Answers to Selected Exercises

The answers listed here are from the Complete Solutions Guide, in which 109!mi/h 55.!100 ft 57.!18!g 59.!7 3 105 kg mercury 61.!a. 22738C,
rounding is carried out at each intermediate step in a calculation in order to 0 K; b.!240.8C, 233 K; c.!20.8C, 293 K; d.!4 3 107 8C, 4 3 107!K 63.!a.!312.4
show the correct number of signi#cant #gures for that step. Therefore, an K; 102.68F; b.!248 K; 2138F; c.!0 K;24598F; d.!1074 K; 14708F 65.!160.8C
answer given here may differ in the last digit from the result obtained by car- 5 oX
5 320.8F 67.! a.! TX 5 (TC 1 10°C) o ; b.! 11.4°X; c.! 152°C; 425 K;
rying extra digits throughout the entire calculation and rounding at the end 14 C
(the procedure you should follow). 306°F 69.! It will "oat (density 5 0.80 g/cm3). 71.! 1 3 106 g/cm3
73.!a.!0.28 cm3; b.!49 carats 75.!3.8 g/cm3 77.!a.!Both are the same mass;
Chapter 1 b.!1.0 mL mercury; c.!Both are the same mass; d.!1.0!L benzene 79.!a. 1.0 kg
19.!A law summarizes what happens, e.g., law of conservation of mass in a feather; b.!100!g water; c.!same 81.!2.77 cm 83.!a. Picture iv represents a
chemical reaction or the ideal gas law, PV 5 nRT. A theory (model) is an gaseous compound. Pictures ii and iii also contain a gaseous compound but
attempt to explain why something happens. Dalton’s atomic theory explains have a gaseous element present. b.! Picture vi represents a mixture of two
why mass is conserved in a chemical reaction. The kinetic molecular theory gaseous elements. c.!Picture v represents a solid element. d.!Pictures ii and
explains why pressure and volume are inversely related at constant tempera- iii both represent a mixture of a gaseous element and a gaseous compound.
ture and moles of gas. 21.!The fundamental steps are (1) making observa- 85.!a. heterogeneous; b.!homogeneous (hopefully); c.!homogeneous; d.!ho-
tions; (2) formulating hypotheses; (3) performing experiments to test the mogeneous (hopefully); e.! heterogeneous; f.! heterogeneous 87.! a.! pure;
hypotheses. The key to the scienti#c method is performing experiments to b. mixture; c.!mixture; d.!pure; e.!mixture (copper and zinc); f.!pure; g.!mix-
test hypotheses. If after the test of time, the hypotheses seem to account sat- ture; h.!mixture; i.!mixture. Iron and uranium are elements. Water is a com-
isfactorily for some aspect of natural behavior, then the set of tested hypoth- pound. Table salt is usually a homogeneous mixture composed mostly of
eses turns into a theory (model). However, scientists continue to perform sodium chloride (NaCl), but it usually will contain other substances that help
experiments to re#ne or replace existing theories. 23.!A qualitative obser- absorb water vapor (an anticaking agent). 89.!Compound 91.!a.!physical;
vation expresses what makes something what it is; it does not involve a num- b.! chemical; c.! physical; d.! chemical 93.! The sphere that "oats has the
ber; e.g., the air we breathe is a mixture of gases, ice is less dense than water, smaller density; this will be the object that has the same mass in a larger
rotten milk stinks. The SI units are mass in grams, length in meters, and volume. So the object with the larger diameter will have the larger volume
volume in the derived units of m3. The assumed uncertainty in a number is and will have the smaller density; the larger sphere will "oat. 95.!0.010!kg
61 in the last signi#cant #gure of the number. The precision of an instru- 97. 1.0 3 105 bags 99.!3.0 3 1017!m 101.!a.!1.1 g; b.!4.9!g 103.!14!g
ment is related to the number of signi#cant #gures associated with an ex- 105.!56.568C 107.!a.!Volume 3 density 5 mass; the orange block is more
perimental reading on that instrument. Different instruments for measuring dense. Since mass (orange) . mass (blue) and volume (orange) , volume
mass, length, or volume have varying degrees of precision. Some instru- (blue), the density of the orange block must be greater to account for the
ments only give a few signi#cant #gures for a measurement while others will larger mass of the orange block. b.! Which block is more dense cannot be
give more signi#cant #gures. 25.!Signi#cant #gures are the digits we as- determined. Since mass (orange) . mass (blue) and volume (orange) . vol-
sociate with a number. They contain all of the certain digits and the #rst un- ume (blue), the density of the orange block may or may not be larger than the
certain digit (the #rst estimated digit). What follows is one thousand indi- blue block. If the blue block is more dense, then its density cannot be so large
cated to varying numbers of signi#cant #gures: 1000 or 1 3 103 (1 S.F.); that the mass of the smaller blue block becomes larger than the orange block
1.0 3 103 (2 S.F.); 1.00 3 103 (3 S.F.); 1000. or 1.000 3 103 (4 S.F.). To mass. c.!The blue block is more dense. Since mass (blue) 5 mass (orange)
perform the calculation, the addition/subtraction signi#cant rule is applied to and volume (blue) , volume (orange), the density of the blue block must be
1.5 2 1.0. The result of this is the one signi#cant #gure answer of 0.5. Next, larger to equate the masses. d.! The blue block is more dense. Since mass
the multiplication/division rule is applied to 0.5/0.50. A one signi#cant num- (blue) . mass (orange) and the volumes are equal, the density of the blue block
ber divided by a two signi#cant number yields an answer with one signi#cant must be larger to give the blue block the larger mass. 109. 8.5 6 0.5!g/cm3
#gure (answer 5 1). 27.!The slope of the TF vs. TC plot is 1.8 (5 9/5) and 111.! 3.648 3 104 cable lengths; 6.671 3 106 m; 3648 nautical miles
the y-intercept is 328F. The slope of TC vs. TK plot is 1 and the y-intercept 113.!Phosphorus would be a liquid. 115.!a.!False; sugar is generally con-
is 22738C. 29. The density of a gas is much smaller than the density of a sidered to be the pure compound sucrose, C12H22O11. b.!False; elements and
solid or a liquid. The molecules in a solid and a liquid are very close together, compounds are pure substances. c.!True; air is a mixture of mostly nitrogen
whereas in the gas phase, the molecules are very far apart. 31.!a. exact; and oxygen gases. d.!False; gasoline has many additives, so it is a mixture.
b.!inexact; c.!exact; d.!inexact 33.!a. 3; b.!4; c.!4; d.!1; e.!7; f.!1; g.!3; h.!3 e.! True; compounds are broken down to elements by chemical change.
35.!a. 3.42 3 1024; b.!1.034 3 104; c.!1.7992 3 101; d.!3.37 3 105 37.!2.85 117.!In a subtraction, the result gets smaller, but the uncertainties add. If the
1 0.280 5 3.13 mL; the graduated cylinder on the left limits the precision of two numbers are very close together, the uncertainty may be larger than the
the total volume; it is the least precise measuring device between the two result. For example, let us assume we want to take the difference of the fol-
graduated cylinders. 39.! a. 641.0; b.! 1.327; c.! 77.34; d.! 3215; e.! 0.420 lowing two measured quantities, 999,999 62 and 999,996 62. The differ-
41.!a. 188.1; b.!12; c.!4 3 1027; d.!6.3 3 10226; e.!4.9; Uncertainty appears ence is 3 6 4. Because of the larger uncertainty, subtracting two similar
in the #rst decimal place. The average of several numbers can be only as numbers is bad practice. 119.! a. 2%; b.! 2.2%; c.! 0.2% 121.! dold 5
precise as the least precise number. Averages can be exceptions to the sig- 8.8 g/cm3, dnew 5 7.17 g/cm3; dnew/dold 5 massnew/massold 5 0.81; The differ-
ni#cant #gure rules. f.!0.22 43.!a.!84.3 mm; b.!2.41 m; c.!2.945 3 1025 cm; ence in mass is accounted for by the difference in the alloy used (if the as-
d.!14.45 km; e.!2.353 3 105 mm; f.!0.9033 mm 45.!a.!8 lb and 9.9 oz; 2014 in; sumptions are correct). 123.!7.0% 125.!a.!One possibility is that rope B
b.! 4.0 3 104 km, 4.0 3 107 m; c.! 1.2 3 1022 m3, 12 L, 730 in3, 0.42 ft3 is not attached to anything and rope A and rope C are connected via a pair of
47.!a.!4.00 3 102 rods; 10.0 furlongs; 2.01 3 103 m; 2.01 km; b.!8390.0 rods; pulleys and/or gears; b.!Try to pull rope B out of the box. Measure the dis-
209.75 furlongs; 42,195 m; 42.195 km 49. a.!0.373 kg, 0.822 lb; b.!31.1 g, tance moved by C for a given movement of A. Hold either A or C #rmly while
156 carats; c.! 19.3 cm3 51.! 24 capsules 53.! 2.91 3 109 knots; 3.36 3 pulling on the other rope. 127.!$160./person; 3.20 3 103 nickels/person;

A31
A32 Answers to Selected Exercises

85.6 £/person 129.!200.08F 5 93.338C; 2100.08F 5 273.338C; 93.338C tion, mass must not change. In this equation we have two oxygen atoms and
5 366.48 K; 273.338C 5 199.82 K; difference of temperatures in 8C 5 four hydrogen atoms both before and after the reaction occurs. 47.!O, 7.94;
166.66; difference of temperatures in K 5 166.66; No, there is not a differ- Na, 22.8; Mg, 11.9; O and Mg are incorrect by a factor of < 2; correct for-
ence of 300 degrees in 8C or K. mulas are H2O, Na2O, and MgO. 49.!Using r 5 5 3 10214 cm, dnucleus 5
3! 3! 1015 g/cm3; using r 5 1 3 1028 cm, datom 5 0.4 g/cm3 51.! 37
Chapter 2 53. Sn, tin; Pt, platinum; Hg, mercury; Mg, magnesium; K, potassium; Ag,
19.!A compound will always contain the same numbers (and types) of atoms. silver 55.!a.!6; b.!6; c.!4; d.!7 57.!a. Metals: Mg, Ti, Au, Bi, Ge, Eu, Am;
A given amount of hydrogen will react only with a speci"c amount of oxy- nonmetals: Si, B, At, Rn, Br; b.!metalloids: Si, Ge, B, At. The elements at the
gen. Any excess oxygen will remain unreacted. 21.!Law of conservation of boundary between the metals and the nonmetals are B, Si, Ge, As, Sb, Te, Po,
mass: mass is neither created nor destroyed. The mass before a chemical re- and At. These elements are all considered metalloids. Aluminum has mostly
action always equals the mass after a chemical reaction. Law of de"nite pro- properties of metals. 59.!a.!transition metals; b.!alkaline earth metals; c.!al-
portion: a given compound always contains exactly the same proportion of kali metals; d.! noble gases; e.! halogens 61.! a.! 178 O; b.! 37 60
17 Cl; c.! 27 Co;
elements by mass. Water is always 1!g H for every 8!g oxygen. Law of mul- d.! 57 131 7
26 Fe; e.! 53 I; f.! 3 Li 63.!a.! 23 19 16
11Na b.! 9F c.! 8O 65.!a. 35 p, 44 n, 35 e;
tiple proportions: When two elements form a series of compounds, the ratios b.!35 p, 46 n, 35 e; c.!94 p, 145 n, 94 e; d.!55 p, 78 n, 55 e; e.!1 p, 2 n, 1 e;
of the mass of the second element that combine with one gram of the "rst f.!26 p, 30 n, 26!e 67.!a.!56 p; 54 e; b. 30 p; 28 e; c.!7 p; 10 e; d.!37 p; 36 e;
element can always be reduced to small whole numbers. For CO2 and CO e.!27 p; 24 e; f.!52 p; 54 e; g.!35 p; 36!e 69. 151 31 118
63 Eu ; 50 Sn
21
71.! 238
92 U,
discussed in Section 2.2, the mass ratios of oxygen that react with 1! g of 92 p, 146 n, 92 e, 0; 40 21 51 31
20 Ca , 20 p, 20 n, 18 e, 21; 23V , 23 p, 28 n, 20 e, 31;
89 79 31 32
39Y, 39 p, 50 n, 39 e, 0; 35 Br , 35 p, 44 n, 36 e, 12; 15 P , 15 p, 16 n, 18 e,
2
carbon in each compound are in a 2:1 ratio. 23.!J. J. Thomson’s study of
cathode-ray tubes led him to postulate the existence of negatively charged 32 73.!a.!lose 2 e2 to form Ra21; b. lose 3 e2 to form In31; c.!gain 3 e2 to
particles, which we now call electrons. Ernest Rutherford and his alpha bom- form P32; d.!gain 2 e2 to form Te22; e.!gain 1 e2 to form Br2; f.!lose 1 e2 to
bardment of metal foil experiments led him to postulate the nuclear atom— form Rb1 75.!a.!sodium bromide; b.!rubidium oxide; c.!calcium sul"de;
an atom with a tiny dense center of positive charge (the nucleus) with elec- d.! aluminum iodide; e.! SrF2; f.! Al2Se3; g.! K3N; h.! Mg3P2 77.! a.! cesium
trons moving about the nucleus at relatively large distances away; the #uoride; b.!lithium nitride; c.!silver sul"de (Silver forms only 11 ions so no
distance is so large that an atom is mostly empty space. 25.!The number Roman numerals are needed); d.!manganese(IV) oxide; e. titanium(IV) ox-
and arrangement of electrons in an atom determines how the atom will react ide; f.!strontium phosphide 79.!a.!barium sul"te; b. sodium nitrite; c.!po-
with other atoms. The electrons determine the chemical properties of an tassium permanganate; d.! potassium dichromate 81. a. dinitrogen tetrox-
atom. The number of neutrons present determine the isotope identity and the ide; b.! iodine trichloride; c.! sulfur dioxide; d. diphosphorus pentasul"de
mass number. 27.!2; the ratio increases 29.!Metallic character increases 83. a.!copper(I) iodide; b.!copper(II) iodide; c. cobalt(II) iodide; d. sodium
as one goes down a family and decreases from left to right across the periodic carbonate; e.!sodium hydrogen carbonate or sodium bicarbonate; f. tetrasul-
table. 31.!In the paste, sodium chloride will dissolve to form separate Na1 fur tetranitride; g.!selenium tetrachloride; h.!sodium hypochlorite; i. bar-
and Cl2 ions. With the ions present and able to move about, electrical im- ium chromate; j.!ammonium nitrate 85.!selenate; selenite; tellurate; tellu-
pulses will be conducted. 33.!a.!This represents ionic bonding, which is rite 87.! a.! SF2; b.! SF6; c.! NaH2PO4; d.! Li3N; e.! Cr2(CO3)3; f. SnF2;
the electrostatic attraction between anions and cations. b.! This represents g. NH4C2H3O2; h.!NH4HSO4; i.!Co(NO3)3; j.!Hg2Cl2; Mercury(I) exists as
covalent bonding, where electrons are shared between two atoms. This could Hg221 ions. k.!KClO3; l.!NaH 89.!a.!Na2O; b.!Na2O2; c.!KCN; d. Cu(NO3)2;
be the space-"lling model for H2O or SF2 or NO2, etc. 35.!Statements a and e.!SeBr4; f.!HIO2; g.!PbS2; h.!CuCl; i.!GaAs (from the positions in the peri-
b are true. Element 118 is a noble gas and will be a nonmetal. For statement odic table, Ga31 and As32 are the predicted ions); j.!CdSe; k.!ZnS; l.!HNO2;
c, hydrogen has mostly nonmetallic properties. For statement d, a family of m.!P2O5 91. a.!nitric acid, HNO3; b.!perchloric acid, HClO4; c. acetic acid,
elements is also known as a group of elements. For statement e, two items HC2H3O2; d.! sulfuric acid, H2SO4; e.! phosphoric acid, H3PO4 93.! There
are incorrect. When a metal reacts with a nonmetal, an ionic compound is should be no difference. The composition of insulin from both sources will
produced and the formula of the compound would be AX2 (since alkaline be the same and therefore it will have the same activity regardless of the
earth metals for 12 ions and halogens form 21 ions in ionic compounds). source. 95.! a. 53 protons, 78 neutrons; b.! 81 protons, 120 neutrons
The correct statement would be: When alkaline earth metal, A, reacts with 97.!26!p, 27 n, 24!e 99.!Only statement a is true. For statement b, X has 34
a halogen, X, the formula of the ionic compound formed should be AX2. protons. For statement c, X has 45 neutrons. For statement d, X is selenium.
37.! a. The composition of a substance depends on the number of atoms 101.!a.!lead(II) acetate; b.!copper(II) sulfate; c. calcium oxide; d.!magnesium
of each element making up the compound (depends on the formula of sulfate; e.!magnesium hydroxide; f.!calcium sulfate; g.!dinitrogen monoxide
the compound) and not on the composition of the mixture from which or nitrous oxide (common) 103.! X 5 Ra, 142 neutrons 105.! a.!Ca3N2;
it was formed. b.! Avogadro’s hypothesis implies that volume ratios calcium nitride; b.!K2O; potassium oxide; c.!RbF; rubidium #uoride; d.!MgS;
are equal to molecule ratios at constant temperature and pressure. magnesium sul"de; e.! BaI2; barium iodide; f.! Al2Se3; aluminum selenide;
H2 1g2 1 Cl2 1g2 n 2HCl 1g2 ; from the balanced equation, the volume of g.! Cs3P; cesium phosphide; h.! InBr3; indium(III) bromide (In forms com-
HCl!produced will be twice the volume of H2 (or Cl2) reacted. 39.!299!g pounds with 11 and 13 ions. You would predict a 13 ion from the position
41.!The ratio of the masses of carbon that combine with 1!g of oxygen is of In in the periodic table.) 107.!a. P; 15 p; 16 n; b.!I; 53 p; 74 n; c.!K; 19!p;
0.751 2 20!n d.!Yb; 70 p; 103!n 109.!The law of multiple proportions does not in-
5 . Note that this supports the law of multiple proportions because
0.375 1 volve looking at the ratio of the mass of one element with the total mass of
this carbon ratio is a small whole number. 43.!For CO and CO2, it is easiest the compounds. To illustrate the law of multiple proportions, we compare the
to concentrate on the mass of oxygen that combines with 1!g of carbon. From mass of carbon that combines with 1.0! g of oxygen in each compound:
the formulas (two oxygen atoms per carbon atom in CO2 vs. one oxygen 27.2 g C 42.9 g C
compound 1: 5 0.374!g C/g O; compound 2: 5 0.751!g C/g O;
atom per carbon atom in CO), CO2 will have twice the mass of oxygen that 72.8 g O 57.1 g O
combines per gram of carbon as compared to CO. For CO2 and C3O2, it is 0.751 2
5 . Because the ratio is a small whole number, this supports the law
easiest to concentrate on the mass of carbon that combines with 1!g of oxy- 0.374 1
gen. From the formulas (three carbon atoms per two oxygen atoms in C3O2 of multiple proportions.
vs. one carbon atom per two oxygen atoms in CO2), C3O2 will have three 111. Number of Protons Number of Neutrons Symbol
times the mass of carbon that combines per gram of oxygen as compared to 19
CO2. As expected, the mass ratios are whole numbers as predicted by the law 9 10 9F
27
of multiple proportions. 45.!Mass is conserved in a chemical reaction be- 13 14 13Al
127
cause atoms are conserved. Chemical reactions involve the reorganization of 53 74 53 I
79
atoms, so formulas change in a chemical reaction, but the number and types 34 45 34 Se
32
of atoms do not change. Because the atoms do not change in a chemical reac- 16 16 16 S
 Answers to Selected Exercises A33

