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Solution Manual For Chemistry And Chemical Reactivity, 9th Edition

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    iii Table of Contents Preface ........................................................................................................................................................................... v Chapter 1 ....................................................................................................................................................................... 1 Basic Concepts of Chemistry Let’s Review.................................................................................................................................................................. 9 The Tools of Quantitative Chemistry Chapter 2 ..................................................................................................................................................................... 20 Atoms, Molecules, and Ions Chapter 3 ..................................................................................................................................................................... 48 Chemical Reactions Chapter 4 ..................................................................................................................................................................... 65 Stoichiometry: Quantitative Information about Chemical Reactions Chapter 5 ..................................................................................................................................................................... 94 Principles of Chemical Reactivity: Energy and Chemical Reactions Chapter 6 ................................................................................................................................................................... 120 The Structure of Atoms Chapter 7 ................................................................................................................................................................... 137 The Structure of Atoms and Periodic Trends Chapter 8 ................................................................................................................................................................... 152 Bonding and Molecular Structure Chapter 9 ................................................................................................................................................................... 174 Bonding and Molecular Structure: Orbital Hybridization and Molecular Orbitals Chapter 10 ................................................................................................................................................................. 190 Gases and Their Properties Chapter 11 ................................................................................................................................................................. 216 Intermolecular Forces and Liquids Chapter 12 ................................................................................................................................................................. 229 The Chemistry of Solids Chapter 13 ................................................................................................................................................................. 245 Solutions and Their Behavior Chapter 14 ................................................................................................................................................................. 270 Chemical Kinetics: The Rates of Chemical Reactions Chapter 15 ................................................................................................................................................................. 295 Principles of Chemical Reactivity: Equilibria Chapter 16 ................................................................................................................................................................. 316 The Chemistry of Acids and Bases Chapter 17 ................................................................................................................................................................. 338 Principles of Reactivity: Other Aspects of Aqueous Equilibria Chapter 18 ................................................................................................................................................................. 369 Principles of Chemical Reactivity: Entropy and Free Energy

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    iv Chapter 19.................................................................................................................................................................. 394 Principles of Chemical Reactivity: Electron Transfer Reactions Chapter 20.................................................................................................................................................................. 419 Environmental Chemistry Chapter 21.................................................................................................................................................................. 431 The Chemistry of the Main Group Elements Chapter 22.................................................................................................................................................................. 457 The Chemistry of the Transition Elements Chapter 23.................................................................................................................................................................. 470 Carbon: More Than Just Another Element Chapter 24.................................................................................................................................................................. 494 Biochemistry Chapter 25.................................................................................................................................................................. 504 Nuclear Chemistry

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    Chapter 1 1 Chapter 1 Basic Concepts of Chemistry I NSTRUCTOR ’ S N OTES This chapter discusses a wide range of basic subjects needed for the study of chemistry. How you use the material will depend on the preparation level of your students. Essentially all of the topics in this chapter would be found in a typical high school chemistry class. However, if students took that course two or three years earlier, or if their performance at that time was inconsistent with their present goal of a professional study for science or engineering, an extensive review might be necessary. Such a review could take two or three lecture periods. If your class consists of students who have been screened by a placement exam or other process to reasonably ensure that they have good abilities in high school chemistry, you may assign most or even all of the chapter for outside reading with only a single class to review and stress key points. The chapter can stand on its own without direct instruction if your students learned the topics previously. For an intermediate approach you could assign sections 1.1-1.4 for student reading then take one lecture for the rest of the chapter. A pre-quiz selected from Chapter 1 Study Questions could help establish what degree of review is needed for your students. S UGGESTED D EMONSTRATIONS 1. Density  Kolb, K. E.; Kolb, D. K. “Method for Separating or Identifying Plastics,” Journal of Chemical Education 1991 , 68 , 348.  Franz, D. A. “Densities and Miscibilities of Liquids and Liquid Mixtures,” Journal of Chemical Education 1991 , 68 , 594.  Checkai, G.; Whitsett, J. “Density Demonstration Using Diet Soft Drinks,” Journal of Chemical Education 1986 , 63 , 515.  Shakhashiri, B. Z. “Density and Miscibility of Liquids,” Chemical Demonstrations: A Handbook for Teachers of Chemistry; University of Wisconsin Press, 1989; Vol. 3, pp. 229–233. 2. Illustration of “Physical Change”  Liquid nitrogen is always a favorite of students. We freeze a banana, a hot dog, a flower, or similar object. 3. Illustration of “Chemical Change”  The first lecture in the course is often begun with a “bang” by setting off several hydrogen-filled balloons in a darkened lecture room. The demonstration is described in Chemical Demonstrations: A Handbook for Teachers of Chemistry; University of Wisconsin Press, 1983; Vol. 1, pp. 106–112.

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    Basic Concepts of Chemistry 2  Other reactions could be done as well, depending on the facilities available. Possibilities include placing small pieces of potassium in water, the thermite reaction (Shakhashiri, Volume 1, page 85), or the reaction of zinc and ammonium nitrate (Shakhashiri, Volume 1, page 51). The latter reaction gives off a large amount of ZnO dust and other irritating fumes. It is not suitable for a room without good ventilation.  For fun, and to give some color, as well as talking about our future study of acid-base reactions, we add aqueous NH 3 to separate flasks containing (i) very dilute acid with phenolphthalein, (ii) Al(NO 3 ) 3 , and (iii) dilute CuSO 4 .  We often have a student contribute a penny to put into concentrated HNO 3 . The reaction brings up a brief discussion of oxidation–reduction processes. The NO 2 gas generated prompts a discussion of air pollution problems, as well as the fuels used in the Lunar Lander and in the Space Shuttle. (CAUTION: NO 2 is a very corrosive gas. Use only in a well ventilated room. We do the reaction by putting the penny in a few milliliters of acid in a 2-L Erlenmeyer flask that is lightly stoppered. This effectively contains the gas.)

