 s − 27.4 × 104 C of charge passed in 1 hour s min mol 1 mol e − 1 mol Co 58.00 ! CHAPTER 11 [Ag + ]anode 0.4 × 104 C × c. 5.485 C 4 mol e − mol 1 mol e − 1 mol I 2 253.0 g Cr × × = 4.76 V = 0.485 C 2 mol e mol I 2 a.0 × 10 −3 = 2. [Ag+]anode = 1. Six moles of e− are needed to produce 1 mol Cr from molten CrO3.4 × 104 C × b. 5.10 0.4 × 104 C × d. 5. 1.485 C 1s × × = 4.86 .4 × 10 −14 M .0 C mol e 1 mol e − 96.8 × 103 s = 1.9 × 1013 1. 1. 0.0591 log 1 [Ag + ]cathode ELECTROCHEMISTRY 0.0591 log [Ag + ]anode [Ag + ]anode = 10 −12.

a a. Mn2+ can be reduced. ELECTROCHEMISTRY 433 2. we must consider the oxidation and reduction of water as potential reactions that can occur. the species that will be reduced at the cathode will have the most positive E o value.→ Br2 + 2 e− E o = −0. Possible cathode reactions are: . For aqueous solutions. and Br− can be oxidized to Br2 (from Table 11.18 V c − E o = −0. The reactions are: Cathode: Mn2+ + 2 e− → Mn Anode: 2 I− → I2 + 2 e− E o = −1. and I− can be oxidized. The oxidation state of bismuth in BiO+ is +3 because oxygen has a !2 oxidation state in this ion. the species that will be oxidized at the anode c will be the reducing agent with the most positive − E o value. more reactions can take place. b. When H2O is present.1).CHAPTER 11 62. Br−. First determine the species present.86 × 10−3 mol Ag − min s 96. The reactions are: Cathode: Ni2+ + 2e− → Ni Anode: 2 Br. Therefore.0 g Bi × 64.87 V a c. we must now consider H2O as a possible oxidizing agent and a possible reducing agent. 3 moles of electrons are required to reduce the bismuth in BiO+ to Bi(s). Al3+ can be reduced. making predictions more difficult.09 V a 65.485 C 1s × × × = 554 s = 9. and then reference Table 11. Species present: Al3+ and F−. there is only one species present that can be oxidized (the anion in simple salts). as is the case when aqueous solutions are electrolyzed. Of all the possible oxidizing agents. Species present: Mn2+ and I-. 10. Ni2+ can be reduced to Ni.23 V c − E o = −1.66 V c − E o = −2.00 C 1 mol e − 1 mol Ag 60 s = 138 s.1 to help you identify each species as a possible oxidizing agent (species reduced) or as a possible reducing agent (species oxidized). Species present: Ni2+.250 L = 1. and F− can be oxidized.86 × 10−3 mol Ag+/0. Species present: Ni2+ and Br-.0 C mol e When molten salts are electrolyzed. and H2O. 1 mol Bi 3 mol e − 96.23 min − 209.54 V a d.485 C mol e [Ag+] = 2. and there is only one species that can be reduced (the cation in simple salts).0 g Bi mol Bi 25. The reactions are: Cathode: Al3+ + 3 e− → Al Anode: 2 F− → F2 + 2 e− E o = −1.30 min × 2.14 × 10−2 M 63. When water is present. 138 s × × × = 2.

23 V a Because Br− is easier to oxidize than H2O (assuming standard conditions). F−.434 Ni2+ + 2e− → Ni 2 H2O + 2 e− → H2 + 2 OH− CHAPTER 11 E o = −0. e. and H2O. The possible cathode reactions are: Mn2+ + 2 e− → Mn 2 H2O + 2 e− → H2 + 2 OH− E o = −1. a. Br− will be oxidized by the above anode reaction. Ni2+ will be reduced by the above cathode reaction.23 V for H2O (assuming standard conditions).83 V for H2O (assuming standard c c conditions). Al3+ and H2O can be reduced. Mn2+ and H2O can be reduced. Species present: Al3+. Possible anode reactions are: 2 Br. H2O is the most easily oxidized and the most easily reduced species present.54 V a − E o = −1. F− and H2O can be oxidized. Species present: Mn2+. The possible anode reactions are: 2 I− → I2 + 2 e− 2 H2O → O2 + 4 H+ + 4 e− − E o = −0. a 66.→ Br2 + 2 e− 2 H2O → O2 + 4 H+ + 4 e− − E o = −1. The reduction potentials are E o = −1. From the potentials. we would a predict H2O to be oxidized at the anode (2 H2O → O2 + 4 H+ + 4 e−). Anode: 2 H2O → O2(g) + 4 H+ + 4 e− . The oxidation potentials are − E o = −2. c I− and H2O can be oxidized.83 V c Reduction of H2O should occur at the cathode because E o for H2O is most positive.09 V a − E o = −1. and H2O. From the potentials. f. SO42−.66 V for Al3+ and E o = −0.18 V c E o = −0. The reactions are: Cathode: 2 H2O + 2 e− → H2(g) + 2 OH−.83 V c ELECTROCHEMISTRY Because it is easier to reduce Ni2+ than H2O (assuming standard conditions). and H2O. Species present: Na+.23 V a Oxidation of I− will occur at the anode because − E o for I− is most positive.23 V c E o = −0.87 V for F− and a − E o = −1. H2O should be reduced at the cathode (2 H2O + 2 e− → H2 + 2 OH−). I−.

40 V 2 H2O + 2e− → H2 + 2 OH− E° = −0.11V = 0.51 V 2 2.68 V 2 0. a significantly higher voltage than predicted is necessary to produce the chemical change (called overvoltage).0) 4 log = 0.77 V − 0. [PdCl4−] = 1 (0.0) 4 log = 0.11 = 0.0591 (1. Mol e− = 50.73 − 0.73 V − When 99% of Pt is plated: Ec = 0.83 V Au(s) will plate out first since it has the most positive reduction potential.050 V = 0.62 − 2− 2 2 0.0591 (1.62 V − 0.0591 (1.80 V Ni2+ + 2 e− → Ni Cd2+ + 2 e− → Cd E° = −0. When water is electrolyzed.74 V 3 0. and finally.0591 (1.0 × 10 − 4 To begin Pt plating: Ec = 0. 100 0.77 − 0.CHAPTER 11 ELECTROCHEMISTRY 435 b.0591 [Cl − ]4 0. 68. 69.033 = 0.020 [PdCl 4 ] Ec = 0.50 V E° = 0.020 0. To begin plating out Pd: Ec = 0.0) 4 log log = 0.62 V 2 2. Thus the volume of O2 generated would be less than expected.77 × 10−2 mol e− min s 96.020) = 0.77 × 10 −2 mol e − = = 3. which is followed by Ni(s).→ Ag E° = 1.62 V − 0.0 min × 60 s 2.73 − 0.1 g Ru Mol Ru = 2.00 Mol Ru 2.590 × 10−2 mol Ru 101.0591 (1.73 − To begin Ir plating: Ec = 0. Cd(s) will plate out last since it has the most negative reduction potential of the metals listed.57 V When 99% of Pd has plated out.485 C 1 mol Ru = 2.618 g Ru × Mol e − 7.00020 M.0) 4 log = 0. 67. Au3+ + 3 e− → Au Ag+ + e.62 V − Ec = 0.050 = 0.50 C 1 mol e − × × = 7. and the measured volume ratio would be greater than 2:1.590 × 10 − 2 mol Ru The charge on the ruthenium ions is +3 (Ru3+ + 3 e− → Ru).23 V E° = −0.62 − 0.0) 4 log = 0. followed by Ag(s).020 . This higher voltage is probably great enough to cause some SO42− to be oxidized instead of H2O.0 × 10 − 4 0.

485 C 1 mol F2 nRT = 0.373 mol)(0. Alkaline earth metals form +2 ions.12 × 10 −4 mol M.94 × 10−2 mol M × × s 96.94 × 10 − 2 mol M Molar mass of M = 72. The order of plating will be Ir(s) first. Mol M = 748 s × 5. The exact potential to apply depends on the oxidation reaction. V = − P 2 mol e 0. so 2 mol of e− are transferred to form the metal M.00 atm K is produced at the cathode: K+ + e− → K 0. −4 mol 5.00 h × 60 min 60 s 10.77 − CHAPTER 11 ELECTROCHEMISTRY 0. 1.10 g K = 29.14 g C 6 H 8 N 2 mol C 6 H 8 N 2 mol e − = 7. F2 is produced at the anode: 2 F− → F2 + 2 e− 2. PV = nRT. 74.44 × 104 C/s or a current of 7.3 g/mol.77 − 0. 150.12 L F2 1. the element is bismuth. 70.436 When 99% of Ir is plated: Ec = 0.485 C × × × × × h 60 min 60 s 108.0 C 1 mol e − × × × = 0. we should be able to separate the three metals.107 g M 209 g = .0) 4 log = 0. MgCl2 was electrolyzed.12 × 10 mol M Molar mass = 71.746 mol e− × 1 mol K 39. where M = unknown metal × × s 96.746 mol e− h min s 96.0 × 10 − 4 Yes.485 C 2 mol e − 0.073 = 0.2 g K × mol K mol e − .70 V 3 2.00 C 1 mol e − 1 mol M = 1. × 103 g C 6 H 8 N 2 1 mol C 6 H 8 N 2 1h 1 min 2 mol e − 96.485 C 3 mol e − 0.373 mol F2.44 × 104 A 73. Pd(s) as the potential is gradually increased.08206 L atm K −1 mol −1 )(298 K ) = 9. since the range of potentials for plating out each metal do not overlap.0591 (1.471 g M = 24.00 C 1 mol e − 1 mol M = 5. followed by Pt(s). and finally.1 s × 2.746 mol e− × V= (0.

and the cathode reaction is 2 H2O + 2 e− → H2 + 2 OH−.0 C 1 mol e − × × × = 1.98 V nF (4 mol e − )(96. The overall reaction is 2 H2O(l) + 2 Cl− (aq) → Cl2(g) + H2(g) + 2 OH− (aq).0 kg Al requires: 1.0 × 102 kJ 26.4 × 104 kJ s min h (Hall process) 437 To melt 1.42 L = 0.00 L of Cl2(g) also will be produced since moles and volume of gas are directly proportional at constant T and P (see Chapter 5 of text).42 L (see Chapter 5 of the text). and Cl− is oxidized in preference to H2O.262 L = 262 mL H2 mol H 2 1 mol O 2 22.00 L of H2(g) is produced.485 C 4 mol e − At STP.17 × 10−2 mol H2 × 22.131 L = 131 mL O2 2 mol H 2 mol O 2 Additional Exercises 77. The anode reaction is 2 Cl− → Cl2 + 2 e−. 76. it takes less than 1% of the energy required to produce the same amount of Al by the Hall process. if 6. and n = 4 for this reaction as it is written. 15 kWh = ELECTROCHEMISTRY 15000 J h 60 s 60 min × × = 5.4 × 107 J or 5. The half-reactions for the electrolysis of water are: (2 e− + 2 H2O → H2 + 2 OH−) × 2 2 H2O → 4 H+ + O2 + 4 e− __________________________ 2 H2O(l) → 2 H2(g) + O2(g) Note: 4 H+ + 4 OH− → 4 H2O. 1.485 C / mol e − ) . H2O is reduced in preference to Na+.98 g mol Al It is feasible to recycle Al by melting the metal because. In the electrolysis of aqueous sodium chloride.0 min × 2 mol H 2 60 s 25. E = − ΔG − (−380 × 10 −3 J ) = = 0. From the 1 : 1 mole ratio between Cl2 and H2 in the overall balanced reaction.0 × 103 g Al × 1 mol Al 10.42 mol L × = 0. then 6. 75. in theory. 1 mole of an ideal gas occupies a volume of 22.17 × 10−2 mol H2 × 1.CHAPTER 11 74.7 kJ × = 4.17 × 10−2 mol H2 min s 96. (CO + O2− → CO2 + 2 e−) × 2 O2 + 4 e− → 2 O2− __________________________ 2 CO + O2 → 2 CO2 ΔG = −nFE. 15.

23 V = 1. wmax = !1320 kJ = ΔG = !nFE. Fuel cells are more efficient in converting chemical energy into electrical energy. eventually reaching zero. wmax is: 1. but this does not occur in any real process because there is always waste energy in a real process. 79. For CO2. The overall reaction in the hydrogen-oxygen fuel cell is 2 H2(g) + O2(g) → 2 H2O(l). Two moles of carbon are in the balanced reaction.438 78. The best that could happen is that all the free energy released would go into doing work. O2 + 2 H2O + 4 e− → 4 OH− E o = 0.40 V + 0. A charged battery is not at equilibrium.485 C/mol e−)E E = 1. !1320 × 103 J = !nFE = !(12 mol e−)(96. The major . See Figure 11. have the reactants continuously supplied and can produce a current indefinitely. so carbon has a +4 oxidiation state. The half-reactions are: 4 e− + O2 + 2 H2O → 4 OH− 2 H2 + 4 OH− → 4 H2O + 4 e− cathode anode Utilizing the standard potentials in Table 11.00 × 103 g H2O produced. Ecell = 0 and ΔG = 0. so n = 12. We get no work out of an equilibrium system. ΔG° = − nFE o = !(4 mol e−)(96. wmax = ΔG° for 2 mol H2O produced.16 for a schematic of this fuel cell.200 kJ = wmax 18.14 J/C = 1. fuel cells. unlike batteries. the H2(g) and O2(g) reactants are continuously supplied.000 J = !475 kJ cell For 1.02 g H 2 O 2 mol H 2 O The work done can be no larger than the free energy change. This dictates a !2 oxidation state for C.14 V 80.40 V c ! E o = 0. CHAPTER 11 ELECTROCHEMISTRY As a battery discharges. Six moles of electrons are transferred per mole of carbon oxidized (C goes from !2 → +4). As with all fuel cells.485 C/mol e−)(1. A battery is useful to us because it can do work as it approaches equilibrium. they are also less massive.83 V = 1. However. Both fuel cells and batteries are galvanic cells that produce cell potentials to do useful work.1. Ecell decreases.23 J/C cell Because standard conditions are assumed. O has a !2 oxidiation state. For C2H5OH. E o = 0.83 V (H2 + 2 OH− → 2 H2O + 2 e−) × 2 a ________________________________________________________ 2 H2(g) + O2(g) → 2 H2O(l) E o = 1. H has a +1 oxidation state. and O has a !2 oxidiation state.23 V for the cell hydrogen-oxygen fuel cell.00 × 103 g H2O × 1 mol H 2 O − 475 kJ × = !13. At equilibrium.23 J/C) = !475.

83. The protected metal becomes the cathode electrode. e. In addition. c. O2(g)–a reactant c.485 C/mol e−)(1. b. 81.10 J/C) = −2. n = 2 mol electrons transferred. H2(g) and O2(g) are an explosive mixture if ignited. Galvanizing: coating steel with zinc. For corrosion of iron to take place. d. Because one mole of Cd appears in the balanced reaction. This corrosion is the oxidation of a pure metal (oxidation number = 0) into its ions. It is oxidized in preference to the protected metal. you must have: a. zinc is more easily oxidized than the iron in the steel. The corrosion of a metal can be viewed as the process of returning metals to their natural state. thus cathodic protection. Salting roads in the winter also increases the severity of corrosion. the added Cr and Ni form oxide coatings on the steel surface. H2O(l)–a reactant. a. Cathodic protection: a more easily oxidized metal is placed in electrical contact with the metal we are trying to protect. At standard conditions: wmax = ΔG° = −nFE°. cars do not rust in dry-air climates. f. Cadmium goes from the zero oxidation state to the +2 oxidation state in Cd(OH)2. wmax = −(2 mol e−)(96. . This only works as long as the painted surface is not scratched. whereas corrosion is a big problem in humid climates. exposed iron surface–a reactant b.CHAPTER 11 ELECTROCHEMISTRY 439 disadvantage is that they are expensive. Zn forms an effective oxide coating over steel. The dissolution of the salt into ions on the surface of a metal increases the conductivity of the aqueous solution and accelerates the corrosion process. much more so than fossil fuels. Durable oxide coatings: covers the metal surface so that no contact occurs between the metal and air. The natural state of metals is to have positive oxidation numbers.12 × 105 J = −212 kJ 82. Alloying: adding chromium and nickel to steel. Paint: covers the metal surface so that no contact occurs between the metal and air. but also provides a medium for ion flow (it provides the salt bridge) d. Sacrificial metal: attaching a more easily oxidized metal to an iron surface. also. ions–needed to complete the salt bridge Because water is a reactant and acts as a salt bridge for corrosion. the more active metal is preferentially oxidized instead of iron.

96 V c − E o = −0. 87.19 V). This red red means that when O2 is coupled with most metals. and Pt) all have standard reduction potentials greater than that of O2. the reduction potential for Mg2+ + 2 e− → Mg is −2. Nitrate cannot oxidize Pt unless there is Cl− in the solution. the oxidation half-reactions.66 V c − Eo = ? (M → M2+ + 2 e−) × 3 a _________________________________________________________________ 3 M(s) + 2 Al3+(aq) → 2 Al(s) + 3 M2+(aq) E o = − E o − 1. The potential oxidizing agents are NO3− and H+. CHAPTER 11 ELECTROCHEMISTRY Metals corrode because they oxidize easily.66 V cell a ΔG° = − nFE o . As expected. E o = 0. its reduction potential is greater than that of O2 (E o = 1. a.37 or E o = −2. which fits the data.44 V a It is easier to oxidize Zn than Fe.485 C/mol e−)( E o ).66 V = 0. This means the reverse reactions.1.1. indicating that they oxidize fairly easily. Therefore. (Al3+ + 3 e− → Al) × 2 E o = −1. Note: The standard reduction potential for Pt → Pt2+ + 2 e− is not in Table 11.76 V. − E o = 2.37 V. Aqua regia has both Cl− and NO3-.755 V (4 Cl− + Pt → PtCl42− + 2 e−) × 3 a _________________________________________________________________________________ 12 Cl−(aq) + 3 Pt(s) + 2 NO3−(aq) + 8 H+(aq) → 3 PtCl42-(aq) + 2 NO(g) + 4 H2O(l) E o = 0. Zn → Zn2+ + 2 e− − E o = 0. 3 e− + 4 H+ + NO3− → NO + 2 H2O E° = 0. so the Zn will be oxidized. O2 is not capable of oxidizing these metals at standard conditions. E o = 0. so corrosion occurs. Au.440 84. −411 × 103 J = −(6 mol e−)(96. Another key point is that the reduction of O2 (which is a reactant in corrosion processes) has a more positive E o than most of the metals (for O2. 86.37 cell a a c From Table 11. protecting the iron of the Monitor's hull. Referencing Table 11. The overall reaction is: (NO3− + 4 H+ + 3 e− → NO + 2 H2O) × 2 E o = 0. Hydrogen ion cannot oxidize Pt under either condition. have positive oxidation potentials.96 V Nitric acid can oxidize Co to Co2+ ( E o > 0). Hence the metal is magnesium.71 V.21 V cell 88. Fe → Fe2+ + 2 e− a − E o = 0.71 V cell cell cell E o = − E o − 1. cell The noble metals (Ag. cell . most metals are associated with negative standard reduction potentials. Pt 85. Co2+ is the primary product assuming standard conditions. but is not strong enough to oxidize Co to cell Co3+ ( E o < 0).40 V).1. the reaction will be spontaneous because E o > 0.

66 V 2 × (Al → Al3+ + 3 e−) a ___________________________________________________________ 3 Ag2S(s) + 2 Al(s) → 6 Ag(s) + 3 S2−(aq) + 2 Al3+(aq) E o = 1.05916 0. 0. assume PNO = 1 atm. For an error of −1 mV.001 V (±1 mV).871 0. From part a.017.01 V cell E o = E o 2S + 1.96 − log 3 3 (16) 5 [H ] [ NO 3 ] E = 0.96 V − P 0. or about ±0.12) = 1.01) = = 102.479 − 0.)] = −582 kJ f r.905 = 1.66.02 pH units if we measure the potential to the nearest ±0. [H+] = 10-3.01 − 1.65 V cell Ag Ag . 3 × (2 e− + Ag2S → 2 Ag + S2−) − E o = 1.08 V No. uncertainty = ±1 mV = ± 0. [H+] = 10−3. [H+] = 10−3. we will be within ±0.96 − (−0.480 − 0. [H+] = [NO3−] = 16 M. E° = log K = nE o 6(1.485) C From oxidation numbers. concentrated nitric acid still will only be able to oxidize Co to Co2+.250 = 3.905.538 = 3. − ΔG o − (−582.481 − 0. n = 6. 89. K = 10102. products − ∑ n r ΔG o reactants = 2(−480.05916 pH pH = 0.05916 pH.250 = 3.) + 3(86) − [3(−40.250 V + 0.05916 pHmax = pHmin = 0.000 J ) = = 1.888.250 = 3.45 × 10102 0. a.538. For an error of +1 mV. Concentrated nitric acid is about 16 mol/L. ΔG° = −nFE°. E = 0.66 = −0.06 × 10−4 M = ±6 × 10−6 M. For this measurement.888 = 1.0591 0.001 V. a.480 V = 0.35 × 10−4 M.0591 1 log + 4 NO − = 0. ΔG° = ∑ n p ΔG o. 90.05916 Thus if the uncertainty in potential is ±0.24 × 10−4 M.0591 E o 2S = ? Ag b.001 V 0.02 pH units.871 = 1. 0. b. then the uncertainty in pH is ±0.01 V nF 6(96.CHAPTER 11 ELECTROCHEMISTRY 441 b.0591 0. E o 2S = 1. Ecell = Eref + 0.29 × 10−4 M. So the uncertainty in [H+] is ±0.

a. 2 [Ag + ]0 1/2 [Cu 2 + ]0 2[Cu 2+ ]0 = = 2Ql 2 (1/2 [ Ag + ]0 ) 2 [Ag + ]0 Q2 = The reaction quotient is doubled because the concentrations are halved. the reaction is closer to equilibrium. which will decrease the cell potential. and because solids do not appear in the reaction quotient expressions. whereas a stress that decreases the tendency of the forward reaction to occur will decrease the cell potential. A galvanic cell cell produces a voltage as the forward reaction occurs. each concentration is halved. Because a reactant ion is removed. this will decrease the tendency of the forward reaction to occur. Q1 = [Cu 2 + ]0 . b. Because Ag(s) is not a reactant in this spontaneous reaction. Added NH3 removes Cu2+ in the form of Cu(NH3)42+.0 M Fe3+ Au 1.442 91. c. Any stress that increases the tendency of the forward reaction to occur will increase the cell potential. Because reactions are spontaneous when Q < K. which will decrease the cell potential. which will decrease the cell potential. CHAPTER 11 ELECTROCHEMISTRY 2 Ag+(aq) + Cu(s) → Cu2+(aq) + 2 Ag(s) E o = 0.0 M Fe2+ 1.34 V = 0. e e Salt bridge Anode Cathode Pt 1. and because Q increases when the solution volume doubles. d. Added Cl− removes Ag+ in the form of AgCl(s). which will increase the cell potential. Because a product ion is removed. 92.46 V. Added Cu2+ (a product ion) will decrease the tendency of the forward reaction to occur. replacing the silver electrode with a platinum electrode will have no effect on the cell potential.0 M Au3+ . a. e. as the volume of solution is doubled.0. this will increase the tendency of the forward reaction to occur.80 .

0591 1 log 3 [Au 3+ ] Since [Fe3+] = [Fe2+] = 1.0 M: 0.0663 mol e− 3. Au3+(aq) + 3 Fe2+(aq) → 3 Fe3+(aq) + Au(s) E cell = E o − cell 0.32.0 4 = = 2.40 × 103 C of charge 1. i.e..99 ≈ 4 Mol Os 0.00 g mol e For the Os cell. Molar mass = 2. 6.31 V = 0.73 V − 3 n [Au 3+ ][Fe 2 + ]3 0. The compound is Os(NO3)4.0166 mol Os. K= [AuCl − ] 1. [Au3+] = 10−21.32 = 4.8 × 10−22 M 0. assume [AuCl4−] ≈ [Au3+]0 ≈ 1.10) Challenge Problems 93.0 M.CHAPTER 11 ELECTROCHEMISTRY E o = 1.73 V cell 443 b.0663 = = 3.73 V − 3(−0.40 × 103 C of charge also was passed. log [Au3+] = −21.8 × 10 )(0.40 × 10 C × = 0. because the equilibrium Au3+ concentration is so small. assume K is large so that the reaction essentially goes to completion. 485 C × × = 6. asumption good (K is large). 1 mol Cr 3 mol e− 96.0591 log log Q = 0.485 C 2 mol e − This is copper (Cu).485 C 190.15 g Cr × − mol Cr 52.40 × 10 C × × 96. 1 mol e − 1 mol Os 3 = 0. identify X by determining its molar mass.42) 1 = − log . 3+ − 4 − 22 4 [Au ][Cl ] (4.2 g Mol e − 0.15 g Os × 96.6 g/mol 1 mol e − 1 mol X 3 6. .0591 [Fe3+ ]3 0.11 g X = 63. For the third cell.0591 [Au 3+ ] Au3+ + 4 Cl− ⇌ AuCl4-. Two moles of electrons are transferred when X2+ is reduced to X.77 = 0.1 × 1025. 6.0166 This salt is composed of Os4+ and NO3− ions. osmium(IV) nitrate.50 − 0. Chromium(III) nitrate [Cr(NO3)3] has chromium in the +3 oxidation state.

10 V − b.240 V (N → N2+ + 2 e−) × 3 a _____________________________________________ 2 M3+ + 3 N → 3 N2+ + 2 M E o = 0.10 = 1.160 V.180 = 0.240 V = 0.97 = 1.0591 log Q n ELECTROCHEMISTRY 0. The overall cell reaction can now be determined.10 V − 0.32 × 10 −3 ).0591 1. We now have to figure out how to get 6 mol e− into the overall balanced equation. Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) E o = 1. 10.63 M.400 V c ! E o = !0. The two possibilities are to have ion charges of +1 and +6 or +2 and +3.97 M Ecell = 1.160 V cell Q = 9.0591 0.32 × 10 −3 = [ N 2+ ]0 [M 3+ ]0 3 2 = (0.10) 3 .485)(0. n=6 n n Six moles of electrons are transferred in the overall balanced reaction.10 + 1.87 mol/L. (M3+ + 3 e− → M) × 2 E o = 0. [M3+] = 0.015 V = 1.10 V cell Ecell = 1.041 V) = 1.400 V – 0. and the Zn2+ concentration will increase by 1. a.04 × 105 J = !104 kJ The maximum amount of work this cell could produce is 104 kJ. only these two combinations yield a 6 when common multiples are determined when adding the reduction half-reaction to the oxidation half-reaction.0591 0.09 V log 2 0.10 V − 0. M must form for +3 charged ions.0 h × 60 min 60 s 10. E = EE ! cell 0.485 C 2 mol e − The Cu2+ concentration decreases by 1.020 = . Because N forms +2 charged ions. 95.180) = !1.10 V − 0.87 mol/L.87 = 1.160 ! 0.87 = 0. 0. CHAPTER 11 Eo = 0. [Zn2+] = 0.33 M 3+ 2 [M ] wmax = ΔG = !nFE = !6(96.14 V log 2 2.63 .120 log(9.50 Ecell = 1.0 C 1 mol e − 1 mol Cu × × × × = 1.0591 [ Zn 2 + ] log 2 [Cu 2+ ] 0.50 − 1.10 V − (!0. [Cu2+] = 2.87 mol Cu produced h min s 96.444 94.

0.06 mol Zn. pOH = 5.10)/0.532 × 10−4.50 mol Cu2+ and 200.5 × 10 − 4 × 100 = 40. Three things could possibly cause this battery to go dead: 1.05916 log[[F−] + 10.0 × 10−5)] log([F−] + 1.4 hours.4 h 2+ − 10.05916 log[F−]. − 122 = 78 g Zn 63.68 × 1037 2+ [Cu ] This is such a large equilibrium constant that virtually all the Cu2+ must react to reach equilibrium.0591 = 1. All the Cu2+ is consumed.0 × 10−4) = −3. Cu2+ is the limiting reagent and will run out first.00.0 × 10−5 M 0.55 g Cu = 119 g Cu mol Cu 1.5 × 10−4.4517. 1.0(1. pH = 9. we would say [F−] was 3.38 g Zn = 122 g Zn mol Zn 445 c. We began with 2. To react all the Cu2+ requires: 2 mol e − 96. 96.38 g Zn = 3.00.87 mol Cu formed × Mass of electrode = 200. [F−] = 2.5 × 10−4. g Zn × 1 mol Zn/65. All the Zn is consumed.50 mol Cu2+ × For equilibrium to be reached: E = 0 = 1. [F−] + 1.0 × 10 −4 2.485 C 1s 1h × × × = 13.2420 − 0.5 × 10−4 M True value is 2. [F−] = 3. [OH−] = 1. Equilibrium is reached (Ecell = 0).0591 [ Zn 2+ ] log 2 [Cu 2+ ] 2.CHAPTER 11 ELECTROCHEMISTRY 65. Emeas = Eref − 0.2420 − 0.534 × 10−4 M b.87 mol Zn consumed × Mass of electrode = 200. a. So the battery will go dead in 13. and by ignoring the [OH−].452.0 × 10−4 = 3. + 119 = 319 g Cu d.% .10 V − [ Zn 2 + ] = K = 102(1.4462 = 0.05916 log[F−] log[F−] = −3. so: Percent error = 1. 3. 2.0 C 3600 s mol Cu mol e 0.4462 = 0.

957 V 2 H2O + NO → NO3− + 4 H+ + 3 e− a _______________________________________________________________________ 2 H+(aq) + 2 NO3−(aq) + NO(g) → 3 NO2(g) + H2O(l) E o = −0. K = 7.0591 b. the cell is dead at equilibrium (E = 0).20% NO2 by moles and Ptotal = 1.0 × 50. 97. HF ⇌ H+ + F− Ka = 99[H+] = 7.3 × 10−6 M.77 × 10−10 = 98.239. 3 × (e− + 2 H+ + NO3− → NO2 + H2O) E o = 0. [HF] d.23 V = 1.182) = = −9.0[OH − ] ELECTROCHEMISTRY 2.30. Typically.2 × 10−4. mol total (2.9 M HNO3 (1. PNO = 1. pH = 5.5 × 10 −4 = 50.70 10.0 × 10 −3 ) 3 .00 atm: PNO 2 = 0. .446 c.03 V − 0. [F−] = 2.2 × 10−4. then [F−]/[HF] = 99. a buffer of pH = 6.20 mol NO 2 × 1.00)C 4 5.5 × 10 −4 = 5.775 V c − E o = −0.03 V cell 0 = 1. a.0591 log K. Let C = concentration of HNO3 = [H+] = [NO3−]. E o = 0.0591 0. K = 10−9. [OH−] = CHAPTER 11 [F − ] 2.0 × 10−3 atm.182 V K = ? cell log K = Eo 3(−0.00 atm = 2. [H+] = 7.0 is used.77 × 10−10 = 3 PNO 2 − PNO × [ H + ]2 × [ NO 3 ]2 = 3 PNO 2 PNO × C 4 If 0. pOH = 6.0020 = 1. 2 Ag+(aq) + Ni(s) → Ni2+(aq) + Ag(s). if 99% is F−.80 V + 0. Let the forward reaction go to completion.239 = 5.00 − 0.5 × 10−4 M.00 atm 100.18 × 1034 2 K is very large. = k[OH − ] 10. 5.14 e. pH = 7. [H + ][F − ] = 7. C = 1.0 × 10−7 M. The buffer controls the pH so that there is little HF present and there is little response to OH−.77 × 10−10 0.

00 − x x x Ka = (4. 0.00 − 4.89 × 10-4 M.0591 [H ] [H ] Now we can solve for the Ka value of the weak acid HA through the normal setup for a weak acid problem. solving.5 M E o = 0. 2 (2 x) (2 x) 2 −18 [Ag+] = 2x = 4.18 × 10 34 447 Before 1.89 × 10 −4 ) 2 x2 .0591 − log Q.39 × 10−7 −4 1. 2 Ag+ + Ni Initial 0 Change +2x Equil.440V) Fe → Fe2+ + 2e− a _________________________________________________ 2 H+(aq) + Fe(s) → H2(g) + Fe3+(aq) E o = 0.0 M 1.3 × 10−18 M.0591 1.5 − x = 1 . Ka = = 2.440 V − 0.00 atm(1. where x = [H+] = 4.00 M ~0 0 Equil.0 M After 0 M 1. Assumptions good.333 V = 0.5 − 2.5 − x 1.18 × 103.000 V c 2 H+ + 2 e− → H2 − E o = −(−0.107(2) 1. 2x K = 7.5 ≈ .6 × 10 99. = log = 103.00 × 10 −3 M ) log 2 [ H + ]2 0. 1.00 − x 1.5 M −x 1.89 × 10 .CHAPTER 11 ELECTROCHEMISTRY 2 Ag+ + Ni → Ni2+ + 2 Ag K = [Ni2+]/[Ag+]2 = 7. first use the electrochemical data to determine the H+ concentration in the half-cell containing the weak acid. x = 2.89 × 10−4 M + 2 + 2 0. [H + ][A − ] HA(aq) ⇌ H+(aq) + A−(aq) Ka = [HA] Initial 1.0 × 10 −3 1.18 × 10 34 ⇌ ← Ni2+ + 2 Ag 1. [H+] = 4.440 V cell Ecell = Eo cell PH 2 × [Fe3+ ] 0. where n = 2 and Q = n [ H + ]2 To determine Ka for the weak acid.621 = 4.5 M Now solve the back-equilibrium problem. M.0 × 10 −3 . [Ni2+] = 1.3 × 10−18 = 1.

0 × 10−4 M 0 Now allow the reaction to get to equilibrium. Cu2+ Initial Equil.0 × 10−4 − x (1. Cu2+ Before After + 4 NH3 2.0 M = [NH3]eq.0 × 10 −4 ⎞ 0.0 M 2. so the reaction lies far to the right.0 × 1013. Let the reaction go to completion.34 V Cu → Cu2+ + 2 e− a _________________________________________________ 2 Ag+(aq) + Cu(s) → 2 Ag(s) + Cu2+(aq) E o = 0.0 × 10−4 M 1. x = [Cu2+] = 6.0591 ⎟ log ⎜ ⎜ 1. [NH3]0 = 2. (Ag+ + e− → Ag) × 2 E o = 0. a.3 × 10 −19 ⎞ 0.0 × 10 −4 − x) 1. E = 0 − ⎛ 1. E° = 0 (concentration cell).0591 ⎟ . 0 x + 4 NH3 2. Cu2+(aq) + 4 NH3(aq) ⇌ Cu(NH3)42+(aq). E = 0.0 → Cu(NH3)42+ 0 1.46 V cell .80 V c − E o = −0.12 V 2 ⎠ ⎝ b.00 M Cu2+ a.0 + 4x → Cu(NH3)42+ 1.54 V log ⎜ ⎟ ⎜ 1.448 100. e CHAPTER 11 ELECTROCHEMISTRY e Salt bridge Anode Cathode Cu 1. because [Cu2+] << [NH3].0 × 1013.00 ⎟ .0 × 10-4 M Cu2+ Cu 1.00 2 ⎠ ⎝ 101.3 × 10−19 M ≈ 4 4 x(2.0 + 4 x) x ( 2 .0 × 10 −4 = 1.0 ) Thus E = 0 − ⎛ 6.0 × 10−4 1. E = 0.0 M 2. Also. Koverall = K1•K2•K3•K4 = 1.

0 + 0.03.46 V − 0.3 × 10 −5 ) 2 log [Cu 2+ ] [Cu 2+ ] − 0.3 × 10 −5 ) 2 [Cu2+] = 1.16 V 2 (1.30 = 0. This reaction requires 8.6 M 2+ 4 [Cu ][ NH 3 ] ( 2 × 10 −12 ) [ NH 3 ]4 Because 1. The total moles of NH3 added is 0. [NH3] = 0.52 V = 0.0-L solution will be larger than 8. 0.0591 (1.3 × 10 −5 ) 2 K = 1.0591 2 . Ksp = 1. Therefore.0 M NH3 to react with all the Cu2+ in the balanced equation. = 10−2.6 mol plus the 8.0 × 1013 = [Cu ( NH 3 ) 2+ ] ( 2.0 log = 0.0 mol NH3 necessary to form 2.0591 [Cu 2 + ] 0.6 mol NH3 was added. essentially all the 2. 8. n [Ag + ]2 449 Ecell = E o − cell To calculate Ecell.06(2) = = −2.6 = 8. Therefore.6 mol NH3 remains at equilibrium.3 × 10−3 0.46 V − 0. we need to use the Ksp data to determine [Ag+].CHAPTER 11 ELECTROCHEMISTRY [Cu 2 + ] 0. AgCl(s) ⇌ Ag+(aq) + Cl−(aq) 0 s 0 s Ksp = 1.3 × 10−5 mol/L Ecell = 0.6 × 10-10 = [Ag+][Cl−] Initial s = solubility (mol/L) Equil. the moles of NH3 added to 1.0 M Cu2+ will react to form 2. Cu2+(aq) + 4 NH3(aq) ⇌ Cu(NH4)42+(aq) Because K is very large for the formation of Cu(NH3)42+.0) 4 = . At equilibrium.6 × 10−12 = 2 × 10−12 M (We carried extra significant figures in the calculation.) Note: Our assumption that the 2.0 M Cu(NH3)42+. where n = 2 and Q = . In order to calculate how much NH3 is present at equilibrium.0 L of solution is present.0 M Cu(NH3)42+. s = [Ag+] = 1. Now we can solve for the equilibrium [NH3].0 × 1013 = [Cu ( NH 3 ) 2+ ] 4 2+ [Cu ][ NH 3 ]4 b.46 V − n 2 (1.6 × 10−10 = s2. we need to use the electrochemical data to determine the Cu2+ concentration.0591 log Q.0 mol since some NH3 must be present at equilibrium.03 = 9. Ecell = E o − cell 0. .3 × 10 −5 ) 2 (1.0591 log log Q. K = 1. 0. the forward reaction is dominant.0 M Cu2+ essentially reacts to completion is excellent as only 2 × 10−12 M Cu2+ remains after this reaction.