113. Atom/Ion Protons Neutrons Electrons 1022 atoms N; b.!3.76 3 1022 atoms N; c.!4.78 3 1021 atoms N 65.!2.77 3
120
1019 molecules; 3.26 mg Cl 67.! a.! 0.9393 mol; b.! 2.17 3 1024 mol;
50 Sn 50 70 50 c.!2.5 3 1028 mol 69.!a.!4.01 3 1022 atoms N; b.!5.97 3 1022 atoms N;
25 21
12 Mg 12 13 10 c.! 3.67 3 1022 atoms N; d.! 6.54 3 1022 atoms N 71.! 176.12 g/mol;
56 21
26 Fe 26 30 24 2.839 3 1022 mol C6H8O6; 1.368 3 1022 molecules 73.!a.!165.39 g/mol;
79
34 Se 34 45 34 b.! 3.023 mol; c. 3.3 g; d.! 5.5 3 1022 atoms; e.! 1.6 g; f.! 1.373 3 10219! g
35
17 Cl 17 18 17 75.!a.!50.00% C, 5.595% H, 44.41% O; b.!55.80% C, 7.025% H, 37.18% O;
63
29 Cu 29 34 29 c.! 67.90% C, 5.699% H, 26.40% N 77.! NO 79.! 6.54 3 104 g/mol
81.!a.!39.99% C, 6.713% H, 53.30% O; b.!40.00% C, 6.714% H, 53.29% O;
115. carbon tetrabromide, CBr4; cobalt(II) phosphate, Co3(PO4)2; magne-
c.! 40.00% C, 6.714% H, 53.29% O (all the same except for rounding
sium chloride, MgCl2; nickel(II) acetate, Ni(C2H3O2)2; calcium nitrate,
differences) 83.! a. NO2; b.! CH2; c.! P2O5; d.! CH2O 85.! C3H6O2
Ca(NO3)2 117.!K will lose 1 e2 to form K1. Cs will lose 1 e2 to form Cs1.
87. compound! I: HgO; compound II: Hg2O 89.! SN; S4N4 91.! C3H5Cl;
Br will gain 1 e2 to form Br2. Sulfur will gain 2 e2 to form S22. Se will gain
C6H10Cl2 93.! CH2O 95.! C3H4, C9H12 97.! a.! C6H12O6(s) 1 6O2(g) n
2 e2 to form Se22. 119.! Cu, Ag, and Au 121.! C:H 5 8:18 or 4:9
6CO2(g) 1 6H2O(g); b.! Fe2S3(s) 1 6HCl(g) n 2FeCl3(s) 1 3H2S(g);
123.!The alchemists were incorrect. The solid residue must have come from MnO2
c.! CS2(l) 1 2NH3(g)! n H2S(g) 1 NH4SCN(s) 99.! 2H2O2(aq) h
the #ask. 125.!a.!The compounds are isomers of each other. Isomers are
compounds with the same formula but the atoms are attached differently, 2H2O(l) 1 O2(g) 101.! a.! 3Ca(OH)2(aq) 1 2H3PO4(aq) n 6H2O(l) 1
resulting in different properties. b.!When wood burns, most of the solid ma- Ca3(PO4)2(s); b.! Al(OH)3(s) 1 3HCl(aq) n AlCl3(aq) 1 3H2O(l);
terial is converted to gases, which escape. c.! Atoms are not an indivisible c.!2AgNO3(aq) 1 H2SO4(aq) n Ag2SO4(s) 1 2HNO3(aq) 103.!a.!2C6H6(l)
particle. Atoms are composed of electrons, neutrons, and protons. d.!The two 1 15O2(g) n 12CO2(g) 1 6H2O(g); b. 2C4H10(g) 1 13O2(g) n 8CO2(g) 1
hydride samples contain different isotopes of either hydrogen and/or lithium. 10H2O(g); c.!C12H22O11(s) 1 12O2(g) n 12CO2(g) 1 11H2O(g); d.!4Fe(s)
Isotopes may have different masses but have similar chemical properties. 1 3O2(g) n 2Fe2O3(s); e. 4FeO(s) 1 O2(g) n 2Fe2O3(s) 105.!a.!SiO2(s)
127.!CO2 129.!tantalum(V) oxide; the formula would have the same sub- 1 2C(s) n Si(s) 1 2CO(g); b.!SiCl4(l) 1 2Mg(s) n Si(s) 1 2MgCl2(s);
scripts, Ta2S5; 40 protons 131.!Ge41; 99Tc c.!Na2SiF6(s) 1 4Na(s) n Si(s) 1 6NaF(s) 107.!CaF2 ? 3Ca3(PO4)2(s) 1
10H2SO4(aq) + 20H2O(l) n 6H3PO4(aq) 1 2HF(aq) + 10CaSO4 ? 2H2O(s)
Chapter 3 109.! 7.26! g Al; 21.5! g Fe2O3; 13.7! g Al2O3 111.! 4.355 kg 113.! 72.3! g
25. The atomic mass of any particular isotope is a relative mass to a speci"c 115.!a.!0.076 g; b.!0.052!g 117.!32 kg 119.!7.2 3 104!g 121.!2NO(g) 1
standard. The standard is one atom of the carbon-12 isotope weighing exactly O2(g) n 2NO2(g); NO is limiting. 123.!a.!1.22 3 103 g; 284!g H2 unre-
12.0000 u. One can determine from experiment how much heavier or lighter acted 125.!0.301!g H2O2; 1.75!g HCl in excess 127.!2.81 3 106!g HCN;
any speci"c isotope is than 12C. From this information, we assign an atomic 5.63 3 106! g H2O 129.! 72.9% 131.! 82.9% 133.! 1.20 3 103 kg 5
mass value to that isotope. For example, experiment tells one that 16O is about 1.20! metric tons 135.! 12C1H216O 137.! 6 139.! 71.40% C, 8.689% H,
4/3 heavier than 12C, so a mass of 4/3(12.00) 5 16.00!u is assigned to 16O. The 5.648% F, 14.26% O 141.! Sulfur 143.! C8H11O3N 145.! 1360 g/mol
atomic mass listed in the periodic table is also an average mass. Most elements 147.! 9.25! 3 1022! H atoms 149.! 4.30 3 1022 mol; 2.50! g 151.! 5
in nature occur as a mixture of isotopes. The atomic mass of an element is the 153.! 42.8% 155.! 81.1! g 157.! 86.2% 159.! C20H30O 161.! 14.3% X,
average mass of all the isotopes that make up a speci"c element, weighted by 85.7% Z 163.! 1.242 mol Mg3(PO4)2; 1.846 mol Ca(NO3)2; 0.7291 mol
abundance. 27.!Each person would have 90 trillion dollars. 29.!Only in b K2CrO4; 3.761!mol N2O5 165.!C7H8O 167.!a.!false; this is what is done
are the empirical formulas the same for both compounds illustrated. In b, gen- when equations are balanced; b.!false; the coef"cients give molecule ratios
eral formulas of X2Y4 and XY2 are illustrated, and both have XY2 for an em- as well as mole ratios between reactants and products; c.!false; the reactants
pirical formula. 31.!The mass percent of a compound is a constant no matter are on the left, with the products on the right; d.!true; e.!true; in order for
what amount of substance is present. Compounds always have constant com- mass to be conserved, there must be the same number of atoms as well as the
position. 33.! c 35.! The theoretical yield is the stoichiometric amount of same type of atoms on both sides. 169.! 51.7! g Na2SO3; 7.39! g H2O
product that should form if the limiting reactant is completely consumed and 171.!I:!NH3; II: N2H4; III: HN3. If we set the atomic mass of H equal to 1.008,
the reaction has 100% yield. 37.!The information needed is mostly the coef- the atomic mass for nitrogen is 14.01. 173.! C7H5N3O6 175. 5.7! g FeO
"cients in the balanced equation and the molar masses of the reactants and and 22.4!g Fe2O3 177.!40.08% 179.!N4H6 181.!1.8 3 106!g Cu(NH3)4Cl2;
products. For percent yield, we would need the actual yield of the reaction and 5.9 3 105! g NH3 183.! 207 u, Pb 185.! Al2Se3 187.! LaH2.90 contains
the amounts of reactants used. 1 9
La21, or 10.% La21, and La31, or 90.% La31 189.! 0.48 mol
a. mass of CB produced 5 1.00 3 104 molecules A2B2 3 10 10
191.! a.! 113 Fe atoms; b.! mass 5 9.071 3 10220 g; c.! 540 Ru atoms
1 mol A2B2 2 mol CB molar mass of CB 193.!M!5 Y, X 5 Cl, yttrium(III) chloride; 1.84!g
3 3
6.022 3 1023 molecules A2B2 1 mol A2B2 mol CB
2 atoms A Chapter 4
b. atoms of A produced 5 1.00 3 104 molecules A2B2 3 17. a.! Polarity is a term applied to covalent compounds. Polar covalent
1 molecule A2B2
c. mol of C reacted 5 1.00 3 104 molecules A2B2 3 compounds have an unequal sharing of electrons in bonds that results in an
unequal charge distribution in the overall molecule. Polar molecules have a
1 mol A2B2 2 mol C
3 partial negative end and a partial positive end. These are not full charges as
6.022 3 1023 molecules A2B2 1 mol A2B2
in ionic compounds, but are charges much less in magnitude. Water is a polar
actual mass molecule and dissolves other polar solutes readily. The oxygen end of water
d. % yield 5 3 100; The theoretical mass of CB produced
theoretical mass (the partial negative end of the polar water molecule) aligns with the partial
was calculated in part a.!If the actual mass of CB produced is given, then the positive end of the polar solute while the hydrogens of water (the partial
percent yield can be determined for the reaction using the percent yield equa- positive end of the polar water molecule) align with the partial negative end
tion. 39.! 207.2 u, Pb 41.! 185! u 43.! 48% 151Eu and 52% 153Eu of the solute. These opposite charged attractions stabilize polar solutes in
45. There are three peaks in the mass spectrum, each 2 mass units apart. This water. This process is called hydration. Nonpolar solutes do not have perma-
is consistent with two isotopes, differing in mass by two mass units. 47.!4.64 3 nent partial negative and partial positive ends; nonpolar solutes are not stabi-
10220!g Fe 49.!1.00 3 1022 atoms C 51.!Prozac: 309.32 g/mol; Zoloft: lized in water and do not dissolve. b.!KF is a soluble ionic compound so it is
306.22 g/mol 53.! a. 17.03 g/mol; b.! 32.05 g/mol; c.! 252.08 g/mol a strong electrolyte. KF(aq) actually exists as separate hydrated K1 ions and
55.!a. 0.0587 mol NH3; b.!0.0312 mol N2H4; c.!3.97 3 1023 mol (NH4)2Cr2O7 hydrated F2 ions in solution: C6H12O6 is a polar covalent molecule that is a
57.!a. 85.2!g NH3; b.!160. g N2H4; c.!1260!g (NH4)2Cr2O7 59.!a. 70.1!g N; nonelectrolyte. C6H12O6 is hydrated as described in part a.!c. RbCl is a solu-
b.!140. g N; c.!140. g N 61.!a. 3.54 3 1022 molecules NH3; b.!1.88 3 1022 ble ionic compound so it exists as separate hydrated Rb1 ions and hydrated
molecules N2H4; c.!2.39 3 1021 formula units (NH4)2Cr2O7 63.!a. 3.54 3 Cl2 ions in solution. AgCl is an insoluble ionic compound so the ions stay
A34 Answers to Selected Exercises

together in solution and fall to the bottom of the container as a precipitate. Ca21(aq) 1 SO422(aq) n CaSO4(s); d.! K2S(aq) 1 Ni(NO3)2(aq) n
d. HNO3 is a strong acid and exists as separate hydrated H1 ions and hy- 2KNO3(aq) 1 NiS(s); 2K1(aq) 1 S22(aq) 1 Ni21(aq) 1 2NO32(aq) n
drated NO32 ions in solution. CO is a polar covalent molecule and is hy- 2K1(aq) 1 2NO32(aq) 1 NiS(s); Ni21(aq) 1 S22(aq) n NiS(s)
drated as explained in part a. 19.!Only statement b is true. A concentrated 55. a.!CuSO4(aq) 1 Na2S(aq) n CuS(s) 1 Na2SO4(aq); Cu21(aq) 1 S22(aq)
solution can also contain a nonelectrolyte dissolved in water, e.g., concen- n CuS(s); the gray spheres are the Na1 spectator ions and the blue-green
trated sugar water. Acids are either strong or weak electrolytes. Some ionic spheres are the SO422 spectator ions; b.! CoCl2(aq) 1 2NaOH(aq) n
compounds are not soluble in water, so they are not labeled as a speci#c type Co(OH)2(s) 1 2NaCl(aq); Co21(aq) 1 2OH2(aq) n Co(OH)2(s); the gray
of electrolyte. 21.!Bromides: NaBr, KBr, and NH4Br (and others) would be spheres are the Na1 spectator ions and the green spheres are the Cl2 specta-
soluble and AgBr, PbBr2, and Hg2Br2 would be insoluble. Sulfates: Na2SO4, tor ions; c.!AgNO3(aq) 1 KI(aq) n AgI(s) 1 KNO3(aq); Ag1(aq) 1 I2(aq)
K2SO4, and (NH4)2SO4 (and others) would be soluble and BaSO4, CaSO4, n AgI(s); the red spheres are the K1 spectator ions and the blue spheres are
and PbSO4 (or Hg2SO4) would be insoluble. Hydroxides: NaOH, KOH, and the NO32 spectator ions 57.! a. Ba21(aq) 1 SO422(aq) n BaSO4(s);
Ca(OH)2 (and others) would be soluble and Al(OH)3, Fe(OH)3, and Cu(OH)2 b. Pb21(aq) 1 2Cl2(aq) n PbCl2(s); c.! no reaction; d.! no reaction;
(and others) would be insoluble. Phosphates: Na3PO4, K3PO4, and (NH4)3PO4 e. Cu21(aq) 1 2OH2(aq) n Cu(OH)2(s) 59.!Ca21, Sr21, or Ba21 could all
(and others) would be soluble and Ag3PO4, Ca3(PO4)2, and FePO4 (and oth- be present. 61. 0.607! g 63.! 0.668! g 65.! 2.82! g 67.! a.! 2KOH(aq) 1
ers) would be insoluble. Lead: PbCl2, PbBr2, PbI2, Pb(OH)2, PbSO4, and PbS Mg(NO3)2(aq) n Mg(OH)2(s) 1 2KNO3(aq); b.! magnesium hydroxide;
(and others) would be insoluble. Pb(NO3)2 would be a soluble Pb21 salt. c. 0.583 g; d.!0!M OH2, 5.00 3 1022!M Mg21, 0.100!M K1, 0.200!M NO32
23. The Brønsted–Lowry de#nitions are best for our purposes. An acid is a 69. 23 u; Na 71.! a. 2HClO4(aq) 1 Mg(OH)2(s) n Mg(ClO4)2(aq) 1
proton donor and a base is a proton acceptor. A proton is an H1 ion. Neutral 2H2O(l); 2H1(aq) 1 2ClO42(aq) 1 Mg(OH)2(s) n Mg21(aq) 1 2ClO42(aq)
hydrogen has 1 electron and 1 proton, so an H1 ion is just a proton. An acid– 1 2H2O(l); 2H1(aq) 1 Mg(OH)2(s) n Mg21(aq) 1 2H2O(l); b.!HCN(aq) 1
base reaction is the transfer of an H1 ion (a proton) from an acid to a base. NaOH(aq) n NaCN(aq) 1 H2O(l); HCN(aq) 1 Na1(aq) 1 OH2(aq) n
25. a.!The species reduced is the element that gains electrons. The reducing Na1(aq) 1 CN2(aq) 1 H2O(l); HCN(aq) 1 OH2(aq) n H2O(l) 1 CN2(aq);
agent causes reduction to occur by itself being oxidized. The reducing agent c.! HCl(aq) 1 NaOH(aq) n NaCl(aq) 1 H2O(l); H1(aq) 1 Cl2(aq) 1
is generally listed as the entire formula of the compound/ion that contains the Na1(aq) 1 OH2(aq) n Na1(aq) 1 Cl2(aq) 1 H2O(l); H1(aq) 1 OH2(aq)
element oxidized. b.!The species oxidized is the element that loses electrons. n H2O(l) 73.! a. KOH(aq) 1 HNO3(aq) n H2O(l) 1 KNO3(aq);
The oxidizing agent causes oxidation to occur by itself being reduced. The b. Ba(OH)2(aq) 1 2HCl(aq) n 2H2O(l) 1 BaCl2(aq); c. 3HClO4(aq)
oxidizing agent is generally listed as the entire formula of the compound/ion 1 Fe(OH)3(s) n 3H2O(l) 1 Fe(ClO4)3(aq); d. AgOH(s) 1 HBr(aq) n
that contains the element reduced. c.!For simple binary ionic compounds, the AgBr(s) 1 H2O(l); e.! Sr(OH)2(aq) 1 2HI(aq) n 2H2O(l) 1 SrI2(aq)
actual charges on the ions are the oxidation states. For covalent compounds, 75.! a. 100. mL; b.! 66.7 mL; c.! 50.0 mL 77.! 2.0 3 1022 M excess OH2
nonzero oxidation states are imaginary charges the elements would have if 79. 0.102!M 81.!43.8 mL 83.!0.4178!g 85.!a. K, 11; O, 22; Mn, 17;
they were held together by ionic bonds (assuming the bond is between two b.!Ni, 14; O, 22; c.!Na, 11; Fe, 12; O, 22; H, 11 d. H, 11; O, 22; N, 23;
different nonmetals). Nonzero oxidation states for elements in covalent com- P, 15; e.!P, 13; O, 22; f.!O, 22; Fe, 1 83 ; g.!O, 22; F, 21; Xe, 16; h.!S, 14;
pounds are not actual charges. Oxidation states for covalent compounds are F, 21; i.!C, 12; O, 22; j.!C, 0; H, 11; O, 22 87.!a.!23; b.!23; c.!22;
a bookkeeping method to keep track of electrons in a reaction. d.!12; e.!11; f.!14; g.!13; h.!15; i.!0
27.!
89. Oxidizing Reducing Substance Substance
Redox? Agent Agent Oxidized Reduced
Br– Cl– 2+ Cl–
Na+ Mg a. Yes Ag1 Cu Cu Ag1
Na+ Mg2+
Br– Cl– Cl– Cl–
b. No — — — —
Na+ c. No — — — —
Br– Mg2+ Cl– d. Yes SiCl4 Mg Mg SiCl4 (Si)
e.!No — — — —
a. b.
c. For answers c–i, we will describe what should be in each solution. For c, In b, c, and e, no oxidation numbers change from reactants to products.
the drawing should have three times as many NO32 anions as Al31 cations. 91. a.! 3I2(aq) 1 2H1(aq) 1 ClO2(aq) n I32(aq) 1 Cl2(aq) 1 H2O(l);
d. The drawing should have twice as many NH41 cations as SO422 anions. b.!7H2O(l) 1 4H1(aq) 1 3As2O3(s) 1 4NO32(aq) n 4NO(g) 1 6H3AsO4(aq)
e. The drawing should have equal numbers of Na1 cations and OH2 anions. c.! 16H1(aq) 1 2MnO42(aq) 1 10Br2(aq) n 5Br2(l) 1 2Mn21(aq) 1
f. The drawing should have equal numbers of Fe21 cations and SO422 anions. 8H2O(l) d.! 8H1(aq) 1 3CH3OH(aq) 1 Cr2O722(aq) n 2Cr31(aq) 1
g.!The drawing should have equal numbers of K1 cations and MnO42 anions. 3CH2O(aq) 1 7H2O(l) 93.! a.! 2H2O(l) 1 Al(s) 1 MnO42(aq) n
h.!The drawing should have equal numbers of H1 cations and ClO42 anions. Al(OH)42(aq) 1 MnO2(s); b.!2OH2(aq) 1 Cl2(g) n Cl2(aq) 1 OCl2(aq) 1
i.!The drawing should have equal numbers of NH41 cations and C2H3O22 H2O(l); c.!OH2(aq) 1 H2O(l) 1 NO22(aq) 1 2Al(s) n NH3(g) 1 2AlO22(aq)
anions. 29.!CaCl2(s) n Ca21(aq) 1 2Cl2(aq) 31.!a. 0.2677 M; b.!1.255 95.!4NaCl(aq) 1 2H2SO4(aq) 1 MnO2(s) n 2Na2SO4(aq) 1 MnCl2(aq) 1
3 1023 M; c.!8.065 3 1023!M 33.!a.!MCa21 5 1.00 M, MNO32 5 2.00 M; Cl2(g) 1 2H2O(l) 97.!1.622 3 1022!M 99.!a.!4.46 3 1022 M; b.!24.8 mL
b. MNa1 5 4.0 M, MSO422 5 2.0 M; c.!MNH41 5 MCl2 5 0.187 M; d. MK1 5 101.!We should weigh out between 4.24 and 4.32!g of KIO3. We should weigh
0.0564 M, MPO432 5 0.0188!M 35.!100.0 mL of 0.30!M AlCl3 37.!4.00!g it to the nearest milligram or 0.1 mg. Dissolve the KIO3 in water, and dilute
39.!0.0472!g 41.!a.!Place 20.0!g NaOH in a 2-L volumetric "ask; add water to the mark in a 1-L volumetric "ask. This will produce a solution whose
to dissolve the NaOH and #ll to the mark. b.!Add 500. mL of the 1.00!M NaOH concentration is within the limits and is known to at least the fourth decimal
stock solution to a 2-L volumetric "ask; #ll to the mark with water. c.!As in a, place. 103.! increase by 0.019 M 105.! Ca21(aq) 1 C2O422(aq) n
instead using 38.8! g K2CrO4. d.! As in b, instead using 114 mL of 1.75! M CaC2O4(s) 107.!a. AgNO3, Pb(NO3)2, and Hg2(NO3)2 would form precipi-
K2CrO4 stock solution. 43.!MNH41 5 0.272 M, MSO422 5 0.136!M 45.!4.5!M tates with the Cl2 ion; Ag1(aq) 1 Cl2(aq) n AgCl(s); Pb21(aq) 1 2Cl2(aq)
47. 5.94 3 1028! M 49.! Aluminum nitrate, magnesium chloride, and ru- n PbCl2(s); Hg221(aq) 1 2Cl2(aq) n Hg2Cl2(s); b.!Na2SO4, Na2CO3, and
bidium sulfate are soluble. 51.! a.! No precipitate forms; b.! Al(OH)3(s); Na3PO4 would form precipitates with the Ca21 ion; Ca21(aq) 1 SO422(aq)
c.!CaSO4(s); d.!NiS(s) 53.!a.!No reaction occurs because all possible prod- n CaSO4(s); Ca21(aq) 1 CO322(aq) n CaCO3(s); 3Ca21(aq) 1 2PO432(aq)
ucts are soluble salts. b.!2Al(NO3)3(aq) 1 3Ba(OH)2(aq) n 2Al(OH)3(s) 1 n Ca3(PO4)2(s); c.!NaOH, Na2S, and Na2CO3 would form precipitates with
3Ba(NO3)2(aq); 2Al31(aq) 1 6NO32(aq) 1 3Ba21(aq) 1 6OH2(aq) n the Fe31 ion; Fe31(aq) 1 3OH2(aq) n Fe(OH)3(s); 2Fe31(aq) 1 3S22(aq)
2Al(OH)3(s) 1 3Ba21(aq) 1 6NO32(aq); Al31(aq) 1 3OH2(aq) n n Fe2S3(s); 2Fe31(aq) 1 3CO322(aq) n Fe2(CO3)3(s); d.!BaCl2, Pb(NO3)2,
Al(OH)3(s); c.!CaCl2(aq) 1 Na2SO4(aq) n CaSO4(s) 1 2NaCl(aq); Ca21(aq) and Ca(NO3)2 would form precipitates with the SO422 ion; Ba21(aq) 1
1 2Cl2(aq) 1 2Na1(aq) 1 SO422(aq) n CaSO4(s) 1 2Na1(aq) 1 2Cl2(aq); SO422(aq) n BaSO4(s); Pb21(aq) 1 SO422(aq) n PbSO4(s); Ca21(aq) 1
SO422(aq) n CaSO4(s); e.!Na2SO4, NaCl, and NaI would form precipitates
 Answers to Selected Exercises A35