8) = = 3. assumptions good. [Ag+] = 0.7 × 10 7 = ≈ + 2 2 [Ag ][ NH 3 ] x(13. K= Ag+ 1.5 × 10 ) ⎦ E = 1.0591 (1.5 × 10−10 M = [Ag+].56 = 0.20 − 0.7 × 107 New initial [Ag( NH 3 ) 2 ] 1.027 M + 2 + 2 0.027/2) = 9.38. = 103.2 × 103) = 1.0 log ⎢ log = 1.00 ← −x 1.0) 2 Solving: x = 3.80 V (Ag+ + e− → Ag) × 2 c − E o = 0. E = E° − ⎡ ⎤ 0.10(2) (1.0591 [ Pb 2+ ] 0. (Ag+ + e− → Ag) × 2 CHAPTER 11 E o = 0. From the problem: 2s = 0.0 + 2x ⇌ Ag(NH3)2+ 0 1.1 × 103(8.8) log log . and then solve the backequilibrium problem.13) Pb → Pb2+ + 2 e− a ______________________________________________ 2 Ag+(aq) + Pb(s) → 2 Ag(s) + Pb2+(aq) E o = 0.0591 [Ag ] [Ag ] Ag2SO4(s) ⇌ 2 Ag+(aq) + SO42−(aq) 0 2s 0 s Ksp = [Ag+]2[SO42-] Initial s = solubility (mol/L) Equil.8) 0.7 × 107 Because K is large.93 V − + 2 n 2 [Ag ] [Ag + ]2 log (1.00 .00 − x K = 1.40 V Cd → Cd2+ + 2 e− a _________________________________________________ E o = 1.0 +2x 13.0591 1. E o = 0.027 M. we will let the reaction go to completion.8 × 10−6 103.20 V − + 2 −10 2 ⎥ 2 2 [Ag ] ⎣ (3. s = 0.93 V cell E = E° − 0. 1.027)2(0.0591 [Cd 2 + ] 0.00 − x 1.0 + 2 x) x(13.83 V = 0.80 V c ELECTROCHEMISTRY − E o = −(−0.20 V 2 Ag+(aq) + Cd(s) → Cd2+(aq) + 2 Ag(s) cell Overall complex ion reaction: Ag+(aq) + 2 NH3(aq) → Ag(NH3)2+(aq) K = K1K2 = 2. Before After Change Equil.64 V . 0.00 M 0 x x + + 2 NH3 15.450 102.0 M 13.38.027/2 Ksp = (2s)2(s) = (0.

0591 4(1.6 × 104 J f f M3+ + e− → M2+ EE = ΔGE = 9.53 V cell H Zr Yes. M 2+ . K ≈ 10104 n 0.9 × 104 J Because M and e− have ΔG o = 0: −2.7 × 10 4 ) = = −0. (2 H2O + 2 e− → H2 + 2 OH−) × 2 Zr + 4 OH− → ZrO2•H2O + H2O + 4 e− ______________________________________ 3 H2O(l) + Zr(s) → 2 H2(g) + ZrO2•H2O(s) c.9 × 104 J = ! ΔG o. f M3+ + 3 e− → M ΔGE = !nFEE = !3(96.9 × 104 J f f f M2+ + 2 e− → M ΔGE = !nFEE = !2(96.1: 2 H2O + 2 e− → H2 + 2 OH− E° = -0. the reduction of H2O to H2 by Zr is spontaneous at standard conditions since E o > 0.69 V 105. n E° = 0.53) log K. We will solve this problem by applying the equation ΔGE = !nFEE to the half-reactions.0591 1000 g 1 mol Zr 2 mol H 2 × × = 2. kJ E = E° − 0.0591 log Q.485) E° = −0. ΔG o. M 3+ = 2.10) = −2. M 2+ = 9.6 × 104 J – (2. M3+ + e− → M2+ nF (1)(96.7 × 104 J − ΔG o − (6.83 V E o = E o 2 O − E o = !0.50) = −9. log K = = 104.69 V.53 J/C) = −5. a. ΔG o for e− = 0.485)(0.00 × 103 kg Zr × .36 V = 1.22 g Zr mol Zr d. From Table 11.6 × 104 J −9.9 × 104 J) = 6. M 3+ . E = 0 and Q = K.90 × 105 J = −590. ELECTROCHEMISTRY 451 Standard reduction potentials can only be manipulated and added together when electrons in the reduction half-reaction exactly cancel with the electrons in the oxidation half-reaction. at equilibrium.6 × 104 J = ! ΔG o.83 V + 2. 1.485 C/mol e−)(1.19 × 104 mol H2 kg 91. ΔG° = −nFE° = −(4 mol e−)(96.CHAPTER 11 104. cell b.485)(0. ΔG o.

we must know the initial [V2+].3 × 106 L H2 P 1. n [Cu 2+ ] 1.0400 mol V2+ [V2+]0 = 0.452 2. Ecell = E o − cell 0. n [Cu 2 + ] 1.016 g H 2 = 4.54 V − (−0.08206 L atm K −1 mol −1 )(1273 K ) = = 2. equal moles of both reactants must be present at .5000 L × L mol H 2 EDTA 2− = 0. Neither alternative is pleasant. where n = 2 and Q = = .00 M To determine Ecell.0400 M 1. Marathon Problems 106.54 V − b. equal moles of V2+ and H2EDTA2− are reacted at the stoichiometric point. Therefore. but venting the radioactive hydrogen is the less unpleasant of the two alternatives. At the stoichiometric point.20 V V → V2+ + 2 e− a _________________________________________________ E o = 1.98 V = 1. moles H2EDTA2− added = moles V2+ present initially. Cu2+ + 2 e− → Cu E o = 0.0 atm e.0400 log = 1. Probably yes. 0. Use the electrochemical data to solve for the equilibrium [V2+].0413) = 1.0591 log Q.00 L 0. less radioactivity overall was released by venting the H2 than what would have been released if the H2 had exploded inside the reactor (as happened at Chernobyl).34 V c − E o = 1.44)(2)/0.00 Ecell = 1.0591 = 1.0591 [V 2+ ] log .0800 mol H 2 EDTA 2− 1 mol V 2 + × Mol V2+ present initially = 0.0591 [V 2+ ] log 2 1.3 × 10−15 M H2EDTA2−(aq) + V2+(aq) ⇌ VEDTA2−(aq) + 2 H+(aq) K= [ VEDTA 2− ][H + ]2 [H 2 EDTA 2 − ][V 2+ ] In this titration reaction.42 × 104 g H2 mol H 2 ELECTROCHEMISTRY V= nRT (2.58 V 2 1.0591 0.0400 mol V 2+ = 0.00 M [V2+] = 10−(0.54 V − 0.19 × 10 4 mol)(0.19 × 104 mol H2 × CHAPTER 11 2. which can be determined from the stoichiometric point data. a.54 V Cu2+(aq) + V(s) → Cu(s) + V2+(aq) cell Ecell = E o − cell [V 2+ ] [V 2+ ] 0.

0 mL of H2EDTA2− has been added to 1. because [V2+] at equilibrium is very small compared to the initial 0.2500 = 1.5000 L) = 0. so [H+] = 10−10. E2+ + 2 e− → E must have a potential of !0. Therefore.54 − log 2+ 2 1.00 = 1. because we have a buffer solution. EE = 0. we get the following table of potentials.19 V 0. 0.81 V C2+ + 2 e− → C !0.54 − (−0.0400 mol).0591 (0.94 V A2+ + 2 e− → A !0.0200 / 1.6 × 108 2− 2+ −15 −15 [H 2 EDTA ][V ] (1.81 V or 0.00 V From the data.0200 mol of V2+ remains in 1.0591 [V 2+ ] 0.81 V.53 V !0.0400 M V2+. let’s assume B2+ + 2 e− → B E° = 0.00 + 0.81 V. B2+ + 2 e− → B E2+ + 2 e− → E D2+ + 2 e− → D 0.0 × 10 −10 ) 2 = = 1.59 V 107. the reaction essentially goes to completion.00 L + 0. so [H2EDTA2−] = [V2+] = 1.54 V − 0.00 V !0. In addition.81 V 0. Exactly one-half the 0. At equilibrium. Ecell = 1.00 L of 0. Setting the reduction potential at !0.0400 mol/(1. We will arbitrarily choose E to have a potential of !0. when B/B2+ and E/E2+ are together as a cell.94 V . [VEDTA2−] = 0.00 V A2+ + 2 e− → A !0.0400 M concentration.00 V.53 V From largest to smallest: D2+ + 2 e− → D B2+ + 2 e− → B E2+ + 2 e− → E 0.25 L solution.0531) = 1.0267)(1.81 for E and 0.00 2 [Cu ] Ecell = 1. For example.3 × 10−15 M.00 for B.0400 mol of V2+ present initially has been converted into VEDTA2−.19 V C2+ + 2 e− → C !0.0267 M.3 × 10 ) c.25) log = 1. Calculating K for the reaction: K= [ VEDTA 2− ][H + ]2 (0.3 × 10 )(1. Begin by choosing any reduction potential as 0. the pH is assumed not to change. 250.81 V since E may be involved in either the reduction or the oxidation half-reaction. At the halfway point. Finally.CHAPTER 11 ELECTROCHEMISTRY 453 equilibrium.0 × 10−10 M. The moles of VEDTA2− produced will equal the moles of V2+ reacted (= 0.

00 V.28 V ELECTROCHEMISTRY C2+ + 2 e− → C !0.28 V 0. We get: D2+ + 2 e− → D B2+ + 2 e− → B A2+ + 2 e− → A E2+ + 2 e− → E 0.00 V !0. the second table is correct.41 V Of course. .00 V !0.53 V !0.72 V One way to determine which table is correct is to add metal C to a solution with D2+ and metal D to a solution with C2+. Let’s call this 0.81 V.53 V 0. If C comes out of solution. since the reduction potential of E could have been assumed to 0. the first table is correct.72 V 0. we can also get: C2+ + 2 e− → C E2+ + 2 e− → E A +2e →A B +2e →B D2+ + 2 e− → D 2+ − 2+ -− 0. If D comes out of solution.41 V 0.81 V instead of !0.454 CHAPTER 11 A2+ + 2 e− → A is in the middle.

ν = c 3.00 × 108 m/s = = 1.0 × 1010 s−1 λ 1.0 × 10 m hc 6. 455 . the speed of light. From Figure 12.0 × 10 m E = Because both waves are examples of electromagnetic radiation.6 × 10 −3 m = 2.02 × 10 23 photons = = 12 J/mol photon mol 22.0 × 10 −23 J 6.5 × 1012 s−1 −4 λ 2.0 × 1010 s−1 = 2. c.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY Light and Matter 21.3 of the text.63 × 10−34 J s × 3.00 × 108 m / s = = 3. Because frequency and photon energy are both inversely proportional to wavelength. Wave a shows 4 wavelengths and wave b shows 8 wavelengths.00 × 108 m/s = = 9.0 × 10−23 J/photon 2. both waves travel at the same speed. both of these waves represent infrared electromagnetic radiation.9 × 10−22 J −4 λ 2. ν = c 3.0 × 10−4 m 8 Wave b: λ = Wave a has the longer wavelength. wave b will have the higher frequency and larger photon energy since it has the shorter wavelength. The wavelength is the distance between consecutive wave peaks.6 × 10 −3 m = 4.63 × 10 −34 J s × 3.0 × 10−4 m 4 1. Wave a: λ = 1.0 × 10 − 2 m E = hν = 6.

4 × 104 J/mol photon mol d. Frequency and photon energy are directly related (E = hv). E = hν = 6. E = hν = hc 6.0 × 1013 s −1 = 4. .1 × 10 6 s −1 From the wavelength calculated above. Because 5.3.00 × 10−7 m E 3.4 × 1013 s −1 EMR will have less energetic photons.1 MHz electromagnetic radiation is FM radiowaves.97 × 10−19 J/photon electromagnetic radiation is visible (green) light.645 × 10 −19 J Referencing Figure 12.63 × 10 −34 J s × 6. λ = λ E 4.456 23.7 kJ 1 mol × = 4. c.9979 × 108 m / s = = 4.00 × 108 m / s = = 8.02 × 10 23 photons = 4. 107.97 × 10 −19 J The 3.6261 × 10 −34 J s × 2.799 m ν 107.0 × 10−18 J/photon 1m λ 25 nm × 1 × 109 nm 8. hc hc 6. From Figure 12.4 × 1013 s −1 EMR has a lower frequency than 6.022 × 10 23 photons × = 2.63 × 10 −34 J s × 3. a.0 × 10 −6 m 13 −1 ν 6. 24. λ = c 2. the 5.8 × 106 J/mol × photon mol 25.645 × 10−22 kJ = 4. 2. this is infrared EMR.7 nm .277 × 10−7 m = 427. λ = CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY c 3. The energy needed to remove a single electron is: 279.00 × 108 m / s = = 5.9979 × 108 m / s = = 2.0 × 10 s b.0 × 10 −20 J 6.626 × 10 −34 J s × 2.12 × 10−10 m electromagnetic radiation is X rays.3 of the text.998 × 108 m / s = = 5. λ = hc 6.0221 × 10 23 E = 26.645 × 10−19 J mol 6.0 × 1013 s −1 EMR.0 × 10 −18 J 6.0 × 10 −20 J/photon 4.

0 × 107 m/s 30.626 × 10 −34 J s)(2. EK = 7. . Electromagnetic radiation.461 × 10−19 J = 4. The energy to remove a single electron is: 208. e. which were thought to be particles.461 × 10−22 kJ = 3.% of speed of light = 0. The wave-particle duality is summed up by saying all matter exhibits both particulate and wave properties. Some evidence supporting wave properties of matter are: 1. This is true for all matter. Albert Einstein explained the photoelectric effect by applying quantum theory.998 × 108 m / s) = = 7. 2. Light having a frequency below the minimum results in no electrons being emitted.36 × 10−19 J = maximum KE 28. wave properties of matter are only important for small particles with a tiny mass.00 × 108 m/s = 3. The electron microscope uses electrons in a fashion similar to the way in which light is used in a light microscope.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 457 The photon energy and frequency order will be the exact opposite of the wavelength ordering because E and ν are both inversely related to λ. whereas light at or higher than the minimum frequency does cause electrons to be emitted. 29. From the previously calculated wavelengths.4 kJ 1 mol × = 3.82 × 10−19 J − 3. a.82 × 10−19 J −9 λ 254 × 10 m Ephoton = EK + Ew. have a wavelength associated with them. which was thought to be a pure waveform. electrons. However. Electrons can be diffracted like light.g. The light must have a certain minimum frequency (energy) in order to remove electrons from the surface of a metal. the excess energy is transferred into kinetic energy for the emitted electron.. 10. The wave properties of larger particles are not significant. For light having a frequency higher than the minimum frequency. Planck’s discovery that heated bodies give off only certain frequencies of light and Einstein’s study of the photoelectric effect support the quantum theory of light.461 × 10−19 J = Ew 23 mol 6. electrons.022 × 10 Energy of 254-nm light is: E = hc (6.10 × 3. The photoelectric effect refers to the phenomenon in which electrons are emitted from the surface of a metal when light strikes it. Conversely. transmits energy as if it has particulate properties. the order of photon energy and frequency is: FM radiowaves < visible (green) light < X rays longest λ shortest λ lowest ν highest ν smallest E largest E 27.

The term quantized refers to the allowed energy levels for the electron in hydrogen. the electron in hydrogen can only have specific energies.31 × 10 m × (0.0100 × 2. v= . 31.68 × 10 −26 kg 6.3 × 105 m/s 9. Each orbit has a specific energy associated with it.0 × 10 m / s Note: For units to come out. m= h 6.63 × 10 −34 J s = = 3.63 × 10 −34 J s = 7. Therefore.0 × 102 nm = 1. λ = h 6.0100 × 2. The Bohr model assumes that the electron in hydrogen can orbit the nucleus at specific distances from the nucleus. The meaning of this number is that we do not have to worry about the wave properties of large objects.675 × 10 kg b.4 × 10 −2 nm . λ= h h . not all energies are allowed.0 × 10 m 6.626 × 10 −34 J s = = 1. λ= h 6.2 g/mol atom mol kg The element is calcium (Ca).675 × 10 kg × (0.998 × 10 m/s) h h 6. λ= 32. the mass must be in kg since 1 J = 1 kg m2/s2.4 × 10 −25 nm mv 0.0 × 10 −9 m: v = 33.998 × 10 m/s) 6.3 × 103 m/s −31 −7 9.0 × 10 −7 m: λm mv v = 6. Hydrogen Atom: The Bohr Model 34.055 kg × 35 m/s This number is so small that it is insignificant.0 nm = 1.626 × 10 −34 J s = = 5.11 × 10 −31 kg × 1.63 × 10 −34 J s = 2. a. We cannot detect a wavelength this small.626 × 10 −34 kg m 2 / s = = 6.32 × 10 −13 m − 27 8 mv 1.4 × 10 −34 m = 3.63 × 10 −34 J s = 7.3 × 103 m/s .4 × 10 −11 m = 2.11 × 10 kg × 1.68 × 10 − 26 kg / atom −15 8 λv 3. for λ = 1. b.022 × 10 23 atoms 1000 g × × = 40. λ = − 31 7 mv 9. v = −12 − 27 mv λm 75 × 10 m × 1. .0 × 10 −9 m For λ = 1.11 × 10 kg × 3.458 λ= CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY h 6.

The photon energies absorbed or emitted must be exactly equal to the energy difference between any two allowed energy levels.7 nm From Figure 12.178 × 10−18 J ⎜ 2 − 2 ⎟ = −2. it does not explain emission spectra for elements/ions having more than one electron.0.567 × 10−7 m = 656. λ = = λ ΔE 3. therefore.6261 × 10 −34 J s × 2.2500 . The Bohr model predicted the exact wavelengths of light that would be emitted for a hydrogen atom. Although the Bohr model has great success for hydrogen and other one-electron ions. The fundamental flaw is that we cannot know the exact motion of an electron as it moves about the nucleus.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 459 The great success of the Bohr model is that it could explain the hydrogen emission spectrum.3. |ΔE| = Ephoton = hν = 6. for a spectral transition.9979 × 108 m / s hc = 4. . respectively. ΔE = Ef − Ei: ⎛ 1 1 ⎞ ΔE = −2.178 × 10−18 J ⎜2 3 ⎟ ⎝ ⎠ ⎛1 1⎞ ⎜ − ⎟ ⎝4 9⎠ ΔE = −2. The electron in H moves about the allowed energy levels by absorbing or emitting certain photons of energy.084 × 10 J This is visible electromagnetic radiation (green-blue light). ΔE = −2. For the H atom (Z = 1): En = -2.025 × 10−19 J The photon of light must have precisely this energy (3.864 × 10−7 m = 486.025 × 10−19 J). ⎛ 1 1⎞ a. Because not all energies are allowed in hydrogen (energy is quantized). ⎛ 1 1 ⎞ b. and a negative value of ΔE always corresponds to an emission of light.6261 × 10 −34 J s × 2. well-defined circular orbits are not appropriate.9979 × 108 m / s hc hc . this is visible electromagnetic radiation (red light).178 × 10−18 J ⎜ 2 − 2 ⎟ = −4. not all energies of EMR are absorbed/emitted.084 × 10−19 J ⎜2 4 ⎟ ⎠ ⎝ λ = 6. 35. ΔE = −2. A positive value of ΔE always corresponds to an absorption of light.1111) = −3.4 nm = −19 ΔE 4.178 × 10−18 J/n2.178 × 10−18 J × (0.025 × 10 −19 J = 6.178 × 10−18 J ⎜ 2 − 2 ⎟ ⎜n ni ⎟ ⎝ f ⎠ where ni and nf are the levels of the initial and final states.

False.178 × 10−18 J ⎜ 2 − 2 ⎟ = −1.120 × 10−8 m = 91.178 × 10 J ⎛ 1⎞ ⎛1⎞ To ionize from n = 3.634 × 10 −18 J This is ultraviolet electromagnetic radiation. ΔE = −2.8 nm E a.9979 × 108 m / s = 1. d.178 × 10−18 J = Ephoton ⎜1 ⎟ ⎝ ⎠ λ = hc (6.420 × 10−19 J.9979 × 108 m / s hc = 1. ΔE = 0 − E3 = RH ⎜ 2 ⎟ = 2.6 nm λ = 1.6261 × 10 J s × 2. True c.634 × 10−18 J ⎜1 2 ⎟ ⎠ ⎝ −34 6.9979 × 108 m / s) = = 9. E and λ are inversely proportional to each other (E = hc/λ).460 CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY ⎛1 1 ⎞ c.178 × 10−18 J ⎜ 2 − 2 ⎟ = −1.6261 × 10 −34 J s)(2. True e.208 × 10−7 m = 820. n = 2 is the first excited state. 36. ΔE = 2. λ = 37. ⎛1⎞ ΔE = E∞ − E1 = −E1 = RH ⎜ 2 ⎟ = RH . False.059 × 10−19 J ⎜3 4 ⎟ ⎠ ⎝ λ= 6.178 × 10−18 J ⎜ ⎟ ⎜3 ⎟ ⎝9⎠ ⎝ ⎠ ΔE = Ephoton = 2.059 × 10 J This is infrared electromagnetic radiation.876 × 10−6 m or 1876 nm = −19 ΔE 1. the energy difference between n = 3 and n = 2 is smaller than the energy difference to n = 2 electronic transition than for the n = 3 to n = 1 transition. hc = 8.6261 × 10 −34 J s × 2. and n = 3 is the second excited state. ⎛ 1 1 ⎞ d. ΔE = −2. the ground state in hydrogen is n = 1 and all other allowed energy states are called excited states.216 × 10−7 m = 121. . b. False. it takes less energy to ionize an electron from n = 3 than from the ground state.20 nm −18 E 2. Ionization from n = 1 corresponds to the transition ni = 1 → nf = ∞ where E∞ = 0.

210. ⎛ 1 ⎞ ΔE = E4 ! En = -En = 2.250. 2 = 0.178 × 10−18 J ⎜n ni ⎟ ⎠ ⎝ f λ = ⎛ 1 1⎞ ⎜ − 2 ⎟ = 2.0204.2296 = − 2 .9979 × 108 m / s = = 5.178 × 10−18 J ⎜ 2 − 2 ⎟ ⎜2 n ⎟ ⎠ ⎝ 1 1 1 0.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 461 38.178 × 10 −18 J ⎜ 2 ⎟ ⎝n ⎠ . ⎛ 1 1 ⎞ −5. ⎛ 1 1 ⎞ ΔE = −2.4 nm will excite an electron from the n = 2 to the n = 6 energy level.001 × 10−19 J because we have an emission.104 × 10−7 m = 410.840 × 10 −19 J Visible light with λ = 410.6261 × 10 −34 J s × 2.001 × 10−19 J λ 397.57 × 10 −19 J ΔE = !4. visible light (λ ≈ 400−700 nm) is not energetic enough to excite an electron in hydrogen from n = 1 to n = 5.500 × 10−8 m = 95. 39.57 × 10 −19 J = En – E5 = !2. |ΔE| = Ephoton = hc 6. = 0.57 × 10 −19 J because we have an emission. n2 = 4.091 × 10−18 J = Ephoton ⎜ 52 1 ⎟ ⎠ ⎝ hc 6.9979 × 108 m / s = = 9.091 × 10 −18 J Because wavelength and energy are inversely related.001 × 10−19 J = E2 − En = −2.2 × 10 −9 m ΔE = −5.178 × 10 −18 J ⎜ 2 − 2 ⎟ 5 ⎠ ⎝n 1 1 1 − = 0. n = 7 4 n n 40. |ΔE| = Ephoton = hν = 6. 1 ⎞ ⎛ 1 !4. ⎛ 1 1 ⎞ ΔE = −2.00 nm E 2.626 × 10 −34 J s × 6. 41.178 × 10−18 J ⎜ 2 − 2 ⎟ = −2. n = 2 2 2 25 n n The electronic transition is from n = 5 to n = 2.90 × 1014 s −1 = 4.6261 × 10 −34 J s × 2.9979 × 108 m / s = = 4.6261 × 10 −34 J s × 2.4 nm E 4.840 × 10−19 J ⎜6 2 ⎟ ⎠ ⎝ λ = hc 6.178 × 10−18 J ⎜ 2 − 2 ⎟ = 4.

The electronic transition is n = 1 → n = ∞ (E∞ = 0).178 × 10 −18 J (Z2)/n2.0221 × 10 23 atoms = 1311.6 kJ/mol × 32 = 1.866 × 105 kJ/mol 43.6 kJ/mol × (26)2 = 8.9979 × 108 m/s = = 7.36 × 10 −19 J = −9 λ 1460 × 10 m ⎛ 1 ⎞ Ephoton = ΔE = 1. IE = 1311.) We get this by combining IE = 2. the ionization energy per mole is given as: IE = 1311. where RH = 2.462 Ephoton = CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY hc 6. This is called the ionization energy (IE).839 × 10 −19 J The general energy equation for one-electron ions is En = !2.178 × 10−18 J (l)2 = 2.178 × 10−18 J.) Z = 3. H: Z = 1.6 kJ × × = atom mol 1000 J mol b. For one electron species. IE = 1311.178 × 10−18 J (Z2) and: 2. n = 4 ⎝n ⎠ 42.178 × 10 −18 ⎜ 2 ⎟.839 × 10 −19 J −9 λ 253.6261 × 10 −34 J s × 2. IE = 1311. the IE is given by the energy of state n = 1 (ΔE = E∞ − E1 = −E1 = RHZ2/l2 = RHZ2).180 × 104 kJ/mol Z = 6. where Z = atomic number. Z = 4 for Be3+ ⎟ ⎠ . Ephoton = hc 6.9979 × 108 m / s = 1.6 kJ/mol × 62 = 4. He+: c. IE = 2.178 × 10 −18 J (Z)2 ⎜ 2 − 2 ⎜n ni ⎝ f ⎞ ⎟ . Li2+: d.6 kJ/mol ≈ 1312 kJ/mol × × atom 1000 J mol For any one-electron species. and Z = atomic number n2 (nuclear charge).36 × 10 −19 J = 2.626 × 10 −34 J s × 2. ⎛ 1 1 ΔE = !2.6 kJ/mol × 22 = 5246 kJ/mol (Assume n = 1 for all.4 × 10 m ΔE = 7.178 × 10 −18 J 6. IE = 1311.0. Because E∞ = 0.722 × 104 kJ/mol e. C5+: Z = 2.178 × 10−18 J/atom IE = 2.178 × 10 −18 J 1 kJ 6.6 kJ 2 (Z ) mol (We will carry an extra significant figure.0221 × 10 23 atoms 1 kJ 1311. En = − R H Z2 . a. n2 = 16. Fe25+: Z = 26.

p = mv. 46.04 × 10 −16 J ΔE = 47.220 nm ΔE λ 9. Δx = = = 5.626 × 10 −34 J s) 2 = 9. En = n2h 2 9h 2 4h 2 5h 2 .626 × 10 −34 J s)( 2.20 × 10−10 m = 0.79 × 10−4 m −32 4π Δp 4π 4 × 3.11 × 10 kg m / s) b.109 × 10 −31 kg)( 40. the same as the units of Planck's constant. 2 = 0. nf = 4 −18 25 nf nf 2.06249. Linear momentum p is equal to mass times velocity.64 × 10−33 m 4 π Δp 4 × 3.626 × 10 −34 J s = = 3.0 × 10 −12 m) 2 hc (6. Wave Mechanics and Particle in a Box 44. The diameter of an H atom is roughly 1. a.998 × 108 m / s) hc .839 × 10 −19 J = !2.0 × 10−8 cm.100 m / s c.178 × 10 −18 (4)2 ⎜ 2 − 2 ⎟ ⎜n 5 ⎟ ⎝ f ⎠ 7.100 m/s = ΔpΔx ≥ h 6. Δp = mΔv = 9. λ = = = 2.11 × 10−31 kg × 0.626 × 10 −34 J s h .145 kg × 0.178 × 10 × 16 This emission line corresponds to the n = 5 → n = 4 electronic transition. d. Units of ΔpΔx = kg × kg m 2 kg m 2 m ×m= = ×s=J×s s s s2 9. ΔE = E5 − E1 = (52 − 12) = 8mL2 8mL2 8mL2 ΔE = 24(6. Units of ΔE × Δt = J × s.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 463 ⎛ 1 1 ⎞ ΔE = !7. The uncertainty in position is much larger than the size of the atom.142 × (9. The uncertainty is insignificant compared to the size of a baseball.04 × 10−16 J 8(9.142 × 0.839 × 10 −19 1 1 1 + = 2 . En = h2 24h 2 n2h 2 . Δx = h 6.11 × 10 −32 kg m s 45. ΔE = E3 − E2 = − = 8mL2 8mL2 8mL2 8mL2 .

0 × 10 −9 m) 2 1.46 × 10−20 J = 48.626 × 10 −34 J s) 2 5h 2 = . Total area = 1.998 × 108 m / s) = = 2. En will decrease.0.6261 × 10 −34 J s)( 2.109 × 10 −31 kg) L2 8mL2 ΔE = 2.506 × 10 −20 = 25. 8mL2 . L = 3.626 × 10 −34 J s)( 2.374 × 10 −5 m ΔE = 1. En = n2h 2 .446 × 10−20 J = n 2 (6. 8mL2 1. 50.0 × 10 −9 m) 2 − (6.46 × 10−20 J −9 λ 8080 × 10 m 5(6. n = 1 for ground state.446 × 10−20 J λ 1.50 × 10−9 m = 3. as L increases. 51.50 nm 8(9.446 × 10−20 = (6. area of one hump = 1/3 Shaded area = 1/6 = probability of finding the electron between x = 0 and x = L/6 in a one-dimensional box with n = 3.626 × 10 −34 J s) 2 8(9. En decreases. ΔE = En − E1 = n2h 2 12 h 2 − 8mL2 8mL2 ΔE = hc (6. En = n2h 2 .464 ΔE = CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY hc (6.02 × 10 − 22 as L increases.02 × 10−22)n2 − 6.02 × 10−22. from equation.109 × 10 −31 kg) (10. n = 5 6.109 × 10 −31 kg) (10.626 × 10 −34 J s) 2 8(9. n2 = 49. and the spacing between energy levels will also decrease.9979 × 108 m / s) = = 1.

c. etc. For ℓ = 3. For n = 2. ℓ cannot be a negative number. Each solution is an allowed energy level called a wave function or an orbital. Quantum numbers give the allowed solutions to Schrödinger equation. n cannot equal zero. 1f. e. and number of nodes. 53. For n = 3. 1d. 3. 2.. d. The specific rules for assigning values to the quantum numbers n. energy. For ℓ = 1. f. R. The quantum numbers in parts b and c are allowed. The penetrating term refers to the fact that there is a higher probability of finding a 4s electron closer to the nucleus than a 3d electron. ℓ. so 3f orbitals are forbidden. Orbitals and Quantum Numbers 52. 2d.. ms cannot equal !1. The 2p and 3p orbitals differ from each other in their size. . mℓ cannot equal 2. The 1p. 4. R ≠ 3. etc. For n = 1. d. ℓ: Gives the type (shape) of orbital. 4. so 1p.9. Each wave function solution is described by three quantum numbers. In Section 12. 55. we cannot see if they are spinning. mℓ: Gives information about the direction in which the orbital is pointing. ℓ = 3 is not possible. 54. For n = 3. A nodal surface in an atomic orbital is a surface in which the probability of finding an electron is zero. The physical significance of the quantum numbers are: n: Gives the energy (it completely specifies the energy only for the H atom or ions with one electron) and the relative size of the orbitals. This leads to a lower energy for the 4s orbital relative to the 3d orbitals in polyelectronic atoms and ions. 2f. 1d. and mℓ are covered in Section 12. a. The quantum numbers in part a are allowed. It refers to the ability of the two electrons that can occupy any specific orbital to produce two differently oriented magnetic moments. The spin is a convenient model. R ≠ 1. 10−10 m box: E1 = (1 × 1020 m−2) 8m 8m As expected. 3. and mR.. ℓ cannot be a negative number. mℓ can range from -3 to +3. R ≠ 2.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 465 Using numbers: 10−6 m box: E1 = h2 h2 (1 × 1012 m−2). 5. and 1f orbitals are forbidden. the electron in the 1 × 10−6 m box has the lowest ground state energy. the spin quantum number ms is discussed. n. and 3f orbitals are not allowed solutions to the Schrödinger equation.10. thus +4 is not allowed. The 2p orbitals differ from each other in the direction in which they point in space. so 2d and 2f orbitals are forbidden. etc. b. Since we cannot locate electrons.

where r is the distance from the nucleus. 2 electrons (specifies one atomic orbital). the nodes occur at r = (7. ℓ = 4 (9 orbitals). 62.90)ao = 1. ℓ = 2 (5 orbitals). 2 electrons (specifies one atomic orbital). 58. ψ2 gives the probability of finding the electron at that point. 57. 0 electrons (ℓ ≠ 1 when n = 1).46 × 1028 For r = ao and θ = 90°: ψ 2 p z = 0 because cos 90° = 0. 14 electrons (7 orbitals have 4f designation).466 56. 2p ψ2 ψ2 r 3p r 61. 2s. 7py. 6d x 2 − y 2 . total for n = 5 is 25 orbitals.01 × 10−10 m. ψ2 = 2. and 3d orbitals are possible. 3p. ψ300 = 0 when 27 − 18σ + 2σ2 = 0. 4f. the xy plane is a node for the 2pz atomic orbital. ψ2 = 0. 18 electrons (3s.76 × 10−10 m and at r = (1. CHAPTER 12 5p: three orbitals QUANTUM MECHANICS AND ATOMIC THEORY 4d: five orbitals 3d z 2 : one orbital n = 5: ℓ = 0 (1 orbital). 2 electrons (specifies one atomic orbital). 1p. n = 3. ℓ = 2 (5). ℓ = 1 (3). 60. ℓ = 3 (7 orbitals).90. three 3p orbitals.10)ao = 3. n = 4: ℓ = 0 (1). . because σ = r/ao. and five 3d orbitals). Solving using the quadratic formula: σ = 18 ± (18) 2 − 4(2)(27) 4 = 18 ± 108 4 σ = 7. We can never be 100% certain of the location of the electrons due to Heisenburg’s uncertainty principle. ℓ = 1 (3 orbitals). there are one 3s orbital. ℓ = 3 (7). A node occurs when ψ = 0. total for n = 4 is 16 orbitals.29 × 10 ⎠ 3/ 2 (1) e−1/2 cos 0 = 1.10 or σ = 1. 59. The diagrams of the orbitals in the text give only 90% probabilities of where the electron may reside. For r = ao and θ = 0° (Z = 1 for H): ψ 2pz ⎛ ⎞ 1 1 ⎜ ⎟ = 1/ 2 ⎜ −11 ⎟ 4(2 π) ⎝ 5.57 × 1014.

4. The key is that the outermost electrons are the valence electrons.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 467 Polyelectronic Atoms 63. The h block has R = 5. 1. 2. ℓ = 0. 2. or 3. !3. !2. 3. There are 25 orbitals with n = 5. for ℓ = 1. When atoms interact with each other. !1. respectively. 4. 1. n = 3. d. 64. 1. 4. a. 2. In the s block. 0. 2. They can hold 50 electrons. ℓ = 2: this combination is not possible (ℓ ≠ 2 for n = 2). !4. and 9 of these electrons can have ms = +1/2. 7. each orbital holding two electrons. Elements in the same group have similar valence electron configurations and. 4. ms = +1/2: for n = 5. mR = !3. p (6 e−). Four distinct orbitals. 2. n = 2. 1. There are 5 degenerate 3d orbitals that can hold a total of 10 electrons. 1. j. !2. 3. !1. !1. the s block is two elements wide. 2. it will be the outermost electrons that are involved in these interactions. have similar chemical properties. the h block would be 22 elements wide. ℓ = 1: these define a set of 2p orbitals. ℓ = 2: these quantum numbers define a set of 3d orbitals. d (10 e−) and f (14 e−) orbitals present. These orbitals can hold 18 electrons. 5. The number of degenerate g orbitals is 9. 3. Valence electrons are the electrons in the outermost principal quantum level of an atom (those electrons in the highest n value orbitals). !2. n = 3: 3s. there are 7 degenerate f orbitals (R = 3. 0. and other properties of atoms. n = 2. g. The electrons in the lower n value orbitals are all inner core or just core electrons. With 11 degenerate h orbitals. 9 for each value of ℓ. how tightly the nucleus holds these outermost electrons determines atomic size. 3). i. Thus no electrons can have this set of quantum numbers. the g block would be 18 elements wide. and 3d orbitals all have n = 3. mR = !5. h. 65. Number of orbitals = 1. The g block corresponds to R = 4. 3. e. b. we have one orbital (R = 0. as a result. The widths of the various blocks in the periodic table are determined by the number of electrons that can occupy the specific orbital(s). There are 3 degenerate 2p orbitals that can hold a total of 6 electrons. mR = 0) that can hold two electrons. ℓ = 0. mℓ = +1: for n = 5. . n = 1. 0. ionization energy. so the f block is 14 elements wide. For the f block. all can have mℓ = +1. 5. Zero electrons in an atom can have these quantum numbers. 3p. With 9 orbitals. and 25 of these electrons can have ms = +1/2. n = 5. ℓ = 0. !3. 1. This comes from the 9 possible mR values when R = 4 (mR = !4. 2. Total number of electrons to fill these orbitals is 32. The four quantum numbers completely specify a single electron. 3. In addition. 4). n = 5. c. n = 4: ℓ can be 0. f. thus 8 electrons. Thus we have s (2 e−). mℓ = 0: these define a 1s orbital that can hold 2 electrons. It is impossible for n = 0. 3.

468 66. Cu. Mo. Ru. This is chromium. a. Cd: [Kr]5s24d10 S: [Ne]3s23p4. Pt. Ge: [Ar]4s23d104p2. Rh. Tc. c. Cr has 6 unpaired electrons. Se: [Ar]4s23d104p4 67. Rh. Cl: ls22s22p63s23p5 or [Ne]3s23p5 Sr: 1s22s22p63s23p64s23d104p65s2 or [Kr]5s2 Pb: [Xe]6s24f145d106p2 As:122s22p63s23p64s23d104p3 or [Ar]4s23d104p3 W: [Xe]6s24f145d4 Cf: [Rn]7s25f10* *Note: Predicting electron configurations for lanthanide and actinide elements is difficult since they have 0. Al: [Ne]3s23p1. Sc: 1s22s22p63s2 3p64s23d1. Cs: 1s22s22p63s2 3p64s23d104p65s24d105p66s1 Eu: 1s22s22p63s2 3p64s23d104p65s24d105p66s24f65d1* Pt: 1s22s22p63s2 3p64s23d104p65s24d105p66s24f145d8* Xe: 1s22s22p63s2 3p64s23d104p65s24d105p6. CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY Si: 1s22s22p63s23p2 or [Ne]3s23p2. Ga: 1s22s22p63s23p64s23d104p1 or [Ar]4s23d104p1 As: [Ar]4s23d104p3. Br: 1s22s22p63s2 3p64s23d104p5 *Note: These electron configurations were written down using only the periodic table. The following are complete electron configurations. Exceptions: Cr. This is the actual Cf configuration. Pd. Tc. but only the nonmetal I would be expected to form a covalent compound with the nonmetal F. this will be element 120. 1. Ag. which is an exception to the predicted filling order. d. Ru. and Au. Fe: 1s22s22p63s2 3p64s23d6 P: 1s22s22p63s2 3p3. From the periodic table. Noble gas shorthand notation could also be used. and Pt do not correspond to the supposed extra stability of half-filled and filled subshells. or 2 electrons in d orbitals. 69. One would predict an ionic compound to form between the metal In and the nonmetal F. Rn: [Xe]6s24f145d106p6. Pd. and the next most is 5 unpaired electrons for Mn. Both In and I have one unpaired 5p electron. note that the next discovered noble gas will also have 4f electrons (as well as 5f electrons). I: [Kr]5s24d105p5 ↑↓ ↑↓ ↑ 5p Element 120: [Rn]7s25f146d107p68s2 b. Actual electron configurations are: Eu: [Xe]6s24f7 and Pt: [Xe]6s14f145d9 68. 70. . Nb.