with the Hg221 ion; Hg221(aq) 1 SO422(aq) n Hg2SO4(s); Hg221(aq) 1 pressure of NH3. The partial pressure of H2 will be three times the partial
2Cl2(aq) n Hg2Cl2(s); Hg221(aq) 1 2I2(aq) n Hg2I2(s); f.!NaBr, Na2CrO4, pressure of N2. 37.!CO2 39.!From the plot, Ne appears to behave most
and Na3PO4 would form precipitates with the Ag1 ion; Ag1(aq) 1 Br2(aq) n ideally. 41.!a.!3.6 3 103 mm Hg; b. 3.6 3 103 torr; c.!4.9 3 105 Pa; d.!71!psi
AgBr(s); 2Ag1(aq) 1 CrO422(aq) n Ag2CrO4(s); 3Ag1(aq) 1 PO432(aq) n 43.! 65 torr, 8.7 3 103 Pa, 8.6 3 1022 atm 45.! a.! 642 torr, 0.845 atm;
Ag3PO4(s) 109.! Ba 111.! 1.465% 113.! 2.00! M 115.! 180.2 g/mol 8.56 3 104 Pa; b.! 975 torr; 1.28 atm; 1.30 3 105 Pa; c.! 517 torr; 850.! torr
117.! C6H8O6 119.! 4.05% 121.! 63.74% 123.! 4H1(aq) 1 Mn(s) 1 47.!0.972!atm 49.!8.01 L 51.!a.!14.0 L; b.!4.72 3 1022 mol; c.!678!K;
2NO32(aq) n Mn21(aq) 1 2NO2(g) 1 2H2O(l); 3H2O(l) 1 2Mn21(aq) 1 d.! 133 atm 53.! 88.9! g He; 44.8! g H2 55.! 0.0449 mol 57. a.! 69.6! K;
5IO42(aq) n 2MnO42(aq) 1 5IO32(aq) 1 6H1(aq) 125.!2.979 3 1023!M b.! 32.3 atm 59.! 1.1 3 1022 air particles 61.! 1.27 mol 63.! PB 5 2PA
127.!747 mL 129.!0.052!M 131.!0.328!M 133.!MgSO4: S has an oxida- 65.!a. 12.8 atm; b.!161 K; c.!620. K 67.!5.1 3 104 torr 69.!The volume of
tion state of 16. PbSO4: Lead has an oxidation state of 12. O2: O has an the balloon increases from 1.00! L to 2.82 L, so the change in volume is
oxidation state of zero. Ag: Ag has an oxidation state of zero. CuCl2: Copper 1.82!L. 71.!3.21!g Al 73.!135!g NaN3 75.!1.5 3 107!g Fe, 2.6 3 107!g
has an oxidation state of 12. 135.! a. 2.5 3 1028 M; b.! 8.4 3 1029 M; 98% H2SO4 77.!33.2!g 79.!2.47 mol H2O 81.!a.!2CH4(g) 1 2NH3(g) 1
c.!1.33 3 1024 M; d.!2.8 3 1027!M 137.!a. 24.8% Co, 29.7% Cl, 5.09% H, 3O2(g) n 2HCN(g) 1 6H2O(g); b.!13.3!L 83.!Cl2 85.!12.6 g/L 87.!PHe!5
40.4% O; b.!CoCl2 ? 6H2O; c.!CoCl2 ? 6H2O(aq) 1 2AgNO3(aq) n 2AgCl(s) 0.50 atm, PNe 5 0.30 atm, PAr 5 0.20 atm 89.! PHe 5 18.4 atm; PO2 5
1 Co(NO3)2(aq) 1 6H2O(l), CoCl2 ? 6H2O(aq) 1 2NaOH(aq) n Co(OH)2(s) 4.63!atm; PTOTAL 5 23.0 atm 91.!PH2 5 317 torr, PN2 5 50.7 torr, PTOTAL 5
1 2NaCl(aq) 1 6H2O(l), 4Co(OH)2(s) 1 O2(g) n 2Co2O3(s) 1 4H2O(l) 368!torr 93.!PHe 5 50.0 torr; PNe 5 76.0 torr; PAr 5 90.0 torr; PTOTAL 5
139. 14.6! g Zn and 14.4! g Ag 141.! 0.123! g SO422, 60.0% SO422; 216.0 torr 95. 0.230 97.! a.! xCH4 5 0.412, xO2 5 0.588; b.! 0.161 mol;
61% K2SO4 and 39% Na2SO4 143.! 4.90! M 145.! Y, 2.06 mL/min; Z, c.!1.06!g CH4, 3.03!g O2 99. 0.990 atm; 0.625!g 101.!18.0% 103.!46.5%
4.20 mL/min 147. 57.6 mL 149.! 4.7 3 1022! M 151.! Citric acid has 105.!PTOTAL 5 6.0 atm; PH2 5 1.5 atm; PN2 5 4.5 atm 107.!PN2 5 0.98 atm;
three acidic hydrogens per citric acid molecule. 153.!0.07849 6 0.00016!M PTOTAL 5 2.9 atm 109.!Both CH4(g) and N2(g) have the same average kinetic
or 0.0785 6 0.0002! M 155.! a.! 7H2O(l) 1 2Cr31(aq) 1 3S2O822(aq) n energy at the various temperatures. 273 K, 5.65 3 10221 J/molecule; 546 K,
Cr2O722(aq) 1 14H1(aq) 1 6SO422(aq); 14H1(aq) 1 6Fe21(aq) 1 1.13 3 10220 J/molecule 111.!CH4: 652 m/s (273 K); 921 m/s (546 K); N2:
Cr2O722(aq) n 2Cr31(aq) 1 6Fe31(aq) 1 7H2O(l); b.! 3.00 3 1024 cm 493 m/s (273 K); 697 m/s (546 K) 113.!The number of gas particles is con-
157.!3(NH4)2CrO4(aq) 1 2Cr(NO2)3(aq) n 6NH4NO2 (aq) 1 Cr2(CrO4)3(s); stant, so at constant moles of gas, either a temperature change or a pressure
7.34!g 159.!X 5 Se; H2Se is hydroselenic acid; 0.252!g change results in the smaller volume. If the temperature is constant, an in-
crease in the external pressure would cause the volume to decrease. Gases are
mostly empty space, so gases are easily compressible. If the pressure is con-
Chapter 5
stant, a decrease in temperature would cause the volume to decrease. As the
23. higher than; 13.6 times taller; When the pressure of the column of liquid
temperature is lowered, the gas particles move with a slower average velocity
standing on the surface of the liquid is equal to the pressure exerted by air on
and don’t collide with the container walls as frequently and as forcefully. As
the rest of the surface of the liquid, then the height of the column of liquid
a result, the internal pressure decreases. In order to keep the pressure constant,
is a measure of atmospheric pressure. Because water is 13.6 times less
the volume of the container must decrease in order to increase the gas particle
dense than mercury, the column of water must be 13.6 times longer than
collisions per unit area.
that of mercury to match the force exerted by the columns of liquid standing
on the surface. 25. The P versus 1yV plot is incorrect. The plot should be 115. Wall-Collision
linear with positive slope and a y-intercept of zero. PV 5!k so P 5!k (1/V), Average KE Average Velocity Frequency
which is in the form of the straight-line equation y 5 mx 1 b. 27.! d 5
a. Increase Increase Increase
(molar mass)PyRT; density is directly proportional to the molar mass of the
b. Decrease Decrease Decrease
gas. Helium, which has the smallest molar mass of all the noble gases, will
c. Same Same Increase
have the smallest density. 29.!At STP (T 5 273.2!K and P 5 1.000 atm),
d. Same Same Increase
the volume of 1.000 mole of gas is:
0.08206 L atm 117. a.! All the same; b.! Flask C 119.! NO 121.! The relative rates of
1.000 mol 3 3 273.2 K effusion of 12C16O, 12C17O, and 12C18O are 1.04, 1.02, and 1.00. Advantage:
nRT K mol
V5 5 5 22.42!L CO2 isn’t as toxic as CO. Disadvantage: Can get a mixture of oxygen iso-
P 1.000 atm
topes in CO2, so some species would effuse at about the same rate.
The volume of 1.000 mole of any gas is 22.42 L, assuming the gas behaves 123.! a.! 12.24 atm; b.! 12.13 atm; c.! The ideal gas law is high by 0.91%.
ideally. Therefore, the molar volume of He(g) and N2(g) at STP both equal 125.! 5.2 3 1026 atm; 1.3 3 1014 atoms He/cm3 127.! S(s) 1 O2(g) n
22.42 L/mol. If the temperature increases to 25.0°C (298.2 K), the molar SO2(g); 2SO2(g) 1 O2(g) n 2SO3(g); SO3(g) 1 H2O(l) n H2SO4(aq)
volume of a gas will be larger than 22.42 L/mol because volume and tem- 129.!a.!0.19 torr; b.!6.6 3 1021 molecules CO/m3; c.!6.6 3 1015 molecules
perature are directly related at constant pressure. If 1.000 mole of a gas is CO/cm3
collected over water at a total pressure of 1.000 atm, the partial pressure of 131. a. b.!
the collected gas will be less than 1.000 atm because water vapor is present
(Ptotal 5 Pgas 1 PH2O ). At some partial pressure below 1.000 atm, the molar P
volume of a gas will be larger than 22.42 L/mol because volume and pressure
PV
are inversely related at constant temperature. 31.! a.! As temperature in-
creases, the average kinetic energy will increase; b.!As temperature increases,
the average velocity of the gas molecules will increase; c.! At constant T
temperature, the lighter the gas molecules (the smaller the molar mass), the
faster the average velocity. 33.! No; At any nonzero Kelvin temperature,
there is a distribution of kinetic energies. Similarly, there is a distribution of
V
velocities at any nonzero Kelvin temperature. 35.! 2NH3(g) n N2(g) 1
3H2(g); At constant P and T, volume is directly proportional to the moles of c.! d.!
gas present. In the reaction, the moles of gas double as reactants are con-
verted to products, so the volume of the container should double. At constant T P
V and T, P is directly proportional to the moles of gas present. As the moles
of gas double, the pressure will double. The partial pressure of N2 will be 1y2
the initial pressure of NH3 and the partial pressure of H2 will be 3/2 the initial V V
A36 Answers to Selected Exercises

e.! f.! 33.!16 kJ 35.!70. J 37.!375!J heat transferred to the system 39.!213.2 kJ
41.!11.0!L 43.!q 5 30.9 kJ, w 5 212.4 kJ, DE 5 18.5 kJ 45.!This is an
P endothermic reaction, so heat must be absorbed to convert reactants into
PV
products. The high-temperature environment of internal combustion engines
T
provides the heat. 47. a.!endothermic; b.!exothermic; c.!exothermic; d.!endo-
thermic 49.! a.! 1650 kJ released; b.! 826 kJ released; c.! 7.39 kJ released;
1/V d.!34.4 kJ released 51.!4400!g C3H8 53.!When a liquid is converted into a
gas, there is an increase in volume. The 2.5 kJ/mol quantity can be consid-
ered as the work done by the vaporization process in pushing back the atmo-
P sphere. 55.! H2O(l); 2.30 3 103 J; Hg(l); 1408C 57.! Al(s) 59.! 311! K
61.!23.78C 63.!0.25 J/8C ? g 65.!266 kJ/mol 67.!170 J/g; 20. kJ/mol
133. 0.772 atm ? L; in Example 5.3, 1.0 mole of gas was present at 08C. The
69.!39.28C 71.!–25 kJ/g; –2700 kJ/mol 73.!a.!31.5 kJ/8C; b.!21.10 3
moles of gas and/or the temperature must have been different for Boyle’s
103 kJ/mol 75.!2220.8 kJ 77.!1268 kJ; No, because this reaction is very
data. 135.! PHe 5 582 torr, PXe 5 18 torr 137.! 13.3% 139.! 1490
endothermic, it would not be a practical way of making ammonia due to the
141.!24 torr 143.!4.1 3 106!L air; 7.42 3 105!L H2 145.!C2H3N; C2H3N
high energy costs. 79.!–202.6 kJ 81.!2713 kJ 83.!The enthalpy change
147.!C12H21NO; C24H42N2O2 149.!Processes b, c, and d will all result in a
for the formation of one mole of a compound from its elements, with all
doubling of the pressure. Process b doubles the pressure because the absolute
substances in their standard states. Na(s) 1 12 Cl2(g) n NaCl(s); H2(g) 1
temperature is doubled (from 200. K to 400. K). Process c has the effect of 1
2 O2(g) n H2O(l); 6Cgraphite(s) 1 6H2(g) 1 3O2(g) n C6H12O6(s); Pb(s) 1
halving the volume, which would double the pressure by Boyle’s law. Pro-
Srhombic(s) 1 2O2(g) n PbSO4(s) 85.!a.!2940. kJ; b.!2265 kJ; c.!2176 kJ
cess d doubles the pressure because the moles of gas are doubled (28!g N2 is
87.!a.!2908 kJ, 2112 kJ, 2140. kJ; b.!12NH3(g) 1 21O2(g) n 8HNO3(aq)
1!mol of N2 and 32!g O2 is 1!mol of O2). Process a won’t double the pressure
1 4NO(g) 1 14H2O(g), exothermic 89.! 22677 kJ 91.! 2169 kJ/mol
because 28 g O2 is less than 1 mol of gas, and process e won’t double the
93.!132 kJ 95.!229.67 kJ/g 97.!For C3H8(g), 250.37 kJ/g vs. 247.7 kJ/g
temperature since the absolute temperature is not doubled (goes from 303!K
for octane. Because of the low boiling point of propane, there are extra safety
to 333!K). 151.!DV 5 142 L 153.!51.4 g 155.!All the gases have the
hazards associated with storing the propane in high-pressure compressed gas
same average kinetic energy since they are all at the same temperature. The
tanks. 99.!1.05 3 105!L 101.!4900!g 103.!a. 2SO2(g) 1 O2(g) n 2SO3(g);
average velocity order from slowest to fastest is F2!, N2 ,!He. 157.!13.4%
w . 0; b.!COCl2(g) n CO(g) 1 Cl2(g); w , 0; c.!N2(g) 1 O2(g) n 2NO(g);
CaO, 86.6% BaO 159.!C2H6 161.!a.!8.7 3 103!L air/min; b.!xCO 5 0.0017,
w 5 0; Compare the sum of the coef"cients of all the product gases in the
xCO2 5 0.032, xO2 5 0.13, xN2 5 0.77, xH2O 5 0.067 163.!a.!1.01 3 104!g;
balanced equation to the sum of the coef"cients of all the reactant gases.
b.!6.65 3 104 g; c.!8.7 3 103!g 165. a.!Due to air’s larger average molar
When a balanced reaction has more moles of product gases than moles of
mass, a given volume of air at a given set of conditions has a higher density
reactant gases, then the reaction will expand in volume (DV is positive) and
than helium. We need to heat the air to greater than 258C to lower the air
the system does work on the surroundings (w , 0). When a balanced reac-
density (by driving air out of the hot-air balloon) until the density is the
tion has a decrease in the moles of gas from reactants to products, then the
same as that for helium (at 258C and 1.00 atm). b.!2150!K 167.!C3H8 is the
reaction will contract in volume (DV is negative) and the surroundings does
most likely identity. 169.!row 7 171.!0.023!mol 173.!4.8 g/L; UF3 will
compression work on the system (w . 0). When there is no change in the
effuse 1.02 times faster.
moles of gas from reactants to products, then DV 5 0 and w 5 0.
105.!a.!C12H22O11(s) 1 12O2(g) n 12CO2(g) 1 11H2O(l); b.!25630 kJ/mol
Chapter 6
107.!3.0!miles 109.!4.2 kJ heat released 111.!The calculated DH value
13. Path-dependent functions for a trip from Chicago to Denver are those
will be less positive (smaller) than it should be. 113.! 25.918C
quantities that depend on the route taken. One can #y directly from Chicago
115.! 12 C 1 F n A 1 B 1 D; 47.0 kJ 117.!a.!632 kJ; b.!C2H2(g) 119.!28!g
to Denver or one could #y from Chicago to Atlanta to Los Angeles and then
121.!a.!2361 kJ; b.!2199 kJ; c.!2227 kJ; d.!2112 kJ 123.!Work is done
to Denver. Some path-dependent quantities are miles traveled, fuel consump-
by the surroundings on the system when there is a compression. This
tion of the airplane, time traveling, airplane snacks eaten, etc. State functions
will occur when the moles of gas decrease when going from reactants
are path-independent; they only depend on the initial and "nal states. Some
to products. This will occur for reactions a and c. The other reactions have
state functions for an airplane trip from Chicago to Denver would be longi-
an increase in the moles of gas as reactants are converted to products.
tude change, latitude change, elevation change, and overall time zone
In these reactions, the system does PV work on the surroundings.
change. 15.!Both q and w are negative. 17.!a. 446 kJ released; b.!446 kJ
125.!3.97 3 103 kJ heat is released 127.!51.5°C 129.!An element in its
released 19.!exothermic, evolved
standard state has a standard enthalpy of formation equal to zero. At 25°C
21.
and 1 atm, chlorine is found as Cl2(g) and hydrogen is found as H2(g). So
H2O 1l2 1 12 CO2 1g2 S 12 CH4 1g2 1 O2 1g2 DH1 5 212 12891 kJ2
1 1 these two elements (a and b) have enthalpies of formation equal to zero. The
2 CH 4 1g 2 1 O2 1g 2 S 2 CO2 1g 2 1 H2 O 1g 2 DH2 5 12 12803 kJ2
other two choices (c and d) do not have the elements in their standard state.
H2O 1l2 S H2O 1g2 DH 5 DH1 1 DH2 5 44 kJ The standard state for nitrogen is N2(g) and the standard state for chlorine is
23. The zero points for DH f8 values are elements in their standard state. All Cl2(g). 131. w 5 22940 J; DE 5 27.8 kJ 133.!25 m2 135.!1 3 104 steps
substances are measured in relationship to this zero point. 25.!No matter 137.! 56.9 kJ 139.! q! 5 DH! 5 28.51! kJ, w! 5 1.83! kJ, DE! 5 26.68! kJ
how insulated your thermos bottle, some heat will always escape into the 141.!1.74!kJ 143.!3.3 cm
surroundings. If the temperature of the thermos bottle (the surroundings) is
high, less heat initially will escape from the coffee (the system); as a result Chapter 7
your coffee will stay hotter for a longer period of time. 27.! Fossil fuels 23. The equations relating the terms are vl 5 c, E 5 hv, and E 5 hcyl. From
contain carbon; the incomplete combustion of fossil fuels produces CO(g) the equations, wavelength and frequency are inversely related, photon energy
instead of CO2(g). This occurs when the amount of oxygen reacting is not and frequency are directly related, and photon energy and wavelength are in-
suf"cient to convert all of the carbon in fossil fuels to CO2. Carbon monox- versely related. The unit of 1 joule (J) 5 1 kg m2/s2. This is why you must
ide is a poisonous gas to humans. 29.! 150! J 31.! a.! Potential energy is change mass units to kg when using the de Broglie equation. 25.!The photo-
energy due to position. Initially, ball A has a higher potential energy than ball electric effect refers to the phenomenon in which electrons are emitted from
B because the position of ball A is higher than that of ball B. In the "nal the surface of a metal when light strikes it. The light must have a certain mini-
position, ball B has the higher position, so ball B has the higher potential mum frequency (energy) in order to remove electrons from the surface of a
energy. b.!As ball A rolled down the hill, some of the potential energy lost by metal. Light having a frequency below the minimum results in no electrons
A was converted to random motion of the components of the hill (frictional being emitted, whereas light at or higher than the minimum frequency does
heating). The remainder of the lost potential energy was added to B to ini- cause electrons to be emitted. For light having a frequency higher than the
tially increase its kinetic energy and then to increase its potential energy. minimum frequency, the excess energy is transferred into kinetic energy for the
 Answers to Selected Exercises A37

emitted electron. Albert Einstein explained the photoelectric effect by applying 89. a.! or
quantum theory. 27.!Example 7.3 calculates the de Broglie wavelength of a
ball and of an electron. The ball has a wave length on the order of 10234 m.!This 1s 2s 2p 3s 3s
is incredibly short and, as far as the wave-particle duality is concerned, the b.!
wave properties of large objects are insigni"cant. The electron, with its tiny
mass, also has a short wavelength: on the order of 10210 m.! However, this 1s 2s 2p 3s 3p
wavelength is signi"cant as it is on the same order as the spacing between at-
oms in a typical crystal. For very tiny objects like electrons, the wave proper- or
ties are important. The wave properties must be considered, along with the
particle properties, when hypothesizing about the electron motion in an atom. 4s 3d 3d
29. The Bohr model was an important step in the development of the current c.!
quantum mechanical model of the atom. The idea that electrons can occupy
only certain, allowed energy levels is illustrated nicely (and relatively easily). 1s 2s 2p 3s 3p
We talk about the Bohr model to present the idea of quantized energy levels.
31. When the p and d orbital functions are evaluated at various points in space,
the results sometimes have positive values and sometimes have negative val-
ues. The term phase is often associated with the 1 and 2 signs. For example, 4s 3d 4p
a sine wave has alternating positive and negative phases. This is analogous to 91.! Si: 1s22s22p63s23p2 or [Ne]3s23p2; Ga: 1s22s22p63s23p64s23d104p1 or
the positive and negative values (phases) in the p and d orbitals. 33.!a.!m#; [Ar]4s23d104p1; As: [Ar]4s23d104p3; Ge: [Ar]4s23d104p2; Al: [Ne]3s23p1; Cd:
b.!n; c.!ms; d.!# 35.!If one more electron is added to a half-"lled subshell, [Kr]5s24d10; S: [Ne]3s23p4; Se: [Ar]4s23d104p4 93.!a.!2; b.!10; c.!10; d.!0
electron–electron repulsions will increase because two electrons must now oc- 95.! a.! I: [Kr]5s24d105p5; b.! element 120: [Rn]7s25f 146d107p68s2; c. Rn:
cupy the same atomic orbital. This may slightly decrease the stability of the [Xe]6s24f 145d106p6; d.! Cr: [Ar]4s13d 5 97.! a. S; b.! N; c.! Se2 99.! a.! 18;
atom. 37.!The valence electrons are strongly attracted to the nucleus for ele- b.!30; c.!8; d.!40
ments with large ionization energies. One would expect these species to read- 101.!B: 1s22s22p1 N: 1s22s22p3
ily accept another electron and have very exothermic electron af"nities. The n , m, ms n , m, ms
noble gases are an exception; they have a large ionization energy but an endo-
thermic electron af"nity. Noble gases have a "lled valence shell. The added 1s 1 0 0 112 1s 1 0 0 112
electron must go into a higher n!value atomic orbital, which would have a sig- 1s 1 0 0 212 1s 1 0 0 212
ni"cantly higher energy. This is unfavorable. 39.!For hydrogen and hydrogen- 2s 2 0 0 112 2s 2 0 0 112
like (one electron) ions, all orbitals with the same value of n have the same
energy. For polyatomic atoms/ions, the energy of the orbitals also depends 2s 2 0 0 212 2s 2 0 0 212
on!,. Because there are more nondegenerate energy levels for polyatomic atoms/ 2p 2 1 21 112 2p 2 1 21 112
ions as compared with hydrogen, there are many more possible electronic tran-
2p 2 1 0 112
sitions resulting in more complicated line spectra. 41.! Yes, the maximum
number of unpaired electrons in any con"guration corresponds to a minimum 2p 2 1 11 112
in electron–electron repulsions. 43.! a.! n; b.! n! and! # 45.! 4.5! 3! 1014! s–1 For boron, there are six possibilities for the 2p electron. For nitrogen, all the
47.!3.0 3 1010 s21, 2.0 3 10223 J/photon, 12 J/mol 49.!9.4 3 1014 s21 to 2p electrons could have ms 5 212 . 103.!1A: 1, ns1, Li, 2s1; 2A: 2, ns2, Ra,
1.1!3 1015 s21 51.!Wave a has the longer wavelength (4.0 3 1024 m). Wave!b 7s2; 3A: 3, ns2np1, Ga, 4s24p1; 4A: 4, ns2np2, Si, 3s23p2; 5A: 5, ns2np3, Sb,
has the higher frequency (1.5 3 1012 s21) and larger photon energy (9.9! 3 5s25p3; 6A: 6, ns2np4, Po, 6s26p4; 7A: 7, ns2np5, Ts, 7s27p5; 8A: 8, ns2np6, Ne,
10222! J). Since both of these waves represent electromagnetic radiation, they 2s22p6 105.!none; an excited state; energy released 107.!C, O, Si, S, Ti,
both should travel at the same speed, c, the speed of light. Both waves repre- Ni, Ge, Se 109.! Li (1 unpaired electron), N (3 unpaired electrons), Ni
sent infrared radiation. 53.!1.50 3 1023 atoms 55.!427.7 nm 57.!276!nm (2!unpaired electrons), and Te (2 unpaired electrons) are all expected to be
59. a.!2.4 3 10211 m; b. 3.4 3 10234!m 61.!1.6!3 10227 kg 63.!a.!656.7 nm paramagnetic because they have unpaired electrons. 111.!a.!S , Se , Te;
(visible); b.!486.4 nm (visible); c. 121.6 nm (ultraviolet) b.!Br , Ni , K; c.!F , Si , Ba 113.!a.!Te , Se , S; b.!K , Ni , Br;
65.! 4 c.! Ba , Si , F 115.! a. He; b.! Cl; c.! element 116; d.! Si; e.! Na1
3 117.! a.! [Rn]7s25f 146d 4; b.! W; c.! SgO3 and SgO422 probably would form
a b
2 (similar to Cr). 119.! Se is an exception to the general ionization trend.
There are extra electron–electron repulsions in Se because two electrons are
E in the same 4p orbital, resulting in a lower ionization energy than expected.
c 121.!a.!As we remove succeeding electrons, the electron being removed is
closer to the nucleus, and there are fewer electrons left repelling it. The re-
maining electrons are more strongly attracted to the nucleus, and it takes
1 more energy to remove these electrons. b.! Al: 1s22s22p63s23p1. For I4, we
67.! a.! 6; b.! n! 5! 4 to n! 5! 3; c.! n 5 4 to n 5 1 69.! n 5 1! n n 5 5, begin removing an electron with n 5 2. For I3, we remove an electron with
l!5!95.00!nm; n 5 2!n n 5 6, l 5 410.4 nm; visible light has suf"cient n!5 3 (the last valence electron). In going from n 5 3 to n 5 2, there is a
energy for the n 5 2!n n 5 6 transition but does not have suf"cient energy big jump in ionization energy because the n 5 2 electrons are closer to
for the n 5 1!n n 5 5 transition. 71.!n 5 1, 91.20 nm; n 5 2, 364.8 nm the nucleus on average than the n 5 3 electrons. Since the n 5 2 electrons
73.!n 5 2 75.!a. 5.79 3 1024 m; b. 3.64 3 10233 m; c.!The diameter of an are closer, on average, to the nucleus, they are held more tightly and require
H atom is roughly 1.0 3 1028 cm. The uncertainty in position is much larger a much larger amount of energy to remove compared to the n 5 3 electrons.
than the size of the atom. d.!The uncertainty is insigni"cant compared to the In general, valence electrons are much easier to remove than inner-core elec-
size of a baseball. 77.!n 5 1, 2, 3, . . . ; , 5 0, 1, 2, . . . (n 2 1); m, 5 2,, trons. 123.!a.!C, Br; b.!N, Ar; c.!C, Br 125. Al (244), Si (2120), P!(274),
. . . , 22, 21, 0, 1, 2, . . . , 1,. 79.!b.!For , 5 3, m, can range from 23 to S (2200.4), Cl (2348.7); Based on the increasing nuclear charge, we would
13; thus 14 is not allowed. c.!n cannot equal zero. d.!, cannot be a negative expect the electron af"nity (EA) values to become more exothermic as we go
number. 81.!c 2 gives the probability of "nding the electron at that point. from left to right in the period. Phosphorus is out of line. The reaction for the
83.! He: 1s2; Ne: 1s22s22p6; Ar: 1s22s22p63s23p6; each peak in the diagram EA of P is
corresponds to a subshell with different values of n.!Corresponding subshells
P 1g2 1 e2 S P2 1g2
are closer to the nucleus for heavier elements because of the increased nu-
clear charge. 85.!3; 1; 5; 25; 16 87.!a.!32; b. 8; c.!25; d.!10; e.!6 3 Ne 4 3s23p3!!!! 3 Ne 4 3s23p4
A38 Answers to Selected Exercises

The additional electron in P2 will have to go into an orbital that already has 189. a.!Fr: [Rn]7s1, Fr1: [Rn] 5 [Xe]6s24f145d106p6; b.!7.7 3 1022 Fr atoms;
one electron. There will be greater repulsions between the paired electrons in c.!2.27790 3 10222!g
P2, causing the EA of P to be less favorable than predicted based solely on at-
tractions to the nucleus. 127.!a.!Se , S; b.!I , Br , F , Cl 129.!Electron–
Chapter 8
electron repulsions are much greater in O2 than in S2 because the electron
goes into a smaller 2p orbital versus the larger 3p orbital in sulfur. This re- 19.!a. This diagram represents a polar covalent bond as in HCl. In a polar
sults in a more favorable (more exothermic) EA for sulfur. 131.!a. Se31(g) covalent bond, there is an electron-rich region (indicated by the red color) and
n Se41(g) 1 e2; b.! S2(g) 1 e2! n S22(g); c.! Fe31(g) 1 e2! n Fe21(g); an electron-poor region (indicated by the blue color). In HCl, the more elec-
d. Mg(g) n Mg1(g) 1 e2 133.!C: 1s22s22p2; in the ground state, carbon tronegative Cl atom has a slightly greater ability to attract the bonding elec-
has three different orbitals that hold electrons. Each orbital will have a sepa- trons, which in turn produces a dipole moment. b.!This diagram represents an
rate peak on the PES spectrum, so we should have three different peaks in the ionic bond as in NaCl. Here, the electronegativity differences between the Na
spectrum. The peak at the lowest binding energy corresponds to the peak and Cl are so great that the valence electron of sodium is transferred to the
with the easiest electrons to remove. This will be the 2p electrons. The peak chlorine atom. This results in the formation of a cation, an anion, and an ionic
at the highest energy corresponds to the 1s orbital electrons since they will bond. c.!This diagram represents a pure covalent bond as in H2. Both atoms
have the largest binding energy. The area under each peak is directly related attract the bonding electrons equally, so there is no bond dipole formed. This
to the number of electrons in each orbital. Since all orbitals in carbon have is illustrated in the electrostatic potential diagram as there is no one region
two electrons, each peak area will be equal. This is shown on the PES spec- that is red nor one region that is blue (there is no speci"c partial negative end
trum for carbon: three peaks with equal area. 135.! potassium peroxide, and no speci"c partial positive end). 21.!(NH4)2SO4 and Ca3(PO4)2 are com-
K2O2; K21 unstable 137.!6.582 3 1014 s21; 4.361 3 10219!J 139.!Yes; the pounds with both ionic and covalent bonds. 23.!Electronegativity increases
ionization energy general trend decreases down a group and the atomic ra- left to right across the periodic table and decreases from top to bottom.
dius trend increases down a group. The data in Table 7.8 con"rm both of Hydrogen has an electronegativity value between B and C in the second row,
these general trends. 141.!No; lithium metal is very reactive. It will react and identical to P in the third row. Going further down the periodic table,
somewhat violently with water, making it completely unsuitable for human H!has an electronegativity value between As and Se (row 4) and identical to
consumption. Lithium has a small "rst ionization energy, so it is more likely Te (row 5). It is important to know where hydrogen "ts into the electronega-
that the lithium prescribed will be in the form of a soluble lithium salt (a tivity trend, especially for rows 2 and 3. If you know where H "ts into the
soluble ionic compound with Li1 as the cation). 143.!a. 6Li(s) 1 N2(g) n trend, then you can predict bond dipole directions for nonmetals bonded to
2Li3N(s); b.!2Rb(s) 1 S(s) n Rb2S(s) 145.!a.!6; b.!O, S, Se, and Te; c.!K2X hydrogen. 25.!For ions, concentrate on the number of protons and the number
would be the predicted formula, where X is the unknown nonmetal. of electrons present. The species whose nucleus holds the electrons most tightly
d.! smaller; e.! smaller 147.! 386 nm 149.! 200! s 151.! l 5 4.104 3 will be smallest. For example, compare the size of an anion to the neutral atom.
1025!cm so violet light is emitted. 153.!a.!true for H only; b.!true for all The anion has more electrons held by the same number of protons in the
atoms; c.!true for all atoms 155.!1p: n 5 1,  5 1 is not possible; 3f: n 5 3, nucleus. These electrons will not be held as tightly, resulting in a bigger size for
 5 3 is not possible; 2d: n 5 2,  5 2 is not possible. In all three incorrect the anion as compared to the neutral atom. For isoelectronic ions, the same
cases, n!5!. The maximum value  can have is n 2 1, not n. 157.!smallest number of electrons are held by different numbers of protons in the various ions.
size: O; largest size: K; smallest 1st ionization energy: K; largest 1st ioniza- The ion with the most protons holds the electrons tightest and has smallest size.
tion energy: N 159.!Valence electrons are easier to remove than inner-core 27.!Fossil fuels contain a lot of carbon and hydrogen atoms. Combustion of
electrons. The large difference in energy between I2 and I3 indicates that this fossil fuels (reaction with O2) produces CO2 and H2O. Both these compounds
element has two valence electrons. The element is most likely an alkaline have very strong bonds. Because much stronger product bonds are formed than
earth metal because alkaline earth metals have two valence electrons. reactant bonds broken, combustion reactions are very exothermic.
161.!a.!146 kJ; b.!407 kJ; c.!1117 kJ; d.!1524 kJ 163.!251 nm 165.!15 29.! C q O
167.!The number of electrons with  5 1 is 15. The number of electrons with Carbon: formal charge 5 21; oxygen: formal charge 5 11
m 5 0 is 15. The number of electrons with m 5 1 is 7. 169.!a.!Te; b.!Ge;
c.!F 171.!a.!true; b.!false; cations are smaller than the parent atom; c.!false; Electronegativity predicts the opposite polarization with the partial negative
all ionization energies are endothermic; d.!true; e.!true; this is hard to predict end of the molecule around the more electronegative oxygen atom. The two
because the general atomic radius trends go against each other when going opposing effects seem to partially cancel to give a much less polar molecule
from Li to Al. Figure 7.37 of the text was used to answer this question. than expected.
173.!S 175.!a.!line A, n 5 6 to n 5 3; line B, n 5 5 to n 5 3; b.!121.6 nm 31.! a.! C , N , O; b.! Se , S , Cl; c.! Sn , Ge , Si; d.! Tl , Ge , S
177.!X 5 C, m 5 5; C51 is the ion. 179.!For r 5 a0 and u 5 08, c2 5 2.46 33.!a.!GeOF; b.!POCl; c.!SOF; d.!TiOCl 35.!Order of electronegativity
3 1028. For r 5 a0 and u 5 908, c2 5 0. As expected, the xy plane is a node from Fig. 8.3: a.!C (2.5) , N (3.0) , O (3.5), same; b.!Se (2.4) , S (2.5) , Cl
for the 2pz atomic orbital. (3.0), same; c.!Si 5 Ge 5 Sn (1.8), different; d.!Tl (1.8) 5 Ge (1.8) , S (2.5),
different. Most polar bonds using actual electronegativity values: a.!SiOF and
181.!a.! 1 2 GeOF equal polarity (GeOF predicted); b.! POCl (same as predicted);
3 4 c.! SOF (same as predicted); d.! TiOCl (same as predicted) 37.! Incorrect:
b,! d,! e; b.! d2ClOId1; d.! nonpolar bond so no dipole moment; e.! d2OOPd1
5 6 7 8 9 10 11 12
39.!a.!ionic; b.!covalent; c.!polar covalent; d.!ionic; e.!polar covalent; f.!cova-
13 14 15 16 17 18 19 20 lent 41.!FOH . OOH . NOH . COH . POH 43.!a. Has a permanent
b.!2, 4, 12, and 20; c.!There are many possibilities. One example of each for- dipole; b.!has no permanent dipole; c.!has no permanent dipole; d.!has a per-
mula is XY 5 1 1 11, XY2 5 6 1 11, X2Y 5 1 1 10, XY3 5 7 1 11, and manent dipole; e.! has no permanent dipole; f.! has no permanent dipole.
X2Y3 5 7 1 10; d.!6; e.!0; f.!18 183.!The ratios for Mg, Si, P, Cl, and Ar are 45.! Al31: [He]2s22p6; Ba21: [Kr]5s24d105p6; Se22: [Ar]4s23d104p6; I2:
about the same. However, the ratios for Na, Al, and S are higher. For Na, the [Kr]5s24d105p6 47.!a.!Li1 and N32 are the expected ions. The formula of the
second IE is extremely high because the electron is taken from n 5 2 (the "rst compound would be Li3N (lithium nitride). b.! Ga31 and O22; Ga2O3,
electron is taken from n 5 3). For Al, the "rst electron requires a bit less energy gallium(III) oxide or gallium oxide; c.!Rb1 and Cl2; RbCl, rubidium chloride;
than expected by the trend due to the fact it is a 3p electron. For S, the "rst d.!Ba21 and S22; BaS, barium sul"de 49.!a. Mg21 and Al31: 1s22s22p6; K1:
electron requires a bit less energy than expected by the trend due to electrons 1s22s22p63s23p6; b.! N32, O22, and F2: 1s22s22p6; Te22: [Kr]5s24d105p6
being paired in one of the p orbitals. 185.!a.!Zeff 5 43.33; b.!Silver is element 51.!a.!Sc31; b.!Te22; c.!Ce41, Ti41; d.!Ba21 53.!a. F2, O22, or N32; b.!Cl2,
47, so Z 5 47 for silver. Our calculated Zeff value is less than 47. Electrons in S22, or P32; c.!F2, O22, or N32; d.!Br2, Se22, or As32 55.!Se22, Br2, Rb1,
other orbitals can penetrate the 1s orbital. Thus a 1s electron can be slightly Sr21, Y31, and Zr41 are some ions that are isoelectronic with Kr. The size
shielded from the nucleus, giving a Zeff close to but less than Z. 187.!Solving trend is
for the molar mass of the element gives 40.2 g/mol; this is calcium. Zr41 , Y31 , Sr21 , Rb1 , Br2 , Se22.
 Answers to Selected Exercises A39

57.!a. Cu!. Cu1 .!Cu21; b. Pt21 . Pd21 . Ni21; c.!O22!. O2 .!O; d. La31 – –
. Eu31 . Gd31 . Yb31; e.!Te22 . I2 . Cs1 . Ba21 . La31 59.!a. NaCl, 93.!a.!NO2– šPN
O
"
šOO
šð
" mn ðš
O š š
"ON PO
"
Na1 smaller than K1; b. LiF, F2 smaller than Cl2; c.!MgO, O22 greater charge
–