2p6. 32 electrons have n = 5 as one of their quantum numbers b. 4d10. All the electrons are paired in Hg. 40 electrons have spin-up. Element 115. 18 total electrons with n = 3. Cr has 6 unpaired electrons. c. 5p6. Uup. ℓ = 3 are f orbitals. is in Group 5A under Bi (bismuth): Uup: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s25f146d107p3 a. 4f14 and 5f14 are the f orbitals used. 30 electrons are in d atomic orbitals. 1s 2s 2p 3s 3p or 4s 72. Cu has 1 unpaired electron. 3p6. . and 3d10 electrons. and 5f14. we have 3s2. there are 4(2) = 8 electrons in pz atomic orbitals. 5s2. The two exceptions are Cr and Cu. 3p6. so one-half of the electrons are spin-up (ms = +1/2) and the other half are spin-down (ms = !1/2).CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY ↑ ↑ ↑ ↑ ↑ 3d 469 Cr: [Ar]4s13d5 ↑ 4s 71. 4s 3d Hg: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d10 a. From the electron configuration for Hg. Because we have 4 sets of filled np orbitals and two electrons can occupy the pz orbital. 5p6. Cr: 1s22s22p63s23p64s13p5. 1s 2s 2p 3s 3p or 4s 4s 3d or 3d Cu: 1s22s22p63s23p64s13d10. each set of np orbitals contain one pz atomic orbital. d. b. 4p6. 5d10. 3d10. They are all filled so 28 electrons have ℓ = 3. 5d10. 73.

3d 75. not paramagnetic because no unpaired electrons are present. 2s N: 1s22s22p3 ↑ ↑ ↑ . The number of electrons with mℓ = 1 is 11 × (2 e−) + 1 × (1 e−) = 23 electrons. and there are 2 orbitals with mℓ = 1 for the various f orbitals used. For elements 1-36. 5p Ba: [Xe]6s2 ↑↓ . the elements with configurations nd2 or nd8 have two unpaired . 5d 76.470 CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY c. 2p Ni: [Ar]4s23d8 ↑↓ ↑↓ ↑↓ ↑ ↑ . The first 112 electrons are all paired. For the d block. either 56 electrons have ms = !1/2 or 59 electrons have ms = !1/2. d. 74. S. the second d electron should be in a different orbital with spin parallel. Eleven of these orbitals are filled with 2 electrons. p. and the ones with no unpaired electrons are not paramagnetic (they are called diamagnetic). and the 7p orbitals are only half-filled. the elements with either ns2np2 or ns2np4 valence electron configurations have 2 unpaired electrons. and Ge (with ns2np2) and elements O. not paramagnetic because no unpaired electrons. Therefore. paramagnetic with 2 unpaired electrons. paramagnetic with 3 unpaired electrons. paramagnetic with 1 unpaired electron. there are 4 orbitals with mℓ =1 for the various d orbitals used. There are 6 orbitals with mℓ = 1 for the various p orbitals used. these are elements C. Si. the three electrons are spin parallel. None of the s block elements have 2 unpaired electrons. one-half of these electrons (56 e−) will have ms = !1/2. and Se (with ns2np4). In the p block. The 3 electrons in the 7p orbitals singly occupy each of the three degenerate 7p orbitals. so the 7p electrons either have ms = +1/2 or ms = !1/2. The paramagnetic substances have unpaired electrons. For the ground state. 3d Te: [Kr]5s24d105p4 ↑↓ ↑ ↑ . We have a total of 6 + 4 + 2 = 12 orbitals with mℓ = 1. Li: 1s22s1 ↑ . and f orbitals all have one of the degenerate orbitals with mℓ = 1. paramagnetic with 2 unpaired electrons. d. 4 possibilities. 6s Hg: [Xe]6s24f145d10 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ . 3 2 !1 +1/2 We get the number of unpaired electrons by examining the incompletely filled subshells. Ti : [Ar]4s23d2 n ℓ mℓ 4s 4s 3d 4 4 3 0 0 2 ms 0 +1/2 0 !1/2 !2 +1/2 Only one of 10 possible combinations of mℓ and ms for the first d electron.

and in going to the more stable ground state (↑↓ ↑ ↑ ). 79. there are no unpaired electrons in this oxygen atom. Na. Excited state of boron B ground state: 1s22s22p1 c. In the d block. 2p5: ↑↓ ↑↓ ↑ 5d6: ↑↓ ↑ 4d2: ↑ ↑ ↑ ↑ 3p4: ↑↓ ↑ ↑ 2p5: ↑↓ ↑↓ ↑ 3p6: ↑↓ ↑↓ ↑↓ Ar: [Ne]3s23p6 80. A total of 12 elements from the first 36 elements have one unpaired electron in the ground state. These are elements H. We get the number of unpaired electrons by examining the incompletely filled subshells. 77. a. Excited state of fluorine F ground state: 1s22s22p5 b. these are Ti (3d2) and Ni (3d8). A total of 8 elements from the first 36 elements have two unpaired electrons in the ground state. The general result is that the outer electrons are . and Br (ns2np5) for the first 36 elements. the positive charge from the nucleus increases as protons are added. Ionization energy: P(g) → P+(g) + e−. The p block elements with ns2np1 or ns2np5 valence electron configurations have one unpaired electron. energy would be released. Li. Ground state of neon d. Sc ([Ar]4s23d1) and Cu ([Ar]4s13d10) each have one unpaired electron. and K for the first 36 elements. O: 1s22s22px22py2 (↑↓ ↑↓ ). This configuration would be an excited state. The s block elements with ns1 for a valence electron configuration have one unpaired electrons. Cl. These are elements B. The number of electrons also increase. electron affinity: P(g) + e− → P−(g) Across a period. Al. but these outer electrons do not completely shield the increasing nuclear charge from each other.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 471 electrons. 82. Excited state of iron Fe ground state: [Ar]4s23d6 The Periodic Table and Periodic Properties 81. For elements 1-36. O: [He]2s22p4 O+: [He]2s22p3 O-: [He]2s22p5 Os: [Xe]6s24f145d6 Zr: [Kr]5s24d2 S: F: [Ne]3s23p4 [He]2s22p5 2p4: ↑↓ ↑ ↑ 2p3: ↑ ↑ ↑ Two unpaired e− Three unpaired e− One unpaired e− ↑ Four unpaired e− Two unpaired e− Two unpaired e− One unpaired e− Zero unpaired e− 78. and Ga (ns2np1) and elements F.

an atom in which the outermost electrons are held weakly will have a large radius and a small ionization energy. increases left to right across the periodic table and decreases from top to bottom of the periodic table. this occurs when the fifth electron is removed since we go from the valence electrons in n = 3 to the core electrons in n = 2. There should be another big jump when the thirteenth electron is removed. and the ionization energy increases. this attraction results in energy being released. Electron affinity is the energy change associated with the addition of an electron to a gaseous atom. and size increases from top to bottom of the periodic table.e. energy will always have to be added to break the attraction and remove the electron from a neutral charged atom. S < Se < Te d. Both trends are a function of how tightly the outermost electrons are held by the positive charge in the nucleus. make it slightly easier to remove an electron from sulfur as compared to phosphorus. Ionization energy is the energy it takes to remove an electron from a gaseous atom. which results in larger ionization energies (and smaller size). There is a large jump in ionization energy when going from the removal of valence electrons to the removal of core electrons. The trends of radius and ionization energy should be opposite of each other. Ne < Se < Sr c. Size (radius) decreases left to right across the periodic table. the net positive charge on the resulting ion increases. energy must be added to overcome these repulsions. 84. However. i. ionization energy (IE). Adding an electron is more complicated. which are not present in phosphorus.. 85. when a 1s electron is removed. 86. in general. resulting in a lower ionization energy for aluminum as compared with magnesium. Br < Ni < K e. Conversely. As successive electrons are removed. The ionization energy of sulfur is lower than phosphorus because of the extra electronelectron repulsions in the doubly occupied sulfur 3p orbital. The electron configuration for Si is 1s22s22p63s23p2. F < Si < Ba f. An atom in which the outermost electrons are held tightly will have a small radius and a large ionization energy. Be < Na < Rb b. Which of the two opposing factors dominates determines whether the overall electron affinity for an element is exothermic or endothermic. These added repulsions. This increase in positive charge binds the remaining electrons more firmly. which results in electron-electron repulsions. the added electron will encounter the other electrons. Hence the 3p electron is less tightly bound than a 3s electron. 83.472 CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY more strongly bound as one goes across a period. Aluminum is out of order because the electrons in the filled 3s orbital shield some of the nuclear charge from the 3p electron. Because electrons are always attracted to the positive charge of the nucleus. For silicon. The added electron will be attracted to the nucleus. Ionization energies are always endothermic for neutral charged atoms. . a. O < P < Fe All follow the general radius trend. The ionization energy trend is the opposite of the radius trend.

Element 117 is the next halogen to be discovered (under At). Expected order from IE trend: Be < B < C < N < O B and O are exceptions to the general IE trend. From the general radius trend. This is an exception to the general ionization energy trend across the periodic table. 88. Fe < P < O 473 a. 89. There are 14 elements (the lanthanides) between La and Hf. Size also decreases going across a period. a. The smaller penetrating ability makes it slightly easier to remove an electron from B compared to Be. Sc and Ti along with Y and Zr are adjacent elements. This makes it slightly easier to remove an electron from O compared to N. element 119 is the next alkali metal to be discovered (under Fr). in general. Ba < Si < F f. Sr < Se < Ne c. the halogen (element 117) will be the smallest. and element 120 is the next alkaline earth metal to be discovered (under Ra). . a. this follows the general ionization energy trend. e. Se is an exception to the general ionization energy trend. Na+ has the smallest number of electron-electron repulsions. d. The correct IE ordering. Cl c. which makes it the smallest ion with the largest ionization energy. He b. Si e. this ion has the most electrons compared to the other sulfur species present. O. 90. Te < Se < S d. There are extra electron-electron repulsions in Se because two electrons are in the same 4p orbital. Rb < Na < Be All follow the general ionization energy (IE) trend. S2− has the largest number of electron-electron repulsions. As: [Ar]4s23d104p3. B is an exception because of the smaller penetrating ability of the 2p electron in B compared to the 2s electrons in Be. S2−. Group 6A elements have a lower ionization energy than neighboring Group 5A elements. the general ionization energy trend predicts that Se should have a higher ionization energy than As. d. 87. K c. The IE of O is lower because of the extra electron-electron repulsions present when two electrons are paired in the same orbital. Ba b. Cs.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY b. making Hf considerably smaller. which leads to S2− having the largest size and smallest ionization energy. resulting in a lower ionization energy for Se than predicted. 91. Na+. taking into account the two exceptions. this ion has the fewest electrons compared to the other sodium species present. is: B < Be < C < O < N. K < Ni < Br e. Se: [Ar]4s23d104p4.

SgO3. Cl (−348. The electron affinity trend is very erratic. in which attractions to the nucleus dominate. Sg: [Rn]7s25f146d4 QUANTUM MECHANICS AND ATOMIC THEORY b. N < O < F. UusO4− 94. Like the other halogens: NaUus. It will be in the halogen family and will be most similar to astatine (At). There will be greater repulsions between the paired electrons in P−. UusO3−.6) . This results in a more favorable (more exothermic) EA for sulfur. we would expect the EA to become more exothermic as we go from left to right in the period. F is most exothermic. 93. Mg(Uus)2. Like the other halogens: UusO−. EA(Mg2+) = −IE2(Mg) = −1445 kJ/mol (Table 12. a.4). a. The additional electron in P− will have to go into an orbital that already has one electron. SgO42−. In general. and EA becomes more negative from left to right across a period (with many exceptions). Electron-electron repulsions become important when we try to add electrons to an atom. From the standpoint of electron-electron repulsions. CHAPTER 12 a. this is just the reverse of the second ionization energy for Mg. S (-200. 99. Similar to Cr. W c. and Sg2O72− are some likely possibilities. Thus the overall variation in EA is not as great as ionization energy.7). Considering only electron-nucleus attractions. These two factors are the opposite of each other. O. Uus will have 117 electrons. Al (−44 kJ/mol). 95. Sg2O3. the electron-electron repulsions will be much more severe for O− + e− → O2− than for O + e− → O−. b. Cl is most exothermic (F is an exception). causing the EA of P to be less favorable than predicted based solely on attractions to the nucleus. a.474 92. EA becomes more positive in going down a group. based on the increasing nuclear charge. [Rn]7s25f146d107p5 b. 97. P (−74). larger atoms would have more favorable (more exothermic) electron affinities. Phosphorus is out of line. c. smaller atoms would be expected to have the more favorable (more exothermic) EA values. C(Uus)4. The electron affinity of Mg2+ is ΔH for Mg2+(g) + e− → Mg+(g). I < Br < F < Cl. The reaction for the EA of P is: P(g) + e− → P−(g) [Ne]3s23p3 [Ne]3s23p4 96. O(Uus)2 d. 98. Si (−120). Electron-electron repulsions are much greater in O− than in S− because the electron goes into a smaller 2p orbital versus the larger 3p orbital in sulfur. UusO2−.

the electron affinity trend is very erratic. and Cl.090 × 1014 s −1 λ 589. K.373 × 10 −19 J For 589. Cl+(g) + e− → Cl(g) 100. the ionization energy general trend is to decrease down a group. a. The data in Table 12. E = hν = (6. K2+ ions are not stable. Ar. 2 Rb(s) + S(s) → Rb2S(s) d. IE of Cl−is ΔH for Cl−(g) → Cl(g) + e−. Ar. and Cl (follows the radius trend) The Alkali Metals 101. Higher IE: N.9979 × 108 m / s = = 5. and Mg have positive EA values (unfavorable) due to their electron configurations (see text for detailed explanation).0 × 10 −9 m E = hν = 6. 2 Na(s) + Cl2(g) → 2 NaCl(s) 102.369 × 10 −19 J .582 × 1014 s−1) = 4. EA(Al+) = −IE1(Al) = −580 kJ/mol (Table 12. 6 Li(s) + N2(g) → 2 Li3N(s) c.7 kJ/mol (Table 12.5 × 10 −9 m b. ΔH = IE1(Cl) = 1255 kJ/mol (Table 12. the second ionization energy of K is very large compared to the first. N.6261 × 10 −34 J s × 5. For 589. 2 Cs(s) + 2 H2O(l) → 2 CsOH(aq) + H2(g) 104. It should be potassium peroxide (K2O2) because K+ ions are stable in ionic compounds. Yes.582 × 1014 s−1 λ 455.361 × 10−19 J 105. Larger size: C .8) d. and the atomic radius trend is to increase down a group. EA of Al+ is ΔH for Al+(g) + e− → Al(g). and F (follows the IE trend) c. More favorable EA: C. F has a more positive EA value than expected from its position in the periodic table.9 confirm both of these general trends.0 nm: ν = c 2.6) ΔH = −IE1(Cl) = −1255 kJ/mol = EA(Cl+) a. Mg.626 × 10−34 J s)(6.6 nm: ν = c/λ = 5. ν= c 2. E = hν = 3.090 × 1014 s −1 = 3.9979 × 108 m/s = = 6. Cl(g) → Cl+(g) + e− e. b. K. IE(Cl−) = −EA(Cl) = +348.085 × 1014 s −1 . Br.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 475 b. 103.6) c. Br.

n and ℓ The valence electrons are strongly attracted to the nucleus for elements with large ionization energies. NaH. lithium nitride potassium sulfide rubidium hydride It should be element 119 with ground state electron configuration: [Rn]7s25f146d107p68s1 Additional Exercises 108. a. 107. Li3N.04 × 10−24 J −2 λ 9. Li3P.0221 × 10 23 × = 203.373 × 10 −19 J × QUANTUM MECHANICS AND ATOMIC THEORY 1 kJ 6. e. f.04 × 10 J 1. but atoms with similar sizes and ionization energies should also have similar electron affinities. The noble gases have a large IE but have an endothermic EA. Ephoton = hc 6.476 CHAPTER 12 The energies in kJ/mol are: 3. Adding an electron disrupts this stable arrangement. The noble gases are an exception.0°C = 1. d.18 J × 50.0221 × 10 23 × = 202. Thus going one element right and one element down would result in a similar size for the two elements diagonal to each other.1 kJ/mol 1000 J mol 1 kJ 6.57 × 104 J × 1 photon = 7.57 × 104 J × . Thus the presence of the characteristic spectral lines of an element confirms its presence in any particular sample. n b.998 × 108 m/s = = 2. a. Size decreases from left to right and increases going down the periodic table.9 kJ/mol 1000 J mol b. K2S. 110.70 × 1027 photons − 24 2. Each element has a characteristic spectrum.57 × 104 J.369 × 10 −19 J × 106. 109. Noble gases have a stable arrangement of electrons. J 1. One would expect these species to readily accept another electron and have very exothermic electron affinities. sodium bromide lithium phosphide sodium hydride 3. RbH.75 × 10 m 1s = 20.9 s.626 × 10 −34 J s × 2. The ionization energies will be similar for the diagonal elements since the periodic trends also oppose each other. 112. o Cg 111. Energy to make water boil = s × m × ΔT = 4. resulting in unfavorable electron affinities.0 g × 75. NaBr. 750. Electron affinities are harder to predict. c.

Inner core electrons are always much more difficult to remove than valence electrons since they are closer to the nucleus. a sine wave has alternating positive and negative phases. The general ionization energy trend says that ionization energy increases going left to right across the periodic table. one of the exceptions to this trend occurs between Groups 2A and 3A.CHAPTER 12 113.104 × 10 −7 m × −19 ΔE m 4.178 × 10 −18 J ⎛ 12 − 1 ⎞ = -4. so the n = 6 to n = 2 visible spectrum line is violet.15 × 10 J 100 cm hc 6. and the red plot is Si. ⎛ 1 1 ΔE = !RH ⎜ 2 − 2 ⎜n ni ⎝ f λ= ⎞ ⎟ = !2. Looking at the values for the first ionization energy in the graph.022 × 10 23 λ= hc 6. followed by Mg. the results sometimes have positive values and sometimes have negative values. so the third electron removed is an inner core electron. Mg (the blue plot) is the element with the huge jump between I2 and I3. 117.998 × 108 m / s) = = 3. The term phase is often associated with the + and ! signs. When the p and d orbital functions are evaluated at various points in space. Al should have the lowest first ionization energy value. QUANTUM MECHANICS AND ATOMIC THEORY 1000 m 1s × = 200 s (about 3 minutes) km 3. than the valence electrons.86 × 10−7 m = 386 nm −19 E 5.104 × 10 −5 cm is violet light.15 × 10−19 J mol 6. Mg has two valence electrons. 118.840 × 10 −19 J ⎜ ⎟ ⎟ 62 ⎠ ⎝2 ⎠ 100 cm 6. However.104 × 10 −5 cm From the spectrum.6261 × 10 −34 J s × 2. E= 310.53 × 10 −5 cm is greenish yellow light. For example. λ = 4. the blue plot is Mg. Group 3A elements usually have a lower ionization energy than Group 2A elements.59 × 10 J = 5.00 × 108 m 477 60 × 106 km × 114. kJ 1 mol × = 5. λ= From the spectrum.998 × 108 m / s = = 5. Therefore. with Si having the largest ionization energy.9979 × 108 m / s hc = = 4. λ = 5.15 × 10−22 kJ = 5.626 × 10 −34 J s × 2. 116. on average.53 × 10 −5 cm 115. This is analogous to the positive and negative values (phases) in the p and d orbitals.53 × 10 −7 m × −19 E m 3. . Between these two groups. the green plot is Al.626 × 10 −34 J s × (2.840 × 10 J = 4.

this element would have a smaller radius than barium. From parts b and c. From the ionization energy trend. . All oxygen family elements have ns2np4 valence electron configurations. From the size trend.7 kJ ΔH = 146 kJ IE1 = 735 kJ EA = !327. The large difference in energy between I2 and I3 indicates that this element has two valence electrons. and Te are the nonmetals from the oxygen family (Po is a metal). O. Fe3+(g) + e− → Fe2+(g) Valence electrons are easier to remove than inner core electrons. so this nonmetal is from the oxygen family. Because oxygen family nonmetals form -2 charged ions in ionic compounds. b. Mg(g) → Mg+(g) + e− F(g) + e−→ F-(g) _____________________________________________________________________________ Mg(g) + F(g) → Mg+(g) + F−(g) c. The atomic number is 24 which identifies it as chromium. a. Se. this element would have a smaller ionization energy than fluorine. e. c. d. Mg(g) → Mg+(g) + e− 121. 2 + 4 = 6 valence electrons. CHAPTER 12 Na(g) → Na+(g) + e− Cl(g) + e− → Cl−(g) QUANTUM MECHANICS AND ATOMIC THEORY IE1 = 495 kJ EA = !348. a.8 kJ ΔH = 1117 kJ ______________________________________________________________________________ Na(g) + Cl(g) → Na+(g) + Cl−(g) b.8 kJ ΔH = 407 kJ IE2 = 1445 kJ EA = !327. The 4+ ion contains 20 electrons. where X is the unknown nonmetal. K2X would be the predicted formula. a. Thus the electrically neutral atom will contain 24 electrons. Mg(s) → Mg+(s) + e− c. a. S−(g) + e− → S2−(g) e. S. 122. Se3+(g) → Se4+(g) + e− d. This element is most likely an alkaline earth metal since alkaline earth metal elements all have two valence electrons. 123. b.478 119. Mg+(g) → Mg2+(g) + e− F(g) + e− → F−(g) _______________________________________________________________________ Mg+(g) + F(g) → Mg2+(g) + F−(g) d. we get: Mg(g) + F(g) → Mg+(g) + F−(g) Mg+(g) + F(g) → Mg2+(g) + F−(g) ______________________________________________________________________ ΔH = 407 kJ ΔH = 1117 kJ ΔH = 1524 kJ Mg(g) + 2 F(g) → Mg2+(g) + 2 F−(g) 120.

124. The remaining electrons are more strongly attracted to the nucleus. we remove an electron with n = 3 (the last valence electron). we begin removing an electron with n = 2. b.CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 479 b. c.01 × 1023 atoms × 50 24 Cr d. The electron affinity for Al4+ is ΔH for the reaction: Al4+(g) + e− →Al3+(g) ΔH = −I4 = −11. hence the first period would have four elements. there are 6 electrons in s orbitals. for I4. In going from n = 3 to n = 2 there is a big jump in ionization energy because the n = 2 electrons are much closer to the nucleus on average than the n = 3 electrons. The greater the number of electrons. In general. Cr is an exception to the normal filling order. b. 2 . 28 None of the noble gases and no subatomic particles had been discovered when Mendeleev published his periodic table. d. a. For I3. they are held more tightly and require a much larger amount of energy to remove compared to the n = 3 electrons. the greater the size. which has 2s and 2p orbitals. which can only have 1s orbitals.9 g × = 24. As we remove succeeding electrons. . This is the isotope f. 1s22s22p63s23p64s13d5 is the ground state electron configuration for Cr. a. the electron being removed is closer to the nucleus. 12 e. valence electrons are much easier to remove than inner core electrons. c. 1 mol 49. The first period corresponds to n = 1. Size trend: Al4+ < Al3+ < Al2+ < Al+ < Al 125.9 g mol 6. and there are fewer electrons left repelling it. The second period corresponds to n = 2.600 kJ/mol d.022 × 10 23 atoms g. These four orbitals can each hold four electrons. Each orbital could hold 4 electrons. The ground state electron configuration of the ion must be: 1s22s22p63s23p64s03d2. and it takes more energy to remove these electrons. 3. Since the n = 2 electrons are closer to the nucleus. There are 26 neutrons in the nucleus. The 1s orbital could hold 4 electrons. c. A total of 16 elements would be in the second period. 20 126. There was no reason to predict an entire family of elements. Mendeleev ordered his table by mass. Al: 1s22s22p63s23p1. Al4+. Thus there was no element out of place in terms of reactivity. he had no way of knowing there were gaps in atomic numbers (they hadn't been invented yet).

480
127.

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY

At x = 0, the value of the square of the wave function must be zero. The particle must be inside the box. For ψ = A cos(Lx), at x = 0, cos(0) = 1 and ψ2 = A2. This violates the boundary condition. Because two electrons can occupy each energy level, the n = 1 and n = 2 energy levels are filled and the first excited state is n = 3. En = n2h 2 9h 2 4h 2 5h 2 ; ΔE = E3 − E2 = − = 8mL2 8mL2 8mL2 8mL2 5(6.626 × 10 −34 J s) 2 = 9.47 × 10−19 J −31 −10 2 8(9.109 × 10 kg) (5.64 × 10 m) hc 6.626 × 10 −34 (2.998 × 108 m/s) = = 2.10 × 10−7 m = 210. nm ΔE 9.47 × 10 −19 J

128.

ΔE =

λ = 129.

a. Because wavelength is inversely proportional to energy, the spectral line to the right of B (at a larger wavelength) represents the lowest possible energy transition; this is n = 4 to n = 3. The B line represents the next lowest energy transition, which is n = 5 to n = 3, and the A line corresponds to the n = 6 to n = 3 electronic transition. b. Because this spectrum is for a one-electron ion, En = −2.178 × 10−18 J (Z2/n2). To determine ΔE and, in turn, the wavelength of spectral line A, we must determine Z, the atomic number of the one electron species. Use spectral line B data to determine Z. ⎛ Z2 Z2 ⎞ ΔE5 → 3 = −2.178 × 10−18 J ⎜ 2 − 2 ⎟ = −2.178 × 10−18 ⎜3 5 ⎟ ⎝ ⎠ E = ⎛ 16Z 2 ⎞ ⎜ ⎟ ⎜ 9 × 25 ⎟ ⎝ ⎠

hc 6.6261 × 10 −34 J s(2.9979 × 108 m / s) = = 1.394 × 10−18 J −9 λ 142.5 × 10 m

Because an emission occurs, ΔE5 → 3 = −1.394 × 10−18 J. ⎛ 16 Z 2 ⎞ 2 2+ ⎟ ΔE = −1.394 × 10−18 J = −2.178 × 10−18 J ⎜ ⎜ 9 × 25 ⎟ , Z = 9.001, Z = 3; the ion is Li . ⎝ ⎠ Solving for the wavelength of line A: 1 ⎞ ⎛1 ΔE6 → 3 = −2.178 × 10−18(3)2 ⎜ 2 − 2 ⎟ = −1.634 × 10−18 J 6 ⎠ ⎝3 λ = 6.6261 × 10 −34 J s(2.9979 × 108 m / s) hc = = 1.216 × 10−7 m = 121.6 nm −18 ΔE 1.634 × 10 J

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY

481

Challenge Problems
130. λ = h ; v rms = mv 3RT ; λ = m
h m 3RT m

=

h 3RTm

For one atom, R =

8.3145 J 1 mol = 1.381 × 10−23 J K−1 atom−1 × K mol 6.022 × 10 23 atoms 6.626 × 10 −34 J s m 3(1.381 × 10
− 23

2.31 × 10−11 m =

)(373 K )

, m = 5.32 × 10−26 kg = 5.32 × 10−23 g

Molar mass =

5.32 × 10 −23 g 6.022 × 10 23 atoms = 32.0 g/mol × atom mol

The atom is sulfur (S). 131. For one-electron species, En = − R H Z 2 /n 2 . IE is for the n = 1 → n = ∞ transition. So: IE = E∞ − E1 = −E1 = R H Z 2 /n 2 = RHZ2 4.72 × 10 4 kJ 1 mol 1000 J × × = 2.178 × 10−18 J (Z2); solving: Z = 6 23 mol kJ 6.022 × 10 Element 6 is carbon (X = carbon), and the charge for a one-electron carbon ion is 5+ (m = 5). The one-electron ion is C5+. 132.
1 ⎞ ⎛ 1 For hydrogen: ΔE = !2.178 × 10−18 J ⎜ 2 − 2 ⎟ = !4.574 × 10 −19 J 5 ⎠ ⎝2

For a similar blue light emission, He+ will need about the same ΔE value. For He+: En = !2.178 × 10 −18 J (Z2/n2), where Z = 2:

⎛ 22 22 ⎞ ΔE = !4.574 × 10 −19 J = !2.178 × 10−18 J ⎜ 2 − 2 ⎟ ⎜n 4 ⎟ ⎠ ⎝ f
0.2100 = 4 4 4 − , 0.4600 = 2 , 2 16 nf nf

nf = 2.949

The transition from n = 4 to n = 3 for He+ should emit similar-colored blue light as the n = 5 to n = 2 hydrogen transition; both these transitions correspond to very nearly the same energy change.

482
133.

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY

a. Because the energy levels Exy are inversely proportional to L2, the nx = 2, ny = 1 energy level will be lower in energy than the nx = 1, ny = 2 energy level since Lx > Ly. The first three energy levels Exy in order of increasing energy are: E11 < E21 < E12 The quantum numbers are: Ground state (E11) First excited state (E21) Second excited state (E12)

→ nx = 1, ny = 1 → nx = 2, ny = 1 → nx = 1, ny = 2
2 2 ny ⎞ h 2 ⎛ nx ⎜ + 2 ⎟ 8m ⎜ L2x Ly ⎟ ⎝ ⎠

b. E21 → E12 is the transition. Exy =

E12 =

⎤ 1.76 × 1017 h 2 h2 ⎡ 12 22 + ⎢ ⎥ = 8m ⎣ (8.00 × 10 −9 m) 2 (5.00 × 10 −9 m) 2 ⎦ 8m ⎤ 1.03 × 1017 h 2 h2 ⎡ 22 12 + ⎢ ⎥ = 8m ⎣ (8.00 × 10 −9 m) 2 (5.00 × 10 −9 m) 2 ⎦ 8m
1.76 × 1017 h 2 1.03 × 1017 h 2 7.3 × 1016 h 2 = − 8m 8m 8m

E21 =

ΔE = E12 − E21 =

ΔE =

(7.3 × 1016 m −2 ) (6.626 × 10 −34 J s) 2 = 4.4 × 10−21 J 8(9.11 × 10 −31 kg ) hc 6.626 × 10 −34 J s(2.998 × 108 m/s) = = 4.5 × 10−5 m − 21 ΔE 4.4 × 10 J

λ = 134.

The ratios for Mg, Si, P, Cl, and Ar are about the same. However, the ratios for Na, Al, and S are higher. For Na, the second IE is extremely high since the electron is taken from n = 2 (the first electron is taken from n = 3). For Al, the first electron requires a bit less energy than expected by the trend due to the fact it is a 3p electron. For S, the first electron requires a bit less energy than expected by the trend due to electrons being paired in one of the p orbitals.
1 ⎛Z⎞ ⎜ ⎟ ψ1s = π ⎜ a0 ⎟ ⎝ ⎠ 1 ⎛ 1 ⎞ ⎜ ⎟ ψ1s = π ⎜ a0 ⎟ ⎝ ⎠
3/ 2

135.

e−σ; Z = 1 for H, σ =

Zr −r = , a0 = 5.29 × 10−11 m a0 a0

3/ 2

⎛−r⎞ exp⎜ ⎟ ⎜a ⎟ ⎝ 0⎠

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY
⎛ − 2r ⎞ 1⎛ 1 ⎞ = ⎜ ⎟ exp⎜ ⎜a ⎟ ⎜ a ⎟ ⎟ π⎝ 0 ⎠ ⎝ 0 ⎠
3

483

Probability is proportional to ψ :
3

2

ψ 12 s

(units of ψ2 = m−3)

a.

ψ 12 s

⎡ − 2 ( 0) ⎤ 1⎛ 1 ⎞ 30 −3 (at nucleus) = ⎜ ⎟ exp ⎢ ⎥ = 2.15 × 10 m ⎜a ⎟ π⎝ 0 ⎠ a0 ⎦ ⎣

If we assume this probability is constant throughout the 1 × 10−3 pm3 volume, then the 2 total probability p is ψ1s × V. 1.0 × 10−3 pm3 = (1.0 × 10−3 pm) × (1 × 10−12 m/pm)3 = 1.0 × 10−39 m3 Total probability = p = (2.15 × 1030 m−3) × (1.0 × 10−39 m3) = 2.2 × 10−9 b. For an electron that is 1.0 × 10−11 m from the nucleus: ψ 12 = s

⎡ − 2(1.0 × 10 −11 ) ⎤ ⎞ 1⎛ 1 30 −3 ⎜ ⎟ exp ⎢ ⎥ = 1.5 × 10 m π ⎜ 5.29 × 10 −11 ⎟ (5.29 × 10 −11 ) ⎦ ⎝ ⎠ ⎣

3

V = 1.0 × 10−39 m3; p = ψ 12 × V = 1.5 × 10−9 s

⎡ − 2(53 × 10 −12 ) ⎤ 29 3 −39 c. ψ 12 = 2.15 × 1030 m−3 exp ⎢ ⎥ = 2.9 × 10 ; V = 1.0 × 10 m s (5.29 × 10 −11 ) ⎦ ⎣
p = ψ 12 × V = 2.9 × 10−10 s d. V = 4 π [(10.05 × 10−12 m)3 − (9.95 × 10−12 m)3] = 1.3 × 10−34 m3 3

We shall evaluate ψ 12 at the middle of the shell, r = 10.00 pm, and assume ψ 12 is constant s s from r = 9.95 to 10.05 pm. The concentric spheres are assumed centered about the nucleus. ⎡ − 2(10.0 × 10 −12 m) ⎤ 30 −3 ψ 12 = 2.15 × 1030 m−3 exp ⎢ ⎥ = 1.47 × 10 m s −11 ⎣ (5.29 × 10 m) ⎦ p = (1.47 × 1030 m−3) (1.3 × 10−34 m3) = 1.9 × 10−4 e. V =
4 π [(52.95 × 10−12 m)3 − (52.85 × 10−12 m)3] = 4 × 10−33 m3 3

Evaluate ψ 12 at r = 52.90 pm: ψ 12 = 2.15 × 1030 m−3 (e−2) = 2.91 × 1029 m−3; p = 1 × 10−3 s s 136. a. Lx = Ly = Lz; Exyz =
2 2 2 h 2 ( n x + n y + nz )

8mL2

484
E111 =

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY

3h 2 h2 6h 2 ; E112 = (12 + 12 + 22) = 8mL2 8mL2 8mL2
h2 9 h2 (12 + 22 + 22) = 8mL2 8mL2

E122 =

b. E111: only a single state; E112: triple degenerate, either nx, ny or nz can equal 2; E122: triple degenerate, either nx, ny or nz can equal 1; E222: single state Cubic Box E222 E122 Rectangular box ____ These are no longer degenerate. _____ _____ These are no longer degenerate. _____ _____ _____

E112

E111
2 2 2 h 2 ( n x + n y + nz )

137.

Exyz =

8mL2

, where L = Lx = Ly = Lz.

The first four energy levels will be filled with the 8 electrons. The first four energy levels are: E111 = h 2 + 12 + 12 8mL2 = 3h 2 8mL2 (These three energy levels are degenerate.)

E211 = E121 = E112 =

6h 2 8mL2

The next energy levels correspond to the first excited state. The energy for these levels are: E221 = E212 = E122 =
9h 2 8mL2

(These three energy levels are degenerate.)

The electronic transition in question is from one of the degenerate E211, E121, or E112 levels to one of the degenerate E221, E212, or E122 levels.

CHAPTER 12
ΔE =

QUANTUM MECHANICS AND ATOMIC THEORY

485

9h 2 6h 2 3h 2 − = 8mL2 8mL2 8mL2 3(6.626 × 10 −34 J s) 2 = 8.03 × 10−20 J −31 −9 2 8(9.109 × 10 kg )(1.50 × 10 m) hc (6.626 × 10 −34 J s)(2.998 × 108 m / s) = = 2.47 × 10−6 m = 2470 nm ΔE 8.03 × 10 − 20 J p = 1, q = 1, r = 0, s = ±1/2 (2 elements) p = 2, q = 1, r = 0, s = ±1/2 (2 elements) p = 3, q = 1, r = 0, s = ±1/2 (2 elements) p = 3, q = 3, r = -2, s = ±1/2 (2 elements) p = 3, q = 3, r = 0, s = ±1/2 (2 elements) p = 3, q = 3, r = +2, s = ±1/2 (2 elements)

ΔE =

λ =

138.

a. 1st period: 2nd period: 3rd period:

4th period:

p = 4; q and r values are the same as with p = 3 (8 total elements)

1 3 5 6 7 8

2 4 9 10 11 12

13 14 15 16 17 18 19 20
b. Elements 2, 4, 12, and 20 all have filled shells and will be least reactive. c. Draw similarities to the modern periodic table. XY could be X+Y−, X2+Y2− or X3+Y3−. Possible ions for each are: X+ could be elements 1, 3, 5, or 13; Y- could be 11 or 19. X2+ could be 6 or 14; Y2− could be 10 or 18. X3+ could be 7 or 15; Y3− could be 9 or 17.

Note: X4+ and Y4− ions probably won’t form.

486

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XY2 will be X2+(Y−)2; see preceding information for possible ions. X2Y will be (X+)2Y2−; see preceding information for possible ions. XY3 will be X3+(Y−)3; see preceding information for possible ions. X2Y3 will be (X3+)2(Y2−)3; see preceding information for possible ions. d. From a, we can see that eight electrons can have p = 3. e. p = 4, q = 3, r = 2, s = ±1/2 (2 electrons) f. p = 4, q = 3, r = −2 , s = ±1/2 (2) p = 4, q = 3, r = 0, s = ±1/2 (2) p = 4, q = 3, r = +2, s = ±1/2 (2) A total of 6 electrons can have p = 4 and q = 3. g. p = 3, q = 0, r = 0; this is not allowed; q must be odd. Zero electrons can have these quantum numbers. h. p = 5, q = 1, r = 0 p = 5, q = 3, r = −2, 0, +2 p = 5, q = 5, r = -4, -2, 0, +2, +4 i. p = 6, q = 1, r = 0, s = ±1/2 (2 electrons) p = 6, q = 3, r = −2, 0, +2; s = ±1/2 (6) p = 6, q = 5, r = −4, −2, 0, +2, +4; s = ±1/2 (10) Eighteen electrons can have p = 6. 139. a. Assuming the Bohr model applies to the 1s electron, E1s = −RHZ2/n2 = −RHZ2eff, where n = 1. IE = E∞ − E1s = 0 – E1s = RHZ2eff 2.462 × 10 6 kJ 1 mol 1000 J × × = 2.178 × 10−18 J (Zeff)2 23 mol kJ 6.0221 × 10 Solving: Zeff = 43.33

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY

487

b. Silver is element 47, so Z = 47 for silver. Our calculated Zeff value is slightly less than 47. Electrons in other orbitals can penetrate the 1s orbital. Thus a 1s electron can be slightly shielded from the nucleus, giving a Zeff close to but less than Z. 140. The third IE refers to the following process: E2+(g) → E3+(g) + e− ΔH = IE3. The electron configurations for the 2+ charged ions of Na to Ar are: Na2+: Mg2+: 1s22s22p5 1s22s22p6 Al2+: Si2+: P2+: S2+: Cl2+: Ar2+: [Ne]3s1 [Ne]3s2 [Ne]3s23p1 [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4

IE3 for sodium and magnesium should be extremely large compared with the others because n = 2 electrons are much more difficult to remove than n = 3 electrons. Between Na2+ and Mg2+, one would expect to have the same trend as seen with IE1(F) versus IE1(Ne); these neutral atoms have identical electron configurations to Na2+ and Mg2+. Therefore, the 1s22s22p5 ion (Na2+) should have a lower ionization energy than the 1s22s22p6 ion (Mg2+). The remaining 2+ ions (Al2+ to Ar2+) should follow the same trend as the neutral atoms having the same electron configurations. The general IE trend predicts an increase from [Ne]3s1 to [Ne]3s23p4. The exceptions occur between [Ne]3s2 and [Ne]3s23p1 and between [Ne]3s23p3 and [Ne]3s23p4. [Ne]3s23p1 is out of order because of the small penetrating ability of the 3p electron as compared with the 3s electrons. [Ne]3s23p4 is out of order because of the extra electron-electron repulsions present when two electrons are paired in the same orbital. Therefore, the correct ordering for Al2+ to Ar2+ should be Al2+ < P2+ < Si2+ < S2+ < Ar2+ < Cl2+, where P2+ and Ar2+ are out of line for the same reasons that Al and S are out of line in the general ionization energy trend for neutral atoms.