ð
than OH2; d.!Fe(OH)3, Fe31 greater charge than Fe21; e.!Na2O, O22 greater – –

ð
NO3– ðOð ðOð ðOð
charge than Cl2; f.!MgO, Mg21 smaller than Ba21, and O22 smaller than S22. B A A
61.! 2411 kJ/mol 63.! The lattice energy for Mg21O22 will be much more N mn N mn N
D G J G D M
exothermic than for Mg1O2. 65.!161 kJ/mol 67.!Ca21 has greater charge ý½O" ýO" "Oý½ ý½O " "Oý
"O½ý
than Na1, and Se22 is smaller than Te22. Charge differences affect lattice en-
ergy values more than size differences, and we expect the trend from most
N2O4 O O O O
exothermic to least exothermic to be:
N N N N
CaSe . CaTe . Na2Se . Na2Te
O O O O
(22862) (22721) (22130) (22095)
69.!a. 2183 kJ; b.!2109 kJ 71.!242 kJ 73.!21282 kJ 75.!21228 kJ
77.! 485 kJ/mol 79.! a. Using standard enthalpies of formation, DH8! 5
2184 kJ vs. 2183 kJ from bond energies; b.!Using standard enthalpies of O O O O
formation, DH 5 292 kJ vs. 2109 kJ from bond energies. Bond energies N N N N
give a reasonably good estimate for DH, especially when all reactants and
O O O O
products are gases. 81.!a. Using SF4 data: DSF 5 342.5 kJ/mol. Using SF6
data: DSF 5 327.0 kJ/mol. b.!The SOF bond energy in the table is 327 kJ/mol.
– – –
The value in the table was based on the SOF bond in SF6. c.!S(g) and F(g)
b.! OCN– ðš
O O C q Nð
"
š š
O P C PN
" " ð Oq C Oš
Nð
"
are not the most stable forms of the elements at 258C. The most stable forms
are S8(s) and F2(g); DH8f 5 0 for these two species. 83.!158.4 kJ/mol vs.
– – –
160. kJ/mol in Table 8.5 SCN– ðš
S O C q Nð š š
S P C PN š
ð S q C O"
Nð
" " "
85. a.! F O F b. O P O c. C q O
– – –
H N3– ðš
N O N q Nð
"
š
NPN P š
" N
"
š
ð Nq N O "
Nð
A
d. H O C O H e. HO N O H f. HO O O H OF
g. HO
A A 95. H H
H H A A
H H EC N E H H H KC H E H
C C C C
87. a.! Cl b.! Cl O N O Cl B A A B
A A
E H KCH
C E N ECH
C
Cl O C O Cl Cl H C H H C H
A A A
Cl H H
97. With resonance all carbon–carbon bonds are equivalent (we indicate this
c. Cl O Se O Cl d. I O Cl
with a circle in the ring), giving three different structures:
89.!H—Be—H H Cl Cl Cl
B Cl
H H
Cl
91.! F
F Cl
PF5 P F
F Localized double bonds would give four unique structures.
F 99.! H H
O C OO
ý k

H C N P C PO mn H C NP mn
F
F H H
SF4 S
F H
F
H C N OC q O

F H

ClF3 101. Longest n shortest COO bond: CH3OH . CO322 . CO2 . CO;
Cl F
weakest!n strongest COO bond: CH3OH , CO322 , CO2 , CO
F
103. F +1 F 0
B A
–
_ B –1 B 0
Br3 Br O Br O Br D G D G
0 F F 0 0 F F 0

Row 3 and heavier nonmetals can have more than 8 electrons around them The "rst Lewis structure obeys the octet rule but has a 11 formal charge on the
when they have to. Row 3 and heavier elements have empty d orbitals that most electronegative element there is, #uorine, and a negative formal charge
are close in energy to valence s and p orbitals. These empty d orbitals can on a much less electronegative element, boron. This is just the opposite of what
accept extra electrons. we expect: negative formal charge on F and positive formal charge on B. The
other Lewis structure does not obey the octet rule for B but has a zero formal
A40 Answers to Selected Exercises

charge on each element in BF3. Since structures generally want to minimize for-
ðš
Fð
mal charge, BF3 with only single bonds is best from a formal charge point of view. A
105.!a–f and h all have similar Lewis structures: c. CF4 E CH Tetrahedral, nonpolar
š
F A #
ð# š
Fð
ðš Fð
ð#
Yð
A
š
ðY O XO Y šð " " "
SeF4 ð"F O Se O"Fð See-saw, polar
š A š D G
ðY ð ð"F ð ð" Fð
š
" " " – F F
–
g. ClO3 ðO "ð
" O Cl O O Kr
A KrF4 Square planar, nonpolar
ðO"ð F F

Formal charges: a.!11; b.!12; c.!13; d.!11; e.!12; f.!14; g.!12; h.!11 š ðš
Fð ð
F A š
ð# F
D D#
107. F O O F d. IF5 I
# Square pyramid, polar
š G Gš
ð#
F Fð
#
Formal charge: 0 0 0 0
Oxidation number: !1 "1 "1 !1 "
"
ðF ð
Oxidation numbers are more useful. We are forced to assign 11 as the oxida- F A
ð" "
G
tion number for oxygen. Oxygen is very electronegative and 11 is not a AsF5 "DAs O"Fð Trigonal bipyramid, nonpolar
A
stable oxidation state for this element. ð"
F ðFð
"
109. Cl S S Cl
129. Element E is a halogen (F, Cl, Br, or I); trigonal pyramid; ,109.58
111. H CqN H 131. "
ð Fð
G
H C PC C O C H # ½ #
"D N P NG" NPN#
P

D
! O H F
ð" Fð
" Fð
ð"

113. [87] a.! tetrahedral, 109.58; b.! trigonal pyramid, ,109.58; c.! V-shaped, Polar Nonpolar
,109.58; d.! linear, no bond angle in diatomic molecules. [93] a.! NO22: 133.!a.!radius: N1 , N , N2; I.E.: N2 , N , N1; b.!radius: Cl1 , Cl , Se
V-shaped, ,1208; NO32: trigonal planar, 1208; N2O4: trigonal planar about both ,! Se2; I.E.: Se2 , Se , Cl , Cl1; c.! radius: Sr21 , Rb1 , Br2; I.E.:
N atoms, 1208; b.!all are linear, 1808 115.!Br32: linear; ClF3: T-shaped; SF4: Br2!, Rb1 , Sr21; 135. a.!1549 kJ; b.!1390. kJ c.!1312 kJ; d.!1599 kJ
see-saw 117.!a.!V-shaped or bent; b.!see-saw; c.!trigonal pyramid; d.!trigo- 137.!a.!NaBr: In NaBr2, the sodium ion would have a 12 charge assuming
nal bipyramid; e.! tetrahedral 119.! a.! trigonal planar; 1208; b.! V-shaped; each bromine has a 21 charge. Sodium doesn’t form stable Na21 com-
,1208 121.!a.!linear; 1808; b.!T-shaped; ,908; c.!see-saw; ,908 and ,1208; pounds. b.!ClO42: ClO4 has 31 valence electrons so it is impossible to satisfy
d.!trigonal bipyramid; 908 and 1208 123.!SeO2 (bond dipoles do not cancel the octet rule for all atoms in ClO4. The extra electron from the 21 charge in
each other out in SeO2) 125.!ICl3 and TeF4 (bond dipoles do not cancel each ClO42 allows for complete octets for all atoms. c.!XeO4: We can’t draw a
other out in ICl3 and TeF4) Lewis structure that obeys the octet rule for SO4 (30 electrons), unlike XeO4
(32 electrons). d. SeF4: Both compounds require the central atom to expand
127. a.!OCl2 V-shaped, polar its octet. O is too small and doesn’t have low-energy d orbitals to expand its
O
D G octet (which is true for all row 2 elements). 139.!a.!Both have one or more
Cl Cl
1808 bond angles; both are made up entirely of Xe and Cl; both have the in-
dividual bond dipoles arranged so they cancel each other (both are nonpolar);
KrF2 š
F OýKr
ð# k š
Fð Linear, nonpolar
# O# both have lone pairs on the central Xe atom; both have a central Xe atom that
has more than 8 electrons around it. b.! All have lone pairs on the central
BeH2 HOBeOH Linear, nonpolar atom; all have a net dipole moment (all are polar). 141.!25681 kJ 143.!Yes,
each structure has the same number of effective pairs around the central
SO2 š
S V-shaped, polar atom. (We count a multiple bond as a single group of electrons.)
ýOJ GO k 145. –
" ½ " F F
F
(one other resonance structure possible) GAD
G TeD
ðOð F F
B
b. SO3 S Trigonal planar, nonpolar
The lone pair of electrons around Te exerts a stronger repulsion than the
ýOD GO k
½ ! ½ ! bonding pairs. The stronger repulsion pushes the four square planar F atoms
(two other resonance structures possible) away from the lone pair, reducing the bond angles between the axial F atom
and the square planar F atoms. 147.!a.!nonpolar covalent; b.!ionic; c.!ionic;
#
NF3 Trigonal pyramid, polar d.! polar covalent; e.! polar covalent; f.! polar covalent; g.! polar covalent;
N
E Hš h.!ionic 149.!a.!O22!. O2 .!O; b.!Fe21!. Ni21 .!Zn21; c.!Cl2!. K1
F A #
š
ð# Fð
ð#Fð .!Ca21 151.!2303 kJ 153.!CO2: carbon dioxide, linear; NH3: ammonia
(nitrogen trihydride), trigonal pyramid; SO3: sulfur trioxide, trigonal planar;
H2O: water (dihydrogen monoxide), V-shaped or bent; ClO42: perchlorate
F
ion, tetrahedral 155.!a. 25 3 10218 J; b.!26 3 10218!J 157. 17 kJ/mol
IF3 I F T-shaped, polar 159.!See Fig. 8.11 to see the data supporting MgO as an ionic compound.
F Note that the lattice energy is large enough to overcome all of the other pro-
 Answers to Selected Exercises A41

cesses (removing 2 electrons from Mg, and so on). The bond energy for O2 Note: OH, CH, H2C, CH2, and CH3 are short-hand notation. In this notation,
(247 kJ/mol) and electron af"nity (737 kJ/mol) are the same when making single bonds to the various H atoms are assumed. Most of the bond angles in
CO. However, the energy needed to ionize carbon to form a C21 ion must be the molecule are predicted to be 109.5 degrees because most of the carbon
too large. Figure 7.32 shows that the "rst ionization energy for carbon is atoms exhibit tetrahedral geometry. The exceptions are the two carbons with
about 350 kJ/mol greater than the "rst IE for magnesium. If all other num- the *. These two carbons exhibit trigonal planar geometry and are predicted
bers were equal, the overall energy change would be 250 kJ/mol (see Fig. to have 120-degree bond angles. Because most of the carbon atoms exhibit
8.11). It is not unreasonable to assume that the second ionization energy for tetrahedral geometry, the molecule is not planar. 171.!X is iodine; square
carbon is more than 250 kJ/mol greater than the second ionization energy for pyramid 173.! [Ar]4s13d5 5 Cr; [Ne]3s23p3 5 P; [Ar]4s23d104p3 5 As;
magnesium. This would result in a positive DH value for the formation of CO [Ne]3s23p5 5 Cl; Cr , As , P , Cl
as an ionic compound. One wouldn’t expect CO to be ionic if the energetics
were unfavorable. 161.!As the halogen atoms get larger, it becomes more Chapter 9
dif"cult to "t three halogen atoms around the small nitrogen atom, and the 11. In hybrid orbital theory, some or all of the valence atomic orbitals of the
NX3 molecule becomes less stable. 163.!reaction i: 22636 kJ; reaction ii: central atom in a molecule are mixed together to form hybrid orbitals; these
23471 kJ; reaction iii: 23543 kJ; Reaction iii yields the most energy per kg hybrid orbitals point to where the bonded atoms and lone pairs are oriented.
(28085 kJ/kg) The s bonds are formed from the hybrid orbitals overlapping head to head
165.! H OCO N with an appropriate orbital on the bonded atom. The p bonds in hybrid orbital
M theory are formed from unhybridized p atomic orbitals. The p orbitals overlap
COH
D side to side to form the p bond where the p electrons occupy the space above
C ONOH
A and below a line joining the atoms p the internuclear axis). Assuming the
H OCOH z-axis is the internuclear axis, then the pz atomic orbital will always be hybrid-
A ized whether the hybridization is sp, sp2, sp3, dsp3 or d 2sp3. For sp hybridiza-
HO N O C O C O O O H
A A B tion, the px and py atomic orbitals are unhybridized; they are used to form two
H H O p bonds to the bonded atom(s). For sp2 hybridization, either the px or py
We would expect 1208 bond angles about the carbon atom labeled 1 and atomic orbital is hybridized (along with the s and pz orbitals); the other p or-
,109.58 bond angles about the nitrogen atom labeled 2. The nitrogen bond bital is used to form a p bond to a bonded atom. For sp3 hybridization, the
angles should be slightly smaller than 109.58 due to the lone pair of electrons s and all of the p orbitals are hybridized; no unhybridized p atomic orbitals are
on nitrogen. present, so typical p bonds do not form with sp3 hybridization. For dsp3 and
d 2sp3 hybridization, we just mix in one or two d orbitals into the hybridization
167.!a. Two possible structures exist; each has a T-shaped molecular structure: process. Which speci"c d orbitals are used is not important to our discussion.
F I 13.!We use d orbitals when we have to; i.e., we use d orbitals when the central
atom on a molecule has more than eight electrons around it. The d orbitals are
Br I Br F necessary to accommodate the electrons over eight. Row 2 elements never
I I have more than eight electrons around them so they never hybridize d orbitals.
We rationalize this by saying there are no d orbitals close in energy to the
90° bond angle between I atoms 180° bond angle between I atoms valence 2s and 2p orbitals (2d orbitals are forbidden energy levels). However,
b.!Three possible structures exist; each has a see-saw molecular structure: for row 3 and heavier elements, there are 3d, 4d, 5d, etc. orbitals that will be
close in energy to the valence s and p orbitals. It is row 3 and heavier nonmet-
O O F
O F O als that hybridize d orbitals when they have to. For sulfur, the valence elec-
Xe Xe Xe trons are in 3s and 3p orbitals. Therefore, 3d orbitals are closest in energy and
F F O are available for hybridization. Arsenic would hybridize 4d orbitals to go with
F O F the valence 4s and 4p orbitals while iodine would hybridize 5d orbitals since
90° bond angle 180° bond angle 120° bond angle the valence electrons are in n 5 5.
between O atoms between O atoms between O atoms šP CPO
š
15.!O
" "
c. Three possible structures exist; each has a square pyramid molecular struc-
The darker green orbitals about carbon are sp hybrid orbitals. The lighter
ture:
green orbitals about each oxygen are sp2 hybrid orbitals, and the gold orbit-
– – –
F Cl Cl als about all of the atoms are unhybridized p atomic orbitals. In each double
Cl Cl Cl F F Cl bond in CO2, one s and one p bond exists. The two carbon—oxygen s
Te Te Te bonds are formed from overlap of sp hybrid orbitals from carbon with a sp2
Cl F Cl F Cl F hybrid orbital from each oxygen. The two carbon—oxygen p! bonds are
formed from side-to-side overlap of the unhybridized p atomic orbitals from
One F atom is 180° Both F atoms are 90° Both F atoms are 90°
carbon with an unhybridized p atomic orbital from each oxygen. These two
from lone pair. from lone pair and 90° from lone pair and 180°
p!bonds are oriented perpendicular to each other as illustrated in the "gure.
from each other. from each other.
17. Bonding and antibonding molecular orbitals are both solutions to the
169. CH3 CH2 CH2 CH3 quantum mechanical treatment of the molecule. Bonding orbitals form when
CH CH2 CH in-phase orbitals combine to give constructive interference. This results in
H H H enhanced electron probability located between the two nuclei. The end result
CH3 CH3 is that a bonding MO is lower in energy than the atomic orbitals of which it
C C
is composed. Antibonding orbitals form when out-of-phase orbitals com-
H2C C CH2
H bine. The mismatched phases produce destructive interference leading
H H
CH3 H to a node in the electron probability between the two nuclei. With electron
C C C CH2 distribution pushed to the outside, the energy of an antibonding orbital is
H2C C C H higher than the energy of the atomic orbitals of which it is composed.
H 19.!The localized electron model does not deal effectively with molecules con-
C *
C CH2 taining unpaired electrons. We can draw all of the possible resonance structures
*
HO C C for NO, but still not have a good feel for whether the bond in NO is weaker or
H H stronger than the bond in NO2. MO theory can handle odd electron species
H
without any modi"cations. In addition, hybrid orbital theory does not predict
that NO2 is paramagnetic. The MO theory correctly makes this prediction.
A42 Answers to Selected Exercises
"
21. H2Oð O f. "ð ð a <1208, see-saw, dsp3, polar
ð
ð
D D b
F
F A
ð"
f
H H H b <908

f ff
"aE Te ð
H2O has a tetrahedral arrangement of the electron pairs about the O atom that F A
ð"
requires sp3 hybridization. Two of the sp3 hybrid orbitals are used to form ð"Fð
bonds to the two hydrogen atoms, and the other two sp3 hybrid orbitals hold
"
the two lone pairs on oxygen. "
g.! ðFð a 5 908, trigonal bipyramid, dsp3, nonpolar
F Af a "
ð"
23.!H2COð ðOð G b 5 1208

f
b As O"Fð

f
B " DA

f
C F ðFð
ð"
D D "
H H
The central carbon atom has a trigonal planar arrangement of the electron " "
h. ð" ý kO F ð
FOKr linear, 1808, dsp3, nonpolar
pairs that requires sp2 hybridization. Two of the sp2 hybrid orbitals are used " "
to form the two bonds to hydrogen. The other sp2 hybrid orbital forms the s "
bond to oxygen. The unchanged (unhybridized) p orbital on carbon is used to i. ðFð square planar, 908, d 2sp3, nonpolar
form the p bond between carbon and oxygen. " "D "
F O Kr
ð" " O"Fð
25.!Ethane: H H D
ð"
Fð
H C C H
" "
H H j.! ð Fð Fð octahedral, 908, d2sp3, nonpolar
" A D" "
The carbon atoms are sp3 hybridized. The six COH bonds are formed from FO
ð" O Se OO"
"D A
Fð
the sp3 hybrid orbitals on C with the 1s atomic orbitals from the hydrogen ð"F ð Fð
atoms. The carbon–carbon bond is formed from an sp3 hybrid orbital on each "
C atom.
k. F l. F
Ethanol: H H F F
I I F
H C C O H F F
F
H H
The two C atoms and the O atom are all sp3 hybridized. All bonds are formed square pyramid, <908, T-shaped, <908,
from these sp3 hybrid orbitals. The COH and OOH bonds form from sp3 d2sp3, polar dsp3, polar
hybrid orbitals and the 1s atomic orbitals from the hydrogen atom. The 35.!The p bond forces all six atoms into the same plane. 37.!a. There are
COC and COO bonds are formed from sp3 hybrid orbitals on each atom. 33 s and 9!p bonds. b.!All C atoms are sp2 hybridized since all have a trigo-
27. [87] All are sp3 hybridized. [93] a.! NO22, sp2; NO32, sp2; N2O4, both nal planar arrangement of the electrons. 39.!Biacetyl:
N atoms are sp2 hybridized; b.!All are sp hybridized. 29.!All exhibit dsp3 ý Ok
2
hybridization. 31. The molecules in Exercise 119 all exhibit sp2 hybridi- H B sp
A E C H Kš
h
Oð
h
zation about the central atom; the molecules in Exercise 120 all exhibit sp3
H O C sp3 C
hybridization about the central atom. 33.!a.!tetrahedral, 109.58, sp3, non-
h

A A
h

polar H HO COH
A
" H
ðF ð
A All CCO angles are 1208. The six atoms are not forced to lie in the same
"EC H" plane. 11!s and 2!p bonds; Acetoin:
F A "
ð" Fð
Fð
ð" sp ý O k2

b. trigonal pyramid, ,109.58, sp3, polar H H Bf a

f

A A EC E H E
f

HO C O C CE
f

" "
f
A Af b A H
f

F ON "
ð" 3
H ðO ð sp H
D G G
Fð
ð" Fð
" H
sp3

c. V-shaped, ,109.58, sp3, polar angle a 5 1208, angle b 5 109.58, 13!s bonds and 1!p bond

ýO k 41.!a. H N
"D G k A e x
a
ð"
F F HO N C
k ý D D
CO N c O H2C P C f g
M M J D
O b NO C d C O O O CH3
d. trigonal planar, 1208, sp2, nonpolar D B h
# NH2 O
ðF ð Azodicarbonamide Methyl cyanoacrylate
A
B Note: NH2, CH2, and CH3 are shorthand for carbon atoms singly bonded to
kFD GFk hydrogen atoms. b.!In azodicarbonamide, the two carbon atoms are sp2 hybrid-
k ý k ý ized. The two nitrogen atoms with hydrogens attached are sp3 hybridized and
e. linear, 1808, sp, nonpolar the other two nitrogens are sp2 hybridized. In methyl cyanoacrylate, the
CH3!carbon is sp3 hybridized, the carbon with the triple bond is sp hybridized,
HOBeOH and the other three carbons are sp2 hybridized. c.!Azodicarbonamide contains
 Answers to Selected Exercises A43