IE

Na2+

Mg2+

Al2+

Si2+

P2+

S2+

Cl2+

Ar2+

488

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY

Note: The actual numbers in Table 12.6 support most of this plot. No IE3 is given for Na2+, so you cannot check this. The only deviation from our discussion is IE3 for Ar2+ which is greater than IE3 for Cl2+ instead of less than.

Marathon Problem
141. a. Let λ = wavelength corresponding to the energy difference between the excited state, n = ?, and the ground state, n = 1. Use the information in part a to first solve for the energy difference ΔE1 → n, and then solve for the value of n. From the problem, λ = (λradio/3.00 × 107). ΔE1 → n =
hc (3.00 × 10 7 ) hc hc = , λradio = ΔE1 → n λ (λ radio / 3.00 × 10 7 )

λradio =

c ν radio

=

c ; equating the two λradio expressions gives: 97.1 × 10 6 s −1

c hc (3.00 × 10 7 ) , ΔE1 → n = h(3.00 × 107)(97.1 × 106) = ΔE1 → n 97.1 × 10 6 ΔE1 → n = 6.626 × 10−34 J s(3.00 × 107)(97.1 × 106 s−1) = 1.93 × 10−18 J Now we can solve for the n value of the excited state.

⎛ 1 1⎞ ΔE1 → n = 1.93 × 10−18 J = −2.178 × 10−18 ⎜ 2 − 2 ⎟ ⎜n 1 ⎟ ⎝ ⎠
1 − 1.93 × 10 −18 + 2.178 × 10 −18 = = 0.11, n = 3 = energy level of the excited n2 2.178 × 10 −18 state b. From de Broglie’s equation: λ = h 6.626 × 10 −34 J s = = 1.28 × 10−6 m mv 9.109 × 10 −31 kg (570. m / s)

Let n = V = principal quantum number of the valence shell of element X. The electronic transition in question will be from n = V to n = 3 (as determined in part a). ΔEn

→3

⎛ 1 1 ⎞ = −2.178 × 10−18 J ⎜ 2 − 2 ⎟ ⎜3 n ⎟ ⎝ ⎠
hc 6.626 × 10 −34 J s(2.998 × 108 m / s) = = 1.55 × 10−19 J λ 1.28 × 10 −6 m

|ΔEn → 3| =

CHAPTER 12

QUANTUM MECHANICS AND ATOMIC THEORY
1 ⎞ ⎛1 ΔEn → 3 = −1.55 × 10−19 J = −2.178 × 10−18 J ⎜ − 2 ⎟ n ⎠ ⎝9

489

1 = n2

⎛1⎞ − 1.55 × 10 −19 + 2.178 × 10 −18 ⎜ ⎟ ⎝ 9 ⎠ = 0.040, n = 5 −18 2.178 × 10

Thus V = 5 = the principal quantum number for the valence shell of element X; i.e., element X is in the fifth period (row) of the periodic table (element X = Rb − Xe). c. For n = 2, we can have 2s and 2p orbitals. None of the 2s orbitals have mℓ = −1, and only one of the 2p orbitals has mℓ = −1. In this one 2p atomic orbital, only one electron can have ms = −1/2. Thus, only one unpaired electron exists in the ground state for element X. From period 5 elements, X could be Rb, Y, Ag, In, or I because all of these elements only have one unpaired electron in the ground state.

⎛ Z2 ⎞ d. For a one-electron ion, En = −2.178 × 10−18 J ⎜ 2 ⎟ , where Z = atomic number. ⎜n ⎟ ⎝ ⎠ For He+, Z = 2. The ground state (n = 1) energy for hydrogen is −2.178 × 10−18 J. Equating the two energy level values: ⎛ 22 ⎞ −2.178 × 10−18 J ⎜ 2 ⎟ = −2.178 × 10−18 J, n = 2 ⎜n ⎟ ⎝ ⎠
Thus the azimuthal quantum number (ℓ) for the subshell of X that contains the unpaired electron is 2, which means the unpaired electron is in the d subshell. Although Y and Ag are both d-block elements, only Y has one unpaired electron in the d block. Silver is an exception to the normal filling order; Ag has the unpaired electron in the 5s orbital. The ground-state electron configurations are: Y: [Kr] 5s24d1 and Ag: [Kr] 5s14d10 Element X is yttrium (Y).

CHAPTER 13 BONDING: GENERAL CONCEPTS
Chemical Bonds and Electronegativity
11. Electronegativity is the ability of an atom in a molecule to attract electrons to itself. Electronegativity is a bonding term. Electron affinity is the energy change when an electron is added to a substance. Electron affinity deals with isolated atoms in the gas phase. A covalent bond is a sharing of electron pair(s) in a bond between two atoms. An ionic bond is a complete transfer of electrons from one atom to another to form ions. The electrostatic attraction of the oppositely charged ions is the ionic bond. A pure covalent bond is an equal sharing of shared electron pair(s) in a bond. A polar covalent bond is an unequal sharing. Ionic bonds form when there is a large difference in electronegativity between the two atoms bonding together. This usually occurs when a metal with a small electronegativity is bonded to a nonmetal having a large electronegativity. A pure covalent bond forms between atoms having identical or nearly identical eletronegativities. A polar covalent bond forms when there is an intermediate electronegativity difference. In general, nonmetals bond together by forming covalent bonds, either pure covalent or polar covalent. Ionic bonds form due to the strong electrostatic attraction between two oppositely charged ions. Covalent bonds form because the shared electrons in the bond are attracted to two different nuclei, unlike the isolated atoms where electrons are only attracted to one nuclei. The attraction to another nuclei overrides the added electron-electron repulsions. 12. a. There are two attractions of the form
(+1)(−1) , where r = 1 × 10−10 m = 0.1 nm. r

⎡ (+1)(−1) ⎤ −18 −18 V = 2 × (2.31 × 10−19 J nm) ⎢ ⎥ = −4.62 × 10 J = −5 × 10 J ⎣ 0.1 nm ⎦

b. There are 4 attractions of +1 and −1 charges at a distance of 0.1 nm from each other. The two negative charges and the two positive charges repel each other across the diagonal of the square. This is at a distance of 2 × 0.1 nm.

490

CHAPTER 13

BONDING: GENERAL CONCEPTS
⎡ (+1)(+1) ⎤ ⎢ ⎥ ⎢ 2 (0.1) ⎥ ⎣ ⎦
⎡ (−1)(−1) ⎤ + 2.31 × 10−19 ⎢ ⎥ ⎢ 2 (0.1) ⎥ ⎣ ⎦

491

⎡ (+1)(−1) ⎤ −19 V = 4 × (2.31 × 10−19) ⎢ ⎥ + 2.31 × 10 ⎣ 0 .1 ⎦

V = −9.24 × 10−18 J + 1.63 × 10−18 J + 1.63 × 10−18 J = −5.98 × 10−18 J = −6 × 10−18 J
Note: There is a greater net attraction in arrangement b than in a.

13.

Using the periodic table, we expect the general trend for electronegativity to be: 1. Increase as we go from left to right across a period 2. Decrease as we go down a group a. C < N < O d. Tl < Ge < S b. Se < S < Cl e. Rb < K < Na c. Sn < Ge < Si f. Ga < B < O

14.

The most polar bond will have the greatest difference in electronegativity between the two atoms. From positions in the periodic table, we would predict: a. Ge−F b. P−Cl c. S−F d. Ti−Cl e. Sn−H f. Tl−Br

15.

The general trends in electronegativity used in Exercises 13.13 and 13.14 are only rules of thumb. In this exercise we use experimental values of electronegativities and can begin to see several exceptions. The order of EN using Figure 13.3 is: a. C (2.6) < N (3.0) < O (3.4) same as predicted

b. Se (2.6) = S (2.6) < Cl (3.2) different c. Si (1.9) < Ge (2.0) = Sn (2.0) different e. Rb (0.8) = K (0.8) < Na (0.9) different Most polar bonds using actual EN values: a. Si−F (Ge−F predicted) c. S−F (same as predicted) e. C−H (Sn−H predicted) 16. b. P−Cl (same as predicted) d. Ti−Cl (same as predicted) f. Al−Br (Tl−Br predicted) d. Tl (2.0) = Ge (2.0) < S (2.6) different f. Ga (1.8) < B (2.0) < O (3.4) same

Electronegativity values increase from left to right across the periodic table. The order of electronegativities for the atoms from smallest to largest electronegativity will be H = P < C < N < O < F. The most polar bond will be F‒H since it will have the largest difference in

492

CHAPTER 13

BONDING: GENERAL CONCEPTS

electronegativities, and the least polar bond will be P‒H since it will have the smallest difference in electronegativities (ΔEN = 0). The order of the bonds in decreasing polarity will be F‒H > O‒H > N‒H > C‒H > P‒H. 17. Ionic character is proportional to the difference in electronegativity values between the two elements forming the bond. Using the trend in electronegativity, the order will be: Br‒Br < N‒O < C‒F < Ca‒O < K‒F least most ionic character ionic character Note that Br‒Br, N‒O and C‒F bonds are all covalent bonds since the elements are all nonmetals. The Ca‒O and K‒F bonds are ionic, as is generally the case when a metal forms a bond with a nonmetal. 18. F Cl Br I (IE − EA) 2006 kJ/mol 1604 1463 1302 (IE − EA)/502 4.0 3.2 2.9 2.6 EN (text) 4.0 3.2 3.0 2.7 2006/502 = 4.0

The values calculated from IE and EA show the same trend as (and agree fairly closely) with the values given in the text.

Ionic Compounds
19. Anions are larger than the neutral atom, and cations are smaller than the neutral atom. For anions, the added electrons increase the electron-electron repulsions. To counteract this, the size of the electron cloud increases, placing the electrons further apart from one another. For cations, as electrons are removed, there are fewer electron-electron repulsions, and the electron cloud can be pulled closer to the nucleus. Isoelectronic: same number of electrons. Two variables, the number of protons and the number of electrons, determine the size of an ion. Keeping the number of electrons constant, we only have to consider the number of protons to predict trends in size. The ion with the most protons attracts the same number of electrons most strongly, resulting in a smaller size. 20. All of these ions have 18 e−; the smallest ion (Sc3+) has the most protons attracting the 18 e−, and the largest ion has the fewest protons (S2−). The order in terms of increasing size is Sc3+ < Ca2+ < K+ < Cl− < S2−. In terms of the atom size indicated in the question:

K+

Ca2+

Sc3+

S2-

Cl-

CHAPTER 13
21.

BONDING: GENERAL CONCEPTS
b. Pt2+ > Pd2+ > Ni2+ c. O2− > O− > O

493

a. Cu > Cu+ > Cu2+ d. La3+ > Eu3+ > Gd3+ > Yb3+

e. Te2− > I− > Cs+ > Ba2+ > La3+

For answer a, as electrons are removed from an atom, size decreases. Answers b and d follow the radius trend. For answer c, as electrons are added to an atom, size increases. Answer e follows the trend for an isoelectronic series, i.e., the smallest ion has the most protons. 22. a. Mg2+: 1s22s22p6 K+: Tl+: 1s22s22p63s23p6 [Xe]6s24f145d10 Sn2+: Al3+: As3+: Te2-: Rb+: Se2−: [Kr]5s24d10 1s22s22p6 [Ar]4s23d10 [Kr]5s24d105p6 [Ar]4s23d104p6 [Ar]4s23d104p6

b. N3−, O2− and F−: 1s22s22p6 c. Be2+: Ba2+: I−: 23. 1s2 [Kr]5s24d105p6 [Kr]5s24d105p6

a. Cs2S is composed of Cs+ and S2−. Cs+ has the same electron configuration as Xe, and S2− has the same configuration as Ar. b. SrF2; Sr2+ has the Kr electron configuration, and F− has the Ne configuration. c. Ca3N2; Ca2+ has the Ar electron configuration, and N3− has the Ne configuration. d. AlBr3; Al3+ has the Ne electron configuration, and Br− has the Kr configuration.

24.

a. Sc3+

b. Te2−

c. Ce4+ and Ti4+

d. Ba2+

All of these have the number of electrons of a noble gas. 25. Se2−, Br-, Rb+, Sr2+, Y3+, and Zr4+ are some ions that are isoelectronic with Kr (36 electrons). In terms of size, the ion with the most protons will hold the electrons tightest and will be the smallest. The size trend is: Zr4+ < Y3+ < Sr2+ < Rb+ < Br- < Se2− smallest largest 26. Lattice energy is proportional to Q1Q2/r, where Q is the charge of the ions and r is the distance between the ions. In general, charge effects on lattice energy are greater than size effects. a. LiF; Li+ is smaller than Cs+. b. NaBr; Br- is smaller than I−.

c. BaO; O2− has a greater charge than Cl-. d. CaSO4; Ca2+ has a greater charge than Na+.

494

CHAPTER 13
e. K2O; O2− has a greater charge than F−. f.

BONDING: GENERAL CONCEPTS
Li2O; The ions are smaller in Li2O.

27.

a. Al3+ and S2− are the expected ions. The formula of the compound would be Al2S3 (aluminum sulfide). b. K+ and N3−; K3N, potassium nitride c. Mg2+ and Cl−; MgCl2, magnesium chloride d. Cs+ and Br−; CsBr, cesium bromide

28.

Ionic solids can be characterized as being held together by strong omnidirectional forces. i. For electrical conductivity, charged species must be free to move. In ionic solids the charged ions are held rigidly in place. Once the forces are disrupted (melting or dissolution), the ions can move about (conduct).

ii. Melting and boiling disrupts the attractions of the ions for each other. If the forces are strong, it will take a lot of energy (high temperature) to accomplish this. iii. If we try to bend a piece of material, the atoms/ions must slide across each other. For an ionic solid, the following might happen:

− + − + − + − + − + − + − +
Strong attraction

− + − + − + − − + − + − + −
Strong repulsion

Just as the layers begin to slide, there will be very strong repulsions causing the solid to snap across a fairly clean plane. These properties and their correlation to chemical forces will be discussed in detail in Chapter 16. 29. K(s) → K(g) K(g) → K (g) + e 1/2 Cl2(g) → Cl(g)
− − + + −

ΔH = 64 kJ (sublimation) ΔH = 419 kJ (ionization energy) ΔH = 239/2 kJ (bond energy)

Cl(g) + e → Cl (g) ΔH = !349 kJ (electron affinity) − ΔH = !690. kJ (lattice energy) K (g) + Cl (g) → KCl(s) __________________________________________________________ ΔH ° = !437 kJ/mol K(s) + 1/2 Cl2(g) → KCl(s) f

CHAPTER 13
30.

BONDING: GENERAL CONCEPTS
ΔH = 150. kJ ΔH = 735 kJ ΔH = 1445 kJ ΔH = 154 kJ ΔH = 2(-328) kJ ΔH = −2913 kJ (sublimation) (IE1) (IE2) (BE) (EA) (LE)

495

Mg(s) → Mg(g) Mg(g) → Mg+(g) + e− Mg+(g) → Mg2+(g) + e− F2(g) → 2 F(g) 2 F(g) + 2 e− → 2 F−(g) Mg2+(g) + 2 F−(g) → MgF2(s) Mg(s) + F2(g) → MgF2(s)

______________________________________________________________________________________________

ΔH o = −1085 kJ/mol f

31.

Use Figure 13.11 as a template for this problem. Li(s) → Li(g) → 1/2 I2(g) → I(g) + e− → + Li (g) + I−(g) → Li(g) Li+(g) + e− I(g) I−(g) LiI(s) ΔHsub = ? ΔH = 520. kJ ΔH = 151/2 kJ ΔH = !295 kJ ΔH = !753 kJ

________________________________________________________________________

Li(s) + 1/2 I2(g) → LiI(s)

ΔH = !272 kJ

ΔHsub + 520. + 151/2 ! 295 ! 753 = !272, ΔHsub = 181 kJ 32. Two other factors that must be considered are the ionization energy needed to produce more positively charged ions and the electron affinity needed to produce more negatively charged ions. The favorable lattice energy more than compensates for the unfavorable ionization energy of the metal and for the unfavorable electron affinity of the nonmetal, as long as electrons are added to or removed from the valence shell. Once the valence shell is full, the ionization energy required to remove another electron is extremely unfavorable; the same is true for electron affinity when an electron is added to a higher n shell. These two quantities are so unfavorable after the valence shell is complete that they overshadow the favorable lattice energy, and the higher-charged ionic compounds do not form. a. From the data given, less energy is required to produce Mg+(g) + O−(g) than to produce Mg2+(g) + O2−(g). However, the lattice energy for Mg2+O2− will be much more exothermic than for Mg+O− (due to the greater charges in Mg2+O2−). The favorable lattice energy term will dominate and Mg2+O2− forms. b. Mg+ and O− both have unpaired electrons. In Mg2+ and O2− there are no unpaired electrons. Hence Mg+O− would be paramagnetic; Mg2+O2− would be diamagnetic. Paramagnetism can be detected by measuring the mass of a sample in the presence and absence of a magnetic field. The apparent mass of a paramagnetic substance will be larger in a magnetic field because of the force between the unpaired electrons and the field.

33.

+ EA2. and Se2− is smaller than Te2−. 2 Na(s) → 2 Na(g) 2 Na(g) → 2 Na+(g) + 2 e− S(s) → S(g) S(g) + e− → S−(g) S−(g) + e− → S2−(g) + 2 Na (g) + S2−(g) → Na2S(s) 2 Na(s) + S(s) → Na2S(s) BONDING: GENERAL CONCEPTS _______________________________________________________________________________________ 2ΔHsub.496 34.744 kJ/mol Bond Energies 37. ! 1850. Lattice energy is proportional to the charge of the cation times the charge of the anion. The mean value is: 540 ±50 kJ. CHAPTER 13 Let us look at the complete cycle for Na2S. Q1Q2. S = 277 kJ EA1 = !200. Na = 2(109) kJ 2IE = 2(495) kJ ΔHsub. EA2 = 576 kJ Rb2S: !361 = 2(82) + 2(409) + 277 ! 200. We expect the trend from most exothermic to least exothermic to be: CaSe > CaTe > Na2Se > Na2Te (−2862) (−2721) (−2130) (−2095 kJ/mol) This is what we observe. We can represent the results as EA2 = 4 Ca2+ has a greater charge than Na+. 35. H H + Cl Cl 2H Cl . EA2 = 553 kJ f For each salt: ΔH ° = 2ΔHsub. kJ EA2 = ? LE = !2203 kJ ΔH ° = !365 kJ f ΔH ° = 2ΔH sub . ! 1949 + EA2. 36. S + EA1 + EA2 + LE. M + 2IE + 277 ! 200. !365 = !918 + EA2. The effect of charge on the lattice energy is greater than the effect of size. EA2 = 493 kJ We get values from 493 to 576 kJ. Na + 2IE + ΔHsub. 553 + 576 + 529 + 493 = 538 kJ. = 2(78) + 2(382) + 277 ! 200. Compound FeCl2 FeCl3 Fe2O3 Q1Q2 (+2)(−1) = −2 (+3)(−1) = −3 (+3)(−2) = −6 Lattice Energy −2631 kJ/mol −5339 kJ/mol −14. EA2 = 529 kJ Cs2S: !360. ! 2052 + EA2.) + 2(419) + 277 ! 200. a. + LE + EA2 f K2S: !381 = 2(90.

Sometimes some of the bonds remain the same between reactants and products. Bonds broken: 1 N−N (160. HCl = 2 mol(−92 kJ/mol) = −184 kJ (−183 kJ from bond energies) . kJ/mol) 4 N−H (391 kJ/mol) 2 F−F (154 kJ/mol) Bonds formed: 4 H−F (565 kJ/mol) 1 N≡N (941 kJ/mol) ΔH = 160.CHAPTER 13 BONDING: GENERAL CONCEPTS Bonds formed: 2 H‒Cl (427 kJ/mol) 497 Bonds broken: 1 H‒H (432 kJ/mol) 1 Cl‒Cl (239 kJ/mol) ΔH = ΣDbroken ! ΣDformed. ΔH = 432 kJ + 239 kJ ! 2(427) kJ = !183 kJ b. only break and form bonds that are involved in the reaction. kJ + 4(391 kJ) + 2(154 kJ) − [4(565 kJ) + 941 kJ] = −1169 kJ 38. H H C N+2 H H H C H H N H Bonds broken: 1 C≡N (891 kJ/mol) 2 H−H (432 kJ/mol) Bonds formed: 1 C−N (305 kJ/mol) 2 C−H (413 kJ/mol) 2 N−H (391 kJ/mol) ΔH = 891 kJ + 2(432 kJ) − [305 kJ + 2(413 kJ) + 2(391 kJ)] = −158 kJ H H N H N H +2 F F 4 H F+ N N d. o a. N N+ 3 H H 2H N H H Bonds broken: 1 N ≡ N (941 kJ/mol) 3 H‒H (432 kJ/mol) Bonds formed: 6 N‒H (391 kJ/mol) ΔH = 941 kJ + 3(432) kJ ‒ 6(391) kJ = ‒109 kJ c. ΔH = 2ΔH f . To save time.

3x = 717. ΔH = 305 ! 347 = !42 kJ Note: Sometimes some of the bonds remain the same between reactants and products. H H C H C C N H 39. and then 2x = bond energy for AB. ΔH = !285 kJ = x + 432 kJ – [2(2x)]. To save time. H H C H H C H O H+3O O 2O C O +3 H O H Bonds broken: 5 C−H (413 kJ/mol) 1 C−C (347 kJ/mol) 1 C−O (358 kJ/mol) 1 O−H (467 kJ/mol) 3 O=O (495 kJ/mol) Bonds formed: 2 × 2 C=O (799 kJ/mol) 3 × 2 O−H (467 kJ/mol) ΔH = 5(413 kJ) + 347 kJ + 358 kJ + 467 kJ + 3(495 kJ) – [4(799 kJ) + 6(467 kJ)] = −1276 kJ 41. Let x = bond energy for A2. 40. ΔH = 2ΔH o. bond energies seem to give a reasonably good estimate for the enthalpy change of a reaction. The estimate is especially good for gas phase reactions. only break and form bonds that are involved in the reaction. H C N H Bonds broken: 1 C‒N (305 kJ/mol) Bonds formed: 1 C‒C (347 kJ/mol) ΔH = ΣDbroken ! ΣDformed. x = 239 kJ/mol = bond energy for A2 .498 CHAPTER 13 BONDING: GENERAL CONCEPTS b. NH 3 = 2 mol(-46 kJ/mol) = −92 kJ (−109 kJ from bond energies) f Comparing the values for each reaction. H−C/C−H + 5/2 O=O → 2 O=C=O + H−O−H Bonds broken: 2 C−H (413 kJ/mol) 1 C/C (839 kJ/mol) 5/2 O = O (495 kJ/mol) Bonds formed: 2 × 2 C=O (799 kJ/mol) 2 O−H (467 kJ/mol) ΔH = 2(413 kJ) + 839 kJ + 5/2 (495 kJ) – [4(799 kJ) + 2(467 kJ)] = !1228 kJ 42.

a. H 4 H H C H N BONDING: GENERAL CONCEPTS 499 H N H + 5 O N O N O 12 H O O H + 9 N N + 4 O C O Bonds broken: 9 N‒N (160.) + 4(305) + 12(413) + 12(391) + 10(607) + 10(201) − [24(467) + 9(941) + 8(799)] ΔH = 20. OH H H * C * C * H H C N H H C * C C N H + H * O H .069 kJ = −5681 kJ 44. kJ/mol) 4 N‒C (305 kJ/mol) 12 C‒H (413 kJ/mol) 12 N‒H (391 kJ/mol) 10 N=O (607 kJ/mol) 10 N‒O (201 kJ/mol) Bonds formed: 24 O‒H (467 kJ/mol) 9 N≡N (941 kJ/mol) 8 C=O (799 kJ/mol) ΔH = 9(160.CHAPTER 13 43. I.388 kJ − 26. H C H H C * H O + H * C N H * O H C H C * C H N H Bonds broken (*): 1 C‒O (358 kJ) 1 C‒H (413 kJ) Bonds formed (*): 1 O‒H (467 kJ) 1 C‒C (347 kJ) ΔHI = 358 kJ + 413 kJ − (467 kJ + 347 kJ) = −43 kJ II.

kJ/mol) Bonds formed: 4 C≡N (891 kJ/mol) 6 × 2 H‒O (467 kJ/mol) 1 N≡N (941 kJ/mol) ΔH = 12(413) + 6(630.) − [4(891) + 12(467) + 941] = −1373 kJ c. 46.500 Bonds broken (*): CHAPTER 13 BONDING: GENERAL CONCEPTS Bonds formed (*): 1 H‒O (467 kJ/mol) 1 C=C (614 kJ/mol) 1 C‒O (358 kJ/mol) 1 C‒H (413 kJ/mol) 1 C‒C (347 kJ/mol) ΔHII = 358 kJ + 413 kJ + 347 kJ − [467 kJ + 614 kJ] = +37 kJ ΔHoverall = ΔHI + ΔHII = −43 kJ + 37 kJ = −6 kJ b. It must be necessary for some other reason. the high temperature is not needed to provide energy. This will be discussed in Chapter 15 on kinetics. The reason is to increase the speed of the reaction. H H 2 H C C H C H + 2 H H H N H + 3 O2 2 H H C C H C N + 6 H O H Bonds broken: 2 × 3 C‒H (413 kJ/mol) 2 × 3 N‒H (391 kJ/mol) 3 O=O (495 kJ/mol) Bonds formed: 2 C≡N (891 kJ/mol) 6 × 2 O‒H (467 kJ/mol) ΔH = 6(413) + 6(391) + 3(495) − [2(891) + 12(467)] = −1077 kJ 45. Because both reactions are highly exothermic. H H C O H + C O H H H H O C C O H . H H 4 H C C H C H + 6 NO 4 H H H C C H C N + 6 H O H + N N Bonds broken: 4 × 3 C‒H (413 kJ/mol) 6 N=O (630.

8 kJ + 4(79. kJ. HI(g) → H(g) + I(g) H(g) → H+(g) + e− I(g) + e− → I−(g) ΔH = 1390. These energy changes are due to intermolecular forces and will be discussed in Chapter 16. Using SF4 data: SF4(g) → S(g) + 4 F(g) ΔH° = 4DSF = 278.2 kJ ___________________________________________________________________ HI(g) → H+(g) + I−(g) d.7 kJ ____________________________________________________________________ HCl(g) → H+(g) + Cl−(g) c. kJ DSF = 1370. kJ ΔH = 1599 kJ _____________________________________________________________________ H2O(g) → H+(g) + OH−(g) 48. H2O(g) → OH(g) + H(g) H(g) → H+(g) + e− OH(g) + e− → OH−(g) ΔH = 1312 kJ ΔH = 467 kJ ΔH = 1312 kJ ΔH = −180. kJ ΔH = 295 kJ ΔH = 1312 kJ ΔH = −295. kJ = 342.CHAPTER 13 BONDING: GENERAL CONCEPTS Bonds formed: 1 C‒C (347 kJ/mol) 1 C=O (745 kJ/mol) 1 C‒O (358 kJ/mol) 501 Bonds broken: 1 C≡O (1072 kJ/mol) 1 C‒O (358 kJ/mol) ΔH = 1072 + 358 − (347 + 745 + 358) = −20. kJ CH3OH(g) + CO(g) → CH3COOH(l) ΔH° = −484 kJ − [(−201 kJ) + (−110.0 kJ) − (−775 kJ) = 1370.5 kJ)] = −173 kJ Using bond energies.8 kJ ___________________________________________________________________ HF(g) → H+(g) + F−(g) b. a. bond energies give a much poorer estimate for ΔH as compared with gas phase reactions. Bond energies do not account for the energy changes that occur when liquids and solids form instead of gases. a. HF(g) → H(g) + F(g) H(g) → H+(g) + e− F(g) + e− → F−(g) ΔH = 565 kJ ΔH = 1312 kJ ΔH = −327. ΔH = −20. 47. For this reaction. The major reason for the large discrepancy is that not all species are gases in this exercise. HCl(g) → H(g) + Cl(g) H(g) → H+(g) + e− Cl(g) + e− → Cl−(g) ΔH = 1549 kJ ΔH = 427 kJ ΔH = 1312 kJ ΔH = −348.5 kJ/mol 4 mol SF bonds .

1 kJ) = 1166. f 49.0 kJ/mol 6 b.0 kJ) − (−46. ΔH o = 0 for these two species. c. Unless noted otherwise. you can (and will) become very adept at drawing Lewis structures. The value in the table was based on the S‒F bond in SF6. These steps are (1) count the valence electrons available in the molecule/ion. In these compounds.7 kJ + 3(216. NH3(g) → N(g) + 3 H(g) ΔH° = 3DNH = 472.8 kJ + 6(79. After counting valence electrons and drawing the skeletal structure. Keep in mind that practice makes perfect. the first two steps are always the same. H2O. S(g) and F(g) are not the most stable form of the element at 25°C and 1 atm. ΔH o for H(g) equals one-half the f f H‒H bond energy. We place the remaining electrons around the various atoms in an attempt to satisfy the octet rule (or duet rule for H). Lewis Structures and Resonance 51. However. There is good agreement. the atom listed first is assumed to be the atom in the middle.8 kJ DNH = 1166. Drawing Lewis structures is mostly trial and error. After practicing. and all other atoms in the formula are attached to this atom. The most notable exceptions to the rule are formulas that begin with H. 8 kJ = 388.0 kJ) − (−1209 kJ) = 1962 kJ DSF = 1962 kJ = 327. the atom listed second is assumed to be the central atom.6 is 327 kJ/mol. . ΔH o for H(g) is ΔH° for the reaction: 1/2 H2(g) → H(g). and (2) attach all atoms to each other with single bonds (called the skeletal structure).93 kJ/mol 3 mol NH bonds Dcalc = 389 kJ/mol compared with 391 kJ/mol in the table. Hydrogen can never be a central atom since this would require H to have more than two electrons.g.. H2CO. The most stable forms are S8(s) and F2(g). 50. etc. called the central atom.502 CHAPTER 13 Using SF6 data: SF6(g) → S(g) + 6 F(g) BONDING: GENERAL CONCEPTS ΔH° = 6DSF = 278. the rest is trial and error. e. The S‒F bond energy in Table 13.

O C H H f. H2CO has 2(1) + 4 + 6 = 12 valence electrons. H P H H H P H H Skeletal structure Lewis structure Skeletal structure Lewis structure Skeletal structure uses 4 e−. F Se F g. CO2 has 4 + 2(6) = 16 valence electrons. O i. H C N H C N b. CHCl3 has 4 + 1 + 3(7) = 26 valence electrons. h. 6 e− remain c. H Cl C Cl Skeletal structure Cl Cl H C Cl Lewis structure Cl H H N H Lewis structure H + Note: Subtract valence electrons for positive charged ions. e. NH4+ has 5 + 4(1) ! 1 = 8 valence electrons. SeF2 has 6 + 2(7) = 20 valence electrons. Skeletal structures uses 6 e−. PH3 has 5 + 3(1) = 8 valence electrons. HCN has 1 + 4 + 5 = 10 valence electrons. O2 has 2(6) = 12 valence electrons. H Br . 2 e− remain d. C O O O HBr has 1 + 7 = 8 valence electrons.CHAPTER 13 BONDING: GENERAL CONCEPTS 503 a.

O O S O O 2- Note: A negatively charged ion will have additional electrons to those that come from the valence shell of the atoms. SO42− has 6 + 4(6) + 2 = 32 valence electrons. POCl3 has 5 + 6 + 3(7) = 32 valence electrons. 8 + 4(6) = 32 e− PO43−. . O O Cl O O - Note: All these species have the same number of atoms and the same number of valence electrons. This is a valid Lewis structure.504 52. XeO4. O Cl P Cl Skeletal structure Cl Cl O P Cl Lewis structure Cl BONDING: GENERAL CONCEPTS Note: This structure uses all 32 e− while satisfying the octet rule for all atoms. They also have the same Lewis structure. CHAPTER 13 a. 5 + 4(6) + 3 = 32 e− O 3O O O Xe O O O P O ClO4− has 7 + 4(6) + 1 = 32 valence electrons.

. c. 6 + 3(6) + 2 = 26 e− 2- 505 b. 6 + 2(7) = 20 e− Cl S Cl Lewis structure PCl2−. ClO2− has 7 + 2(6) + 1 = 20 valence electrons. a. 53. O N O O N O 54. The skeletal structure is: O ‒ N ‒ O To get an octet about the nitrogen and only use 18 e− . 7 + 3(6) + 1 = 26 e− PO33−. 5 + 3(6) + 3 = 26 e− 3O P O O Cl O O O Note: Species with the same number of atoms and valence electrons have similar Lewis structures. F N F F F N F F O S O O Skeletal structure Lewis structure ClO3−. O Cl O O Cl O - Skeletal structure SCl2.CHAPTER 13 BONDING: GENERAL CONCEPTS SO32−. NO2− has 5 + 2(6) + 1 = 18 valence electrons. 5 + 2(7) + 1 = 20 e− Cl P Cl - Note: Species with the same number of atoms and valence electrons have similar Lewis structures. NF3 has 5 + 3(7) = 26 valence electrons. we must form a double bond to one of the oxygen atoms. Molecules/ions that have the same number of valence electrons and the same number of atoms will have similar Lewis structures.

We can draw three resonance structures for OCN−. We can draw three resonance structures for NO3−.506 CHAPTER 13 BONDING: GENERAL CONCEPTS Because there is no reason to have the double bond to a particular oxygen atom. Each Lewis structure uses the correct number of electrons and satisfies the octet rules. N N N N N N N N N . OCN− has 6 + 4 + 5 + 1 = 16 valence electrons. with the double bond rotating between the three oxygen atoms.and SCN-. We can draw four resonance structures for N2O4. NO3− has 5 + 3(6) + 1 = 24 valence electrons. As with OCN. S C N S C N S C N N3− has 3(5) + 1 = 16 valence electrons. Resonance structures occur when you have multiple bonds that can be in various positions. we can draw two resonance structures. so each is a valid Lewis structure. Three resonance structures can be drawn. We say the actual structure is an average of these two resonance structures. three different resonance structures can be drawn. O N O N O O O O N N O O O N O N O O O N O N O O b. O N O O O O N O O O N O N2O4 has 2(5) + 4(6) = 34 valence electrons. O C N O C N O C N SCN− has 6 + 4 + 5 + 1 = 16 valence electrons.

Two resonance structures are possible. H H C H O C O O N O O This is the skeletal structure with complete octets about oxygen atoms (46 electrons used). but there are only six electrons around one of the carbon atoms and the nitrogen atom. H H C H H H C H O C O O N O O C O O N O O H H C H O (last form not important) O C O O N O O 57. CH3NCO has 4 + 3(1) + 5 + 4 + 6 = 22 valence electrons. Three resonance structures are possible.e. . O S O O O O S O O O S O 56.. we form two double bonds. PAN (H3C2NO5) has 3(1) + 2(4) + 5 + 5(6) = 46 valence electrons. BONDING: GENERAL CONCEPTS 507 Ozone: O3 has 3(6) = 18 valence electrons. O S O O S O Sulfur trioxide: SO3 has 6 + 3(6) = 24 valence electrons. Two unshared pairs must become shared: i. This structure has used all 46 electrons. The order of the elements in the formula give the skeletal structure. O O O O O O Sulfur dioxide: SO2 has 6 + 2(6) = 18 valence electrons.CHAPTER 13 55. Two resonance structures can be drawn.

Two resonance structures can be drawn for benzene. this helps explain the equivalent bonds within the molecule that experiment tells us we have. We say the electrons in the multiple bond(s) are delocalized in the molecule. then we can draw only three different dichlorobenzenes. . The actual structure of benzene is an average of these two resonance structures. Benzene has 6(4) + 6(1) = 30 valence electrons. A common characteristic of resonance structures is a multiple bond(s) that moves from one position to another.508 CHAPTER 13 BONDING: GENERAL CONCEPTS H H C H N C O H H C H N C O H H C H N C O 58. again. all carbon-carbon bonds are equivalent with a bond length and bond strength somewhere between a single and a double bond. Resonance occurs when more than one valid Lewis structure can be drawn for a particular molecule. i. Any one of the resonance structures indicates different types of bonds within that molecule.e.. we could draw four different molecules: Cl Cl Cl Cl Cl Cl Cl Cl If the double bonds in the benzene ring exhibit resonance. We will use a hexagon to represent the six-membered carbon ring. If no resonance exists. The circle in the hexagon in the following illustrations represent the delocalization of the three double bonds in the benzene ring (see Exercise 13. This helps us rationalize why the bonds in a molecule that exhibit resonance are all equivalent in length and strength. and we will omit the four hydrogen atoms and the three lone pairs of electrons on each chlorine. H H C C H C H C C C H H H H C C C H H C C C H H 59. hence none of the individual resonance structures are correct.59). We think of the actual structure as an average of all the resonance structures. 60. This is not correct.

59. all carbon-carbon bonds are equivalent.CHAPTER 13 BONDING: GENERAL CONCEPTS 509 Cl Cl Cl Cl Cl Cl With resonance. That only three isomers are observed supports the concept of resonance.61). 61. There would be five structures if there were no resonance. . CH3 H N B H N H B N B H H CH3 H N B N H CH3 B N B CH3 H H H3C N B N H H B N B H H CH3 H N B N CH3 CH3 B N B H H There are four different dimethylborazines. Borazine (B3N3H6) has 3(3) + 3(5) + 6(1) = 30 valence electrons. The possible resonance structures are similar to those of benzene in Exercise 13. all the structures drawn above plus an additional one related to the first Lewis structure above (see following illustration). H H N B H N H B N B H H H H N B N H H B N B H H 62. and CH3 is shorthand for three hydrogen atoms singly bonded to a carbon atom. The circles in these structures represent the ability of borazine to form resonance structures (see Exercise 13. We can’t distinguish between a single and double bond between adjacent carbons that have a chlorine attached.

so OF4 does not exist. BH3. NO+ has 10 valence electrons.510 CHAPTER 13 BONDING: GENERAL CONCEPTS CH3 B N CH3 and CH3 B N CH3 63. XeF2 has 22 valence electrons and it is impossible to satisfy the octet rule for all atoms with this number of electrons. The Lewis structures are: N O + N O Because a triple bond is stronger than a double bond. it is an exception to the octet rule. For statement d. whereas NO− has 12 valence electrons. OF4 would also have to be an exception to the octet rule. In real life. NO2. When resonance structures can be drawn. 2(5) + 4(6) = 34 e− N O O O N O N O O Plus others b. Because OF4 has the same number of valence electrons as SF4. 5 + 3(1) = 8 e− N H H H . For statement a. you can think of the bonding as an average of all of the resonance structures. However. NO+ has a stronger bond. Statements a and c are true. Even though each Lewis structure implies the two O−O bonds are different. both of the O−O bonds are equivalent. 3 + 3(1) = 6 e− H B H H Plus other resonance structures NH3. two resonance structures can be drawn for ozone: O O O O O O When resonance structures can be drawn. The best Lewis structure is: F Xe F For statement c. the actual bond lengths and strengths are all equal to each other. 5 + 2(6) = 17 e− N2O4. For statement b. SF4 has five electron pairs around the sulfur in the best Lewis structure. 64. Row 2 elements such as O never have more than 8 electrons around them. this is not the case in real life. a.

By dimerizing to form N2O4. the boron atom satisfies the octet rule by accepting a lone pair of electrons from NH3 to form a fourth bond. 3(7) + 1 = 22 e− F S SF4. 6 + 6(7) = 48 e− ClF5. These empty d orbitals can accept extra electrons. and if it has to. NO2 has an odd number of electrons.CHAPTER 13 BONDING: GENERAL CONCEPTS 511 BH3NH3. 65. For example. P in PF5 has its five valence electrons in the 3s and 3p orbitals. BH3 is electron-deficient. so it is impossible to satisfy the octet rule. In reaction b. giving a species whose Lewis structure can satisfy the octet rule. In general. 6 + 4(7) = 34 e− F F Cl F Row 3 and heavier nonmetals can have more than 8 electrons around them when they have to. Boron has only six electrons around it. These s and p orbitals have room for three more electrons. odd-electron species are very reactive. PF5. 5 +5(7) = 40 valence electrons F F F P F F ClF3. 7 + 3(7) = 28 e− F F Br3−. 66. 7 + 5(7) = 42 e− F Br Br Br F F S F F F F F F Cl F F F . P can use the empty 3d orbitals for any electrons above 8. By forming BH3NH3. the odd electron on two NO2 molecules can pair up. Row 3 and heavier elements have empty d orbitals that are close in energy to valence s and p orbitals. SF6. 6 + 8 = 14 e− H H B N H H H H In reaction a.

That is. then: Longest → shortest C‒O bond: CH3OH > CO32− > CO2 > CO Weakest → strongest C‒O bond: CH3OH < CO32− < CO2 < CO Single bond between C and O . CO32− has 4 + 3(6) + 2 = 24 valence electrons.512 XeF4. CO32 (24 e -): O O C O 2- O C O O 2- O C O O 2- Average of 1 1/3 bond between C and O H CH3OH (14 e -): H C O H H As the number of bonds increases between two atoms. O C Double bond between C and O. the three C‒O bond lengths are all equivalent. The Lewis structures for the various species are below: CO (10 e−): CO2 (16 e−): O C O Triple bond between C and O. bond strength increases and bond length decreases. with a length somewhere between a single and a double bond. With this in mind. The actual bond length of 136 pm is consistent with this resonance view of CO32−. 68. O C O O O 2- O C O 2- O C O O 2- Three resonance structures can be drawn for CO32−. The actual structure for CO32− is an average of these three resonance structures. 8 + 4(7) = 36 e− F Xe F F F CHAPTER 13 BONDING: GENERAL CONCEPTS 67.

1/2(2) = -1 . FC = 5 .2 .1/2(6) = +1 O FC = 6 .6 . From the Lewis structure. FC = 5 .6 .1/2(8) = +1 . Formal Charge 70. The nitrogen-oxygen bond length of 119 pm is between a single (147 pm) and a double bond (115 pm). .1/2(6) = 0 FC = 6 .4 . We can adequately describe the structure of N2O using the resonance forms: N N O N N O Assigning formal charges for all three resonance forms: N -1 N +1 O 0 N 0 N +1 O -1 N -2 N +1 O +1 For: N . Same for N N N O .4 . bond strength increases and bond length decreases. N . FC = 6 .1/2(2) = -2 . Single bond between N and N. . BONDING: GENERAL CONCEPTS 513 N2 (10 e -): N2F4 (38 e -) : N F N N F N F N F F Triple bond between N and N. The nitrogen-nitrogen bond length of 112 pm is between a double (120 pm) and a triple (110 pm) bond.CHAPTER 13 69. FC = 5 .1/2(4) = -1 and N . As the number of bonds increase between two atoms. FC = 5 .2 .1/2(4) = 0 . N2F2 (24 e -): F N Double bond between N and N. O . the shortest to longest N-N bonds is N2 < N2F2 < N2F4. The third resonance structure shown below doesn’t appear to be as important as the other two since there is no evidence from bond lengths for a nitrogen-oxygen triple bond or a nitrogen-nitrogen single bond as in the third resonance form.

FC = 7 − 1/2(8) = +3 e. The best choice is to form a double bond to O since this will give O a formal charge of zero and single bonds to Cl for the same reason. FC = 8 − 1/2(8) = +4 h. FC = 0 b. FC = 5 − 1/2(8) = +1 f. O O S O O 2- S. 8 + 4(6) = 32 e− O Xe O O S.514 CHAPTER 13 BONDING: GENERAL CONCEPTS We should eliminate N‒N≡O since it has a formal charge of +1 on the most electronegative element (O). O Cl P Cl Cl P. Must form six bonds to S to minimize formal charge of S. This is consistent with the observation that the N‒N bond is between a double and triple bond. PO4− . FC = 5 − 1/2(8) = +1 c. a. and that the N‒O bond is between a single and double bond. N. Must have five bonds to P to minimize formal charge of P. and ClO3−. ClO3−. XeO4. PO43−: P. FC = 6 − 1/2(8) = +2 d. SO42−: S. ClO4− and PO43−. POCl3: P. 5 + 4(6) + 3 = 32 e− O O N O O 3- O Cl O O Cl. ClO4−: Cl. FC = 5 − 1/2(8) = +1 For SO42−. SO2Cl2.52a for the Lewis structures of POCl3. FC = 7 − 2 − 1/2(6) = +2 72. See Exercise 13. All of these compounds/ions have similar Lewis structures to those of SO2Cl2 and XeO4 shown below. ClO4−. 7 + 3(6) + 1 = 26 e− Xe. only one of the possible resonance structures is drawn. SO42−. 6 + 2(6) + 2(7) = 32 e− O Cl S O Cl O b. NO43−. FC = 0 . a. 71. FC = 6 − 1/2(8) = +2 g.

We can’t . only S2Cl2 can have a Lewis structure with a formal charge of zero on all atoms. Cl will need one bond and three lone pairs for a formal charge of zero [FC = 7 – 6 – 1/2(2) = 0]. Must form five bonds to P to to minimize formal charge. O 3- 515 c. S3Cl3 (39 valence electrons). we will need each sulfur in the Lewis structure to have two bonds to it and two lone pairs [FC = 6 – 4 – 1/2(4) = 0]. FC = 0 h. O Cl O O Cl. We wouldn’t expect this resonance form to exist. 73. Must form seven bonds to Cl to minimize formal charge. FC = 0 g. FC = 0 e. etc. O O Cl O O Cl. FC = 0 O P O O P. O Formal charge C N O C N O C N 0 0 -1 -1 0 0 +1 0 -2 . Since chlorine wants only one bond to it. The structure is: Cl S S Cl 74. it will not be a central atom here. FC = 0 f. For a formal charge of zero on S.CHAPTER 13 BONDING: GENERAL CONCEPTS d. O O Xe O O Xe. OCN− has 6 + 4 + 5 + 1 = 16 valence electrons. the formula could be SCl (13 valence electrons). With this in mind. SCl. The following structure has a zero formal charge for N: O O N O O 3- but N does not expand its octet. 6 + 7 = 13. O Cl S O Cl S. S2Cl2 (26 valence electrons).

All are V-shaped.5° b. <109.54 a. ≈ 120°. 180° c.5° c. 120° about both N atoms b. The Lewis structures are in Exercises 13.5° e.5° 13. NO2−: V-shaped. Note: PH3 and SeF2 both have lone pairs of electrons on the central atom.5° h and i.5° d. CO2: linear. <109.52 and 13. CHCl3: tetrahedral. .51 a. making fulminate more reactive (less stable). we cannot predict the exact number. 120° N2O4: trigonal planar. only one of the possible resonance structures is necessary to predict the correct structure because all resonance structures give the same structure. Molecular Structure and Polarity 75.52 a. H2CO: trigonal planar. but there is no bond angle in either. <109. O2 and HBr are both linear. When resonance is possible. All are trigonal pyramid. and N3− are all linear with 180° bond angles. 13. However. which result in bond angles that are something less than predicted from a tetrahedral arrangement (109. <109. 109. 120° g. 180° b. 13. SCN−. 109. NH4+: tetrahedral. The third places a positive formal charge on the most electronegative atom in the ion and a -2 formal charge on N. For these cases we will just insert a less than sign to indicate this phenomenon. NO3−: trigonal planar. OCN−.51.54. SeF2: V-shaped or bent.5°). 13. CNO−: C Formal charge N O C N O C N O -2 +1 0 -1 +1 -1 -3 +1 +1 All the resonance structures for fulminate (CNO−) involve greater formal charges than in cyanate (OCN−).5° f. 109. PH3: trigonal pyramid. The structures and bond angles for each follow.516 CHAPTER 13 BONDING: GENERAL CONCEPTS Only the first two resonance structures should be important. All are tetrahedral. HCN: linear. The first step always is to draw a valid Lewis structure when predicting molecular structure.

5°. All the structures are based on a trigonal planar geometry. F F Si F F V-shaped. SiF4 has 4 + 4(7) = 32 valence electrons. BONDING: GENERAL CONCEPTS 517 a. b. all angles are 109. P Cl d. but only SeO3 is described as having a trigonal planar structure. SCl2 has 6 + 2(7) = 20 valence electrons Cl Cl Cl S Cl Trigonal pyramid. but only SiF4 has a tetrahedral structure. all angles are <109. e. 6 + 3(6) = 24 e− 120o O O Se 120o 120o O O O Se O O O Se O SeO3 has a trigonal planar molecular structure with all bond angles equal to 120°. Note: In PCl3. We consider only the relative positions of the atoms when describing the molecular structure. SeO3.CHAPTER 13 76. 6 + 2(6) = 18 e− Se O O o ≈ 120 O Se O SeO2 has a V-shaped molecular structure. PCl3 has 5 + 3(7) = 26 valence electrons. SeO2. . Molecular structure always describes the relative positions of the atoms. c. Note: Both SeO3 and SeO2 structures have three effective pairs of electrons about the central atom. We would expect the bond angle to be approximately 120° as expected for trigonal planar geometry. Note that any one of the resonance structures could be used to predict molecular structure and bond angles.5°. and SiF4. SCl2. there are four pairs of electrons about the central atom in each case.5°. All the structures are based on a tetrahedral geometry. Tetrahedral. angle is <109.

consider ClF3 (28 valence electrons): F Cl F F The central Cl atom is surrounded by five electron pairs. F Te F d. Cl ≈ 90 o Cl ≈ 90 o I Cl T-shaped. For example. Br3− would have a linear molecular structure. TeF4 has 6 + 4(7) = 34 valence electrons. 90 o 120 o ≈ 120 o F F ≈ 90 o Cl Cl Cl P Cl Cl See-saw or teeter-totter or distorted tetrahedron Trigonal bipyramid . Since there are three bonded atoms and two lone pairs of electrons about Cl.66). which requires a trigonal bipyramid geometry. The ClICl angles are ≈ 90°. Since the lone pairs will take up more space. From the Lewis structures (see Exercise 13.518 77. PCl5 has 5 + 5(7) = 40 valence electrons. 79. b. The actual bond angles will be slightly less than 90° due to the stronger repulsive effect of the lone pair electrons as compared to the bonding electrons. ICl3 has 7 + 3(7) = 28 valence electrons. Cl Xe 180o Cl There are five pairs of electrons about the central Xe atom. XeF4 would have a square planar molecular structure and ClF5 would have a square pyramid molecular structure. The structure will be based on a trigonal bipyramid geometry. XeCl2 has 8 + 2(7) = 22 valence electrons.65). 78. The most stable arrangement of the atoms in XeCl2 is a linear molecular structure with a 180° bond angle. ClF3 would have a T-shaped molecular structure. a. we describe the molecular structure of ClF3 as T-shaped with predicted bond angles of about 90°. and SF4 would have a see-saw molecular structure. the ClICl bond angles will probably be slightly less than 90°. CHAPTER 13 BONDING: GENERAL CONCEPTS From the Lewis structures (see Exercise 13. c.

Se O O . 90° bond angles Note: All these species have six pairs of electrons around the central atom. All three structures are based on the octahedron. these molecules are SeO3 and SeO2. Cl Cl Cl Se Cl Cl Cl Square planar. 81. a. but only SeO2 has an overall net dipole moment. Since O is more electronegative than Se. the two Se‒O bond dipoles do not cancel when summed together. Let us consider the molecules with three pairs of electrons around the central atom first. but only SeCl6 has an octahedral molecular structure. Thus PCl5 is the only one we describe the molecular structure as trigonal bipyramid. Hence SeO3 is nonpolar since the overall molecule has no resulting dipole moment. 7 + 5(7) = 42 e≈ 90o Cl Cl Cl b. and the positive end is around the Se atom. but only in PCl5 are all the pairs bonding pairs. All the structures are based on a trigonal bipyramid geometry.CHAPTER 13 BONDING: GENERAL CONCEPTS 519 All the species in this exercise have five pairs of electrons around the central atom. either of the two resonance structures can be used. ≈ 90° bond angles c. the negative end of the dipole moment is between the two O atoms. Note that to predict polarity for SeO2. 80. SeCl6 has 6 + 6(7) = 48 valence electrons. In SeO2. we had to begin with the trigonal bipyramid geometry to get to the structures (and bond angles) of the others. and both have a trigonal planar arrangement of electron pairs. ICl5 . Still. The net effect of the three bond dipoles from the three polar Se‒O bonds in SeO3 will be to cancel each other out when summed together. hence SeO2 has a net dipole moment (is polar). 90° bond angles Octahedral. XeCl4 . Both these molecules have polar bonds. 8 + 4(7) = 36 e- 90o Cl Cl 90o I 90o Cl Cl Xe Cl Cl 90o Square pyramid. The arrow in the following illustration represents the overall dipole moment in SeO2.

The same is true for XeCl4: Cl Xe Cl Cl Cl When the four bond dipoles are added together. and in PCl3 and SCl2 the individual bond dipoles do not cancel. SCl2. Polar bonds 2. All have polar bonds. For SCl2. and PCl5) all have a trigonal bipyramid arrangement of electron pairs. The molecules in Exercise 13. so each has an overall net dipole moment. the negative end is between the more electronegative Cl atoms. and SeCl6) all have an octahedral arrangement of electron pairs. ICl3. they cancel each other.520 CHAPTER 13 BONDING: GENERAL CONCEPTS The other molecules in Exercise 13. 83. they all cancel each other and XeCl4 has no overall dipole moment. the negative end of the dipole moment is between the more electronegative chlorine atoms. hence ICl5 has a dipole moment. and XeCl2 has no dipole moment (is nonpolar).76 (PCl3. and SiF4) have a tetrahedral arrangement of electron pairs. so SeCl6 has no dipole moment. For TeF4 and ICl3. For PCl3. so PCl5 has no dipole moment. XeCl4. The molecules in Exercise 13. The bond dipoles from the five P‒Cl bonds in PCl5 cancel each other when summed together. 82. Therefore. The two general requirements for a polar molecule are: 1. but only ICl5 has an overall dipole moment. SiF4 has no net dipole moment (is nonpolar). TeF4. and PCl3 and SCl2 have net dipole moments (are polar). A structure such that the bond dipoles of the polar bonds do not cancel . All of these molecules have polar bonds. The six bond dipoles in SeCl6 all cancel each other. but only TeF4 and ICl3 have dipole moments. the arrangement of these molecules is such that the individual bond dipoles do not all cancel. and the positive end of the dipole moment is around S. in SiF4 the individual bond dipoles cancel when summed together.79 (XeCl2. ICl5 has a structure in which the individual bond dipoles do not all cancel. The bond dipoles in XeCl2 also cancel: Cl X e Cl Since the bond dipoles from the two Xe‒Cl bonds are equal in magnitude but point in opposite directions. All of these molecules have polar bonds.80 (ICl5. and the positive end is around P.

≈120E ≈90E The arrows indicate the individual bond dipoles in the three molecules (the arrows point to the more electronegative atom in the bond. the 4 Xe−F bond dipoles are also symmetrically arranged. 90E ≈90E F F ≈120E F S F See-saw. we sum the effect of all of the individual bond dipoles. 8 + 4(7) = 36 e− F F 521 CF4. To determine the polarity of the overall molecule. CO2 is nonpolar because the individual bond dipoles cancel each other out. and XeF4 is also nonpolar. but COS is polar. 4 + 4(7) = 32 valence electrons F C F F F Xe F F Tetrahedral. we also have four polar bonds. the molecule is not symmetric any more. In XeF4. 6 + 4(7) = 34 e− Square planar. The individual bond dipoles cancel out when summed together. All three of these molecules have polar bonds. CO2.5E SF4. In CF4. 4 + 6 + 6 = 16 e− O C O S C O CO2 and COS both have linear molecular structures with a 180° bond angle. . SF4 is polar. 109. which will be the partial negative end of the bond dipole). 4 + 2(6) = 16 e− COS. ≈90E.CHAPTER 13 BONDING: GENERAL CONCEPTS XeF4. But in SF4 the bond dipoles are not symmetrically arranged. By replacing an O with a less electronegative S atom. In SF4. and they do not cancel each other out. It is the positioning of the lone pair that disrupts the symmetry in SF4. The individual bond dipoles do not cancel because the C−S bond dipole is smaller than the C−O bond dipole resulting in a polar molecule. giving a nonpolar molecule. The net result is for all the individual C−F bond dipoles to cancel each other out. the fluorines are symmetrically arranged about the central carbon atom.

The EO3− ion has a trigonal pyramid molecular structure with bond angles of less than 109. a.522 84. the bond angle between the Cl atoms on the diagonal in XeCl4 are 180E apart from each other. XeCl4 and XeCl2 in the preceding problem.5°. b.. Although we haven’t emphasized this. With three lone pairs. XeCl2 has a linear molecular structure with a 180E bond angle. SO2 has a Vshaped molecular structure with a bond angle of about 120E. 87. For statement a. not maximize them. whereas KrF4 has a square planar molecular structure).5E bond angle. For statement d. x = 6 valence electrons for element E 86. . Some possible identities are F. 26 = x + 3(6) + 1. 8 + 2(7) = 22 e− Xe Cl Cl Cl Xe Cl Square planar. In SeF4 the bond dipoles in this see-saw molecule do not cancel each other out. However. and the Lewis structure has 28 valence electrons. In addition. A lone pair on a central atom does not guarantee a polar molecule. so SeF4 is polar.g. 85. 8 + 4(7) = 36 e− Cl Cl CHAPTER 13 BONDING: GENERAL CONCEPTS XeCl2. we no longer have a 120E bond angle in XeCl2. CS2 is linear with a 180E bond angle and SCl2 is V-shaped but with an approximate 109. Note that there are molecules that have lone pairs and are nonpolar. 28 = x + 2(7) + 6 + 2. The formula is EF2O2−. x = 7 valence electrons Element E is a halogen because halogens have seven valence electrons. Let x = number of valence electrons of element E. central atoms adopt a geometry to minimize electron repulsions. e. 180E. nonpolar Both compounds have a central Xe atom and terminal Cl atoms. For statement b. The Lewis structure has 26 valence electrons. The three compounds do not have the same bond angle. The reason the bond dipoles are not symmetrically arranged in these compounds is that they all have at least one lone pair of electrons on the central atom. The bond dipoles do not cancel out each other when summed together. but all are polar covalent compounds. and both compounds do not satisfy the octet rule. Only statement c is true. both are nonpolar because the Xe−Cl bond dipoles and lone pairs around Xe are arranged in such a manner that they cancel each other out. Br. nonpolar Linear. making them nonpolar molecules (CF4 has a tetrahedral molecular structure. XeCl4. 90E. XeCl2 has three lone pairs and two bonded chlorine atoms around it. all the molecules have either a trigonal planar geometry or a trigonal bipyramid geometry. and I. EO3− is the formula of the ion. We didn’t draw the Lewis structures. both of which have 120E bond angles. The last item in common is that both have 180E bond angles. Cl. which disrupts the symmetry. The bond dipoles in CF4 and KrF4 are arranged in a manner that they all cancel each other out.

88. Note: All four species contain three atoms. 6 + 2(6) = 18 e− S H Be H O O Linear. These lone pair electrons require more room than the bonding electrons. The molecule is nonpolar because the two Kr‒F bond dipoles cancel each other. They cancel each other. and the bond angle is compressed more than in NH3 where N has only one lone pair. Some possible identities for E are S. and molecules that do not have an overall dipole moment are called nonpolar molecules. Only one resonance structure is shown. nonpolar. polar. BeH2. V-shaped.CHAPTER 13 BONDING: GENERAL CONCEPTS 523 Element E must belong to the Group 6A elements since E has six valence electrons. OCl2. The S‒O bond dipoles do not cancel. SO2. The bond angle for H2O is the smallest because oxygen has two lone pairs on the central atom. polar. E must also be a Row 3 or heavier element since this ion has more than eight electrons around the central E atom (Row 2 elements never have more than eight electrons around them). Molecules that have an overall dipole moment are called polar molecules. They have different structures because the number of lone pairs of electrons around the central atom are different in each case. which tends to compress the angles between the bonding pairs. nonpolar. . KrF2. BeH2 is nonpolar. H2O and NH3 have lone pair electrons on the central atoms.77) with bond angles of ≈90°. Se and Te. so SO2 is polar (has a net dipole moment). 2 + 2(1) = 4 e− Linear. The resulting dipole moment is shown in the drawing. Be‒H bond dipoles are equal and point in opposite directions. a. 6 + 2(7) = 20 e− O Cl Cl Cl O Cl 89. OCl2 is polar because the two O−Cl bond dipoles don’t cancel each other. The ion has a T-shaped molecular structure (see Exercise 13. 8 + 2(7) = 22 e− F Kr F V-shaped.

I F F T-shaped. Note: Each molecule has the same number of atoms but different structures because of differing numbers of lone pairs around each central atom. 4 + 4(7) = 32 e− F C F F F SeF4. bond dipoles cancel. bond dipoles do not cancel. polar. F Trigonal pyramid. Kr Square planar. SO3. bond dipoles cancel. polar. Note: Again.524 b. bond dipoles cancel. 6 + 4(7) = 34 e− F F F Se F Tetrahedral. nonpolar. 6 + 3(6) = 24 e− O S O O CHAPTER 13 BONDING: GENERAL CONCEPTS NF3. KrF4. IF3 has 7 + 3(7) = 28 valence electrons. polar. bond dipoles do not cancel. c. 5 + 3(7) = 26 eN F F F Trigonal planar. Only one resonance structure is shown. nonpolar. . bond dipoles do not cancel. each molecule has the same number of atoms but different structures because of differing numbers of lone pairs around the central atom. nonpolar. 8 + 4(7) = 36 valence electrons F F F F See-saw. CF4.

The overall dipole will point from C (positive end) to the midpoint of the two Cl atoms (negative end). C Cl Cl . The three C‒Cl bond dipoles in CHCl3 add together to give an overall dipole moment for the molecule. Let’s consider just the C and two of the Cl atoms. δ+ δ! C‒Cl is the charge distribution for each C‒Cl bond. H C H Cl Cl The C‒H bonds are assumed nonpolar since the electronegativities of C and H are about equal. 90. CCl4 is a tetrahedral molecule where all four C‒Cl bond dipoles cancel when added together. bond dipoles cancel. a. 7 + 5(7) = 42 e− F F F I F F Square pyramid. polar. In CHCl3 the C‒H bond is essentially nonpolar. Trigonal bipyramid. There will be a net dipole pointing in the direction of the middle of the two Cl atoms. nonpolar. The overall dipole will have the negative end at the midpoint of the three chlorines and the positive end around the carbon. bond dipoles do not cancel. Note: Yet again. the two individual C‒Cl bond dipoles add together to give an overall dipole moment for the molecule.CHAPTER 13 BONDING: GENERAL CONCEPTS AsF5. the molecules have the same number of atoms but different structures because of the presence of differing numbers of lone pairs. 5 + 5(7) = 40 e− F F F As F F 525 d. In CH2Cl2. IF5. H C Cl Cl Cl CCl4 is nonpolar.

In each molecule the individual bond dipoles cancel to give no net overall dipole moment. b. . and its valence shell contains only 2s and 2p orbitals (four orbitals) and cannot expand its octet. CO2 is a linear molecule with two equivalence bond dipoles that cancel. i.526 CHAPTER 13 BONDING: GENERAL CONCEPTS There will be an equal and opposite dipole arising from the other two Cl atoms. The general structure of the trihalide ions is: X X X Bromine and iodine are large enough and have low-energy. However. NH3 is polar. CO2 is nonpolar. the presence of the lone pair makes the PH3 molecule slightly polar. The net dipole is in the direction of the lone pair and has a magnitude about one third that of the NH3 dipole. Additional Exercises 92. which is also a linear molecule. δ! δ+ H N H H H P H H N‒H 91. is polar because the nonequivalent bond dipoles do not cancel. Fluorine is small. The lowest-energy d orbitals in F are 3d. they are too high in energy compared with 2s and 2p to be used in bonding. All these molecules are nonpolar even though they all contain polar bonds. Combining: Cl C Cl Cl Cl The two dipoles cancel. P‒H bonds are nonpolar. empty d orbitals to accommodate the expanded octet. The 3 N‒H bond dipoles add together to give a net dipole in the direction of the lone pair. δ+ N δ− O N c. N2O. All these molecules have polar bonds that are symmetrically arranged about the central atoms.. We would predict PH3 to be nonpolar on the basis of electronegativitity. and CCl4 is nonpolar.e.

O C O H O H The Lewis structures for the reactants and products are: O C O H O H H O H + O C O Bonds broken: 2 C‒O (358 kJ/mol) 1 O‒H (467 kJ/mol) Bonds formed: 1 C=O (799 kJ/mol) 1 O‒H (467 kJ/mol) ΔH = 2(358) + 467 ! (799 + 467) = !83 kJ. BONDING: GENERAL CONCEPTS 527 CO32− has 4 + 3(6) + 2 = 24 valence electrons. - H O O C O H O O C O H2CO3 has 2(1) + 4 + 3(6) = 24 valence electrons. TeF5− has 6 + 5(7) + 1 = 42 valence electrons.CHAPTER 13 93. 222- O C O O O C O O O C O O HCO3− has 1 + 4 + 3(6) + 1 = 24 valence electrons. 94. F F F Te F F - . hence CO2 and H2O are more stable than H2CO3. the carbon-oxygen double bond is stronger than two carbon-oxygen single bonds.

These are different compounds and not resonance structures. Here. makes the compound a better acid. the bond dipoles are symmetrically arranged. so this molecule is polar. In the second possible structure the F atoms are 180° apart. so they do cancel out each other. b. In the first structure the F atoms are 90° apart from each other. Therefore. 98. If we can draw resonance forms for the anion after loss of H+. measurement of the dipole moment would differentiate between the two compounds. d.528 CHAPTER 13 BONDING: GENERAL CONCEPTS The lone pair of electrons around Te exerts a stronger repulsion than the bonding pairs. and the NX3 molecule becomes less stable. O is too small and doesn’t have low-energy d orbitals to expand its octet (which is true for all Row 2 elements).. SeF4: Both compounds require the central atom to expand its octet. 96. it becomes more difficult to fit three halogen atoms around the small nitrogen atom. the sodium ion would have a 2+ charge. as are the Cl atoms. ClO4−: ClO4 has 31 valence electrons. XeO4: We can’t draw a Lewis structure that obeys the octet rule for SO4 (30 electrons). The stable species are: a. c. pushing the four square-planar F's away from the lone pair and thus reducing the bond angles between the axial F atom and the square-planar F atoms. 95. NaBr: In NaBr2. we can argue that the extra stability of the anion causes the proton to be more readily lost. The extra electron from the 1− charge in ClO4− allows for complete octets for all atoms. XeF2Cl2. . assuming that each bromine has a 1− charge. 8 + 2(7) + 2(7) = 36 e− Cl Xe Cl Polar F F F Cl Xe Cl Nonpolar F The two possible structures for XeF2Cl2 are above. As the halogen atoms get larger. i. and the Cl atoms are also 90° apart. Sodium doesn’t form stable Na2+ compounds. unlike with XeO4 (32 electrons). 97. so it is impossible to satisfy the octet rule for all atoms in ClO4. and this molecule is nonpolar. The individual bond dipoles would not cancel in this molecule.e.

will be smaller than Cl and have a larger IE. c. b.CHAPTER 13 a. The seven protons in the nucleus will hold the electrons most tightly in N+ and least tightly in N−. with more electron-electron repulsions than Se. Radius: Cl+ < Cl < Se < Se−. extra resonance forms can be drawn for the anion that are not possible when the H+ is present. O O O O O In all three cases. Radius: Sr2+ < Rb+ < Br−. IE: Se− < Se < Cl < Cl+ The general trends tell us that Cl has a smaller radius than Se and a larger IE than Se. BONDING: GENERAL CONCEPTS 529 O H C O H O C O - b. N+ has the smallest radius with the largest ionization energy (IE). Cl+. IE: Br. and N− is the largest species with the smallest IE. will be larger than Se and have a smaller IE.< Rb+ < Sr2+ . which leads to enhanced stability. 99. O CH 3 C CH O C CH 3 CH 3 O C CH O C CH 3 c. Therefore. a. IE: N− < N < N+ N+ has the fewest electrons held by the seven protons in the nucleus whereas N− has the most electrons held by the seven protons. Radius: N+ < N < N−. with fewer electron-electron repulsions than Cl. Se−.

00 g of compound: 42. 103.81 g). have valence electrons in the s and p orbitals. which form covalent bonds to each other. 100.00 g – 42. This orbital can hold two electrons. 101.253 mol F × 1 mol X = 0. so hydrogen follows the duet rule. The ion with the fewest protons (Br−) will hold the electrons least tightly and will have the largest radius and smallest IE. This is probably not a great estimate for this reaction because this is not a gas-phase reaction. Nonmetals. O H C N H C H H C H H H C H H H O C N H C H H H 102. Assuming 100.253 mol F 19. where bond energies work best.4506 mol X 5 mol F This number of moles of X has a mass of 57.81 g F × 1 mol F = 2. O O CH3CH2O * H + HO * CCH3 CH3CH2O * CCH3 + H * OH Bonds broken (*): O−H C−O Bonds formed (*) O−H C−O We make the same bonds that we have to break in order to convert reactants into products. Double bonds to the other two C–N bonds would require carbon in each case to have 10 valence electrons (which carbon never does). there is room for only eight valence electrons (the octet rule). This molecule has 30 valence electrons. The valence shell for hydrogen is just the 1s orbital. Since there are four total s and p orbitals. we would predict ΔH = 0 for this reaction using bond energies. Therefore. The species with the most protons (Sr2+) will hold the electrons most tightly and will have the smallest radius and largest IE.19 g (= 100. The only C–N bond that can possibly have a double bond character is the N bound to the C with O attached. The molar mass of X is: .530 CHAPTER 13 BONDING: GENERAL CONCEPTS These ions are isoelectronic.00 g F The number of moles of X in XF5 is: 2.

CHAPTER 13 BONDING: GENERAL CONCEPTS 531 57. two possible structures exist. BrFI2. each C atom must satisfy the octet rule by forming four bonds (with no lone pairs).5° bond angles about the nitrogen atom labeled 2. each has a T-shaped molecular structure. For nitrogen atoms to have a formal charge of zero. 105. Yes. 7 + 5(7) = 42 e− F F F I F F The molecular structure is square pyramid. each N atom must satisfy the octet rule by forming three bonds and have one lone pair of electrons. With these bonding requirements in mind. each O atom must satisfy the octet rule by forming two bonds and have two lone pairs of electrons.9 g/mol. is: H C C 2 H H N H C C H N C H N H H C O O 1 H We would expect 120° bond angles about the carbon atom labeled 1 and ~109. (A multiple bond is counted as a single group of electrons. where all atoms have a formal charge of zero. F Br I I I Br I F 106. 90° bond angles between I atoms 180° bond angle between I atoms .4506 mol X IF5. The nitrogen bond angles should be slightly smaller than 109. each structure has the same number of effective pairs around the central atom.5° due to the lone pair of electrons on nitrogen. then the Lewis structure of histidine. 0.19 g X = 126. giving the same predicted molecular structure for each compound/ion.) a. This is element I. For carbon atoms to have a formal charge of zero. For oxygen atoms to have a formal charge of zero. 7 + 7 + 2(7) = 28 e−. 104.

532 CHAPTER 13 BONDING: GENERAL CONCEPTS b. F Kr F Hyperconjugation assumes that the overall bonding in KrF2 is a combination of covalent and ionic contributions (see Section 13. we have a trigonal bipyramid arrangement of electron pairs with a linear molecular structure. three possible structures exist. 8 + 2(7) = 22 e-. O Xe F F O F F O Xe O O O F Xe F 90° bond angle between O atoms c. from the Lewis structure. each has a square pyramid molecular structure. each has a see-saw molecular structure. 8 + 2(6) + 2(7) = 34 e−. Both F atoms are 90° from the lone pair and 90° from each other. XeO2F2. F Te Cl F Cl Cl Cl Cl Cl Te F F F Cl Cl Te Cl F One F is 180° from the lone pair. two resonance structures are possible that keep the linear structure.12 of the text for discussion of hyperconjugation). 180° bond angle between O atoms 120° bond angle between O atoms TeF2Cl3−. Challenge Problems 107. F Kr + F F - + Kr F - . three possible structures exist. Using hyperconjugation. KrF2. Both F atoms are 90° from the lone pair and 180° from each other. 6 + 2(7) + 3(7) + 1 = 42 e−.

BONDING: GENERAL CONCEPTS 533 The skeletal structure of caffeine is: H O H C H N C O H N C H H H C C C C N H H C N H For a formal charge of zero on all atoms. the bonding requirements are: a. d. b. c. Four bonds and no lone pairs for each carbon atom Three bonds and one lone pair for each nitrogen atom Two bonds and two lone pairs for each oxygen atom One bond and no lone pairs for each hydrogen atom Following these guidelines gives a Lewis structure that has a formal charge of zero for all the atoms in the molecule. The Lewis structure is: H O H C H N C O H N C H H H C C C C N H H C N H .CHAPTER 13 108.

Note that the lattice energy is large enough to overcome all of the other processes (removing two electrons from Mg. The most likely structures are: 111. ionizing carbon to form a C2+ ion must be too large. See Figure 13. etc.). a. N O N O N O O O N O N N O O N O N O N O O O N O N N O O There are other possible resonance structures. If all other numbers were equal.35 to see that the first ionization energy for carbon is about 400 kJ/mol greater than the first IE for magnesium. the overall energy change would be down to ~200 kJ/mol (see Figure 13. b. but these are most likely. The bond energy for O2 (247 kJ/mol) and electron affinity (737 kJ/mol) are the same when making CO. See Figure 12.534 109. .11). The NNN and all ONN and ONO bond angles should be about 120°. kJ) ΔH = 2(166 kJ) ΔH = 2(427 kJ) ΔH = 2(!349 kJ) ΔH = !(432 kJ) ΔH = !562 kJ 2 Li(s) + 2 HCl(g) → 2 LiCl(s) + H2(g) 110. However.11 to see the data supporting MgO as an ionic compound. N(NO2)2− contains 5 + 2(5) + 4(6) + 1 = 40 valence electrons. It is not unreasonable that the second ionization energy for carbon is more than 200 kJ/mol greater than the second ionization energy of magnesium. CHAPTER 13 2 Li+(g) + 2 Cl−(g) → 2 LiCl(s) 2 Li(g) → 2 Li+(g) + 2 e− 2 Li(s) → 2 Li(g) 2 HCl(g) → 2 H(g) + 2 Cl(g) 2 Cl(g) + 2 e− → 2 Cl−(g) 2 H(g) → H2(g) BONDING: GENERAL CONCEPTS ____________________________________________________________________________ ΔH = 2(!829 kJ) ΔH = 2(520.

d. C6H6N12O12 → 6 CO + 6 N2 + 3 H2O + 3/2 O2 The NO2 groups have one N‒O single bond and one N=O double bond. 113. i. and the compounds do not form. 112. This is especially true due to the fact that we must also vaporize the metal and often break a bond on a diatomic gas. kJ/mol) 1 N=N (418 kJ/mol) 3 N‒O (201 kJ/mol) 1 N=O (607 kJ/mol) ___________________________ Bonds formed: 2 N≡N (941 kJ/mol) 4 H‒O (467 kJ/mol) 1 O=O (495 kJ/mol) ___________________________ ΣDformed = 4245 kJ ΣDbroken = 3352 kJ ΔH = ΣDbroken − ΣDformed = 3352 kJ − 4245 kJ = −893 kJ d.bonds in any one of the resonance structures above. Often the sign of the sum of the first two processes is positive (or unfavorable). The same argument can be made for MgO compared to MgO2 or Mg2O. and each carbon atom has one C‒H single bond. negative (ΔH < 0) b. To estimate ΔH. All these assumptions give an estimated ΔH value which is too negative. we completely ignored the ionic interactions between NH4+ and N(NO2)2−. This is a bad assumption since molecules that exhibit resonance generally have stronger overall bonds than predicted. While Na2Cl (or NaCl2) would have a greater lattice energy than NaCl. . The energy to make the ions is too unfavorable or the lattice energy is not favorable enough. Bonds broken: 4 N‒H (391 kJ/mol) 1 N‒N (160. break and form all bonds. often negative (ΔH < 0) (3) Allowing the metal cation and nonmetal anion to come together: LE. negative quantity. we assumed the bond energies in Table 13.6 applied to the N(NO2).CHAPTER 13 BONDING: GENERAL CONCEPTS 535 c. (1) Removing an electron from the metal: IE. For example. e. the change is +167 kJ/mol (unfavorable). positive (ΔH > 0) (2) Adding an electron to the nonmetal: EA. the sum must be negative (exothermic). NH4N(NO2)2 → 2 N2 + 2 H2O + O2. the lattice energy must be a large. and the electron affinity for F is −328 kJ/mol. the ionization energy for Na is +495 kJ/mol. a. a. i. Overall.e. For an ionic compound to form.. c. The lattice energy must be favorable enough to overcome the endothermic process of forming the ions. the energy to make a Cl2− ion (or Na2+ ion) must be larger (more unfavorable) than what would be gained by the larger lattice energy. We must break and form all bonds. In addition.