3!p bonds and methyl cyanoacrylate contains 4!p bonds. d.!a: <109.5°, b: 1208, c. Square pyramid; d 2sp3
c: <120°, d: 1208, e: 1808, f: 1208, g: <109.5°, h: 1208 43.!To complete the O F
Lewis structure, add lone pairs to complete octets for each atom. a.!6; b.!4; F F F F
c.!The center N in ONPNPN group; d.!33 s; e.!5 p; f.!1808; g.!<109.58; Xe or Xe
h.!sp3 45.!a.!The bonding molecular orbital is on the right and the antibond- F F F O
ing molecular orbital is on the left. The bonding MO has the greatest electron
probability between the nuclei, while the antibonding MO has greatest elec- d. T-shaped; dsp3
tron probability on either side of the nuclei. b.!The bonding MO is lower in F O
energy. Because the electrons in the bonding MO have the greatest probabil-
ity of lying between the two nuclei, these electrons are attracted to two O Xe or F Xe
different nuclei, resulting in a lower energy. 47.!a.!H21, H2, H22; b.!He221
F F
and He21 49.! a.! (s2s)2; B.O. 5 1; diamagnetic (0 unpaired electrons);
b. (s2s)2(s2s*)2(p2p)4; B.O. 5 2; diamagnetic (0 unpaired electrons); c. (s3s)2 e. Trigonal bipyramid; dsp3
(s3s*)2(s3p)2(p3p)4(p3p*)2; B.O. 5 2; paramagnetic (2 unpaired electrons)
F F O
51.!N21 and N22 both have bond orders of 2.5. 53.!The peroxide ion has a O O F
bond order of 1 and the superoxide ion has a bond order of 1.5. The superoxide Xe O or Xe F or Xe F
ion with the larger bond order should have the shorter (and stronger) bond. O O O
55.! a.! (s2s)2(s2s*)2(p2p)4(s2p)2; B.O. 5 3; diamagnetic; b. (s2s)2(s2s*)2(p2p)4 F O O
(s2p)1; B.O. 5 2.5; paramagnetic; c.!(s2s)2(s2s*)2(p2p)4; B.O. 5 2; diamagnetic; 69.!a.!No, some atoms are attached differently; b.!Structure 1: All N atoms
bond length: CO , CO1 , CO21; bond energy: CO21 , CO1 , CO 57.!H2; are sp3 hybridized, all C atoms are sp2 hybridized; structure 2: All C and N
B2; C222 atoms are sp2 hybridized; c.!The "rst structure with the carbon–oxygen dou-
59. ble bonds is slightly more stable.
71.
! ! O O
C H H C H H
" ! ! "
H H
O C C O H O C C O H
" " H C C H C C
H mn H
H C C C H C C C
N H N H
H H
61.!a.!The electrons would be closer to F on the average. The F atom is more
electronegative than the H atom, and the 2p orbital of F is lower in energy a.!21!s bonds; 4!p bonds (The electrons in the 3!p bonds in the ring are de-
than the 1s orbital of H; b.!The bonding MO would have more #uorine 2p localized.) b.! angles a, c, and g: <109.58; angles b, d, e, and f: <1208;
character because it is closer in energy to the #uorine 2p orbital; c.!The anti- c. 6 sp2 carbons; d.!4 sp3 atoms; e.!Yes, the p electrons in the ring are delocal-
bonding MO would place more electron density closer to H and would have ized. The atoms in the ring are all sp2 hybridized. This leaves a p orbital
a greater contribution from the higher-energy hydrogen 1s atomic orbital. perpendicular to the plane of the ring from each atom. Overlap of all six of
63.![:C { C:]22 sp hybrid orbitals form the s bond and the two unhybridized these p orbitals results in a p molecular orbital system where the electrons
p atomic orbitals from each carbon form the two p bonds. are delocalized above and below the plane of the ring (similar to benzene in
Fig. 9.47 of the text). 73.!267 kJ/mol; this amount of energy must be sup-
MO: (s2s)2(s2s*)2(p2p)4(s2p)2, B.O. 5 (8 2 2)/2 5 3
plied to break the p bond.
Both give the same picture, a triple bond composed of a s bond and two p
75.!a. H Trigonal planar, nonpolar, 1208, sp2
bonds. Both predict the ion to be diamagnetic. Lewis structures deal well with
diamagnetic (all electrons paired) species. The Lewis model cannot really pre- B
dict magnetic properties. 65.!O3 and NO22 have identical Lewis structures, H H
so we need to discuss only one of them. The Lewis structures for O3 are
! ! b.!N2F2
"
" KOH ½ mn ½ HOK " ð Fð
G
O" ½O" " O½ "O # ½ #
"D N P NG" NPN#
Localized electron model: The central oxygen atom is sp2 hybridized, which D
F
ð" Fð
" Fð
ð"
is used to form the two s bonds and hold the lone pair of electrons. An un-
changed (unhybridized) p atomic orbital forms the p bond with the neigh- Polar Nonpolar
boring oxygen atoms. The actual structure of O3 is an average of the two V-shaped about both N atoms, <1208, sp2
resonance structures. Molecular orbital model: There are two localized s
bonds and a p bond that is delocalized over the entire surface of the mole- These are distinctly different molecules.
cule. The delocalized p bond results from overlap of a p atomic oribtal on
c. H Trigonal planar about all C atoms,
each oxygen atom in O3. H H nonpolar, 1208, sp2
67.!a.!Trigonal pyramid; sp3 C C C C
H H
Xe H
O O
O 77.!a.!The NNO structure is correct. From the Lewis structures we would
predict both NNO and NON to be linear, but NON would be nonpolar. NNO
b. Tetrahedral; sp3 is polar.
" "
O b.! ý½ N P N P Oý½ mn ð N q NO O N O N q Oð
" ð mn ð "
Xe –1 +1 0 0 +1 –1 –2 +1 +1 Formal
O O charges
O
A44 Answers to Selected Exercises

The central N is sp hybridized. We can probably ignore the third resonance All of the carbon atoms in the rings have a trigonal planar arrangement of
structure on the basis of formal charge. c."sp hybrid orbitals on the center N electron pairs, so these !ve carbon atoms are sp2 hybridized. The other
overlap with atomic orbitals (or hybrid orbitals) on the other two atoms to three carbon atoms are sp3 hybridized because they have a tetrahedral ar-
form two s bonds. The remaining p orbitals on the center N overlap with rangement of electron pairs. The three nitrogen atoms that are bonded to a
p orbitals on the other N to form two p bonds. 79. In O2, an antibonding OCH3 group all have the CON bond formed from overlap of an sp3 hybrid
electron is removed, which will increase the bond order to 2.5 [5 (8 2 3)/2]. orbital from carbon with an sp3 hybrid orbital from nitrogen. Note that each
The bond order increases as an electron is removed, so the bond strengthens. of these nitrogen atoms has a tetrahedral arrangement of electron pairs,
In N2, a bonding electron is removed, which decreases the bond order to hence they are sp3 hybridized. There are eight lone pairs of electrons, and
2.5"5 [(7 2 2)/2]. So the bond strength weakens as an electron is removed the molecule has four p bonds (each double bond contains one p bond).
from N2. 81." F2: (s2s)2(s2s*)2(s2p)2(p2p)4(p2p*)4; F2 should have a lower 91. N2: (s2s)2(s2s*)2(p2p)4(s2p)2; N21: (s2s)2(s2s*)2(p2p)4(s2p)1; N22: (s2s)2
ionization energy than F. The electron removed from F2 is in a p2p* antibond- (s2s*)2(p2p)4(s2p)2(p2p*)1
ing molecular orbital, which is higher in energy than the 2p atomic orbitals
93. H
from which the electron in atomic #uorine is removed. Since the electron re- A
moved from F2 is higher in energy than the electron removed from F, it should O H OCOH
H H A
be easier to remove an electron from F2 than from F. 83."p molecular orbital C C N
H N C
85. š
Se š
Se COH
ýOJ GO k mn ýOG JO k MC C
N
" ½ " ½ " ½ O N
A
& H OCOH
A
EP
A Hšð
š
ðCl
& ðClð Cl
& H
&
6 C and N atoms exhibit 120° bond angles;
& & 6 C and N atoms are sp3 hybridized;
Two other resonance
NP N P &
& O 0 C and N atoms are sp hybridized;
structures are possible.
25 σ bonds and 4 π bonds
& & Two other resonance 95."a."NCN22:
S PC P&
& O
structures are possible. 2– " 2– " 2–
ý NP C P N ý mn ð N q C O"
Nð N O C q Nð
mn ð "
& ½ ½
P H +1 0 –1 H 0 0 0
E A Hš
ðš
F
& Fð G G
ð&Fð & H2NCN: N P C P N k% mn N O C q Nð
D D %
H H
All of these compounds are polar. In each compound, the bond dipoles do not
cancel each other out, leading to a polar compound. SeO2 is the only com- Favored by formal charge
pound exhibiting ,120-degree bond angles. PCl3 and PF3 both have a tetra- Dicyandiamide:
hedral arrangement of electron pairs, so these are the compounds that have
H H
central atoms that are sp3 hybridized. NNO and COS both have a linear mo- "0D "0D
lecular structure. –1 0 +1 0 D G N 0 0 % 0 0 N
ý NP C P N P C D G
+ ½ H mn ð Nq C ON P C H Favored
87. F O G G0 by formal
F 0½ N O H ðN
A D G charge
Cl Cl
F O H H H
F
O F
see-saw, dsp3 tetrahedral, sp3 Melamine:

Note: Similar to Exercise 67 c, d, and e, F3ClO has one additional Lewis H H

A " "A " "
structure that is possible, and F3ClO2 (below) has two additional Lewis struc- HO "
N N NO H H O"
N NOH
G E N DA N
G N E DA
tures that are possible. The predicted hybridization is unaffected. C C H C C H
B A mn A B
O ½ NH KN# ½ NK HN#
F trigonal bipyramid C C
F Cl A A
F dsp3 H N HO Nð
O A
H H
89. A Lewis structure for this compound is:
b."NCN22: C is sp hybridized. Each resonance structure predicts a different
H hybridization for the N atoms. For the remaining compounds, we will predict
A
O H OCOH hybrids for the favored resonance structures only.
H H A
C C #
N H NH2
H N C G ½ " G m 3
COH N O C q Nð ð N q C O NP C sp
MC C D m D m
m
m

m
m

N
m

H sp3
m

O N sp sp 2
sp ½ NH2
A
H OCOH Melamine: N in NH2 groups are all sp3 hybridized. Atoms in ring are all sp2
A hybridized; c."NCN22: 2"s and 2"p bonds; H2NCN: 4"s and 2"p bonds; di-
H
cyandiamide: 9"s and 3"p bonds; melamine: 15"s and 3"p bonds; d."The p
 Answers to Selected Exercises A45

system forces the ring to be planar just as the benzene ring is planar. e.!The decreases. b.!increase T: increase rate; c.!increase surface area: increase rate
structure 25.! C2H5OH 1l2 nC2H5OH 1g2 is an endothermic process. Heat is absorbed
½ when liquid ethanol vaporizes; the internal heat from the body provides this
ðN q C ON " heat, which results in the cooling of the body. 27.!Sublimation will occur,
M
C O NO H allowing water to escape as H2O(g). 29.! The strength of intermolecular
D A
ðN forces determines relative boiling points. The types of intermolecular forces
D G H
H H for covalent compounds are London dispersion forces, dipole forces, and hy-
drogen bonding. Because the three compounds are assumed to have similar
best agrees with experiment because it has three different CN bonds. This molar mass and shape, the strength of the London dispersion forces will be
structure is also favored on the basis of formal charge. 97.!a.!25-nm light about equal among the three compounds. One of the compounds will be non-
has suf"cient energy to ionize N and N2 and to break the triple bond in N2. polar so it only has London dispersion forces. The other two compounds will
Thus, N2, N21, N, and N1 will all be present, assuming excess N2. b.!85.33 nm be polar so they have additional dipole forces and will boil at a higher tem-
, l # 127 nm; c.!The ionization energy of a substance is the energy it takes perature than the nonpolar compound. One of the polar compounds will have
to completely remove an electron. N2: (s2s)2(s2s*)2(p2p)4(s2p)2; the electron an H covalently bonded to either N, O, or F. This gives rise to the strongest
removed from N2 is in the s2p molecular orbital, which is lower in energy than type of covalent intermolecular force, hydrogen bonding. This compound ex-
the 2p atomic orbital from which the electron in atomic nitrogen is removed. hibiting hydrogen bonding will have the highest boiling point while the polar
Since the electron removed from N2 is lower in energy than the electron re- compound with no hydrogen bonding will boil at an intermediate tempera-
moved in N, then the ionization energy of N2 is greater than the ionization ture. 31.!a.!Both CO2 and H2O are molecular solids. Both have an ordered
energy of N. 99.!Both reactions apparently involve only the breaking of the array of the individual molecules, with the molecular units occupying the
NOCl bond. However, in the reaction ONCl n NO 1 Cl some energy is re- lattice points. A difference within each solid lattice is the strength of the inter-
leased in forming the stronger NO bond, lowering the value of DH. Therefore, molecular forces. CO2 is nonpolar and only exhibits London dispersion
the apparent NOCl bond energy is arti"cially low for this reaction. The "rst forces. H2O exhibits the relatively strong hydrogen bonding interactions. The
reaction involves only the breaking of the NOCl bond. 101.! The ground difference in strength is evidenced by the solid phase change that occurs at
state MO electron con"guration for He2 is (s1s)2(s1s*)2 giving a bond order of 1!atm. CO2 sublimes at a relatively low temperature of 2788C. In sublima-
0. Therefore, He2 molecules are not predicted to be stable (and are not stable)
tion, all of the intermolecular forces are broken. However, H2O doesn’t have
in the lowest-energy ground state. However, in a high-energy environment, a solid phase change until 08C, and in this phase change from ice to water,
the electron(s) from the antibonding orbitals in He2 can be promoted into only a fraction of the intermolecular forces are broken. The higher tempera-
higher-energy bonding orbitals, thus giving a nonzero bond order and a “rea- ture and the fact that only a portion of the intermolecular forces are broken are
son” to form. For example, a possible excited-state MO electron con"guration attributed to the strength of the intermolecular forces in H2O as compared to
for He2 would be (s1s)2(s1s*)1(s2s)1, giving a bond order of (3 2 1)/2 5 1. CO2. Related to the intermolecular forces are the relative densities of the solid
Thus excited He2 molecules can form, but they spontaneously break apart as and liquid phases for these two compounds. CO2(s) is denser than CO2(l)
the electron(s) fall back to the ground state, where the bond order equals zero. while H2O(s) is less dense than H2O(l). For CO2(s) and for most solids, the
103.!The species with the smallest ionization energy has the highest energy molecules pack together as close as possible, which is why solids are usually
electron. O2, N222, N22, and O21 all have at least one electron in the high- more dense than the liquid phase. Water is an exception to this. Water mole-
energy p2p* orbitals. Because N222 has the highest ratio of electrons to pro- cules are particularly well suited to interact with each other because each
tons, the p2p* electrons are least attracted to the nuclei and easiest to remove, molecule has two polar OOH bonds and two lone pairs on each oxygen. This
translating into the smallest ionization energy. 105.!a.!The CO bond is polar, can lead to the association of four hydrogen atoms with each oxygen: two by
with the negative end at the more electronegative oxygen atom. We would covalent bonds and two by dipoles. To keep this symmetric arrangement
expect metal cations to be attracted to and to bond to the oxygen end of CO (which maximizes the hydrogen bonding interactions), the H2O(s) molecules
on the basis of electronegativity. b.!The formal charge on C is 21, and the occupy positions that create empty space in the lattice. This translates into a
formal charge on O is 11. From formal charge, we would expect metal cat- smaller density for H2O(s) (less mass per unit volume). b.! Both NaCl and
ions to bond to the carbon (with the negative formal charge). c.!In molecular CsCl are ionic compounds with the anions at the lattice points of the unit cell
orbital theory, only orbitals with proper symmetry overlap to form bonding and the cations occupying the empty spaces created by the anions (called
orbitals. The metals that form bonds to CO are usually transition metals, all of holes). In NaCl, the Cl2 anions occupy the lattice points of a face-centered
which have outer electrons in the d orbitals. The only molecular orbitals of unit cell with the Na1 cations occupying the octahedral holes. Octahedral
CO that have proper symmetry to overlap with d orbitals are the p2p* orbitals,
holes are the empty spaces created by six Cl2 ions. CsCl has the Cl2 ions at
whose shape is similar to that of the d orbitals. Since the antibonding molecu- the lattice points of a simple cubic unit cell with the Cs1 cations occupying
lar orbitals have more carbon character, one would expect the bond to form the middle of the cube. 33.!Chalk is composed of the ionic compound cal-
through carbon. 107.!a.!Li2 bond order 5 1; B2 bond order 5 1; b.!4 elec- cium carbonate (CaCO3). The electrostatic forces in ionic compounds are
trons must be removed; c.!4.5 3 105 kJ 109.!T-shaped and dsp3 hybridized much stronger than the intermolecular forces in covalent compounds. There-
fore, CaCO3 should have a much higher boiling point than the covalent com-
Chapter 10
pounds found in motor oil and in H2O. Motor oil is composed of nonpolar
15. Intermolecular forces are the forces between molecules that hold the sub- COC and COH bonds. The intermolecular forces in motor oil are therefore
stances together in the solid and liquid phases. Hydrogen bonding is a speci"c London dispersion forces. We generally consider these forces to be weak.
type of intermolecular force. In this "gure, the dotted lines represent the hy- However, with compounds that have large molar masses, these London dis-
drogen bonding interactions that hold individual H2O molecules together in persion forces add up signi"cantly and can overtake the relatively strong
the solid and liquid phases (answer a is correct). The solid lines represent the hydrogen bonding interactions in water. 35.!In the ln(Pvap) versus 1yT plot,
OOH covalent bonds. 17.!N2 because it will have the weaker intermolecu- the slope of the straight line is equal to 2DHvap /R. Because DHvap is always
lar forces. 19.!Atoms have an approximately spherical shape. It is impossi- positive, the slope of the line will always be negative. 37.! a.! LD (London
ble to pack spheres together without some empty space between the spheres. dispersion); b.!dipole, LD; c.!hydrogen bonding, LD; d. ionic; e.!LD; f.!di-
21.!An alloy is a substance that contains a mixture of elements and has metal- pole, LD; g.! ionic 39.! a.! OCS; b.! SeO2; c.! H2NCH2CH2NH2; d.! H2CO;
lic properties. In a substitutional alloy, some of the host metal atoms are re- e.! CH3OH 41.! a.! The compound with the stronger intermolecular forces
placed by other metal atoms of similar size (e.g., in brass, pewter, plumber’s will boil at the higher temperature. Both HCl and Ar have about the same
solder). An interstitial alloy is formed when some of the interstices (holes) in molar mass, so the London dispersion forces are approximately equivalent.
the closest packed metal structure are occupied by smaller atoms (e.g., in car- However, HCl is a polar molecule leading to additional dipole forces that the
bon steels). 23.!a.!As intermolecular forces increase, the rate of evaporation
A46 Answers to Selected Exercises