458 kJ ΔH = 12. the Ka value increases to 4 × 10−8 for HOCl. Reaction iii yields the most energy per mole of CL-20.23 g kg 114.623 kJ = −2636 kJ ii. so it will yield the most energy per kilogram. thereby weakening and polarizing the bond. For acids containing the H−O−X grouping.987 kJ ΔH = ΣDbroken − ΣDformed = 12. C6H6N12O12 → 6 CO2 + 6 N2 + 3 H2 Bonds formed: 12 C=O (799 kJ/mol) 6 N≡N (941 kJ/mol) 3 H‒H (432 kJ/mol) _________________ ΣDformed = 16. Bonds formed: 3 C≡O (1072 kJ/mol) 6 C=O (799 kJ/mol) 6 N≡N (941 kJ/mol) 6 H‒O (467 kJ/mol) ___________________________ ΣDformed = 16.623 kJ ΣDbroken = 12. it becomes more effective at withdrawing electron density from the O−H bond.987 kJ − 15. kJ ΔH = 12. Consider HOBr with Ka = 2 × 10−11. This increases the tendency for the molecule to produce a proton. 1 mol 1000 g − 3543 kJ × × = −8085 kJ/kg mol 438.530.987 kJ − 16. and so its acid strength increases.530. . When Br is replaced by the more electronegative Cl.458 kJ = −3471 kJ iii. kJ/mol) 6 N‒O (201 kJ/mol) 6 N=O (607 kJ/mol) ____________________________ ΣDformed = 15. C6H6N12O12 → 3 CO + 3 CO2 + 6 N2 + 3 H2O Note: The bonds broken will be the same for all three reactions. as the electronnegativity of X increases.987 kJ − 16. kJ = −3543 kJ b.536 Bonds broken: CHAPTER 13 BONDING: GENERAL CONCEPTS Bonds formed: 6 C≡O (1072 kJ/mol) 6 N≡N (941 kJ/mol) 6 H‒O (467 kJ/mol) 3/2 O=O (495 kJ/mol) ______________________________ 3 C‒C (347 kJ/mol) 6 C‒H (413 kJ/mol) 12 C‒N (305 kJ/mol) 6 N‒N (160.

If X has a relatively high electronegativity. kJ ΔH = 480. + 1/2 (250. 115. When the compound containing the H−O−X grouping is dissolved in water. kJ __________________________________________________________________________ ΔH o = 1410 kJ f For MX composed of M+ and X−. It will be the polar and relatively weak H−O bond that will tend to break. + 480. composed of either M+ and X− ions or M2+ and X2− ions.) + 2(480.6) (Table 13. kJ ΔH = −4800. releasing a proton. On the other hand. = −660. the O−X bond will be covalent and strong. M(s) + 1/2 X2(g) → MX(s): ΔH o = 110. the O−X bond will remain intact. ΔH = 1/2 (62 kJ) ΔH = 1/2 (149 kJ) ΔH = 1/2 (239 kJ) ΔH = −208 kJ ΔH o = ? f (Appendix 4) (Table 13. M2X composed of M+ and X2− ions. The reaction is: 1/2 I2(s) + 1/2 Cl2(g) → ICl(g) Using Hess’s law: 1/2 I2(s) → 1/2 I2(g) 1/2 I2(g) → I (g) 1/2 Cl2(g) → Cl(g) I(g) + Cl(g) → ICl(g) 1/2 I2(s) + 1/2 Cl2(g) → ICl(g) 116. For MX composed of M2+ and X2−: M(s) → M(g) M(g) → M+(g) + e− M+(g) → M2+(g) + e− 1/2 X2(g) → X(g) X(g) + e− → X−(g) X−(g) + e− → X2−(g) M2+(g) + X2−(g) → MX(s) M(s) + 1/2 X2(g) → MX(s) ΔH = 110. kJ f For M2X composed of M+ and X2− . = –1550. the f enthalpy of formation. The compound with the most negative enthalpy of formation will be the ionic compound most likely to form.6) _______________________________________________________________________________________________ ΔH = 17 kJ so ΔH o = 17 kJ/mol f There are four possible ionic compounds we need to consider. or MX2 composed of M2+ and X− ions. kJ f .) + 1/2 (250. the O−X bond will be ionic and subject to being broken in polar water. if X has a very low electronegativity.6) (Table 13. let’s calculate ΔH o . kJ ΔH = 4750.) – 175 – 1200. kJ) ΔH = −175 kJ ΔH = 920.CHAPTER 13 BONDING: GENERAL CONCEPTS 537 What determines whether X−O−H type molecules are acids or bases in water lies mainly in the nature of the O−X bond. kJ ΔH = 1/2 (250. For each possible ionic compound. 2 M(s) + 1/2 X2(g) → M2X(s): ΔH o = 2(110. They are MX. – 3600. Examples of these ionic substances are the strong bases NaOH and KOH.) – 175 + 920.

and the remainder of the atoms are O and H. then the data in part g tells us that the molar mass of B is 33. In addition. thus there are 0. M(s) + X2(g) → MX2(s): ΔH o = 110. we f would predict the M2X compound most likely to form. Because M2X has the more negative (more favorable) ΔH o value. The formal charge of zero (part b) tells us that there are three bonds to the nitrogen and the nitrogen has one lone pair. The Lewis structures for HNO3 are: O N O O O H O N O H Compound B: This compound is basic (part g) and has one nitrogen (part b). The N and O atoms have a combined molar mass of 30. giving the formula NH3O. HNO3 is a strong acid and is available in concentrated solutions of 16 M (part c). the oxidation state of nitrogen is +5 (part b). Compound A: This compound is a strong acid (part g). compound B is most likely NH2OH. the nitrogen atom in the other ion must have an oxidation state of -3 (part b) and a formal charge of +1.has no acidic properties.0 g/mol (21. Because part b tells us that there are two nitrogens.02198 mol of B. it limits the possibilities. so these are both theoretically possible. NO3-. Marathon Problem 117. then compound C contains the nitrate ion.000 M HCl = 0.0 g/mol. kJ f Only M+X− and (M+)2X2− have exothermic enthalpies of formation. The Lewis structure is: H N H O H Compound C: From parts a and f and assuming compound A is HNO3 .02198 mol = 33. + 4750. Since the molar mass of B is 33. + 480. The highest possible oxidation state of nitrogen is +5. = 1740. The charges of the ions in M2X are M+ and X2−.98 mL of 1. compound C must be a weak acid (part g).0 g/mol.02198 mol HCl. A Lewis structure is: . Because this number is rather small. That is. which must be due to the other ion since NO3. Therefore. there is one nitrogen. From the list of Kb values for weak bases in Appendix 5 of the text. The ammonium ion fits the data.726 g/0. and in HNO3. Also. + 250 + 2(−175) – 3500. the other ion needs to have one N and some H’s.538 CHAPTER 13 BONDING: GENERAL CONCEPTS For MX2 composed of M2+ and X−. Assuming compound B is monobasic. then only one O oxygen atom can be present.0 g/mol). 0. compound A is most likely HNO3. the rest is made up of hydrogens (3 H atoms). Thus compound C is most likely NH4NO3.

A Lewis structure is: + H N H N H O O H Note: One more resonance structure for NO2− can be drawn.00 g = 3. The empirical formula is NOH2. which has an empirical formula mass of 32.25 mol H There is a 1:1:2 mole ratio of N:O:H.0 g O × 1 mol/16. This is also consistent with the information given in parts b and d. Molar mass = 2. thus NH4NO2 is a likely formula.12 mol O 6.0 g/mol. this compound has one less oxygen atom than compound C.008 g = 6. the molecular formula of compound D is N2O2H4 or NH4NO2. Compound E: A basic solution (part g) that is commercially available at 15 M (part c) is ammonium hydroxide (NH4OH).0 g of compound. Data from part e confirm this.7 g N × 1 mol/14. Assuming 100.01 g = 3. we have: 43.CHAPTER 13 BONDING: GENERAL CONCEPTS + H O 539 H H N H O N O - Note: Two more resonance structures can be drawn for NO3-.12 mol N 50.86 g/L(0.08206 L atm K −1 mol −1 )(273 K ) dRT = = 64. The Lewis structure for NH4OH is: H H N H H + O H .3 g H × 1 mol/1.00 atm For a correct molar mass.1 g/mol P 1. Compound D: From part f.

we hybridize orbitals to explain the geometry. We know the geometry. In order to explain the observed geometry (bond angles) that molecules exhibit.. etc. i. we use d orbitals when the central atom on a molecule has more than eight electrons around it. whereas iodine would hybridize 5d orbitals since the valence electrons are in n = 5.e. The hybrid orbitals about a central atom always are directed at the bonded atoms. The valence orbitals of the nonmetals are the s and p orbitals. The lobes of the p orbitals are 90E and 180E apart from each other. Arsenic would hybridize 4d orbitals to go with the valence 4s and 4p orbitals. the valence electrons are in 3s and 3p orbitals. there are 3d. Geometry linear trigonal planar tetrahedral Hybridization sp sp2 sp3 Unhybridized p atomic orbitals 2 1 0 The unhybridized p atomic orbitals are used to form π bonds. so they never hybridize d orbitals. 3d orbitals are closest in energy and are available for hybridization. resulting in a shared electron pair occupying the space above and below the line joining the atoms (the internuclear axis). 4d. Row 2 elements never have more than eight electrons around them.CHAPTER 14 COVALENT BONDING: ORBITALS The Localized Electron Model and Hybrid Orbitals 9. Two unhybridized p atomic orbitals each from a different atom overlap side to side. 10. We rationalize this by saying there are no d orbitals close in energy to the valence 2s and 2p orbitals (2d orbitals are forbidden energy levels). for Row 3 and heavier elements. orbitals that will be close in energy to the valence s and p orbitals. The d orbitals are necessary to accommodate the electrons over eight. We use d orbitals when we have to. then all bond angles shoud be 90E or 180E. If the p orbitals were used to form bonds. 540 . Sigma bonds have shared electrons in the area centered on a line joining the atoms. we need to make up (hybridize) orbitals that point to where the bonded atoms and lone pairs are located. 11. 5d. Therefore. However. For phosphorus. It is Row 3 and heavier nonmetals that hybridize d orbitals when they have to. The orbitals that overlap to form the sigma bonds must overlap head to head or end to end. Hybrid orbitals will always overlap head to head to form sigma bonds. This is not the case.

like the carbon atom. C2H2 has 2(4) + 2(1) = 10 valence electrons. The two O−H bonds are formed from overlap of the sp3 hybrid orbitals from oxygen with the 1s atomic orbitals from the hydrogen atoms. a π bond results where the shared electron pair occupies the space above and below a line joining the atoms in the bond. When two parallel p atomic orbitals overlap. The oxygen atom. cannot be rotated. Sigma bonds. also has a trigonal planar arrangement of the electrons that requires sp2 hybridization. H2CO has 2(1) + 4 + 6 = 12 valence electrons. O H H 13. Atoms that are bonded together by only a sigma bond (single bond) exhibit this rotation phenomenon. COVALENT BONDING: ORBITALS 541 Rotation occurs in a bond as long as the orbitals that go to form that bond still overlap when the atoms are rotating.CHAPTER 14 12. O C H H The central carbon atom has a trigonal planar arrangement of the electron pairs that requires sp2 hybridization. however. the atoms in a double or triple bond cannot rotate (unless the bond is broken). Carbon and oxygen each has one unhybridized p atomic orbital that is parallel with the other. Because π bonds are present in double and triple bonds (a double bond is composed of 1 σ and 1 π bond. 14. The π bonds. and the other two sp3 hybrid orbitals hold the two lone pairs on oxygen. the p orbitals would no longer have the correct alignment necessary to overlap. Two of the four sp3 hybrid orbitals are used to form bonds to the two hydrogen atoms. H2O has 2(1) + 6 = 8 valence electrons. The σ bond in the double bond is formed from overlap of a carbon sp2 hybrid orbital with an oxygen sp2 hybrid orbital. If we try to rotate the atoms in a π bond. The double bond between carbon and oxygen consists of one σ and one π bond. and a triple bond is always 1 σ and 2 π bonds). The π bond in the double bond is formed from overlap of the unhybridized p atomic orbitals. Each O‒H covalent bond is called a sigma (σ) bond since the shared electron pair in each bond is centered in an area on a line running between the two atoms. The p orbitals must be parallel to each other to form the π bond. with the head-to-head overlap. H2O has a tetrahedral arrangement of the electron pairs about the O atom that requires sp3 hybridization. H C C H . The two C−H sigma bonds are formed from overlap of the sp2 hybrid orbitals from carbon with the hydrogen 1s atomic orbitals. remain unaffected by rotating the atoms in the bonds.

The Lewis structure is: H H H C C H H H The carbon atoms are sp3 hybridized. The C‒H σ bond is formed from overlap of a carbon sp hybrid orbital with a hydrogen 1s atomic orbital. each carbon atom has a linear arrangement of the electrons.. The two π bonds in the triple bond are formed from overlap of the two unhybridized p atomic orbitals on each C and N atom. 4 + 6 + 2(7) = 24 valence electrons O C Cl Cl . The triple bond is composed of one σ bond and two π bonds. then each carbon atom has two unhybridized p atomic orbitals. COCl2. C2H6O has 2(4) + 6(1) + 6 = 20 e− H H H C C H H O H The two C atoms and the O atom are sp3 hybridized. both C and N atoms are sp hybridized. Since each carbon atom is sp hybridized. 16. i. The C‒H and O‒H sigma bonds are formed from overlap of sp3 hybrid orbitals with hydrogen 1s atomic orbitals. Ethane. Ethanol.e. The sigma bond is formed from head-to-head overlap of the sp hybrid orbitals from the C and N atoms. All bonds are formed from overlap with these sp3 hybrid orbitals. The sigma bond between to the carbon atoms is formed from overlap of sp hybrid orbitals from each carbon atom.542 CHAPTER 14 COVALENT BONDING: ORBITALS Each carbon atom in C2H2 is sp hybridized since each carbon atom is surrounded by two effective pairs of electrons. The carboncarbon sigma bond is formed from overlap of an sp3 hybrid orbital on each C atom. The six C‒H sigma bonds are formed from overlap of the sp3 hybrid orbitals on C with the 1s atomic orbitals from the hydrogen atoms. C2H6. The two π bonds of the triple bond are formed from parallel overlap of the two unhybridized p atomic orbitals from each carbon. has 2(4) + 6(1) = 14 valence electrons. The triple bond is composed of one σ bond and two π bonds. HCN. 1 + 4 + 5 = 10 valence electrons H C N Assuming N is hybridized. 15. The two C−H sigma bonds are formed from overlap of carbon sp hybrid orbitals with hydrogen 1s atomic orbitals. The C‒C and C‒O sigma bonds are formed from overlap of the sp3 hybrid orbitals on each atom.

b. C is sp hybridized. The π bond is formed from parallel overlap of the unhybridized p atomic orbitals on each atom of C and O. See Exercises 13.54 for the Lewis structures. C is sp2 hybridized. 13.79. CO2. b.80. The σ bond in the double bond is formed from head-to-head overlap of an sp2 orbital from carbon with an sp2 hybrid orbital from oxygen. first determine the arrangement of electron pairs about each central atom using the VSEPR model. SeF2. H2CO. Br is sp3 hybridized. the carbon and oxygen atoms are sp2 hybridized. and the two chlorine atoms are sp3 hybridized. All the central atoms are sp3 hybridized. In NO2− and NO3−. The double bond between the carbon and oxygen atoms consists of one σ and one π bond. d. e.79 for the Lewis structures. a.54 a. the central N atom is also sp hybridized.51 a. Each O atom is sp2 hybridized. In OCN− and SCN−. In N2O4.52 HBr. i. and in N3−. f. . h. PH3. The two C‒Cl σ bonds are formed from overlap of sp2 hybrids from C with sp3 hybrid orbitals from Cl.52. N is sp2 hybridized. All the central atoms are sp3 hybridized. Se is sp3 hybridized. c. See Exercise 13. all have central atoms with dsp3 hybridization because all are based on the trigonal bipyramid arrangement of electron pairs. For the molecules in Exercise 13. CHCl3. To predict the hybridization. g. C is sp3 hybridized. 13. P is sp3 hybridized. 18.CHAPTER 14 COVALENT BONDING: ORBITALS 543 Assuming all atoms are hybridized. 17. and 13. C is sp hybridized.24 of the text to deduce the hybridization required for that arrangement of electron pairs. all have central atoms with d2sp3 hybridization because all are based on the octahedral arrangement of electron pairs. the central carbon atoms in each ion are sp hybridized. c. NH4+.80 for the Lewis structures. O2. both central N atoms are also sp2 hybridized. 13. 13. HCN. For the molecules in Exercise 13. b.51. All the central atoms are sp3 hybridized. See Exercise 13. then utilize the information in Figure 14. N is sp3 hybridized.

5E sp3 nonpolar trigonal pyramid < 109. F a b F Te F F linear 180° g. N F F F tetrahedral 109. H Be H f. a see-saw a) . b) 120E dsp3 nonpolar linear 180E dsp3 nonpolar .544 19.5° because the lone pair requires more space than the bonding pairs.5 sp3 polar trigonal planar 120° sp2 nonpolar e.90° dsp3 polar F As F F F Kr F F trigonal bipyramid a) 90E. a. F b sp nonpolar h. F B F V-shaped < 109°.120°. O F F F d. b) . c. F C F F F CHAPTER 14 COVALENT BONDING: ORBITALS b.5E sp3 polar The angles in NF3 should be slightly less than 109.

F F F F F d2sp3 nonpolar l. octahedral 90° d2sp3 nonpolar F I I F F square pyramid . d2sp3 polar T-shaped . O S O 2- trigonal planar.90E dsp3 polar S O O V-shaped. sp3 . F F Se F F F F square planar 90° k.CHAPTER 14 COVALENT BONDING: ORBITALS 545 i. a. F Kr F F 90o F j. b. 120E Only one resonance form is shown. O S O O S O c. sp2. We can predict the geometry and hybridization from any one of the resonance structures. sp2 (plus two other resonance structures) tetrahedral. 120E. Resonance does not change the position of the atoms. 109.90E 20.5E.

dsp3 j.546 CHAPTER 14 2- COVALENT BONDING: ORBITALS d. bent about S atom with two lone pairs (sp3) . < 109. < 109. S F F tetrahedral. sp3 i. sp3 h. F F S F F F F S F F see-saw. 109.90E c) . .120E see-saw about S atom with one lone pair (dsp3). sp3 hybrids. O S O O O 2- trigonal pyramid.109.90E and . S O O O 2- tetrahedral geometry about each S.5E. .5E. 90E.5E. 109. V-shaped arrangement about peroxide O’s.5E. sp3 g. ≈ 90o F F ≈ 120 o V-shaped.109.5E. sp3 hybrids f. d2sp3 F S F F c S a) . F b a octahedral.5E b) .120E. O O S O O O O S O O e.

There are 13 σ and 1 π bonds in acetoin. and all triple bonds are one σ and two π bonds. The six atoms are not forced to lie in the same plane because of free rotation about the carboncarbon single (sigma) bonds. H H To complete the Lewis structures. The other 3 C atoms are sp3 hybridized. 22. This forces the two CH2 planes to be perpendicular. then the π bond could not form since the p orbitals would no longer be parallel to each other. If the atoms are not in the same plane. Angle a = 120° and angle b = 109. . The center C atom is sp hybridized and is involved in two π bonds.5°. COVALENT BONDING: ORBITALS 547 H C H C H H For the p orbitals to properly line up to form the π bond. sp2 sp3 H H C H H C C O H b O a H C H H sp3 The carbon with the doubly bonded O is sp2 hybridized. H C C C H 23. all six atoms are forced into the same plane. just add lone pairs of electrons to satisfy the octet rule for the atoms with fewer than eight electrons. all double bonds are one σ and one π bond. Acetoin (C4H8O2) has 4(4) + 8(1) + 2(6) = 36 valence electrons. the CH2 planes are mutually perpendicular to each other. O H H C H H C sp3 C C H H sp2 O All CCO angles are 120°. Note: All single bonds are σ bonds. There are 11 σ and 2 π bonds in biacetyl.CHAPTER 14 21. No. Biacetyl (C4H6O2) has 4(4) + 6(1) + 2(6) = 34 valence electrons. The p orbitals used to form each π bond must be perpendicular to each other.

O C H H H O C H H O C N C N O H H C C N N N C H H C C H H C H H .5° + C* +O C H *H sp2 e O + f H The atoms marked with an asterisk must be coplanar with each other. 25. however. CHAPTER 14 COVALENT BONDING: ORBITALS Acrylonitrile: C3H3N has 3(4) + 3(1) + 5 = 20 valence electrons. a) b) c) 120° 120° 180° H a b H C c C H 6 σ and 3 π bonds sp2 sp C N All atoms of acrylonitrile must lie in the same plane.548 24. as well as the atoms marked with a plus. To complete the Lewis structure. The π bond in the double bond dictates that the C and H atoms are all in the same plane and the triple bond dictates that N is in the same plane with the other atoms. The two planes. do not have to coincide with each other due to the rotations about sigma (single) bonds. Methyl methacrylate (C5H8O2) has 5(4) + 8(1) + 2(6) = 40 valence electrons. H H H d) 120° C *H H 14 σ and 2 π bonds e) 120° * * * C C+ d sp3 f) ≈109. just add lone pairs of electrons to satisfy the octet rule for the atoms that have fewer than eight electrons.

. 180° 549 g. compounds based on carbon. b. and 9 sp3 carbons c.5° 109. Using these guidelines. The majority of Lewis structures for organic compounds have all atoms with zero formal charge. carbon atoms in organic compounds will usually form four bonds. Piperine and capsaicin are molecules classified as organic compounds. Also notice that CH3. Therefore. d. 9 sp2. CH2.CHAPTER 14 a. ≈109. 5 π h.5° 26. a. the Lewis structures are: H H f H H C H O H O a H d H H H CH H CH b CH CH c piperine C O e N H H H H H H3C O g O CH2 N h C i CH2 (CH2)3 j CH CH k CH3 CH l H H O H H capsaicin CH3 Note: The ring structures are all shorthand notation for rings of carbon atoms. i.5° i) j) k) l) 120° 109. The nitrogens are sp3 hybridized in each molecule. and CH are shorthand for a carbon atoms singly bonded to hydrogen atoms. a) b) c) d) 120° 120° 120° 120° e) f) g) h) ≈109. nitrogen atoms will form three bonds and complete the octet with one lone pair of electrons. In piperine the first ring contains six carbon atoms and the second ring contains five carbon atoms (plus nitrogen). 33 σ COVALENT BONDING: ORBITALS b.5° .5° 120° 109. 6 d. and oxygen atoms will form two bonds and complete the octet with two lone pairs of electrons. sp3 c. 4 e. and 6 sp3 carbons.e. piperine: 0 sp. The center N in ‒N=N=N group f. 11 sp2.5° 120° 109. capsaicin: 0 sp.

Bond energy and bond length can be measured. C O CHAPTER 14 CO2.36 for the 2p σ bonding. giving an apparent increase in mass in the presence of the field.O. 3(4) + 2(6) = 24 e− O C C C O There is no molecular structure for the diatomic CO molecule. O C O COVALENT BONDING: ORBITALS C3O2. . A greater number of unpaired electrons will give a greater attraction and a greater observed mass increase. The key is that paramagnetic substances have unpaired electrons in the molecular orbital diagram. 31. Bond energy is directly proportional to bond order.34 for the 2s σ bonding and σ antibonding molecular orbitals. See Figure 14. whereas He2 has four valence electrons. The end result is that a bonding MO is lower in energy than the atomic orbitals from which it is composed. Bond length is inversely proportional to bond order. that causes a substance to be attracted into an inducing magnetic field. Bonding orbitals form when in-phase orbitals combine to give constructive interference. Antibonding orbitals form when out-of-phase orbitals combine.550 27. H2: (σ1s)2 He2: (σ1s)2(σ1s*)2 Bond order = B. This results in enhanced electron probability located between the two nuclei. bond order is calculated from the molecular orbital energy diagram (bond order is the difference between the number of bonding electrons and the number of antibonding electrons divided by two). associated with unpaired electrons. With electron distribution pushed to the outside. To determine the type of magnetism. associated with paired electrons. and see Figure 14. Bonding and antibonding molecular orbitals are both solutions to the quantum mechanical treatment of the molecule. The Molecular Orbital (MO) Model 28.O. 29. 4 + 2(6) = 16 e−. Paramagnetic: a kind of induced magnetism. Diamagnetic: a type of induced magnetism. and π antibonding molecular orbitals. σ antibonding. measure the mass of a substance in the presence and absence of a magnetic field. whereas diamagnetic substances have only paired electrons in the MO diagram. and the central carbon atom is sp hybridized. The carbon in CO is sp hybridized. = (2!0)/2 = 1 B. A diamagnetic species will not be attracted by a magnetic field and will not show a mass increase (a slight mass decrease is observed for diamagnetic species). the energy of an antibonding orbital is higher than the energy of the atomic orbitals from which it is composed. π bonding. A substance with unpaired electrons will be attracted by the magnetic field. = (2!2)/2 = 0 30. that causes a substance to be repelled from the inducing magnetic field. CO2 is a linear molecule. C3O2 is a linear molecule with all the central carbon atoms exhibiting sp hybridization. CO. The mismatched phases produce destructive interference leading to a node of electron probability between the two nuclei. H2 has two valence electrons to put in the MO diagram. a. 4 + 6 = 10 e−.

O. so NO+ should be more stable than NO−. N2. See Figure 14. In addition.CHAPTER 14 COVALENT BONDING: ORBITALS 551 H2 has a nonzero bond order. NO+: (σ2s)2(σ2s*)2(π2p)4(σ2p)2 NO−: (σ2s)2(σ2s*)2(π2p)4(σ2p)2(π2p*)2 B.5 for NO and 2 for NO− (see Exercise 14.41 for the MO energy-level diagrams of B2. so they are predicted to be paramagnetic. the bond order is 2. so it should be a very strong (stable) bond. N2 has the highest possible bond order of three. . He2 has a bond order of zero. The He2 molecule is not more stable than the two free He atoms. hybrid orbital theory does not predict that NO− is paramagnetic. 32. and F2 have no unpaired electrons in the MO diagrams. the signs match up) These molecular orbitals are sigma MOs because the electron density is cylindrically symmetric about the internuclear axis.O. b. so MO theory predicts it will exist. = (8!4)/2 = 2 NO+ has a larger bond order than NO− . MO theory can handle odd electron species without any modifications. N2. B2 and O2 have unpaired electrons in their electron configuration. = (8!2)/2 = 3 B. 33. + + + σ* (out-of-phase. NO should have the stronger bond (and it does). N2 maximizes the number of electrons in the lower-energy bonding orbitals and has no electrons in the antibonding 2p molecular orbitals. Therefore. the signs oppose each other) σ (in-phase.41. From the MO energy diagram in Figure 14.31d for the electron configuration of NO−). We can draw all of the possible structures for NO with its odd number of valence electrons but still not have a good feel for whether the bond in NO is weaker or stronger than the bond in NO−. c. From the MO electron configurations. and F2. The MO diagram for these two ions is assumed to be the same as that used for N2. and NO− has 5 + 6 + 1 = 12 valence electrons. they are all diamagnetic. C2. NO+ has 5 + 6 – 1 = 10 valence electrons to place in the MO diagram. so it should not form. The H2 molecule is stable with respect to the two free H atoms. The localized electron model does not deal effectively with molecules containing unpaired electrons. O2. C2. The MO theory correctly makes this prediction. d.

O. then we predict that it can exist (is stable). stable B. Be2: (σ2s)2(σ2s*)2 2 2 2 B. = (4−2)/2 = 1.O. N2: (σ2s)2(σ2s*)2(π2p)4(σ2p)2 B. CN: (σ2s)2(σ2s*)2(π2p)4(σ2p)1 NO: (σ2s)2(σ2s*)2(π2p)4(σ2p)2(π2p*)1 O22+: (σ2s)2(σ2s*)2(σ2p)2(π2p)4 N22+: (σ2s)2(σ2s*)2(π2p)4 If the added electron goes into a bonding orbital. = (8−8)/2 = 0. We could also remove a bonding electron to form N2+. = (8−6)/2 = 1. = (2−1)/2 = 1/2. where the added electron goes into an antibonding orbital). = (2−0)/2 = 1. = (8−8)/2 = 0. and C22− would be expected to have their bond strength weaken as an electron is removed. Of the molecules listed. . stable O2 : (σ2s) (σ2s*) (σ2p) (π2p) (π2p*) 2− 2 2 2 4 4 2 F2 : (σ2s) (σ2s*) (σ2p) (π2p) (π2p*) (σ2p*) B.O. stable b. There are two ways to do this.5. the bond order would increase. Between CN and NO. stable B. stable B. H2+: H2: H2−: H22−: (σ1s)1 (σ1s)2 (σ1s)2(σ1s*)1 (σ1s)2(σ1s*)2 B. N22−: (σ2s)2(σ2s*)2(π2p)4(σ2p)2(π2p*)2 2− 2 2 2 4 4 B. 36. Between O22+ and N22+. not stable 35.O.O. H2. = (2−2)/2 = 0.552 34. CN would most likely form CN− since the bond order increases (unlike NO−. giving a 2 bond order of (8 – 3)/2 = 2.O.O. The bond order for N2+ is also 2. OF has the electron removed from an antibonding orbital. not stable c. H2: (σ1s)2 B2: (σ2s)2(σ2s*)2(π2p)2 C22−: (σ2s)2(σ2s*)2(π2p)4(σ2p)2 OF: (σ2s)2(σ2s*)2(σ2p)2(π2p)4(π2p*)3 The bond strength will weaken if the electron removed comes from a bonding orbital.O. = (1−0)/2 = 1/2.O. so its bond strength increases. making the species more stable and more likely to form. = (8−4)/2 = 2.5 [= (7 – 2)/2]. One is to add an electron to form N2− .O.O. not stable B. 37. stable B2: (σ2s) (σ2s*) (π2p) 2 2 2 4 4 2 Ne2: (σ2s) (σ2s*) (σ2p) (π2p) (π2p*) (σ2p*) B. CHAPTER 14 COVALENT BONDING: ORBITALS If we calculate a nonzero bond order for a molecule. = (2−2)/2 = 0. a. N2+ would most likely form since the bond order increases (unlike O22+ going to O2+). B2. not stable B.5. = (8 – 2)/2 = 3 We need to decrease the bond order from 3 to 2. This added electron goes into one of the π * p orbitals.

= (7-2)/2 = 2. The px orbital does not have proper symmetry to overlap with a 1s orbital. No. The bonding MO would have more fluorine 2p character since it is closer in energy to the fluorine 2p atomic orbital. The antibonding MO will have more hydrogen 1s character since the hydrogen 1s atomic orbital is closer in energy to the antibonding MO. which is higher in energy than the 2p atomic orbitals from which the electron in atomic oxygen is removed. Also. inversely proportional to bond length. which is characteristic of π MOs. The π bonds between S atoms and between C and S atoms are not as strong.5. COVALENT BONDING: ORBITALS 553 The electron configurations are (assuming the same orbital order as that for N2): CO: (σ2s)2(σ2s*)2(π2p)4(σ2p)2 CO+: (σ2s)2(σ2s*)2(π2p)4(σ2p)1 CO2+: (σ2s)2(σ2s*)2(π2p)4 B. The atomic orbitals do not overlap with each other as well as the smaller atomic orbitals of C and O overlap. the valence shell is n = 3. O2 should have a lower ionization energy than O. it should be easier to remove an electron from O2 than from O.O. and Ar22+. 0 unpaired e− Because bond order is directly proportional to bond energy and. 41. 44. in turn. = (6-2)/2 = 2.CHAPTER 14 38. See the illustrations in the solution to Exercise 14. b. Side-to-side overlap of these d orbitals would produce a π molecular orbital. b. 42.O. 40. S22−. the correct bond length order should be: Shortest → longest bond length: CO < CO+ < CO2+ 39. a. 43. 0 unpaired e− B. c. SCl−.33 for the bonding and antibonding MOs in OH. Some possibilities from Row 3 having 14 valence electrons are Cl2. The electron density would be closer to F on average. a. The electron removed from O2 is in a π2p* antibonding molecular orbital. There are 14 valence electrons in the MO electron configuration. O2: (σ2s)2(σ2s*)2(σ2p)2(π2p)4(π2p*)2.O. There would be no probability of finding an electron on the axis joining the two nuclei. The 2px and 2py orbitals are called nonbonding orbitals. = (8-2)/2 = 3. 1 unpaired e− B. The antibonding MO would place more electron density closer to H and would have a greater contribution from the higher-energy hydrogen 1s atomic orbital. and the 2p orbital of F is lower in energy than the 1s orbital of H. c. . the overall overlap is zero. Because the electron removed from O2 is higher in energy than the electron removed from O. The F atom is more electronegative than the H atom.

and 2py electrons have no effect on the bond 2 To form OH+. Bond order = order. We use the concept of delocalized π electrons to explain why molecules that exhibit resonance have equal bonds in terms of strength. The classic example of delocalized π electrons is benzene (C6H6).554 CHAPTER 14 COVALENT BONDING: ORBITALS + + - d. SO2. f. Because the number of bonding electrons and antibonding electrons is unchanged. Because the π electrons can roam about over the entire surface of the molecule. H ↑ 1s HO σ* O ↑↓ 2p x ↑↓ ↑↓ ↑ 2py ↑ 2p z ↑↓ 2p x ↑ 2p y σ 2s ↑↓ 2s e. we say all six of the unhybridized p orbitals overlap.50 shows the π molecular orbital system for benzene. the bond order is still equal to one. 6 + 2(6) = 18 e− S O O O S O . 2px. 45. Instead of just two unhybridized p orbitals overlapping. giving rise to equal bond strengths. Each carbon in benzene is sp2 hybridized. resulting in delocalized π electrons roaming about above and below the entire surface of the benzene molecule. Note: The 2s. Molecules that exhibit resonance have delocalized π bonding. 2−0 = 1. Figure 14. All six of the carbon atoms in benzene have an unhybridized p orbital pointing above and below the planar surface of the molecule. This is a fancy way of saying that the π electrons are not permanently stationed between two specific atoms but instead can roam about over the surface of a molecule. the π electrons are shared by all the atoms in the molecule. leaving one unhybridized p atomic orbital. a nonbonding electron is removed from OH.

CHAPTER 14 COVALENT BONDING: ORBITALS 555 In SO2 the central sulfur atom is sp2 hybridized. The unhybridized p atomic orbital on the central sulfur atom will overlap with parallel p orbitals on each adjacent O atom. With the delocalized π electrons. The sp2 hybrid orbitals are used to form the two sigma bonds to the central atom. all three unhybridized p orbitals overlap at the same time. O3 and NO2−are isoelectronic. The Lewis structures for O3 are: O O O O O O For each of the two resonance forms. so we only need consider one of them since the same bonding ideas apply to both. This is represented as: or . The localized electron view of the π bond utilizes unhybridized p atomic orbitals. the S−O bond lengths in SO2 are equal (and not different. resulting in π electrons that are delocalized over the entire surface of the molecule. resulting in the π electrons moving about above and below the surface of the SO2 molecule. The π bond resonates between the two positions in the Lewis structures: In the MO picture of the π bond. 46. the central O atom is sp2 hybridized with one unhybridized p atomic orbital. as each individual Lewis structure indicates). All three of these p orbitals overlap together.

the central carbon atom is sp2 hybridized. The C−O single bond is formed from overlap of an sp2 hybrid orbital on carbon with an sp3 hybrid orbital from oxygen. The central C atom also has one unhybridized p atomic orbital that overlaps with another p atomic orbital from one of the oxygen atoms to form the π bond in each resonance structure. The π bond in the C−O double bond is formed from overlap of parallel p unhybridized atomic orbitals from C and O. Benzoic acid (C7H6O2) has 7(4) + 6(1) + 2(6) = 46 valence electrons. CHAPTER 14 The Lewis structures for CO32− are (24 e−): O C O O O 2- COVALENT BONDING: ORBITALS O C O 2- O C O O 2- In the localized electron view. the sp2 hybrid orbitals are used to form the three sigma bonds in CO32−. The five C−H sigma bonds are formed from overlap of the sp2 hybridized carbon atoms with hydrogen 1s atomic orbitals. In the molecular orbital model for CO32−. The Lewis structure for benzoic acid is: O C H C C H C H C C C H O H H The circle in the ring indicates the delocalized π bonding in the benzene ring. See Figure 14. The π molecular orbital system for CO32− is analogous to that for NO3− which is shown in Figure 14.556 47.51 of the text. all four atoms in CO32− have a p atomic orbital that is perpendicular to the plane of the ion. The delocalized π bonding system in the ring is formed from overlap of all six unhybridized p atomic orbitals from the six carbon atoms. The six carbons in the ring and the carbon bonded to the ring are all sp2 hybridized. The seven C−C σ bonds are formed from head to head overlap of sp2 hybrid orbitals from each carbon. The C−O σ bond in the double bond is formed from overlap of carbon sp2 hybrid orbital with an oxygen sp2 orbital. All four of these p orbitals overlap at the same time to form a delocalized π bonding system where the π electrons can roam above and below the entire surface of the ion.50 for delocalized π bonding system in the benzene ring. The two benzene resonance Lewis structures have three alternating double bonds in the ring (see Figure 14.48). This localized π bond moves (resonates) from one position to another. . 48.

0078 + 78.46 × 10−46 kg m2 8π 2 (5.000 + 15. a.328 × 10 − 4 cm Wave number = 51.995) 1. ΔE = 2hB(Ji + 1) = hν = hc c .003 + 15.15 × 10 −11 s −1 = 5. µ = .CHAPTER 14 COVALENT BONDING: ORBITALS 557 Spectroscopy 49.918 = 1.75 × 1010 s−1 2 6.7 N m−1 Note: one newton = 1 N = 1 kg m s−2.944 × 1013 s−1 = k 1 k = μ 2 π 1.995 amu νo = 1 1550.60 × 10 −3 m B= 1.995 amu m1 + m 2 = 1.328 × 10−4 cm = ν 5.0078)(78.944 × 1013 s−1 λ μ 1 2π 7. N m −1 1 kg m s −2 × = 5.7 kg s−2 = 411. the force constant: k = 411. cm−1 = 7. νo = 1 2π (14.2398 × 10 − 26 kg N λ= 2.2398 × 10−26 kg μ 14.918) = amu × amu m1 + m 2 1.6524 × 10 − 27 kg Solving for k.998 × 108 m s −1 c = 1.75 × 1010 s −1 ) 8π 2 B (12.995) 1.66054 × 10 −27 kg k amu × . reduced mass = µ = 1. 50.9979 × 1010 cm s−1 × 2650.627 × 1013 s−1 2 π 1.1385 × 10−26 kg I= I = µRe2.000)(15.9979 × 1010 cm s −1 c = 5.66054 × 10 −27 kg m1m 2 (1.66054 × 10 −27 kg m1m 2 = amu × 12.003)(15.15 × 1011 s−1 = 2B(0 + 1) = 2B = λ 2. µ= = 1.6524 × 10−27 kg νo = 1 2π c k = = 2. = 2B(Ji + 1) λ λ 2.627 × 1013 s −1 1 1 = = 1877 cm−1 λ 5.626 × 10 −34 J s h = = 1.