nonpolar Ar does not have. HCl has the stronger intermolecular forces, and it 101.!1680 kJ 103.!1490!g 105.!A: solid; B: liquid; C: vapor; D: solid 1
boils at the higher temperature. b.!HF is capable of hydrogen bonding; HCl is vapor; E: solid 1 liquid 1 vapor (triple point); F: liquid 1 vapor; G: liquid
not. c.!LiCl is ionic, and HCl is a molecular solid with only dipole forces and 1 vapor (critical point); H: vapor; the "rst dashed line (at the lower tempera-
London dispersion forces. Ionic forces are much stronger than the forces for ture) is the normal freezing point, and the second dashed line is the normal
molecular solids. d.!n-Hexane is a larger molecule, so it has stronger London boiling point. The solid phase is denser. 107.! a.! two; b.! higher pressure
dispersion forces. 43.! a.! HBr has dipole forces in addition to LD forces; triple point: graphite, diamond, and liquid; lower pressure triple point:
b.!NaCl, stronger ionic forces; c.!I2, larger molecule so stronger LD forces; graphite, liquid and vapor; c.! It is converted to diamond (the more dense
d.!N2, smallest nonpolar compound present, has weakest LD forces; e.!CH4, solid form); d.!Diamond is more dense, which is why graphite can be con-
smallest nonpolar compound present, has weakest LD forces; f.!HF, can form verted to diamond by applying pressure. 109.!Because the density of the
relatively strong hydrogen bonding interactions, unlike the other compounds; liquid phase is greater than the density of the solid phase, the slope of the
g.! CH3CH2CH2OH, unlike others, has relatively strong hydrogen bonding. solid/liquid boundary line is negative (as in H2O). With a negative slope,
45.!H2O is attracted to glass while Hg is not. 47.!The structure of H2O2 pro- the melting points increase with a decrease in pressure so the normal melting
duces greater hydrogen bonding than water. 49.! 313 pm 51.! 0.704! Å point of X should be greater than 2258C. 111. The covalent bonds within a
53.!1.54 g/cm3 55.!174 pm; 11.6 g/cm3 57.!Ag 59.!edge, 328 pm; radius, molecule are much stronger than the intermolecular forces between mole-
142 pm 61.!face-centered cubic unit cell 63.!For a cubic closest packed cules. Consider water, which exhibits a very strong type of dipole force
structure, 74.06% of the volume of each unit cell is occupied by atoms; in a called hydrogen bonding. When water boils at 1008C, hydrogen bonding in-
simple cubic unit cell structure, 52.36% is occupied. The cubic closest packed termolecular forces that hold the H2O molecules together in the liquid phase
structure provides the more ef"cient means for packing atoms. 65.!Doping are broken, resulting in H2O(l) converting to H2O(g). At 1008C, the covalent
silicon with phosphorus produces an n-type semiconductor. The phosphorus bonds within each water molecule are not broken; if they were to be broken,
adds electrons at energies near the conduction band of silicon. Electrons do then H2(g) and O2(g) would be the produced. It takes a lot more energy than
not need as much energy to move from "lled to un"lled energy levels so con- what is provided at 1008C to break the covalent bonds within a water mole-
duction increases. Doping silicon with gallium produces a p-type semicon- cule; the intramolecular forces within a covalent compound are much stron-
ductor. Because gallium has fewer valence electrons than silicon, holes (un- ger than the intermolecular forces between molecules. 113.!As the physical
"lled energy levels) at energies in the previously "lled molecular orbitals are properties indicate, the intermolecular forces are slightly stronger in D2O
created, which induces greater electron movement (greater conductivity). than in H2O. 115. A: CH4; B: SiH4; C: NH3 117. 4.67 min 119.! XeF2
67.!p-type 69.!5.0 3 102 nm 71.!NaCl: 4Na1, 4Cl2; CsCl: 1Cs1, 1Cl2; 121.!B2H6, molecular; SiO2, network; CsI, ionic; W, metallic 123.!57.8 torr
ZnS: 4Zn21, 4S22; TiO2: 2Ti41, 4O22 73.! CoF2 75.! ZnAl2S4 77.! MF2 125. A mixture of H2O(s) and H2O(l) will be present at 0°C when 215 kJ of
79.!NaCl structure; rO22 5 1.49 3 1028 cm; rMg21 5 6.15 3 1029 cm 81.!The heat are removed from the gas sample. 127. If we extend the liquid–vapor
calculated distance between ion centers is 358 pm. Ionic radii give a distance line of the water phase diagram to below the freezing point, we "nd that su-
of 350. pm. The distance calculated from the density is 8 pm (2.3%) greater percooled water will have a higher vapor pressure than ice at 210°C (see
than that calculated from the table of ionic radii. 83.! a.! CO2: molecular; Fig. 10.44). To achieve equilibrium, there must be a constant vapor pressure.
b.!SiO2: network; c.!Si: atomic, network; d.!CH4: molecular; e.!Ru: atomic, Over time, supercooled water will be transformed through the vapor into ice
metallic; f.!I2: molecular; g.!KBr: ionic; h.!H2O: molecular; i.!NaOH: ionic; in an attempt to equilibrate the vapor pressure. Eventually there will only be
j.!U: atomic, metallic; k.!CaCO3: ionic; l.!PH3: molecular 85.!a.!The unit ice at 210°C along with H2O(g) at the vapor pressure given by the solid–
cell consists of Ni at the cube corners and Ti at the body center or Ti at the vapor line in the phase diagram. 129.!4.65 kg/h 131. CO2 and XeF4 are
cube corners and Ni at the body center. b.!NiTi; c.!Both have a coordination both nonpolar covalent compounds, so they only exhibit London dispersion
number of 8. 87.!CaTiO3; each structure has six oxygens around each Ti. forces. CH3CH2OH and HF are covalent compounds that contain either an
89.!a.!YBa2Cu3O9; b.!The structure of this superconductor material is based NOH, OOH, or FOH bond, so they can form hydrogen bonding forces. SF4
on the second perovskite structure. The YBa2Cu3O9 structure is three of these and ICl5 are polar covalent compounds, so they can exhibit dipole–dipole
cubic perovskite unit cells stacked on top of each other. The oxygens are in forces. 133.! a.! False; the ionic forces in LiF are much stronger than the
the same places, Cu takes the place of Ti, two Ca are replaced by two Ba, and molecular intermolecular forces found in H2S. b.! True; HF is capable of
one Ca is replaced by Y. c.!YBa2Cu3O7 91.!Li, 158 kJ/mol; Mg, 139 kJ/mol. H bonding; HBr is not. c.!True; the larger Cl2 molecule will have the stronger
Bonding is stronger in Li. 93.!898C 95.!28.6 kJ/mol London dispersion forces. d.!True; HCl is a polar compound while CCl4 is a
97.! nonpolar compound. e.! False; the ionic forces in MgO are much stronger
than the molecular intermolecular forces found in CH3CH2OH. 135.! 41
137.!a.!Kr: group 8A; b. SO2: molecular; c. Ni: metallic; d. SiO2: network;
5 e. NH3: molecular; f. Pt: metallic 139. 207 torr
141.!DE 5 27.86 kJ/mol; DH 5 30.79 kJ/mol 143.!46.7 kJ/mol; 90.%

80 4 145. H H H H
H C C O H and H C O C H
60
H H H H
40 Liquid (H-bonding) Gas (no H-bonding)
Temp (°C)

3 Slope 5 > slope 3 > slope 1

20 The "rst structure with the —OH bond is capable of forming hydrogen bond-
Time 4 = 4 × time 2
ing; the other structure is not. Therefore, the liquid (which has the stronger
0 intermolecular forces) is the "rst structure, and the gas is the second structure.
2 147.!The solids with high melting points (NaCl, MgCl2, NaF, MgF2, AlF3)
–20
1 are all ionic solids. SiCl4, SiF4, Cl2, F2, PF5, and SF6 are nonpolar covalent
–40 molecules with LD forces. PCl3 and SCl2 are polar molecules with LD and
dipole forces. In these 8 molecular substances the intermolecular forces are
–60 weak and the melting points low. AlCl3 is intermediate. The melting point
Time indicates there are stronger forces present than in the nonmetal halides,
99. a.!Much more energy is required to break the intermolecular forces when but not as strong as for an ionic solid. AlCl3 illustrates a gradual transition
going from a liquid to a gas than is required to go from a solid to a liquid. from ionic to covalent bonding; from an ionic solid to discrete molecules.
Hence DHvap is much larger than DHfus; b.!113 J; c.!4220 J; d.!4220!J released 149.! TiO1.182 or Ti0.8462O; 63.7% Ti21, 36.3% Ti31 (a 1.75;1 ion ratio)
151.!6.58 g/cm3
 Answers to Selected Exercises A47

153. that of the cells, the cells shrivel as there is a net transfer of water out of the
a cells. This is called crenation. Hemolysis occurs when the red blood cells are
bathed in a solution having lower osmotic pressure than that inside the cell.
Here, the cells rupture as there is a net transfer of water to inside the red
blood cells. 35.! 1.9% 37. 1.06 g/mL; 0.0180 mole fraction H3PO4,
P 0.9820 mole fraction H2O; 0.981 mol/L; 1.02 mol/kg 39.!HCl: 12 M, 17 m,
c b
0.23; HNO3: 16 M, 37 m, 0.39; H2SO4: 18 M, 200 m, 0.76; HC2H3O2: 17 M,
2000 m, 0.96; NH3: 15 M, 23 m, 0.29 41.! 35%; 0.39; 7.3 m; 3.1! M
43.! 10.1% by mass; 2.45 mol/kg 45.! 23.9%; 1.6 m, 0.028, 4.11! N
47.!NaI 1s2 S Na1 1aq2 1 I2 1aq2 DHsoln 5 28 kJ/mol 49. The attraction of
water molecules for Al31 and OH2 cannot overcome the larger lattice energy
T
of Al(OH)3. 51.!a.!CCl4; b.!H2O; c.!H2O; d.!CCl4; e. H2O; f.!H2O; g.!CCl4
As P is lowered, we go from a to b on the phase diagram. The water boils. 53.!a.!NH3; b.!CH3CN; c.!CH3COOH 55.!As the length of the hydrocarbon
The boiling of water is endothermic and the water is cooled 1b S c2 , forming chain increases, the solubility decreases because the nonpolar hydrocarbon
some ice. If the pump is left on, the ice will sublime until none is left. This is chain interacts poorly with the polar water molecules. 57.! 1.04 3
the basis of freeze drying. 1023! mol/L ? atm; 1.14 3 1023 mol/L 59.! 136 torr 61.! 0.918
4 63.! a.! 290 torr; b.! 0.69 65.! xmethanol 5 xpropanol 5 0.500 67.! solution c
155.!The volume of the hole is p 3 1"3 2 12 r 4 3 157.!CdS; n-type 69.!a.!These two molecules are named acetone (CH3COCH3) and water. As
3
159.!253 torr; 6.38 3 1022 atoms discussed in Section 11.4 on nonideal solutions, acetone–water solutions ex-
hibit negative deviations from Raoult’s law. Acetone and water have the abil-
Chapter 11 ity to hydrogen bond with each other, which gives the solution stronger inter-
13. 9.74!M 15.!160 mL 17.!4.5!M 19.!As the temperature increases, the molecular forces compared to the pure states of both solute and solvent. In
gas molecules will have a greater average kinetic energy. A greater fraction the pure state, acetone cannot hydrogen bond with itself, so the middle dia-
of the gas molecules in solution will have kinetic energy greater than the at- gram illustrating negative deviations from Raoult’s law is the correct choice
tractive forces between the gas molecules and the solvent molecules. More for acetone–water solutions. b.! These two molecules are named ethanol
gas molecules will escape to the vapor phase, and the solubility of the gas (CH3CH2OH) and water. Ethanol–water solutions show positive deviations
will decrease. 21.! The levels of the liquids in each beaker will become from Raoult’s law. Both substances can hydrogen bond in the pure state, and
constant when the concentration of solute is the same in both beakers. Be- they can continue this in solution. However, the solute–solvent interactions
cause the solute is less volatile, the beaker on the right will have a larger are weaker for ethanol–water solutions due to the signi"cant nonpolar part of
volume when the concentrations become equal. There will be a larger net ethanol (CH3OCH2 is the nonpolar part of ethanol). This nonpolar part of
transfer of water molecules into the the right beaker than the net transfer of ethanol weakens the intermolecular forces in solution, so the "rst diagram
solute molecules to the left beaker. Eventually the rate that solute and H2O illustrating positive deviations from Raoult’s law is the correct choice for
leave and return to each beaker will become equal when the concentrations ethanol–water solutions. c.!These two molecules are named heptane (C7H16)
become equal. 23.!No. For an ideal solution, DHsoln 5 0. 25.!Normality is and hexane (C6H14). Heptane and hexane are very similar nonpolar sub-
the number of equivalents per liter of solution. For an acid or a base, an stances; both are composed entirely of nonpolar COC bonds and relatively
equivalent is the mass of acid or base that can furnish 1 mole of protons nonpolar COH bonds, and both have a similar size and shape. Solutions of
(if an acid) or accept 1 mole of protons (if a base). A proton is an H1 ion. heptane and hexane should be ideal, so the third diagram illustrating no de-
Molarity is de"ned as the moles of solute per liter of solution. When viation from Raoult’s law is the correct choice for heptane–hexane solutions.
the number of equivalents equals the number of moles of solute, then d.!These two molecules are named heptane (C7H16) and water. The interac-
normality 5 molarity. This is true for acids that only have one acidic proton tions between the nonpolar heptane molecules and the polar water molecules
in them and for bases that accept only one proton per formula unit. Examples will certainly be weaker in solution compared to the pure solvent and pure
of acids where equivalents 5 moles solute are HCl, HNO3, HF, and HC2H3O2. solute interactions. This results in positive deviations from Raoult’s law (the
Examples of bases where equivalents 5 moles solute are NaOH, KOH, and "rst diagram). 71.!101.58C 73.!14.8!g C3H8O3 75.!Tf 5 229.98C, Tb 5
NH3. When equivalents 2 moles solute, then normality 2 molarity. This is 108.28C 77.!6.6 3 1022 mol/kg; 590 g/mol (610 g/mol if no rounding of
true for acids that donate more than one proton (H2SO4, H3PO4, H2CO3, etc.) numbers) 79. a.!DT 5 2.0 3 10258C, p 5 0.20 torr; b.!Osmotic pressure is
and for bases that react with more than one proton per formula unit [Ca(OH)2, better for determining the molar mass of large molecules. A temperature
Ba(OH)2, Sr(OH)2, etc.]. 27.!Only statement b is true. A substance freezes change of 10258C is very dif"cult to measure. A change in height of a column
when the vapor pressures of the liquid and solid phases are the same. When of mercury by 0.2 mm is not as hard to measure precisely.
a solute is added to water, the vapor pressure of the solution at 08C is less 81.!2.51 3 105 g/mol 83.!Dissolve 210!g sucrose in some water and dilute
than the vapor pressure of the solid; the net result is for any ice present to to 1.0!L in a volumetric #ask. To get 0.62 6 0.01 mol/L, we need 212 6
convert to liquid in order to try to equalize the vapor pressures (which never 3! g sucrose. 85.! a.! 0.010! m Na3PO4 and 0.020! m KCl; b.! 0.020! m HF;
can occur at 08C). A lower temperature is needed to equalize the vapor pres- c. 0.020!m CaBr2 87.!a.!Tf 5 2138C; Tb 5 103.58C; b.!Tf 5 24.78C; Tb 5
sures of water and ice, hence the freezing point is depressed. For statement 101.38C 89.! 1.67 91.! a.! Tf 5 20.288C; Tb 5 100.0778C; b. Tf 5
a, the vapor pressure of a solution is directly related to the mole fraction of 20.378C; Tb 5 100.108C 93.! 2.63 (0.0225 m), 2.60 (0.0910 m), 2.57
solvent (not solute) by Raoult’s law. For statement c, colligative properties (0.278 m); iaverage 5 2.60 95.!a. yes; b.!no 97.!Benzoic acid is capable of
depend on the number of solute particles present and not on the identity of hydrogen bonding, but a signi"cant part of benzoic acid is the nonpolar ben-
the solute. For statement d, the boiling point of water is increased because zene ring. In benzene, a hydrogen bonded dimer forms.
the sugar solute decreases the vapor pressure of the water; a higher tempera-
O H
O
ture is required for the vapor pressure of the solution to equal the external D
M
pressure so boiling can occur. 29.!Adding a solute to a solvent increases the C MC
D
O H
O
boiling point and decreases the freezing point of the solvent. Thus, the sol-
vent is a liquid over a wider range of temperatures when a solute is dissolved.
31.!The vapor pressure, boiling point, and osmotic pressure will be the same The dimer is relatively nonpolar and thus more soluble in benzene than in
between the two different solutions. 33.!Isotonic solutions are those that water. Because benzoic acid forms dimers in benzene, the effective solute
have identical osmotic pressures. Crenation and hemolysis refer to phenom- particle concentration will be less than 1.0 molal. Therefore, the freezing-
ena that occur when red blood cells are bathed in solutions having a mis- point depression would be less than 5.12°C (DTf 5 Kf m). 99.!The main
match in osmotic pressure between the inside and the outside of the cell. factor for stabilization seems to be electrostatic repulsion. The center of a
When red blood cells are in a solution having a higher osmotic pressure than colloid particle is surrounded by a layer of same charged ions, with oppo-
A48 Answers to Selected Exercises

sitely charged ions forming another charged layer on the outside. Overall, the rate by affecting the value of the rate constant k.!The value of the rate
there are equal numbers of charged and oppositely charged ions, so the col- constant is dependent on temperature. It also depends on the activation en-
loidal particles are electrically neutral. However, since the outer layers are ergy. A catalyst will change the value of k because the activation energy
the same charge, the particles repel each other and do not easily aggregate for changes. Increasing the concentration (partial pressure) of either O2 or NO
precipitation to occur. Heating increases the velocities of the colloidal parti- does not affect the value of k, but it does increase the rate of the reaction
cles. This causes the particles to collide with enough energy to break the ion because both concentrations appear in the rate law. 15.! In a unimolecular
barriers, allowing the colloids to aggregate and eventually precipitate out. reaction, a single reactant molecule decomposes to products. In a bimolecu-
Adding an electrolyte neutralizes the adsorbed ion layers, which allows col- lar reaction, two molecules collide to give products. The probability of the
loidal particles to aggregate and then precipitate out. 101.!No, the solution simultaneous collision of three molecules with enough energy and orienta-
is not behaving ideally. If the solution were behaving ideally, the freezing tion is very small, making termolecular steps very unlikely. 17.!When the
point would be 21.9°C. 103.! a. Water boils when the vapor pressure rate doubles as the concentration quadruples, the order is 1y2. For a reactant
equals the pressure above the water. In an open pan, Patm < 1.0 atm. In a that has an order of 21, the rate will decrease by a factor of 1y2 when the
pressure cooker, Pinside . 1.0 atm and water boils at a higher temperature. concentrations are doubled. 19.!Two reasons are: 1) the collision must in-
The higher the cooking temperature, the faster the cooking time. b.!When volve enough energy to produce the reaction; i.e., the collision energy must
water freezes from a solution, it freezes as pure water, leaving behind a more equal or exceed the activation energy. 2) the relative orientation of the reac-
concentrated salt solution. c.!On the CO2 phase diagram, the triple point is tants must allow formation of any new bonds necessary to produce prod-
above 1 atm and CO2(g) is the stable phase at 1 atm and room temperature. ucts. 21.!Enzymes are very ef"cient catalysts. As is true for all catalysts,
CO2(l) can’t exist at normal atmospheric pressures, which explains why dry enzymes speed up a reaction by providing an alternative pathway for reactants
ice sublimes rather than boils. In a "re extinguisher, P . 1 atm and CO2(l) to convert to products. This alternative pathway has a smaller activation en-
can exist. When CO2 is released from the "re extinguisher, CO2(g) forms as ergy and, hence, a faster rate. Also true is that catalysts are not used up in the
predicted from the phase diagram. 105.! 0.600 107.! Pideal 5 188.6 torr; overall chemical reaction. Once an enzyme comes in contact with the correct
xacetone 5 0.512, xmethanol 5 0.488; the actual vapor pressure of the solution is reagent, the chemical reaction quickly occurs, and the enzyme is then free to
smaller than the ideal vapor pressure, so this solution exhibits a negative catalyze another reaction. Because of the ef"ciency of the reaction step, only
deviation from Raoult’s law. This occurs when solute–solvent attractions are a relatively small amount of enzyme is needed to catalyze a speci"c reaction,
stronger than for the pure substances. 109.! 776 g/mol 111.! C2H4O3; no matter how complex the reaction. 23.!The rate of a reaction is indepen-
151! g/mol (exp.); 152.10 g/mol (calc.); C4H8O6 113.! 1.97% NaCl dent of the enthalpy change for the reaction. The combustion of carbohy-
115.!a.!100.778C; b.!23.1 mm Hg; c. Assume an ideal solution; assume no drates has a lower activation energy, which is why it is the faster process.
ions form (i 5 1); assume the solute is nonvolatile. 117.! 639 g/mol; 25.!P4: 6.0 3 1024 mol/L ? s; H2: 3.6 3 1023 mol/L ? s 27.!a.!average rate
33.7!torr 119.!3!kJ/mol 121.!0.732 123.!100.25°C 125.!43% NaNO3 of decomposition of H2O2 5 2.31 3 1025 mol/L ? s, rate of production of
and 57% Mg(NO3)2 by mass O2 5 1.16 3 1025 mol/L ? s; b.!average rate of decomposition of H2O2 5
1.16 3 1025 mol/L ? s, rate of production of O2 5 5.80 3 1026 mol/L ? s
0.30y
127. 30.% A: xA 5 , x 5 1 2 xA; 29.!a. mol/L ? s; b.!mol/L ? s; c.!s21; d.!L/mol ? s; e.!L2/mol2 ? s 31.!a. rate 5
0.70x 1 0.30y B k[NO]2[Cl2]; b.!1.8 3 102 L2/mol2 ? min 33.!a. rate 5 k[NOCl]2; b.!6.6 3
y y
50.% A: xA 5 ,x 512 ; 10229 cm3/molecules ? s; c.!4.0 3 1028 L/mol ? s 35.!a. rate 5 k[I2][OCl2];
x1y B x1y b.!3.7 L/mol ? s; c.!0.083 mol/L ? s 37.!a. "rst order in Hb and "rst order in
0.80y
80.% A: xA 5 , x 5 1 2 xA; CO; b.!rate 5 k[Hb][CO]; c.!0.280 L/mmol ? s; d.!2.26 mmol/L ? s 39.!rate
0.20x 1 0.80y B 5 k[H2O2]; ln[H2O2] 5 2kt 1 ln[H2O2]0;
0.30x 0.30x
30.% A: xAV 5 ,x V512 ; 1 1
0.30x 1 0.70y B 0.30x 1 0.70y k 5 8.3 3 1024 s21; 0.037!M 41.!rate 5 k[NO2]2; 5 kt 1 ;
x 3 NO2 4 3 NO2 4 0
50.% A: xAV 5 , x V 5 1 2 xAV; k 5 2.08 3 10 L/mol ? s; 0.131!M 43.!a.!rate 5 k; [C2H5OH] 5 2kt 1
24
x1y B
0.80x [C2H5OH]0; because slope 5 2k, k 5 4.00 3 1025 mol/L ? s; b.! 156 s;
80.% A: xAV 5 , x V 5 1 2 xAV 1 1
0.80x 1 0.20y B c. 313! s 45.! rate 5 k[C4H6]2; 5 kt 1 ; k 5 1.4 3 1022
3 C4H6 4 3 C4H6 4 0
129. 72.5% sucrose and 27.5% NaCl by mass; 0.313 131.!0.050 133.!44%
L/mol ? s 47.! second order; 0.1! M 49.! a.! [A] 52kt 1 [A]0; b.! 1.0 3
naphthalene, 56% anthracene 135.! 20.208C, 100.0568C 137.! a. 46 L;
1022 s; c.! 2.5 3 1024! M 51.! 9.2 3 1023 s21; 75! s 53.! 150. s
b. No; a reverse osmosis system that applies 8.0 atm can only purify water
55.!1.0!3!102!min 57. a.!1.1 3 1022 M; b.!0.025!M 59.!1.6 L/mol ? s
with solute concentrations less than 0.32 mol/L. Salt water has a solute con-
61.! a.! rate 5 k[CH3NC]; b.! rate 5 k[O3][NO]; c.! rate 5 k[O3]; d.! rate 5
centration of 2(0.60 M) 5 1.2!M ions. The solute concentration of salt water
k[O3][O] 63.!Rate 5 k[C4H9Br]; C4H9Br 1 2H2O n C4H9OH 1 Br2 1 H3O1;
is much too high for this reverse osmosis unit to work. 139.!a.!26.6 kJ/mol;
the intermediates are C4H91 and C4H9OH21. 65. The rate law is Rate 5
b.!2657 kJ/mol 141.!i 5 3.00; CdCl2
k[NO]2[Cl2]. If we assume the "rst step is rate determining, we would expect
the rate law to be Rate 5 k1[NO][Cl2]. This isn’t correct. However, if we as-
Chapter 12
sume the second step to be rate determining, then Rate 5 k2[NOCl2][NO]. To
11. One experimental method to determine rate laws is the method of initial
see if this agrees with experiment, we must substitute for the intermediate
rates. Several experiments are carried out using different initial concentra-
NOCl2 concentration. Assuming a fast-equilibrium "rst step (rate reverse 5
tions of reactants, and the initial rate is determined for each experiment. The
rate forward):
results are then compared to see how the initial rate depends on the initial
k1
concentrations. This allows the orders in the rate law to be determined. The k21[NOCl2] 5 k1[NO][Cl2], [NOCl2] 5 [NO][Cl2];
k21
value of the rate constant is determined from the experiments once the orders
substituting into the rate equation:
are known. The second experimental method utilizes the fact that the inte-
grated rate laws can be put in the form of a straight-line equation. Concentra- k 2k 1 k 2k 1
Rate 5 [NO]2[Cl2] 5 k[NO]2[Cl2] where k 5
tion versus time data are collected for a reactant as a reaction is run. These k21 k21
data are then manipulated and plotted to see which manipulation gives a This is a possible mechanism with the second step the rate-determining
straight line. From the straight-line plot we get the order of the reactant, and step because the derived rate law agrees with the experimentally deter-
the slope of the line is mathematically related to k, the rate constant. 13.!All mined rate law.
of these choices would affect the rate of the reaction, but only b and c affect
 Answers to Selected Exercises A49

67." Note that the heights of the second and third humps must be lower than the
!rst-step activation energy. However, the height of the third hump could be
higher than the second hump. One cannot determine this absolutely from the
information in the problem.

E Ea b. F2 S 2F slow
P
F 1 H2 S HF 1 H fast
∆E H 1 F S HF fast

R F2 1 H2 S 2HF
c. F2 was the limiting reactant. 119. a. [B] .. [A], so [B] can be consid-
RC ered constant over the experiments. This gives us a pseudo-order rate-law
69. 341 kJ/mol 71."The graph of ln(k) versus 1yT is linear with slope 5 equation. b. Rate 5 k[A]2[B], k 5 0.050 L2/mol2 ? s. c. i. This mechanism
2EayR 5 21.2 3 104 K; Ea 5 1.0 3 102 kJ/mol 73."9.5 3 1025 L/mol ? s gives the wrong stoichiometry, so it can’t be correct. ii. Rate 5 k[E][A];
75. 518C 77."H3O1(aq) 1 OH2(aq) n 2H2O(l) should have the faster rate. k1 3 A 4 3 B 4 kk1
k1[A][B] 5 k21[E]; [E] 5 ; Rate 5 3 A 4 2 3 B 4 . This mechanism
H3O1 and OH2 will be electrostatically attracted to each other; Ce41 and k21 k21
Hg221 will repel each other (so Ea is much larger). 79."a."NO; b."NO2; gives the correct stoichiometry and gives the correct rate law when it is de-
c. 2.3 81."CH2DOCH2D should be the product. If the mechanism is pos- rived from the mechanism. This is a possible mechanism for this reaction.
sible, then the reaction must be C2H4 1 D2"n CH2DCH2D. If we got this iii. Rate 5 k[A]2. This mechanism gives the wrong derived rate law, so it
product, then we could conclude that this is a possible mechanism. If we got can’t be correct. Only mechanism ii is possible. 121." Rate 5 k[A][B]2,
some other product, e.g., CH3CHD2, then we would conclude that the mecha- k 5 1.4 3 1022 L2/mol2 ? s 123."2.20 3 1025 s21; 5.99 3 1021 molecules
nism is wrong. Even though this mechanism correctly predicts the products of 125. 1.3 3 1025 s21; 112 torr
the reaction, we cannot say conclusively that this is the correct mechanism;
we might be able to conceive of other mechanisms that would give the same Chapter 13
product as our proposed one. 83."The rate depends on the number of reac- 13."No, equilibrium is a dynamic process. Both the forward and reverse reac-
tant molecules adsorbed on the surface of the catalyst. This quantity is pro- tions are occurring at equilibrium, just at equal rates. Thus the forward and
portional to the concentration of reactant. However, when all the catalyst reverse reactions will distribute 14C atoms between CO and CO2. 15." A
surface sites are occupied, the rate becomes independent of the concentration large value for K (K @ 1) indicates there are relatively large concentrations of
of reactant. 85." 2158C 87." a." 20 min; b." 30 min; c." 15 min 89." 427" s product gases and/or solutes as compared with the concentrations of reactant
91. 1.0 3 102 kJ/mol 93. a. second order; b. 20 s; c. 190 s; d. 847 s; gases and/or solutes at equilibrium. A reaction with a large K value is a good
e."31 kJ/mol. 95."6.58 3 1026 mol/L ? s 97."a."25 kJ/mol; b."12 s; source of products. 17."4 molecules H2O, 2 molecules CO, 4 molecules H2,
c." T Interval 54 2 2(Intervals) and 4 molecules CO2 are present at equilibrium. 19."K and Kp are equilib-
rium constants as determined by the law of mass action. For K, the units used
21.08C 16.3"s 218C for concentrations are mol/L, and for Kp, partial pressures in units of atm are
27.88C 13.0"s 288C used (generally). Q is called the reaction quotient. Q has the exact same form
30.08C 12"s 30.8C as K or Kp, but instead of equilibrium concentrations, initial concentrations
are used to calculate the Q value. Q is of use when it is compared to the K
This rule of thumb gives excellent agreement to two signi!cant !gures. value. When Q 5"K (or when Qp 5 Kp), the reaction is at equilibrium. When
99. 12.5 s 101."a. 115 L3/mol3 ? s; b."87.0 s; c."[A] 5 1.27 3 1025 M, [B]"5 Q 2 K, the reaction is not at equilibrium and one can determine what has to
1.00"M 103."The reaction is !rst order with respect to both A and B; rate"5 be the net change for the system to get to equilibrium. 21."We always try to
k[A][B] where k"5 1.6 L/mol · s. 105."35.4 s 107.!a."False; from the half- make good assumptions that simplify the math. In some problems, we can set
life expression for a zero-order reaction in Table 12.6 of the text, there is a up the problem so that the net change, x, that must occur to reach equilibrium
direct relationship between concentration and the half-life value. As the reac- is a small number. This comes in handy when you have expressions like
tion proceeds for a zero-order reaction, the half-life value will decrease be- 0.12 2"x or 0.727 1 2x. When x is small, we assume that it makes little dif-
cause concentration decreases. b. True. c. False; from the half-life expression ference when subtracted from or added to some relatively big number. When
for a !rst-order reaction in Table 12.6, the half-life does not depend on con- this is true, 0.12 2 x < 0.12 and 0.727 1 2x < 0.727. If the assumption holds
centration. d. True; the half-life for a second-order reaction increases with by the 5% rule, then the assumption is assumed valid. The 5% rule refers to x
time because there is an inverse relationship between concentration and the (or 2x or 3x, etc.) that was assumed small compared to some number. If x (or
half-life value. 109."53.9 kJ/mol; the chirping rate will be about 45"chirps 2x or 3x, etc.) is less than 5% of the number the assumption was made against,
k 3 I2 4 3 OCl2 4 then the assumption will be assumed valid. If the 5% rule fails to work, one
per minute at 7.5°C. 111. rate 5 ; k 5 6.0 3 101 s21
3 OH2 4 can generally use a math procedure called the method of successive approxi-
113." a." !rst order with respect to both reactants; b." rate 5 k[NO][O3]; mations to solve the quadratic or cubic equation. 23. There will be a net in-
c." k9 5 1.8 s21; k0 5 3.6 s21; d." k 5 1.8 3 10214 cm3/molecules ? s crease in the amount of N2O present once equilibrium is reestablished. As
k2 k1 1 /2 N2O(g) is added, the reaction will shift right to use up some of the added
115.!a."Rate 5 k3 a b [CO][Cl2]3/2 5 k[CO][Cl2]3/2. b. Cl and COCl
k22 k21 N2O. However, only some of the added N2O will react, not all. The net effect
are intermediates. 117."a."For a three-step reaction with the !rst step limiting, is for the amount of N2O to increase once equilibrium is reestablished. As far
the energy-level diagram could be as the K value is concerned, as long as the temperature didn’t change, K will
remain a constant value.
3 NO 4 2 3 NO2 4 2 3 SiCl4 4 3 H2 4 2
25."a. K 5 ; b. K 5 ; c. K 5 ;
3 N2 4 3 O2 4 3 N2O4 4 3 SiH4 4 3 Cl2 4 2
E
3 PCl3 4 2 3 Br2 4 3
d. K 5 27."a. 0.11; b."77; c."8.8; d."1.7 3 1024 29."4.0 3 106
R 3 PBr3 4 2 3 Cl2 4 3
P 31. 1.7 3 1025 33."6.3 3 10213 35."4.6 3 103
Reaction coordinate 3 H2O 4 PH2O
37. a."K 5 ,K 5 ; b. K 5 [N2][Br2]3,
3 NH3 4 2 3 CO2 4 p PNH32 3 PCO2
3 H2O 4 PH2O
Kp 5 PN2 3 PBr23; c."K 5 [O2]3, Kp 5 PO23; d."K 5 , Kp 5
3 H2 4 PH2
A50 Answers to Selected Exercises

39. only reaction d 41. 1.2 3 10–9 43. 4.07 45.!a. not at equilibrium; donates a proton. NH22 is the conjugate base of the NH3 acid. In the reverse
Q . K, shift left; b.!at equilibrium; c.!not at equilibrium; Q . K, shift left reaction, NH22 accepts a proton. Conjugate acid–base pairs differ only by an
47.! a. decrease; b.! no change; c.! no change; d.! increase 49.! 0.16 mol H1 in the formula. 29.!a.!These would be 0.10!M solutions of strong acids
51.! 3.4 53. 0.056 55.! [N2]0 5 10.0 M, [H2]0 5 11.0! M 57.! [SO3] 5 like HCl, HBr, HI, HNO3, H2SO4, or HClO4. b.!These are salts of the conju-
[NO] 5 1.06 M; [SO2] 5 [NO2] 5 0.54! M 59.! 7.8 3 1022 atm gate acids of the bases in Table 14.3. These conjugate acids are all weak ac-
61.! PSO2 5 0.38 atm; PO2 5 0.44 atm; PSO3 5 0.12 atm 63.! a. [NO] 5 ids. Three examples would be 0.10!M solutions of NH4Cl, CH3NH3NO3, and
0.032 M, [Cl2] 5 0.016 M, [NOCl] 5 1.0 M; b.![NO] 5 [NOCl] 5 1.0 M, C2H5NH3Br. Note that the anions used to form these salts are conjugate bases
[Cl2] 5 1.6 3 1025 M; c.![NO] 5 8.0 3 1023 M, [Cl2] 5 1.0 M, [NOCl] 5 of strong acids; this is because they have no acidic or basic properties in
2.0!M 65. PCOCl2 5 1.0 atm; PCO 5 PCl2 5 8.2 3 1025 atm 67.!0.27 atm water (with the exception of HSO42, which has weak acid properties).
69. PCO2 5 3.39 atm, PCO 5 2.61 atm 71.!a. no effect; b.!shifts left; c. shifts c. These would be 0.10!M solutions of strong bases like LiOH, NaOH, KOH,
right 73. a. no change; b. products increase; c. reactants increase RbOH, CsOH, Ca(OH)2, Sr(OH)2, and Ba(OH)2. d.! These are salts of the
75.!a. right; b.!right; c.!no effect; d.!left; e.!no effect 77.!a. left; b.!right; conjugate bases of the neutrally charged weak acids in Table 14.2. The con-
c.! left; d.! no effect; e.! no effect; f. right 79.! increase 81.! 2.6 3 1081 jugate bases of weak acids are weak bases themselves. Three examples
83.!6.74 3 1026 85.! a.! 0.379 atm; b.! 0.786 87.! [Fe31] 5 2 3 1024 M, would be 0.10!M solutions of NaClO2, KC2H3O2, and CaF2. The cations used
[SCN2] 5 0.08 M, [FeSCN21] 5 0.020!M 89.!1.43 3 1022 atm 91.!pink to form these salts are Li1, Na1, K1, Rb1, Cs1, Ca21, Sr21, and Ba21 since
93.!Added OH2 reacts with H1 to produce H2O. As H1 is removed, the reac- these cations have no acidic or basic properties in water. Notice that these are
tion shifts right to produce more H1 and CrO422. Because more CrO422 the cations of the strong bases that you should memorize. e.!There are two
is produced, the solution turns yellow. 95. 9.0 3 1023! M 97.! 0.50 ways to make a neutral salt. The easiest way is to combine a conjugate base
99. [H2CO] 5 [H2] 5 2.1 3 1025 M; [CH3OH] 5 1.24 M; as formaldehyde of a strong acid (except for HSO42) with one of the cations from the strong
is removed from the equilibrium by forming some other substance, the equi- bases. These ions have no acidic/basic properties in water so salts of these
librium shifts right to produce more formaldehyde. Hence the concentration ions are neutral. Three examples would be 0.10!M solutions of NaCl, KNO3,
of methanol (a reactant) decreases as formaldehyde (a product) reacts to and SrI2. Another type of strong electrolyte that can produce neutral solu-
form formic acid. 101. 6.5 3 1026 M 103. 0.81 tions are salts that contain an ion with weak acid properties combined with
105. a. NOCl NO Cl2 an ion of opposite charge having weak base properties. If the Ka for the weak
acid ion is equal to the Kb for the weak base ion, then the salt will produce a
Initial 2.6 0 0 neutral solution. The most common example of this type of salt is ammo-
Change 22x 12x 1x nium acetate, NH4C2H3O2. For this salt, Ka for NH41 5 Kb for C2H3O22 5
Equilibrium 2.6 2 2x 2x x 5.6 3 10210. This salt, at any concentration, produces a neutral solution.
b. [NO] 5 0.060 M; [Cl2] 5 0.030 M; [NOCl] 5 2.5 M 107. Add N2(g): [N2]
31. a.! H2O 1l2 1 H2O 1l2 m H3O1 1aq2 1 OH2 1aq2 or
will increase overall, [H2] will decrease, and [NH3] will increase. Remove
H2O 1l2 m H1 1aq2 1 OH2 1aq2 !!!K 5 Kw 5 3 H1 4 3 OH2 4
H2(g): [N2] will increase, [H2] will decrease overall, and [NH3] will decrease.
Add NH3(g): [N2] and [H2] will increase, while [NH3] will also increase over- b. HF 1aq2 1 H2O 1l2 m F2 1aq2 1 H3O1 1aq2 or
all. Add Ne(g) at constant volume: no change for [N2], [H2], or [NH3]. In- 3 H1 4 3 F2 4
HF 1aq2 m H1 1aq2 1 F2 1aq2 !!!!K 5 Ka 5
crease temperature (add heat): [N2] and [H2] will increase, while [NH3] will 3 HF 4
decrease. Decrease volume: [N2] and [H2] will decrease, while [NH3] will in- c. C5H5N 1aq2 1 H2O 1l2 m C5H5NH1 1aq2 1 OH2 1aq2
crease. Add a catalyst: no change for [N2], [H2], or [NH3]. 109.! PCO 5 3 C5H5NH1 4 3 OH2 4
0.58 atm, PCO2 5 1.65 atm 111.![NOCl] 5 2.0 M, [NO] 5 0.050 M, [Cl2] 5 K 5 Kb 5
3 C5H5N 4
0.025!M 113. 2.1 3 1023 atm 115.!PNO2 5 0.704 atm, PN2O4 5 0.12 atm
33.!a. H2SO3; b.!HClO3; c. H3PO3; NaOH and KOH are ionic compounds
117. a.!Assuming mol/L units for concentrations, K 5 8.16 3 1047; b.!33.9!L
composed of either Na1 or K1 cations and OH2 anions. When soluble ionic
119. 0.63 121.!0.240 atm 123.!a. 2.33 3 1024; b.!The argon gas will in-
compounds dissolve in water, they form the ions from which they are formed.
crease the volume of the container. This is because the container is a constant-
The acids in this problem are all covalent compounds. When these acids dis-
pressure system, and if the number of moles increases at constant T and P,
solve in water, the covalent bond between oxygen and hydrogen breaks to form
the volume must increase. An increase in volume will dilute the concentra-
H1 ions. 35. a.! This expression holds true for solutions of monoprotic
tions of all gaseous reactants and gaseous products. Because there are more
strong acids having a concentration greater than 1.0 3 1026 M. For example,
moles of product gases than reactant gases (3 moles vs. 2 moles), the dilution
0.10!M HCl, 7.8!M HNO3, and 3.6 3 1024!M HClO4 are solutions where this
will decrease the numerator of K more than the denominator will decrease.
expression holds true. b. This expression holds true for solutions of weak
This causes Q , K and the reaction shifts right to get back to equilibrium.
acids where the two normal assumptions hold. The two assumptions are that
Because temperature was unchanged, the value of K will not change. K is a
the contribution of H1 from water is negligible and that the acid is less than
constant as long as temperature is constant. 125.!192 g; 1.3 atm 127.!33
5% dissociated in water (from the assumption that x is small compared to
some number). This expression will generally hold true for solutions of weak
Chapter 14
acids having a Ka value less than 1 3 1024, as long as there is a signi"cant
21. as an acid: HCO32(aq) 1 H2O(l) 34 CO322(aq) 1 H3O1(aq); as a
amount of weak acid present. Three example solutions are 1.5!M HC2H3O2,
base: HCO32(aq) 1 H2O(l) 34 H2CO3(aq) 1 OH2(aq); as an acid:
0.10!M HOCl, and 0.72!M HCN. c. This expression holds true for strong
H2PO42(aq) 1 H2O(l) 34 HPO422(aq) 1 H3O1(aq); as a base: H2PO42(aq)
bases that donate 2 OH2 ions per formula unit. As long as the concentration
1 H2O(l) 34 H3PO4(aq) 1 OH2(aq). 23.!b, c, and d 25.!10.78 (4 sig-
of the base is above 5 3 1027 M, this expression will hold true. Three ex-
ni"cant "gures); 6.78 (3 signi"cant "gures); 0.78 (2 signi"cant "gures); a pH
amples are 5.0 3 1023! M Ca(OH)2, 2.1 3 1024! M Sr(OH)2, and 9.1 3
value is a logarithm. The numbers to the left of the decimal place identify the
1025!M Ba(OH)2. d. This expression holds true for solutions of weak bases
power of 10 to which [H1] is expressed in scienti"c notation—for example,
where the two normal assumptions hold. The assumptions are that the
10211, 1027, 1021. The number of decimal places in a pH value identi"es the
OH2 contribution from water is negligible and that the base is less than
number of signi"cant "gures in [H1]. In all three pH values, the [H1] should
5% ionized in water. For the 5% rule to hold, you generally need bases with
be expressed only to two signi"cant "gures since these pH values have only
Kb , 1 3 1024 and concentrations of weak base greater than 0.10 M. Three
two decimal places.
examples are 0.10! M NH3, 0.54! M C6H5NH2, and 1.1! M C5H5N. 37.! One
27.!NH3 1 NH3 m NH22 1 NH41
reason HF is a weak acid is that the H—F bond is unusually strong and thus,
Acid Base Conjugate Conjugate
is dif"cult to break. This contributes to the reluctance of the HF molecules to
Base Acid
dissociate in water. 39.!a. HClO4(aq) 1 H2O(l) n H3O1(aq) 1 ClO42(aq)
One of the NH3 molecules acts as a base and accepts a proton to form NH41.
or HClO4(aq) n H1(aq) 1 ClO42(aq); water is commonly omitted from
The other NH3 molecule acts as an acid and donates a proton to form NH22.
Ka reactions. b. CH3CH2CO2H(aq) 34 H1(aq) 1 CH3CH2CO22(aq);
NH41 is the conjugate acid of the NH3 base. In the reverse reaction, NH41
c.! NH41(aq) 34 H1(aq) 1 NH3(aq) 41.! a.! H2O, base; H2CO3, acid;