28 × 10−20 m2. A sketch of the idealized NMR spectrum is: c a b b.75 × 1010 s−1) = 3. O b CH3 C a CH3 C CH3 a a CH3 The different groups of equivalent hydrogen atoms are labeled a and b. Since all H atoms are separated by more than three sigma bonds. Re = bond length = 1.13 × 10−10 m μ 1. c H c H O H c CH2 b H c H c O C CH3 a Because the hydrogens marked by a and the hydrogens marked by b are separated by more than three sigma bonds. b. and c in the following structure). we should have no spin-spin coupling. so: ν = 6(5.75 × 1010 s−1. There are three sets of magnetically equivalent hydrogens (marked a. but they should have relative areas of 9:3 (or 3:1). they will also not exhibit spin-spin coupling. B = 5.46 × 10 −46 kg m 2 I = = 1.45 × 1011 s−1 52. ν = h From part a.1385 × 10 − 26 kg = 113 pm ΔE = 2B(Ji + 1) = 2B(2 +1) = 6B b. Thus we will have three singlet peaks (following our assumptions). Predicting the relative locations of the peaks was not discussed in the text. .558 Re2 = CHAPTER 14 COVALENT BONDING: ORBITALS 1. We are assuming that all the benzene ring hydrogens (marked c) are equivalent and do not exhibit spin-spin coupling. a. Again. but they should be in a 3:2:5 relative area ratio (a:b:c). you do not have the information to predict where the two peaks should be in the idealized NMR spectrum.

CHAPTER 14

COVALENT BONDING: ORBITALS
a

559

b

c.
c H CH2CH3 b a H

c

CH3CH2 a b

CH2CH3 b a H c

The three different groups of equivalent hydrogen atoms are labeled a, b, and c. The H atoms marked c will not exhibit spin-spin coupling, but the H atoms marked a and b will. Since the H atoms marked a in the –CH3 groups neighbor –CH2 groups, a triplet line pattern will result with intensities of 1:2:1. The H atoms marked b in the –CH2 groups neighbor –CH3 groups, so a quartet peak should result with intensities of 1:3:3:1. The relative area ratios of the three different H atoms (a:b:c) should be 9:6:3 (or 3:2:1).

c
53.

b

a

a. The –CH2 group neighbors a –CH3 group, so a quartet of peaks should result (iv). b. The –CH3 H atoms are separated by more than three sigma bonds from other H atoms, so no spin-spin coupling should occur. A singlet peak should result (i). c. The –CH2 H atoms neighbor two H atoms, so a triplet peak should result (iii). d. The two H atoms in the –CH2F group neighbor one H atom, so a doublet peak should result (ii).

54.

C6H12 NMR spectrum: Because only one peak is present, all the hydrogen atoms are equivalent in their environment. Knowing this, then the process is trial and error to come up with the correct structure for C6H12. Following the “organic rules” in Exercise 14.64 and knowing a double bond is present, the only possibility to explain the NMR pattern is:

560

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COVALENT BONDING: ORBITALS

CH3 CH3 C C CH3 CH3
Here, all the H atoms have equivalent neighboring atoms and there would be no spin-spin coupling since all H atoms are separated by more than three sigma bonds. C4H10O spectrum: We have a quartet peak and a triplet peak in the spectrum. The quartet peak indicates hydrogen atom(s) that neighbor three H atoms; the triplet peak indicates hydrogen atom(s) that neighbor two H atoms. Again, following the “organic rules” in Exercise 14.64, the only possibility to explain this NMR pattern is: CH3CH2–O–CH2CH3 This compound has two different “types” of hydrogen atoms (–CH3 and –CH2). The –CH3 hydrogen atoms neighbor the –CH2 group, which would produce the triplet peak, and the –CH2 hydrogen atoms neighbor the –CH3 group, that would produce the quartet peak. From inspection, the relative areas of the two different patterns seems to confirm a 6:4 (or 3:2) ratio as it should be.

Additional Exercises
55. a. XeO3, 8 + 3(6) = 26 e−
Xe O O O

b. XeO4, 8 + 4(6) = 32 e−
O Xe O O O

trigonal pyramid; sp3 c. XeOF4, 8 + 6 + 4(7) = 42 e−
O F Xe F F
2 3

tetrahedral; sp3

d. XeOF2, 8 + 6 + 2(7) = 28 e−
F

F
F

O or F Xe F
3

F or

F Xe F

O

Xe F

O

square pyramid; d sp

T-shaped; dsp

CHAPTER 14

COVALENT BONDING: ORBITALS

561

e. XeO3F2 has 8 + 3(6) + 2(7) = 40 valence electrons.
F O Xe O F O or O O O Xe F or O O F F Xe F O

trigonal bipyramid; dsp3

56.

FClO2 + F− → F2ClO2− F2ClO2−, 2(7) + 7 + 2(6) + 1 = 34 e−
F Cl F -

F3ClO + F− → F4ClO− F4ClO−, 4(7) + 7 + 6 + 1 = 42 e−
F F O Cl F F

O O

dsp3 hybridization

d2sp3 hybridization

Note: Similar to Exercise 14.55c, d, and e, F2ClO2- has two additional Lewis structures that are possible, and F4ClO- has one additional Lewis structure that is possible, depending on the relative placement of the O and F atoms. The predicted hybridization is unaffected.

F3ClO → F− + F2ClO+ F2ClO+, 2(7) + 7 + 6 − 1 = 26 e−
+ Cl F F O

F3ClO2 → F− + F2ClO2+ F2ClO2+, 2(7) + 7 + 2(6) − 1 = 32 e−
O Cl F F O +

sp3 hybridization 57.

sp3 hybridization

a. No, some atoms are in different places. Thus these are not resonance structures; they are different compounds. b. For the first Lewis structure, all nitrogens are sp3 hybridized and all carbons are sp2 hybridized. In the second Lewis structure, all nitrogens and carbons are sp2 hybridized.

562
c. For the reaction:
H O C N H C O N C N H O

CHAPTER 14

COVALENT BONDING: ORBITALS

H

O C N

N C N C O H

O

H

Bonds broken: 3 C=O (745 kJ/mol) 3 C‒N (305 kJ/mol) 3 N‒H (391 kJ/mol)

Bonds formed: 3 C=N (615 kJ/mol) 3 C‒O (358 kJ/mol) 3 O‒H (467 kJ/mol)

ΔH = 3(745) + 3(305) + 3(391) - [3(615) + 3(358) + 3(467)] ΔH = 4323 kJ − 4320 kJ = 3 kJ The bonds are slightly stronger in the first structure with the carbon-oxygen double bonds since ΔH for the reaction is positive. However, the value of ΔH is so small that the best conclusion is that the bond strengths are comparable in the two structures. 58.
Cl C H C Cl H H Cl C C Cl H H Cl C C H Cl

In order to rotate about the double bond, the molecule must go through an intermediate stage where the π bond is broken and the sigma bond remains intact. Bond energies are 347 kJ/mol for a C‒C bond and 614 kJ/mol for a C=C bond. If we take the single bond as the strength of the σ bond, then the strength of the π bond is (614 − 347 = ) 267 kJ/mol. Thus 267 kJ/mol must be supplied to rotate about a carbon-carbon double bond.

CHAPTER 14
59.

COVALENT BONDING: ORBITALS

563

dxz

+

pz

x

x

z z

The two orbitals will overlap side-to-side, so when the orbitals are in-phase, a π bonding molecular orbital would form. 60. N2 (ground state): (σ2s)2(σ2s*)2(π2p)4(σ2p)2, B.O. = 3, diamagnetic (0 unpaired e−) N2 (1st excited state): (σ2s)2(σ2s*)2(π2p)4(σ2p)1(π2p*)1 B.O. = (7 − 3)/2 = 2, paramagnetic (2 unpaired e-) The first excited state of N2 should have a weaker bond and should be paramagnetic. 61. Considering only the 12 valence electrons in O2, the MO models would be:

σ2p*
↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑↓

π 2p * π 2p σ2p σ2s * σ2s

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

O2 ground state

Arrangement of electrons consistent with the Lewis structure (double bond and no unpaired electrons).

It takes energy to pair electrons in the same orbital. Thus the structure with no unpaired electrons is at a higher energy; it is an excited state. 62. a. Yes, both have four sets of electrons about the P. We would predict a tetrahedral structure for both. See part d for the Lewis structures.

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b. The hybridization is sp3 for P in each structure since both structures exhibit a tetrahedral arrangement of electron pairs. c. P has to use one of its d orbitals to form the π bond since the p orbitals are all used to form the hybrid orbitals. d. Formal charge = number of valence electrons of an atom - [(number of lone pair electrons) + 1/2 (number of shared electrons)]. The formal charges calculated for the O and P atoms are next to the atoms in the following Lewis structures.
O -1 Cl P
+1

O Cl Cl P
0

0

Cl

Cl

Cl

In both structures, the formal charges of the Cl atoms are all zeros. The structure with the P=O bond is favored on the basis of formal charge since it has a zero formal charge for all atoms. 63. a. BH3 has 3 + 3(1) = 6 valence electrons.
H B H H

trigonal planar, nonpolar, 120E, sp2

b. N2F2 has 2(5) + 2(7) = 24 valence electrons.
N F N F

Can also be:
F N F N

V-shaped about both N’s; ≈120E about both N’s; both N atoms: sp2

polar These are distinctly different molecules. c. C4H6 has 4(4) + 6(1) = 22 valence electrons.
H H C H C C H H C H

nonpolar

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COVALENT BONDING: ORBITALS

565

All C atoms are trigonal planar with 120E bond angles and sp2 hybridization. Because C and H have about equal electronegativities, the C−H bonds are essentially nonpolar, so the molecule is nonpolar. All neutral compounds composed of only C and H atoms are nonpolar. d. ICl3 has 7 + 3(7) = 28 valence electrons.
Cl ≈ 90 o Cl ≈ 90 o

I
Cl

T-shaped, polar .90E, dsp3

64.

For carbon, nitrogen, and oxygen atoms to have formal charge values of zero, each C atom will form four bonds to other atoms and have no lone pairs of electrons, each N atom will form three bonds to other atoms and have one lone pair of electrons, and each O atom will form two bonds to other atoms and have two lone pairs of electrons. Following these bonding requirements gives the following two resonance structures for vitamin B6:
O H O H g H C H C C f a b C C d e N H H C C C H H H c O H H O H C H C C N O C C C C H H C H H O H

a. 21 σ bonds; 4 π bonds (The electrons in the three π bonds in the ring are delocalized.) b. Angles a), c), and g): ≈109.5°; angles b), d), e), and f): ≈120° c. 6 sp2 carbons; the five carbon atoms in the ring are sp2 hybridized, as is the carbon with the double bond to oxygen. d. 4 sp3 atoms; the two carbons that are not sp2 hybridized are sp3 hybridized, and the oxygens marked with angles a and c are sp3 hybridized. e. Yes, the π electrons in the ring are delocalized. The atoms in the ring are all sp2 hybridized. This leaves a p orbital perpendicular to the plane of the ring from each atom. Overlap of all six of these p orbitals results in a π molecular orbital system where the electrons are delocalized above and below the plane of the ring (similar to benzene in Figure 14.50 of the text).

566
65.

CHAPTER 14
The Lewis structure for caffeine is:
H O H C H N C O H N C H H H C C H C N

COVALENT BONDING: ORBITALS

H

C C N

H

The three C atoms each bonded to three H atoms are sp3 hybridized (tetrahedral geometry); the other five C atoms with trigonal planar geometry are sp2 hybridized. The one N atom with the double bond is sp2 hybridized, and the other three N atoms are sp3 hybridized. The answers to the questions are:

C C C C
66.

6 C and N atoms are sp2 hybridized 6 C and N atoms are sp3 hybridized 0 C and N atoms are sp hybridized (linear geometry) 25 σ bonds and 4 π bonds

We rotated the molecule about some single bonds from the structure given in the question. Following the bonding guidelines outlined in Exercise 14.64, a Lewis structure for aspartame is:
H O H O H C N H H C C H H H C O C O N H H C C H H H C H C C H C H C H C C H

O

Another resonance structure could be drawn having the double bonds in the benzene ring moved over one position.

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COVALENT BONDING: ORBITALS

567

Atoms that have trigonal planar geometry of electron pairs are assumed to have sp2 hybridization, and atoms with tetrahedral geometry of electron pairs are assumed to have sp3 hybridization. All the N atoms have tetrahedral geometry, so they are all sp3 hybridized (no sp2 hybridization). The oxygens double bonded to carbon atoms are sp2 hybridized; the other two oxygens with two single bonds are sp3 hybridized. For the carbon atoms, the six carbon atoms in the benzene ring are sp2 hybridized, and the three carbons double bonded to oxygen are also sp2 hybridized (tetrahedral geometry). Answering the questions:

C C C
67.

9 sp2 hybridized C and N atoms (9 from C’s and 0 from N’s) 7 sp3 hybridized C and O atoms (5 from C’s and 2 from O’s) 39 σ bonds and 6 π bonds (this includes the 3 π bonds in the benzene ring that are delocalized)

a. The Lewis structures for NNO and NON are:
N N N O O N N N N O O N N N N O O N

The NNO structure is correct. From the Lewis structures we would predict both NNO and NON to be linear. However, we would predict NNO to be polar and NON to be nonpolar. Since experiments show N2O to be polar, then NNO is the correct structure. b. Formal charge = number of valence electrons of atoms - [(number of lone pair electrons) + 1/2 (number of shared electrons)].
N
-1

N
+1

O
0

N
0

N
+1

O
-1

N
-2

N
+1

O
+1

The formal charges for the atoms in the various resonance structures are below each atom. The central N is sp hybridized in all the resonance structures. We can probably ignore the third resonance structure on the basis of the relatively large formal charges as compared to the first two resonance structures. c. The sp hybrid orbitals from the center N overlap with atomic orbitals (or appropriate hybrid orbitals) from the other two atoms to form the two sigma bonds. The remaining two unhybridized p orbitals from the center N overlap with two p orbitals from the peripheral N atom to form the two π bonds.
2px sp sp z axis

2py

568
68. O=N‒Cl: NO:

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COVALENT BONDING: ORBITALS

The bond order of the NO bond in NOCl is 2 (a double bond). From molecular orbital theory, the bond order of this NO bond is 2.5 (see Figure 14.43 of the text).

Both reactions apparently only involve the breaking of the N‒Cl bond. However, in the reaction ONCl → NO + Cl, some energy is released in forming the stronger NO bond, lowering the value of ΔH. Therefore, the apparent N‒Cl bond energy is artificially low for this reaction. The first reaction only involves the breaking of the N‒Cl bond.

Challenge Problems
69. a. F2−(g) → F(g) + F−(g) Using Hess’s law: F2−(g) → F2(g) + e− F2(g) → 2 F(g) F(g) + e− → F−(g) F2−(g) → F(g) + F−(g)
ΔH = 290. kJ (IE for F2−) ΔH = 154 kJ (BE for F2 from Table 13.6) ΔH = !327.8 kJ (EA for F from Table12.8) ΔH = ΔH = F2− bond energy

____________________________________________________________________________________________

116 kJ; BE for F2− = 116 kJ/mol

Note that F2− has a smaller bond energy than F2. b. F2: (σ2s)2(σ2s*)2(σ2p)2(π2p)4(π2p*)4 F2 : (σ2s) (σ2s*) (σ2p) (π2p) (π2p*) (σ2p*)
− 2 2 2 4 4 1

B.O. = (8 – 6)/2 = 1 B.O. = (8 – 7)/2 = 0.5

MO theory predicts that F2 should have a stronger bond than F2− because F2 has the larger bond order. As determined in part a, F2 indeed has a stronger bond because the F2 bond energy (154 kJ/mol) is greater than the F2− bond energy (116 kJ/mol). 70. The ground state MO electron configuration for He2 is (σ1s)2(σ1s*)2 giving a bond order of 0. Therefore, He2 molecules are not predicted to be stable (and are not stable) in the lowestenergy ground state. However, in a high-energy environment, electron(s) from the antibonding orbitals in He2 can be promoted into higher-energy bonding orbitals, thus giving a nonzero bond order and a “reason” to form. For example, a possible excited-state MO electron configuration for He2 would be (σ1s)2(σ1s*)1(σ2s)1, giving a bond order of (3 – 1)/2 = 1. Thus excited He2 molecules can form, but they spontaneously break apart as the electron(s) fall back to the ground state, where the bond order equals zero. a. E = hc (6.626 × 10 −34 J s)(2.998 × 108 m / s) = = 7.9 × 10−18 J −9 λ 25 × 10 m

71.

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COVALENT BONDING: ORBITALS
6.022 × 10 23 1 kJ × = 4800 kJ/mol mol 1000 J

569

7.9 × 10−18 J ×

Using ΔH values from the various reactions, 25-nm light has sufficient energy to ionize N2 and N and to break the triple bond. Thus N2, N2+, N, and N+ will all be present, assuming excess N2. b. To produce atomic nitrogen but no ions, the range of energies of the light must be from 941 kJ/mol to just below 1402 kJ/mol.
941 kJ 1 mol 1000 J × × = 1.56 × 10−18 J/photon 23 mol 1 kJ 6.022 × 10

λ =

hc (6.6261 × 10 −34 J s)(2.998 × 108 m / s) = = 1.27 × 10−7 m = 127 nm E 1.56 × 10 −18 J

1402 kJ 1 mol 1000 J × × = 2.328 × 10−18 J/photon 23 mol kJ 6.0221 × 10 λ = hc (6.6261 × 10 −34 J s)(2.9979 × 108 m / s) = = 8.533 × 10−8 m = 85.33 nm E 2.328 × 10 −18 J

Light with wavelengths in the range of 85.33 nm < λ < 127 nm will produce N but no ions. c. N2: (σ2s)2(σ2s*)2(π2p)4(σ2p)2; the electron removed from N2 is in the σ2p molecular orbital, which is lower in energy than the 2p atomic orbital from which the electron in atomic nitrogen is removed. Because the electron removed from N2 is lower in energy than the electron removed from N, the ionization energy of N2 is greater than that for N. 72. The electron configurations are: N2: O2: (σ2s)2(σ2s*)2(π2p)4(σ2p)2 (σ2s)2(σ2s*)2(σ2p)2(π2p)4(π2p*)2
Note: The ordering of the σ2p and π2p orbitals is not important to this question.

N22−: (σ2s)2(σ2s*)2(π2p)4(σ2p)2(π2p*)2 N2−: (σ2s)2(σ2s*)2(π2p)4(σ2p)2(π2p*)1 O2+: (σ2s)2(σ2s*)2(σ2p)2(π2p)4(π2p*)1

The species with the smallest ionization energy has the electron that is easiest to remove. From the MO electron configurations, O2, N22−, N2−, and O2+ all contain electrons in the same higher-energy antibonding orbitals ( π * p ) , so they should have electrons that are easier to 2 remove as compared to N2, which has no π * p electrons. To differentiate which has the easiest 2 π * p to remove, concentrate on the number of electrons in the orbitals attracted to the number 2 of protons in the nucleus.

570

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COVALENT BONDING: ORBITALS

N22− and N2− both have 14 protons in the two nuclei combined. Because N22− has more electrons, one would expect N22− to have more electron repulsions, which translates into having an easier electron to remove. Between O2 and O2+, the electron in O2 should be easier to remove. O2 has one more electron than O2+, and one would expect the fewer electrons in O2+ to be better attracted to the nuclei (and harder to remove). Between N22− and O2, both have 16 electrons; the difference is the number of protons in the nucleus. Because N22− has two fewer protons than O2, one would expect the N22− to have the easiest electron to remove which translates into the smallest ionization energy. 73. The complete Lewis structure follows. All but two of the carbon atoms are sp3 hybridized. The two carbon atoms that contain the double bond are sp2 hybridized (see *).
CH 3 H C H 2C H C H 2C H H O H C C H H CH 3 C *C * C H C H H C CH 2 H CH CH 3 C C H C CH 2 H CH 2 CH 2 CH 2 CH 2 CH CH 3 CH 3

No; most of the carbons are not in the same plane since a majority of carbon atoms exhibit a tetrahedral structure. Note: CH, CH2, and CH3 are shorthand for carbon atoms singly bonded to hydrogen atoms. 74.

2p

2s

O2

O2−

O2+

O

The order from lowest IE to highest IE is: O2− < O2 < O2+ < O.

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COVALENT BONDING: ORBITALS

571

The electrons for O2−, O2, and O2+ that are highest in energy are in the π * p MOs. But for O2−, 2 these electrons are paired. O2− should have the lowest ionization energy (its paired π * p 2 electron is easiest to remove). The species O2+ has an overall positive charge, making it harder to remove an electron from O2+ than from O2. The highest energy electrons for O (in the 2p atomic orbitals) are lower in energy than the π * p electrons for the other species; O will 2 have the highest ionization energy because it requires a larger quantity of energy to remove an electron from O as compared to the other species. 75. a. The CO bond is polar with the negative end around the more electronegative oxygen atom. We would expect metal cations to be attracted to and to bond to the oxygen end of CO on the basis of electronegativity. b. FC (carbon) = 4 − 2 − 1/2(6) = −1 FC (oxygen) = 6 − 2 − 1/2(6) = +1 From formal charge, we would expect metal cations to bond to the carbon (with the negative formal charge). c. In molecular orbital theory, only orbitals with proper symmetry overlap to form bonding orbitals. The metals that form bonds to CO are usually transition metals, all of which have outer electrons in the d orbitals. The only molecular orbitals of CO that have proper symmetry to overlap with d orbitals are the π2p* orbitals, whose shape is similar to the d orbitals (see Figure 14.36). Since the antibonding molecular orbitals have more carbon character, one would expect the bond to form through carbon. 76. The molecular orbitals for BeH2 are formed from the two hydrogen 1s orbitals and the 2s and one of the 2p orbitals from beryllium. One of the sigma bonding orbitals forms from overlap of the hydrogen 1s orbitals with a 2s orbital from beryllium. Assuming the z axis is the internuclear axis in the linear BeH2 molecule, then the 2pz orbital from beryllium has proper symmetry to overlap with the 1s orbitals from hydrogen; the 2px and 2py orbitals are nonbonding orbitals since they don’t have proper symmetry necessary to overlap with 1s orbitals. The type of bond formed from the 2pz and 1s orbitals is a sigma bond since the orbitals overlap head to head. The MO diagram for BeH2 is:

C O

572
Be

CHAPTER 14

COVALENT BONDING: ORBITALS
2H

σ* s σ* p

2p ↑↓ 2s

2px

2py ↑ 1s ↑ 1s

↑↓

σp
↑↓

σs
Bond order = (4 - 0)/2 = 2; the MO diagram predicts BeH2 to be a stable species and also predicts that BeH2 is diamagnetic. Note: The σs MO is a mixture of the two hydrogen 1s orbitals with the 2s orbital from beryllium, and the σp MO is a mixture of the two hydrogen 1s orbitals with the 2pz orbital from beryllium. The MOs are not localized between any two atoms; instead, they extend over the entire surface of the three atoms. 77. One of the resonance structures for benzene is:
H H C C C H

C H C H

C H

To break C6H6(g) into C(g) and H(g) requires the breaking of 6 C‒H bonds, 3 C=C bonds and 3 C‒C bonds: C6H6(g) → 6 C(g) + 6 H(g) ΔH = 6DC‒H + 3DC=C + 3DC‒C

ΔH = 6(413 kJ) + 3(614 kJ) + 3(347 kJ) = 5361 kJ The question asks for ΔH ° for C6H6(g), which is ΔH for the reaction: f 6 C(s) + 3 H2(g) → C6H6(g) ΔH = ΔH ° , C6 H 6 ( g ) f

CHAPTER 14

COVALENT BONDING: ORBITALS

573

To calculate ΔH for this reaction, we will use Hess’s law along with the value ΔH ° for C(g) f and the bond energy value for H2 ( D H 2 = 432 kJ/mol). 6 C(g) + 6 H(g) → C6H6(g) ΔH1 = !5361 kJ

ΔH2 = 6(717 kJ) 6 C(s) → 6 C(g) 3 H2(g) → 6 H(g) ΔH3 = 3(432 kJ) ____________________________________________________________________________________________________________________ ΔH = ΔH1 + ΔH2 + ΔH3 = 237 kJ; ΔH ° , C H ( g ) = 237 kJ/mol f 6 6 ° The experimental ΔH f for C6H6(g) is more stable (lower in energy) by 154 kJ than the ΔH ° calculated from bond energies (83 ! 237 = !154 kJ). This extra stability is related to f benzene’s ability to exhibit resonance. Two equivalent Lewis structures can be drawn for benzene. The π bonding system implied by each Lewis structure consists of three localized π bonds. This is not correct because all C‒C bonds in benzene are equivalent. We say the π electrons in benzene are delocalized over the entire surface of C6H6 (see Section 14.5 of the text). The large discrepancy between ΔH ° values is due to the delocalized π electrons, whose f effect was not accounted for in the calculated ΔH ° value. The extra stability associated with f benzene can be called resonance stabilization. In general, molecules that exhibit resonance are usually more stable than predicted using bond energies. 6 C(s) + 3 H2(g) → C6H6(g) 78. a. The NMR indicates that all hydrogens in this compound are equivalent. A possible structure for C2H3Cl2 that explains the NMR data is:
H H C H Cl C Cl Cl

Note that for organic compounds to have a zero formal charge for all atoms, carbon will always satisfy the octet rule by having four bonds and no lone pairs, oxygen will always satisfy the octet rule by having two bonds and two lone pairs, and Cl will always satisfy the octet rule by having one bond and three lone pairs of electrons. b. We have two “types” of hydrogens. The triplet signal is produced by having two neighboring C−H bonds, whereas the quintet signal is produced by having four neighboring C−H bonds. A possible structure that explains the NMR (number of peaks, types of peaks, and the 2:1 relative intensities of the signals) is:
H Cl C H H C H H C H Cl

574

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c. Data: Three “types” of hydrogens; the singlet peak is produced by having no neighboring C−H bonds, the quartet signal indicates three neighboring C−H bonds, and the triplet indicates two neighboring C−H bonds. A possible structure to explain the NMR is:

Triplet signal
H

Quartet signal
H C H H C H O C O H

Singlet signal

d. Data: Three “types” of hydrogens. A possible structure to explain the NMR is:
H H H C H O C H C C H H H C H H

Doublet signal

Singlet signal

Heptet signal

e. Data: Three “types” of hydrogens. A possible structure to explain the NMR (number of peaks, types of peaks, and relative intensities) is:
H H C H O C H

Triplet H signal

C H

Triplet signal

Quintet signal
Note that the two hydrogens in the –CH2 group have four total neighboring protons (3 + 1), giving the quintet signal. The –CH2 group protons also cause the other “types” of hydrogens to have triplet signals.

and φ3 all must be normalized. A2 = . ∫φ12 dT = 1 = 1 ∫φs2 dT + 4A2∫φpx2 dT + 2 3 1 6 1 1 + 4(A2)(1) + 0 2A ∫φs φpx dT = 3 3 4 A2 = 1 − 1 2 1 = . b. a quartet signal for the b hydrogens. Marathon Problem 80. however. φ2. B = 3 6 2 1 2 .CHAPTER 14 79. The c hydrogen signal should be split into a triplet signal due to the two neighboring b hydrogens. φ1. This O−H hydrogen generally behaves as if it was more than three sigma bonds apart from the b hydrogens. The signal for the b hydrogens should be split into a quintet signal due to the three neighboring a hydrogens plus the neighboring c hydrogen (four total protons). In the second structure. The overall relative areas of the three signals should be in a 3:2:1 ratio due to the number of a. COVALENT BONDING: ORBITALS 575 The two isomers having the formula C2H6O are: H H C H a H C H b O H c H H H H C O H C H The first structure has three types of hydrogens (a. b. all six hydrogens are equivalent. Therefore. In practice. This signal will be a singlet signal because the hydrogens in the two –CH3 groups are more than three sigma bonds apart from each other (no splitting occurs). A = 3 3 6 ∫φ22 dT = 1 = 1 2 1 (−A) ∫φs φpx dT ∫φs dT + A2∫φpx2 dT + B2∫φpy2 dT + 2 3 3 +2 1 1 (B) ∫φs φpy dT − 2AB∫φpx φpy dT = + A2 + B2 + 0 + 0 + 0 3 3 1= 1 1 1 + + B2. and c). so only one signal will appear in the NMR spectrum. so the signals should be seen in three different regions of the NMR spectra. = B2. the spectrum will most likely have a triplet signal for the a hydrogens. and c hydrogens. the c hydrogen bonded to the oxygen does not behave “normally”. and a singlet signal for the c hydrogen. The signal for the a hydrogens will be split into a triplet signal due to the two neighboring b hydrogens.

For example. tangent lines at t ≈ 0 and t = t1 are drawn. the slope of the tangent line is greatest. the reverse reaction is insignificant because no products are present yet. which means the rate is largest at t ≈ 0. We can determine the instantaneous rate at any time during the reaction. t. a [A] b c 0 t1 time t2 An instantaneous rate is the slope of a tangent line to the graph of [A] vs. t. An average rate is determined over some time period. the slope of the dashed line connecting points a and c is the average rate of the reaction over the entire length of time 0 to t2 (average rate = Δ[A]/Δt). it would usually look like the solid line in the following plot. Consider the general reaction: aA → products where rate = − d[A ] dt If we graph [A] vs. At t ≈ 0. at t ≈ 0. The slope of these tangent lines would be the instantaneous rates at t ≈ 0 and t = t1. The average rate is measured over a period of time. whereas an instantaneous rate is determined at one specific time. The rate that is largest is generally the initial rate.CHAPTER 15 CHEMICAL KINETICS Reaction Rates 10. The initial rate is used by convention so that the rate of reaction only depends on the forward reaction. We call the instantaneous rate at t ≈ 0 the initial rate. 576 . On the plot. The reaction rate is defined as the change in concentration of a reactant or product per unit time.

022 × 10 23 molecules = 7. 14. mol ⎛ mol ⎞ Rate = k[Cl] [CHCl3]. product C is produced twice as fast as reactant A is used up. k must have units of L mol s− .5.0120/0. e.4 × 10−3)/4 = 3.CHAPTER 15 11. From the balanced reaction. 1.0 × 10−4 mol L−1 s−1 Δt 4 Δt Δ[H 2 ] 6 Δ[PH 3 ] =− = 6(2. ⎜ ⎝ L ⎠ 16. c. the rate of production of P4 will be 1/4 the rate of disappearance of PH3. a.24 × 10 −12 cm 3 1L 6. mol ⎛ mol ⎞ = k⎜ ⎟ Ls ⎝ L ⎠ d.6 × 10−3 mol L−1 s−1 Δt 4 Δt 13. Using the coefficients in the balanced equation to relate the rates: d[ NH 3 ] d[H 2 ] d[ N 2 ] d[ N 2 ] and =3 = −2 dt dt dt dt So : d[ NH 3 ] 2 d[H 2 ] 1 d[ H 2 ] 1 d[ NH 3 ] =− =− or dt 3 dt 3 dt 2 dt Ammonia is produced at a rate equal to 2/3 of the rate of consumption of hydrogen.0080 = 2. and the rate of production of H2 will be 6/4 the rate of disappearance of PH3. The units for rate are always mol L−1 s−1. k has units of mol L−1 s−1. The coefficients in the balanced reaction relate the rate of disappearance of reactants to the rate of production of products. 0.0048 mol / 2. Rate = k. Rate = − Δ[PH 3 ] − (−0. reactant B is used up 1.0 L) = = 2. b.47 × 108 L mol−1 s−1 × × molecules s mol 1000 cm 3 . By convention. all rates are given as positive values. Δ[P4 ] 1 Δ[ PH 3 ] =− = 2. Rate = k[A]2. ⎛ mol ⎞ 1/2 -1/2 1 ⎟ . A possible balanced equation is 2A + 3B → 4C.4 × 10−3 mol L−1 s−1 Δt s 12. mol ⎛ mol ⎞ = k⎜ ⎟ Ls ⎝ L ⎠ 2 k must have units of s-1.5 times faster than reactant A. = k⎜ ⎟ Ls ⎝ L ⎠ 1/2 1/ 2 k must have units L mol−1 s−1. This corresponds to a 3 to 2 mole ratio between B and A in the balanced equation. CHEMICAL KINETICS 577 0.0080 = 1.4 × 10−3/4 = 6. So the coefficient for C is twice the coefficient for A.0160/0. L2 mol−2 s−1 15. Rate = k[A].

040) y 12.0y. Rate = k[I−]x[S2O82−]y.36 k (0.25 × 10 k (0.00 = 2. k = 180 L mol− min− L L L min ⎝ ⎠ ⎝ ⎠ From the other experiments: k = 180 L2 mol−2 min−1 (second exp. From experiment 1: 0. the reaction is second order with respect to NO. The more variables that change.0y. the harder it is to determine the orders. Also.8 × 102 L2 mol−2 min−1. x = 2. the rate increases by a factor of four.9 × 10− L mol− s− Ls L L ⎝ ⎠⎝ ⎠ . y = 1 0.5 × 10 −6 k (0. In general. 2.20) (0. a. a.0x.20) x = = . k = 3.00 = 2.578 CHAPTER 15 CHEMICAL KINETICS Rate Laws from Experimental Data: Initial Rates Method 17. Or mathematically: 1. Rate = k[NO]2[Cl2]. these types of problems can usually be solved by inspection. Here.36 k (0. as the NO concentration doubles (Cl2 concentration is constant). Or mathematically: Rate = k[NO]x[Cl2]y 0. 4.20) (0. The rate also doubled.10 mol ⎞ 2 2 1 = k⎜ ⎟ ⎜ ⎟ .040) 2 18.5 × 10 −6 mol ⎛ 0. 12. 2.10 mol ⎞ ⎛ 0.45 k (0. k (0.20) x (0.040) (0.10) x Try to examine experiments where only one concentration changes at a time. Thus. The rate constant k can be determined from the experiments.18 k (0. we will solve using a mathematical approach. Rate = k[I−][S2O82−] −6 y 6. y = 1. Thus the reaction is first order with respect to Cl2. k = 180 L2 mol−2 min−1 (third exp.).10) x (0. For the first experiment: 12. so.080 mol ⎞⎛ 0.080)(0.10) y We can get the dependence on NO from the second and third experiments.18 mol ⎛ 0.5 × 10 −6 = .040) y = .040 mol ⎞ 3 1 1 = k⎜ ⎟⎜ ⎟ .10) y (0.080) x (0. b.080)(0.20) y = = .10) x (0.20) y (0. [NO] is held constant and [Cl2] is doubled. but keep in mind that you probably can solve for the orders by simple inspection of the data.0 = 2.0x.) The average rate constant is kmean = 1.25 × 10 k (0.0 = 2. In the first two experiments.10) x (0. 2.020) b. 0. x = 1 −6 x y 6.

k = 6. and the rate doubles.9 × 10−3 L mol−1 s−1 19. b.6 × 10−29 cm3 molecules−1 s−1. 6. n = 2. and 6.280 L µmol−1 s−1 The second and third experiments give similar k values.36 μmol 2.26 µmol L−1 s−1 μmol s L L 21.0500)x(0. From the first experiment: 0. k = 0.7. a.CHAPTER 15 CHEMICAL KINETICS Initial Rate (mol L−1 s−1) 12.280 L µmol−1 s−1. Therefore.619 µmol L−1 s−1 = k(2.66 × 10 4 k ( 2. y = 1 and the reaction is first order in CO.25 × 10−6 5.9 × 10−3 3. From the first two experiments: 2. x = 1. a. Rate = k[NOCl]n.00 × 10−6 k (L mol−1 s−1) 3.9 × 10−3 579 The other values are: kmean = 3.100)y . c.5 × 10−6 6.0n.280 L 3.6) × 10−29 cm3 molecules−1 s−1.6.75 × 10−2 = k(0. respectively.30 × 10−1 = k(0. The mean value for k is 6. d. so kmean = 0.64 × 10 k (1. [CO] triples. using experiments two and three: 2. Rate = k[Hb]x[CO]y Comparing the first two experiments.0 × 1016 ) n = . Rate = k[NOCl]2 3 16 n 6. [CO] is unchanged.9 × 10−3 3.00 µmol/L).100)y and 5. Rate = k[Hb][CO] c.0 × 10 ) ⎛ 3.25 × 10−6 6. 20.98 × 10 4 molecules ⎟ .40 μmol × × = 2.6 × 10−29 cm3 molecules−1 s−1 = k⎜ ⎜ ⎟ cm 3 cm 3 s ⎝ ⎠ The other three experiments give (6.022 × 10 23 molecules 4.00 × 10−6 7. 6. Rate = k[ClO2]x[OH−]y.100)x(0.21 µmol/L)(1.9 × 10−3 3. Therefore. and the rate triples. [Hb] is unchanged.9 × 10−3 3. Comparing the second and third experiments. and the reaction is first order in Hb. [Hb] doubles.6 × 10 −29 cm 3 1L 6.0 × 10 −8 L = × × molecules s mol mol s 1000 cm 3 2 b. Rate = k[Hb][CO] = 0. 4. a.01 = 2.0 × 1016 molecules ⎞ 5.

100 mol/L)2(0.50 × 1018 ) y = 1. x = 1. Rate = k[N2O5]x. and the rate increases by a factor of nine.0y.00 × 10−38 cm6 molecules−2 s−1 = kmean Rate = ⎛ 6.100)y and 1. Rate = 22.694(2. Rate = k[N2O5] (0.100)(0.0500)y Dividing: 2.100) x = 2.74 = 0.0750) x .30 × 10 2 L2 ⎛ 0.15 × 10−1 = k(0.53)x.90 × 10−4 = k(0.80 × 1017 k (3.00 × 1018 molecules/cm3) k = 2.190)x and 8.00x.0750)x Dividing: 2.175 mol ⎞ 0.51 = 2.50)y. y = 1 Rate = k[NO]2[O2].00 × 1016 molecules cm−3 s−1 = k(1.50 × 1018 ) 2 (2.30 × 10−1 mol L−1 s−1 = k(0. from experiment 1: 2.0844 mol ×⎜ = 0. [O2] is unchanged.00 × 10 −38 cm 6 7. The order of O2 is more difficult to determine. x = 2 x (0.050) y The rate law is: Rate = k[ClO2]2[OH−] 2. k = 2. the reaction is second order in NO (32 = 9).100)(0. y = 1 (0. 2. the rate laws for the first two experiments are: 2.26 × 10−3 = k(0.00 × 1018 ) y 1.36 × 1018 molecules ⎟ × × ⎜ ⎜ ⎟ molecules2 s cm 3 cm 3 ⎝ ⎠ 2 Rate = 5.00 = CHAPTER 15 CHEMICAL KINETICS (0.21 × 1018 molecules ⎞ 2. Therefore.50y.00 × 1018 molecules/cm3)2 × (1.13 × 1017 k (2.54 = (0.594 mol L−1 s−1 ⎟ × 2 L L mol s ⎝ ⎠ 2 Rate = k[NO]x[O2]y.30 × 10−1 = k(0.190) x = (2.0500) Comparing the second and third experiments: 2. Comparing the second and third experiments: 3.30 × 102 L2 mol−2 s−1 = kmean b. [NO] is tripled.100 mol/L).580 Dividing the two rate laws: 4.100) y = 2.00 × 1018 ) 2 (1.00 = (0. Comparing the first two experiments.68 × 1018 molecules cm−3 s−1 23. 2.

10) z . s −1 Ls (0.0013 mol / L) (0. 1/2 = 2.0026) x (0.8 × 10 −3 k (0.19 × 10−2 s−1 [ N 2O5 ] 0.012) (0. y = 1 = −3 y z 4. s −1 .0060) (0.10) z = . kmean = 60.10 mol / L) For all experiments. − [OH ] For the first experiment: 9. 2.0013)(0.012)(0.4 × 10 k (0. kmean = 1. .90 × 10 −4 mol L−1 s −1 = = 1. Rate = k[I−]x[OCl−]y[OH−]z.4 × 10 −3 k (0.0013)(0.20) z .3 s −1 = 60. 25.0x.0013)(0.0y. 2. x = 1/2 The order is 1/2 (the square root of the concentration of reactant).0 = 2.10) Comparing the first and sixth experiments: 4. z = !1 = −3 z 9.7 × 10 k (0.0750 mol / L x 24. Comparing the first and second experiments: 18.10) Rate = k[ I − ][OCl − ] .0013) (0.0 = 2.4 × 10 −3 mol (0. Negative orders are seen for substances that hinder or slow down a reaction.19 × 10−2 s−1.012) y (0. x = 1 −3 x y z 9. the presence of OH− decreases the rate of the reaction.CHAPTER 15 k = CHEMICAL KINETICS 581 Rate 8.012 mol / L) =k .4 × 10 k (0.0z.10) Comparing the first and third experiments: 9.012)(0. For a reactant that has an order of !1 and the reactant concentration is doubled: Rate 2 1 = (2) −1 = Rate1 2 The rate will decrease by a factor of 1/2 when the reactant concentration is doubled for a !1 order reaction.7 × 10 −3 k (0. k = 60.012) y (0.0013)(0. x ⎛ [A] ⎞ Rate 2 k[ A]2 = =⎜ 2⎟ x ⎜ [A] ⎟ Rate1 k[ A]1 1 ⎠ ⎝ The rate doubles as the concentration quadruples: 2 = (4)x.

− [A]0 . dt d[A] ∫ [A] = − ∫ k dt [ A ]0 0 [ A ]t t ln[A] [ A ]t [ A ]0 = − kt . dt − 1 [A] [ A ]t [ A ]0 d[A ] ∫ [A]2 = − ∫ k dt [ A ]0 0 1 1 1 1 + = − kt . the second half-life will be 40. the integrated rate law. = kt + [ A ] t [ A ]0 [A]t [ A ]0 [ A ]t t = − kt. s (twice the first half-life value). Therefore. 2k 27. The half-life expression for a second-order reaction is: t1/2 = k[A]0 Rate = k[A]2. [A]t − [A]0 = − kt . Because the 1/[A] versus time plot was linear. s. The slope of the 1/[A] versus time plot equals the rate constant k.60 × 10-2 L mol-1 s-1 [A]0 [A] 1 b. if the first half-life equals 20. [A]t = !kt + [A]0 First order: − d[A] = k[A]. dt [ A ]t [ A ]0 t ∫ d[A] = − ∫ k dt 0 0 t [A] [ A ]t [ A ]0 = − kt . a. This is because the half-life for a zero-order reaction has a direct relationship with concentration (as the concentration decreases by a factor of 2. Zero order: t1/2 = first order: t1/2 = ln 2 1 . ln[A]t − ln[A]0 = − kt . Zero order: − d[A] = k. 28.) = 10.582 CHAPTER 15 CHEMICAL KINETICS Integrated Rate Laws 26. the second half-life will also be 20. ln[A]t = !kt + ln[A]0 Second order: − d[A] = k[A]2 . s. The second half-life for a zero-order reaction will be 1/2(20. k = 3. the half-life decreases by a factor of 2). Because a second-order reaction has an inverse relationship between t1/2 and [A]0. . second order: t1/2 = k k[ A]0 For a first-order reaction. s because the half-life for a first-order reaction is concentration-independent. the rate law. and the rate constant value are: 1 1 = kt + . the reaction is second order in A.

0 min − 2. k = 4.97 × 10 − 2 min −1 c.5% remains). 1 3.CHAPTER 15 CHEMICAL KINETICS 1 3.80 × 10 −3 M 1.00 × 10−5 mol L−1 s−1 b.60 × 10−2)t.3 min = 69. so the reaction is 87. ln(0. and the rate constant value are: Rate = k[C2H5OH]0 = k.60 × 10 −2 L 1 1 1 = kt + × t+ . The slope of the ln[A] versus time plot equals −k. k = 2. the rate law. The half-life expression for a zero-order reaction is t1/2 = [A]0/2k.60 × 10 −2 583 = 9. we must use the integrated rate law to solve. When a first-order reaction is 87.97 × 10 min )t 0 ⎠ ⎝ ⎝ ⎠ t = 3 × t1/2 = 3 × 23.125) = 70.43 × 103 − 357 = (3. c.0% → 25. 2. t1/2 t1/2 t1/2 Or we can use the integrated rate law: ⎛ 2. The half-life expression for a first order rate law is: t1/2 = 0.00 × 10 M 2. the reaction is zero order in C2H5OH. Because the half-life for a second-order reaction depends on concentration. = −4 mol s [A] [A]0 7. The slope of the [C2H5OH] versus time plot equals -k. t = 2.00 × 10 − 2 M ⎟ = −(2. the integrated rate law. the rate law.9 min t= 30.0% → 12. a.80 × 10−3 /2) mol/L. t1/2 = = 23.3 min k k 2. the reaction is first order in A. Therefore.50 × 10−3 M is 1/8 of the original amount of A present initially.6931 = . ln[A] = −kt + ln[A]0.97 × 10 − 2 min −1 a.97 × 10−2 min−1 b. .92 × 103 s For this reaction: t1/2 = L mol s −1 −1 × 2.50 × 10 −3 M ⎞ ⎛ [A] ⎞ −2 −1 ⎟ ⎟ = − kt . and the rate constant value are: Rate = k[A].6931 ln 2 0. Therefore. Because the ln[A] versus time plot was linear. ln⎜ ln⎜ ⎜ [A] ⎟ ⎜ 2.98 × 104 s 29. where [A] = (2.5% complete. then the reaction has gone through 3 half-lives: 100% → 50.80 × 10 −3 mol / L Note: We could have used the integrated rate law to solve for t1/2.5%. [C2H5OH] = −kt + [C2H5OH]0. Because the [C2H5OH] versus time plot was linear.5% complete (or 12. the integrated rate law.

300. and we make another assumption. 3600. For the plots.3 × 10−4 s−1.094 −0. c. 0 mol/L = −(4.3 × 10−4 s−1 Δx 0 − 3600. 1.00 × 10 −5 mol L−1 s −1 The first assumption to make is that the reaction is first order.25 −0.25 × 10 −2 mol / L = = 156 s 2k 2 × 4. Using two points on the curve gives: slope = −k = Δy 0 − (3.25 × 10−2/2) mol/L. then the reaction is not first order. where [C2H5OH] = (1.00 Note: We carried extra significant figures in some of the natural log values in order to reduce round-off error. Time (s) 0 120. The differential − d[H 2 O 2 ] = k[H2O2] and ln[H2O2] = −kt + rate law and integrated rate law are Rate = dt ln[H2O2]0. a graph of ln[H2O2] versus time will yield a straight line. 600.50 −3.59 0. The plot of ln[H2O2] versus time is linear.00 0. Thus the reaction is first order.082 0.25 × 10−2 mol/L t= 31. k = 8.000 −0.13 0.04 −2.25 × 10 −2 mol / L = 313 s 4.99 −1.51 −2. 3000. [C2H5OH] = −kt + [C2H5OH]0 .22 0.00 × 10 −5 mol L−1 s −1 CHEMICAL KINETICS Note: We could have used the integrated rate law to solve for t1/2. 1800. We determine the rate constant k by determining the slope of the ln[H2O2] versus time plot (slope = −k).050 ln[H2O2] 0.91 0. 2400. [H2O2] (mol/L) 1.53 −0. .00 × 10−5 mol L−1 s−1)t + 1.37 0.584 t1/2 = CHAPTER 15 [C 2 H 5 OH]0 1.00) = = −8. we will do this most of the time when the natural log function is involved.78 0. 1200. For a first order reaction. If this plot is not linear.

7 1246 1.3 × 10−2 −4. and 6000.5 × 10−2 −4. s: k = slope = 144 L / mol − 73 L / mol = 1. [H2O2] = e−3. s.9 2180 1. use the integrated rate law.00 M.20 66. The natural log plot is not linear. Because the second order plot of 1/[C4H6] versus t is linear. then try the second order plot of 1/[C4H6] versus t.CHAPTER 15 CHEMICAL KINETICS 585 To determine [H2O2] at 4000.1 × 10−2 −4. If this isn't linear. we carried extra significant figures in the data points.00 ⎠ 32. ⎛ [H 2 O 2 ] ⎞ ln[H2O2] = −kt + ln[H2O2]0 or ln ⎜ ⎜ [H O ] ⎟ = −kt ⎟ ⎝ 2 2 0⎠ ⎛ [H O ] ⎞ ln ⎜ 2 2 ⎟ = −8.9 6210 s 0. a graph of ln[C4H6] versus t should yield a straight line.51 90. Using the points on the line at 1000. The data and the plots follow: Time [C4H6] ln[C4H6] 1/[C4H6] 195 1.3 × 10−4 s−1 × 4000.6 × 10−2 −4. = kt + [C 4 H 6 ] [C 4 H 6 ]0 The slope of the straight line equals the value of the rate constant.99 147 M −1 Note: To reduce round-off error.3. ln[H2O2] = −3. s − 1000.5 604 1. s.037 M ⎝ 1.4 × 10−2 L mol−1 s−1 6000.3 = 0. The first assumption to make is that the reaction is first order. so the reaction is not first order. s .34 76. where [H2O2]0 = 1. the integrated rate law is 1 1 .14 62. For a first-order reaction. we can conclude that the reaction is second order in butadiene.68 × 10−2 M −4. The differential rate law is: Rate = k[C4H6]2 For a second-order reaction.

08 × 10 −4 L .62 2. = kt + = × 2.00 2.00 M −1.250 0. The differential rate law and integrated rate law are Rate = k[NO2]2 and 1 1 = kt + .00) M −1 = = 2. CHAPTER 15 CHEMICAL KINETICS Assume the reaction is first order and see if the plot of ln[NO2] versus time is linear.75 The plot of 1/[NO2] versus time is linear.174 ln[NO2] −0. where 1/[NO2]0= 1/0.20 × 103 3. 1 1 1 2.08 × 10−4 L mol−1 s−1 Δx (1. The data and plots follow.62.965 −1.94 4.00 5. use the integrated rate law.340 0. .749 1/[NO2] (M -1) 2.00 × 103 4.70 × 104 s. try the second order plot of 1/[NO2] versus time. [NO2] = 0. If this isn’t linear. [ NO 2 ] [ NO 2 ]0 The slope of the plot 1/[NO2] versus.386 −1. The reaction is second order in NO2.693 −0.131 M [ NO 2 ] 34. First.25 2. Using a couple of points on the plot: slope = k = Δy (5.079 −1.80 × 104 [NO2] (M) 0. t gives the value of k.80 × 10 4 − 0) s To determine [NO2] at 2. assume the reaction to be first order with respect to O.586 33. Hence a graph of ln[O] versus t would be linear if the reaction is first order.500 M = 2.444 0.00 × 103 1.381 0.70 × 104 s + 2. a. Time (s) 0 1.00 M −1 [ NO 2 ] [ NO 2 ]0 [ NO 2 ] mol s 1 = 7.812 −0.50 × 103 9.75 − 2.500 0.

8 × 108 2.34 19. Thus for this experiment.37 20. the rate law is Rate: k′[O].0 × 102 s−1. the pressure of C2H5OH decreases at a constant rate of 13 torr for every 100. k= 13 torr 1 atm × = 1. b. × 10 − 0) s To determine k.34 − 22. the slope equals −k′ = −k[NO2].0 × 102 s−1 −3 (30. where k′ = k[NO2]. From the graph: slope = 19. In a typical first-order plot. × 10−3 20.CHAPTER 15 CHEMICAL KINETICS t (s) 0 10.7 × 10−4 atm/s 100. k′ = −slope = 1. the reaction is zero order in C2H5OH. From the data. PC 2 H 5OH = −kt + 250.329 atm ⎟ ⎝ ⎠ . torr ⎜ ⎜ 760 torr ⎟ = −kt + 0.23 = −1.34 587 Because the graph is linear.0 × 109 1. its concentration is constant. × 10−3 30. Since the rate of disappearance of C2H5OH is not dependent on concentration. The overall rate law is: Rate = k[NO2][O] Because NO2 was in excess. we can conclude the reaction is first order with respect to O. 1.0 × 10−11 cm3 molecules−1 s−1 35.0 × 102 s−1 = k(1.5 × 108 ln[O] 22. s 760 torr The rate law and integrated rate law are: ⎛ 1 atm ⎞ Rate = k = 1. × 10−3 [O] (atoms/cm3) 5. the actual rate constant: k′ = k[NO2].33 21. For this experiment. s. the slope equals −k.9 × 109 6.7 × 10−4 atm/s.0 × 1013 molecules/cm3) k = 1.

b. The rate dependence on NO is determined from the first set of data since the ozone concentration is relatively large compared to the NO concentration.7 × 108 9.025 M): t1/2 = 1/(10 × 0. s: CHAPTER 15 CHEMICAL KINETICS PC 2 H 5OH = −1.176 atm = 0.7 × 10−4 atm/s × 900. We check for first-order dependence by graphing ln[concentration] versus time for each set of data.1 mol × mol s L 1 k[ A]0 Second half-life ([A]0 is now 0. 700.025) = 4 s 37.9 × 107 ln[NO] 20. a.588 At 900.0 × 108 5.95 18. the reaction is second order with respect to A. a. The slope of the 1/[A] versus time plot will equal k. [NO] (molecules/cm3) 6.1 M c. s + 0.0 × 108 2.1 M = [A]0. The y intercept in the plot will equal 1/[A]0.03 19. the y intercept will be about 10. Because the 1/[A] versus time plot is linear with a positive slope.05 M): t1/2 = 1/(10 × 0. Extending the plot.05) = 2 s Third half-life ([A]0 is now 0. Time (ms) 0 100. so 1/10 = 0.21 20.41 .30 18. [A] = 0. so it is effectively constant. 1000.18 atm = 130 torr 36. the half-life does depend on concentration: t1/2 = First half-life: t1/2 = 1 =1s 10 L 0. 500. For a second-order reaction.4 × 108 1. Slope = k = (60 − 20) L / mol = 10 L mol−1 s−1 (5 − 1) s 1 1 10 L 1 = kt + = = 100.329 atm = 0.01 M × 9s+ [A] [ A ]0 mol s 0 .

k′′ = 3. Rate = k′′[O3] = k[NO][O3]. − 0) × 10 −3 s For ozone experiment. Rate = k[NO][O3] = k′[NO] where k′ = k[O3]. k′′ = −slope = − ( 21.31 21. 300. − 0) × 10 −3 s d. For NO experiment.67 22. [O3] (molecules/cm3) 1.CHAPTER 15 CHEMICAL KINETICS 589 Because ln[NO] versus t is linear. Rate = k′′[O3] and k′′ = −(slope from ln[O3] versus t). Hence the reaction is first order with respect to ozone.4 × 109 ln[O3] 23.8 × 10−14 cm3 molecules−1 s−1 Both values of k agree. From NO experiment.0 × 1010 8.8 s−1 = k(1.0 × 1014 molecules/cm3).8 × 10−14 cm3 molecules−1 s−1 We can check this from the ozone data. b.21 = 1. k′ = 1. Rate = k[NO][O3] is the overall rate law.85 22.03) = 3. c.9 × 109 3. We follow the same procedure for ozone using the second set of data. Rate = k′[NO] and k′ = −(slope from graph of ln[NO] versus t). 100.0 × 1014 molecules/cm3).95 The plot of ln[O3] versus t is linear. 200. k = 1.0 × 109 4. k′ = −slope = − 18.95 − 23. The data and plot are: Time (ms) 0 50.6 s−1 = k(2.4 × 109 7. where k′′ = k[NO].41 − 20.03 22. .6 s−1 (300.8 s−1 (1000. k = 1. the reaction is first order with respect to NO.

20 × 10 −3 mol = 0. (V∞ − Vt ) will also be proportional to the concentration of C6H5N2Cl.3 × 10 −3 L) = 2. subtract that from 2.08206 L atm RT × 323 K K mol Because each mole of C6H5N2Cl that decomposes produces one mole of N2. If the reaction is first order.0 45. Because the rate constant is related to the slope of the straight line.3 7.3 22.0 36.066 3. A product is measured instead of a reactant.664 3. We can find the initial concentration of C6H5N2Cl from the amount of N2 evolved after infinite time when all the C6H5N2Cl has decomposed (assuming the reaction goes to completion).105 2. CHEMICAL KINETICS 2. n= PV 1. The data for such a graph are: t (s) 0 6 9 14 22 30. The quantity (V∞ − Vt ).20 × 10−3 mol N2 = 0.3 39.3 26.00 atm × (58.0 × 10 −3 L We can similarly calculate the moles of N2 evolved at each point of the experiment. Thus we can get the same information by using (V∞ − Vt ) as our measure of [C6H5N2Cl].20 × 10−3 mol to get the moles of C6H5N2Cl remaining. we would favor this approach to get a value for the rate constant. CHAPTER 15 This problem differs in two ways from previous problems: 1. We would then use these results to make the appropriate graph to determine the order of the reaction. will be proportional to the moles of C6H5N2Cl remaining.0 32.588 2. the initial concentration (t = 0) of C6H5N2Cl was: 2.07 .3 mL N2 evolved and Vt = mL of N2 evolved at time t.3 13. a graph of ln(V∞ − Vt ) versus t would be linear.475 3. where V∞ = 58.0 50. Only the volume of a gas is given and not the concentration. Vt (mL) 0 19.590 38.4 (V∞ − Vt ) 58.0550 M 40. and then calculate [C6H5N2Cl] at each time. There is a simpler way to check for the order of the reaction that saves doing a lot of math.9 ln(V∞ − Vt ) 4.

Rate = k[AB]2. t = 62 days 100.CHAPTER 15 CHEMICAL KINETICS 591 We can see from the graph that this plot is linear.0.350 mol / L ⎞ −1 ln⎜ ⎟ ⎜ 2.3 d 1/ 2 0 ⎠ ⎝ 40. and the integrated rate law is ln[C6H5N2Cl] = −kt + ln[C6H5N2Cl]0. s.00 × 10 −2 L mol −1 s −1 = kmean For a second-order reaction: .0% completion.00 mol / L ⎟ = −k × 120. If [A]0 = 100.200 M)2 k = 8. then after 95. as the concentration of AB is doubled.85 × 10−2 d−1 ln⎜ ⎜ [A ] ⎟ = −kt. Solving for k: ⎛ 0. The reaction is second order in AB. For a first-order reaction.6931 = = 4. 3. the initial rate increases by a factor of 4. the integrated rate law is ln([A]/[A]0) = −kt. k was determined to be 6. ⎛ 5.0116 s ⎟ ⎝ ⎠ ⎛ 0. t = 150.0 ⎞ 2 1 ln⎜ ⎟ = -4.0 ⎠ ⎝ 41. 39. The differential rate law is −d[C6H5N2Cl]/dt = Rate = k[C6H5N2Cl].9 × 10−2 s−1. k = 0.250 mol / L ⎞ −1 ln⎜ ⎜ 1. k = t ⎟ 14.00 mol / L ⎟ = −0.0.0116 s × t. Comparing experiments 1 and 2. [A] = 5. From separate data. so the reaction is first order.85 × 10− d− × t. s ⎠ ⎝ ⎛ [A] ⎞ ln 2 0.20 × 10 −3 mol L−1 s −1 = k1(0.

etc.900 mol / L 0. then: [A] = −(5. 1 1 8. t= = 16 s 0. [A] = −kt + [A]0. a. the second half-life. 43./2 = 160.0 min + [A] [A]0 mol min 0.33 × 10 −3 s −1 0 ⎠ 0 ⎝ 44. s = two halflives. ⎛ [A] ⎞ 0.0% complete. CHAPTER 15 CHEMICAL KINETICS 1 1 = = 12.592 t1/2 = 42. The integrated rate law for a second order reaction is 1/[A] = kt + 1/[A]0. M −1. [A] = 1. s.0 × 10−2 mol L−1 s−1)t + 1. this represents two halflives (100% → 50%→ 25%). 30. When a reaction is 75.00 × 10 L mol s × 1. This is both the first half-life. t = = 532 s ⎟ ⎜ [A ] ⎟ = − kt .0 min(0.555 L 1 1 1.00 mol / L a. Because there is no concentration dependence for a first-order half-life.10 M) = 0. 1 1 1.5 s −2 −1 −1 k[AB]0 8.100 mol / L 0.900/2) mol/L 0.0 min = 2 half-lives.100) ln ⎜ = − (4.9 L / mol = 0. t1/2 = 320. k = k t 1/ 2 160. Using the integrated rate law: 0. If k = 5.00 s + .0 L 1 = kt + = 90.0% of the original amount of the reactant remains.33 × 10 −3 s −1 . k= = (0. 320.10 M b. and the halflife expression is t1/2 = 1/k[A]0. so [A] = 0.0% of reactant remains). We could use either to solve for t1/2. s At 90. Successive half-lives increase in time for a second-order reaction. b.1 × 10−2 M = H 80.100[A]0 ln(0. The first-order half-life expression is t1/2 = (ln 2)/k.555 L mol−1 s−1 × t + .00 × 10−3 mol/L . t1/2 = 1 1 1 = 1.11 L / mol = k H 2.900 mol / L 2. [A] = 0.25(0.33 × 10 −3 s −1 ) t . assume reaction is second order in A.100[A]0.0 L mol−1 min−1 . k= = k[ A]0 t1/ 2 [A]0 10.025 M 45.0% complete (25.10 M ) a.00 × 10−3 M. so 25% of original A is remaining. t1/2 = ln 2 ln 2 ln 2 = = 4. 10.00 s mol s b. Therefore.0 × 10−2 mol L−1 s−1 and [A]0 = 1. ln [A] − 4.555 L mol −1 s −1 a.

a. ⎛ 3.693 = = 5. rate = k[A]2[B][C] = k′[A]2 where k′ = k[B][C].0 M. 2 0. 47.12 s−1/(3.0 × 10 − 2 M ⎝ [A] = 2.CHAPTER 15 b.02 M = 2.12 s 0 ⎠ ⎝ ⎝ ⎠ For the reaction: kN = k[B]2. CHEMICAL KINETICS 593 [A]0 = −(5.0.010 M ! 0.21 −2 ⎟ 1. the B concentration is essentially constant during this experiment. the reaction is a pseudo-first-order reaction in A. . [A] reacted = 0. as expected.8 × 10 −3 M ⎞ ⎛ [A] ⎞ −1 ⎟ ⎟ = !kNt.0 × 10−2 s −2 5.00 × 10−3 mol/L [A] = 7. ⎛ [A] ln ⎜ ⎜ 1. For this experiment.12(13. kN = 0.12 s −1 × 13.12 s −1 ⎞ [A] ⎟ = !0. Because [A]0 << [B]0 or [C]0.0 × 10 − 2 M ⎟ = !kN × 8.0 × 10−2 mol L−1 s−1)(5.5 × 10−4 mol/L [B]produced = [A]reacted = 2. so rate = kN[A] where kN = k[B]2.50(1.0 s.50[A]0 = −(5.0 s. t1/2 = = 1. = e−0.0) = 0.5 × 10−4 mol/L = 2. k = 0.00 × 10−3 mol/L − 7.0021 M = 0.008 M [C] reacted = 0.02 M 1 mol A [C]remaining = 2.0 × 10−2)t1/2.0 × 10 ⎠ c. a. [A] = [A]o/2.0 × 10−2)t1/2 + [A]0 because at t = t1/2.0 × 10−3 s) + 1.5 × 10−4 mol/L [A]reacted = 1.00 × 10 −3 ) −0.1 × 10 −3 M d.0 × 10 [A]0 Note: We could have used the t1/2 expression to solve (t1/2 = ). Thus. [A] = −kt + [A]0 = −(5.5 × 10−4 M 46. 2k c. the B and C concentrations remain constant at 1.8 s k' 0.008 M × 2 mol C = 0.3 × 10 −2 L2 mol−2 s−1 b.0 mol/L)2 = 1.00 M for this experiment. Because [B]0 >> [A]0. ln ⎜ ln ⎜ ⎜ [A] ⎟ ⎜ 1.016 M ≈ 0. the concentration of C basically remains constant during this experiment since [C]0 >> [A]0. t1/2 = ln 2 0.0 M .

i.00 × 10 − 4 mol / L [A] = 1/7.27 × 10–5 M = 8.90 × 104 L/mol [A] [A]0 1.90 × 104 L/mol = 1. 1 mol B = 2.00 M )(1. t1/2 = 1 1 = = 87.00 M − 2. c.00 M ) b.26 × 10 M [A] 1.7 × 10–5 mol/L × [B] = 1. Amount A reacted = 1. For this pseudo-second-order reaction: Rate = k′[A]2.594 For this pseudo-second-order reaction: CHAPTER 15 CHEMICAL KINETICS 1 1 1 1 . An elementary step (reaction) is one for which the rate law can be written from the molecularity. a.0 s −1 −1 k '[A ]0 115 L mol s (1.00 min) + −5 [A]0 3. from coefficients in the balanced equation. 1 mol of B reacts with every 3 mol of A. The sum of all the steps in the mechanism gives the balanced chemical reaction.9 × 10–5 M = 1.27 × 10–5 mol/L From the stoichiometry in the balanced reaction. k = k′ 115 L mol −1 s −1 = 115 L3 mol–3 s–1 . b.00 M As we mentioned in part a. k = [B][C] (1. The molecularity is the number of species that must collide to produce the reaction represented by an elementary step in a reaction mechanism.00 × 10–4 M – 1. s + = 7.9 × 10–5 M 3 mol A Reaction Mechanisms 48. 1 1 1 = k′t + = 115 L mol–1 s–1 × 600. = k′t + = k′(3. the concentration of B (and C) remain constant because the A concentration is so small compared to the B (or C) concentration..7 × 10–5 M Amount B reacted = 8.00 × 10 − 4 mol / L) c.e. .00 × 10 − 4 M k′ = 6890 L mol–1 min–1 = 115 L mol–1 s–1 k′ = k[B][C]. The mechanism of a reaction is the series of proposed elementary reactions that may occur to give the overall reaction.

49. we sum all the individual steps of the mechanism. the rate of the reaction is assumed to equal the rate of the slowest step in the mechanism. the rate law derived from a mechanism must agree with the rate law determined from experiment. In a unimolecular reaction. Most reactions occur by a series of steps. 51. the rate law can be written using the coefficients in the balanced equation to determine the orders. Rate = k 52. a. If most reactions were one step. We can only say it is possibly correct if it follows the two requirements just described. the rate law for this mechanism is Rate = k[C4H9Br]. two molecules collide to give products. Because step 1 is the rate determining step. where N = the number of atoms (convention) Because the rate of the slowest elementary step equals the rate of a reaction: Rate = Rate of step 1 = k[NO2]2 The sum of all steps in a plausible mechanism must give the overall balanced reaction. making termolecular steps very unlikely. and the mechanism must give a rate law that agrees with the experimentally determined rate law. The rate-determining step is the slowest elementary reaction in any given mechanism. For elementary reactions.CHAPTER 15 CHEMICAL KINETICS 595 d. Rate = k[O3][O] 14 6C [ C] or Rate = kN. Summing all steps gives: NO2 + NO2 → NO3 + NO NO3 + CO → NO2 + CO2 NO2 + CO → NO + CO2 ___________________________________ 53. e. To get the overall reaction. A mechanism consists of a series of elementary reactions in which the rate law for each step can be determined using the coefficients in the balanced equations. An intermediate is a species that is neither a reactant nor a product but that is formed and consumed in the reaction sequence. The probability of the simultaneous collision of three molecules with enough energy and the proper orientation is very small. For a plausible mechanism. the sum of the elementary steps must give the overall balanced equation for the reaction. In a bimolecular reaction. Summing all steps gives: . Rate = k[O3] e. To derive the rate law from the mechanism. This is not the case. a single reactant molecule decomposes to products. For a mechanism to be acceptable. Rate = k[O3][NO] d. 14 6 50. A mechanism can never be proven absolutely. then all reactants would appear in the overall rate law. and these orders would be the coefficients in the balanced equation. Rate = k[CH3NC] c. b.

not possible k1 [NO][O2] k −1 b. 55. Rate = k2[NO3][NO] and k1[NO][O2] = k−1[NO3] or [NO3] = Rate = k 2 k1 [NO]2[O2].+ H3O+ Intermediates in a mechanism are species that are neither reactants nor products but that are formed and consumed during the reaction sequence in the mechanism. 54. Rate = k1[NO][O2]. However. The rate law is Rate = k[NO]2[Cl2]. To see if this agrees with experiment. substituting into the rate equation: k −1 k 2 k1 k k [NO]2[Cl2] = k[NO]2[Cl2] where k = 2 1 k −1 k −1 This is a possible mechanism with the second step the rate-determining step because the derived rate law agrees with the experimentally determined rate law. When deriving rate laws from a mechanism. This isn't correct. If we assume the first step is rate-determining.596 C4H9Br → C4H9+ + Br− C4H9 + H2O → C4H9OH2+ C4H9OH2+ + H2O → C4H9OH + H3O+ + CHAPTER 15 CHEMICAL KINETICS ___________________________________________________________ C4H9Br + 2 H2O → C4H9OH + Br. If the rate law derived from the mechanism is the same as the experimental rate law. The intermediates for this mechanism are C4H9+ and C4H9OH2+. [NOCl2] = Rate = k1 [NO][Cl2]. k −1 possible c. a. if we assume the second step to be rate-determining. Let's determine the rate law for each mechanism. we would expect the rate law to be Rate = k1[NO][Cl2]. Rate = k1[NO]2. so only mechanism b is a possible mechanism for this reaction. we must substitute for the intermediate NOCl2 concentration. Assuming a fastequilibrium first step (rate reverse = rate forward): k-1[NOCl2] = k1[NO][Cl2]. . not possible k1 [NO]2 k −1 d. Rate = k2[NOCl2][NO]. Rate = k2[N2O2] and [N2O2] = Rate = k 2 k1 [NO]2 . not possible k −1 Only the mechanism in b is consistent. then the mechanism is possible (assuming the sum of all the steps in the mechanism gives the overall balanced equation). we must substitute for all intermediate concentrations.

CHEMICAL KINETICS 597 a. 57. This mechanism also gives the correct experimentally determined rate law. [HSO3−] = k1 [SO32−][H+] k −1 . SO32− and H+. the rate-determining step could contain BrO3− and HSO3− (the intermediate produced in the first step). and HBrO) are known substances. k2[HBrO3][H+] = k-2[H2BrO3+]. k′′ = k2(k1/k-1)1/2. A possible second step is: BrO3− + HSO3− → products (slow) (slow) A likely choice is: BrO3− + HSO3− → SO42− + HBrO2 Followed by: HBrO2 + SO32− → HBrO + SO42− (fast). From a. k1[BrO3−][H+] = k-1[HBrO3] [HBrO3] = Rate = k1 k k k [BrO3−][H+]. k′ = k1. Rate = k3[Br−][H2BrO3+]. Rate = k2[Br][H2]. rate forward reaction = rate reverse reaction. Rate = k2[BrO3−] [HSO3−]. In order to incorporate all these ions into the rate law. [Br] = (k1/k-1)1/2[Br2]1/2 Substituting into the rate equation: Rate = k2(k1/k-1)1/2[Br2]1/2[H2] = k′′[H2][Br2]1/2 c. Because steps 1 and 2 are fast-equilibrium steps. first step: SO32− + H+ → HSO3− The rate law contains BrO3−. Rate = k1[Br2] = k′[Br2] b. This rate law occurs when the second step is assumed rate-determining and the first step is a fast. assuming reaction one is a fast equilibrium step: k1[SO32−][H+] = k-1[HSO3−]. from b.CHAPTER 15 56. from the fast-equilibrium first step (rate forward = rate reverse): k1[Br2] = k-1[Br]2. HBrO2. we must substitute for the intermediate concentration. This rate law occurs when the first step is assumed rate determining. Rate = k[BrO3−][SO32−][H+]. HBrO + SO32− → SO42− + H+ + Br− (fast) All species in this mechanism (HSO3−. [H2BrO3+] = 2 [HBrO3][H+] = 2 1 [BrO3−][H+]2 k −1 k −2 k − 2 k −1 k 3 k 2 k1 [Br-][BrO3-][H+]2 = k[Br-][BrO3−][H+]2 k − 2 k −1 (fast) 58.equilibrium step.

d[intermediate]/dt = 0. Rate = k3[COCl][Cl2]. so k1[MoCl62−] = k-1[MoCl5−][Cl−] + k2[NO3−][MoCl5−] dt [MoCl5−] = k1[MoCl 6 ] 2− − k −1[Cl − ] + k 2 [ NO 3 ] − . To apply the steady-state assumption. CHAPTER 15 k 2 k1 [BrO3−][SO32−][H+] = k[BrO3−][SO32−][H+] k −1 CHEMICAL KINETICS Rate = k2[I−][HOCl]. we write rate laws for all steps where the intermediate is produced and equate the sum of these rate laws to the sum of the rate laws where the intermediate is consumed.. Rate = k k [ NO ][MoCl 6 ] d[ NO 2 ] = 1 2 − 3 − dt k −1[Cl ] + k 2 [ NO 3 ] − − 2− . from the fast-equilibrium first step: k1[OCl−] = k-1[HOCl][OH−]. substituting into the rate equation: k −1 [OH − ] Rate = 60. The steady-state approximation assumes that the concentration of an intermediate remains constant. a. Cl and COCl are intermediates.598 Rate = 59. Rate = d[ NO 2 ] = k2[NO3−][MoCl5−] dt − (Only the last step contains NO2−.e. [COCl] = 2 [CO][Cl] [Cl][CO] k −2 k −2 ⎛ k ⎞ [Cl]2 k = 1 . 61. from the fast-equilibrium reactions 1 and 2: [COCl] k k = 2 . i. a. MoCl5− b. [Cl] = ⎜ 1 [Cl 2 ] ⎟ ⎜k ⎟ [Cl 2 ] k −1 ⎝ −1 ⎠ k ⎛ k ⎞ Thus [COCl] = 2 ⎜ 1 ⎟ k − 2 ⎜ k −1 ⎟ ⎝ ⎠ k ⎛ k ⎞ Rate = k 3 2 ⎜ 1 ⎟ k − 2 ⎜ k −1 ⎟ ⎝ ⎠ 1/ 2 1/ 2 [CO][Cl2]1/2.) We use the steady-state assumption to substitute for the intermediate concentration in the rate law. Substituting into rate law: 1/ 2 [CO][Cl2]3/2 = k[CO][Cl2]3/2 b. Applying the steady-state approximation to MoCl5−: d[MoCl 5 ] = 0. [HOCl] = k 2 k1[I − ][OCl − ] k[I − ][OCl − ] = k −1[OH − ] [OH − ] k1[OCl − ] .

. then k1[B]2 = k-1[B][B*] + k2[B*]. The larger the activation energy. Rate = d[E ] d[B*] = k2[B*]. = 1 2 dt k −1[B] k −1 [B*] = b. the more molecular collisions there are with sufficient energy to convert to products. Temperature Dependence of Rate Constants and the Collision Model 64. The greater the frequency of collisions. apply steady-state approx. a. Only some of all the possible collisions have the correct orientation to convert reactants to products. the slower is the rate. For a reaction to occur. c. it is the reactive portion of each molecule that must be involved in a collision.CHAPTER 15 62. the greater are the opportunities for molecules to react. to O: dt d[O] = 0. b. dt dt k1[ B]2 k1k 2 [B]2 d[E ] . The higher the temperature. Rate = CHEMICAL KINETICS 599 − d[O 3 ] = k1[M][O3] + k2[O][O3] − k-1[M][O2][O]. d. assume = 0. This occurs at a much faster rate than the decomposition of an energetic B molecule (B*). the rate law is: Rate = = k −1[B] + k 2 k −1[B] + k 2 dt k k [ B]2 kk d[E ] = 1 2 [B]. then Rate = The reaction is first order when the rate of the second step is very slow (when k2 is very small). c. and hence the greater is the rate. so k1[M][O3] = k-1[M][O2][O] + k2[O][O3] dt k1[M][O3] − k-1[M][O2][O] = k2[O][O3] Substitute this expression into the rate law: Rate = − d[O 3 ] = 2k2[O][O3] dt k1[O 3 ][M ] k −1[M ][O 2 ] + k 2 [O 3 ] Rearranging the steady-state approximation for [O]: [O] = Substituting into the rate law: Rate = 2 k 2 k 1[O 3 ]2 [ M ] − d[O 3 ] = dt k −1[M ][O 2 ] + k 2 [O 3 ] 63. and the faster is the rate. Collisions between B molecules only transfer energy from one B to another. When k2 << k-1[B]. a.

⎛k ⎞ E ⎛1 1 ⎞ For two conditions: ln ⎜ 2 ⎟ = a ⎜ − ⎜k ⎟ ⎜ T T ⎟ (Assuming A is temperature independent.5% of the original amount of C2H5I remains.5%..3 × 10 s ⎟ ⎝ ⎠ For three half-lives. Partial pressures are directly related to gas concentrations in mol/L: PC 2 H 5I = 894 torr × 0. K − 720.52 × 10 −7 ⎝ ⎞ 1. Ce4+ and Hg22+ will repel each other (so Ea is much larger).1 × 105 J/mol For k at 325EC (598 K): 5 ⎛ 1. k = 1.3145 J K −1 mol −1 ⎜ 555 K − 645 K ⎝ ⎠ ⎞ ⎟ = 5.600 65. 2) The relative orientation of the reactants when they collide must allow formation of any new bonds necessary to produce products.86 × 105 J / mol ⎛ 1 1 ⎟= ⎜