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    Chapter 1 3 S OLUTIONS TO S TUDY Q UESTIONS 1.1 (a) C Carbon (c) Cl Chlorine (e) Mg Magnesium (b) K Potassium (d) P Phosphorus (f) Ni Nickel 1.2 (a) Mn Manganese (c) Na Sodium (e) Xe Xenon (b) Cu Copper (d) Br Bromine (f) Fe Iron 1.3 (a) barium Ba (d) lead Pb (b) titanium Ti (e) arsenic As (c) chromium Cr (f) zinc Zn 1.4 (a) silver Ag (d) tin Sn (b) aluminum Al (e) technetium Tc (c) plutonium Pu (f) krypton Kr 1.5 (a) NaCl is a compound; sodium is an element (b) Sugar is a compound; carbon is an element. (c) Gold chloride is a compound; gold is an element. 1.6 (a) Pt(NH 3 ) 2 Cl 2 is a compound; Pt is an element (b) Copper is an element; copper(II) oxide is a compound (c) Silicon is an element; sand is a compound 1.7 (a) physical property (b) chemical property (c) chemical property (d) physical property (e) physical property (f) physical property 1.8 (a) chemical change (b) physical change (c) chemical change (d) physical change 1.9 (a) Physical properties: color (colorless), physical state (liquid) Chemical property: reactivity (burns in air) (b) Physical properties: color (shiny metal, orange), physical state (liquid) Chemical property: reactivity (aluminum reacts readily with bromine) 1.10 (a) Physical properties: color (white), physical state (solid), density (2.71 g/cm 3 ) Chemical properties: reactivity towards acid (reacts to produce gaseous carbon dioxide) (b) Physical property: color (gray zinc, purple iodine, white compound) Chemical property: reactivity (zinc and iodine react to give a white compound)

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    Basic Concepts of Chemistry 4 1.11. Mechanical energy is used to move the lever, producing electrical and radiant energy 1.12. Mechanical energy, electrical energy, radiant energy 1.13 (a) Kinetic energy (b) Potential energy (c) Potential energy (d) Potential energy 1.14 (a) Potential energy converted to kinetic energy (b) Kinetic energy converted to potential energy (c) Potential energy converted to kinetic energy (d) Kinetic energy converted to potential energy 1.15 (a) Qualitative observations: blue-green color, solid physical state Quantitative observations: density of 2.65 g/cm 3 , mass of 2.5 g (b) Mass is an extensive property; color, physical state, and density are intensive properties (c) 2.5 g · 3 1 cm 2.65 g = 0.94 cm 3 1.16 (a) Qualitative observations: shiny golden metallic appearance, crystals in form of perfect cubes Quantitative observations: length of 0.40 cm on a side, mass of 0.064 g (b) Mass and length are extensive properties; color, luster, and crystalline form are intensive properties (c) 0.064 g/(0.40 cm) 3 = 1.0 g/cm 3 = 1.0 g/mL 1.17 Observation (c) identifies a chemical property. 1.18 Observations (a) and (b) identify chemical properties. 1.19 Calcium: Ca Fluorine: F The shape of the fluorite crystals can be described as interwoven cubes. The overall shape of the crystals indicates that the ions in the solid matrix arrange themselves with alternating calcium and fluoride ions to produce the crystal appearance. 1.20 (a) Copper, Cu Carbon, C Oxygen: O (b) Oxygen is a gas, while copper, carbon, and azurite are solids at room temperature. Oxygen is colorless, while copper has a reddish color and carbon is gray. The gemstone is a bluish color. 1.21 The water can be removed by boiling the solution until all the water is converted to water vapor; the solid left behind will be NaCl.

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    Chapter 1 5 1.22 The non-uniform appearance of the mixture indicates that samples taken from different regions of the mixture would be different—a characteristic of a heterogeneous mixture. Recalling that iron is attracted to a magnetic field while sand is generally not attracted in this way suggests that passing a magnet through the mixture would separate the sand and iron. 1.23 Physical changes: a, b, d Chemical changes: c 1.24 Physical changes: a, d Chemical changes: b, c 1.25 The large colorless block of salt represents the macroscopic view. The spheres represent the microscopic or particulate view. If one can imagine producing multiple “copies” of the particulate view, the macroscopic view will result. 1.26 The orange solid and liquid in the bowl and the orange liquid and gas in the round bottom flask represent the macroscopic views. The spheres represent the particulate view. The particulate view of the solid displays atoms of bromine tightly packed to produce the solid. The liquid view displays molecules of Br 2 with space separating the individual molecules. The gas view displays molecules of Br 2 ; however, the molecules are further apart than in the liquid view. 1.27 The plastic (with a much lower density than CCl 4 ) will float. The aluminum (which is more dense than CCl 4 ) will sink. 1.28 Liquids: mercury and water Solid: copper Of the substances shown, mercury is most dense and water is least dense. 1.29 (a) mixture (b) mixture (c) element (d) compound 1.30 (a) mixture (b) compound (c) mixture (d) mixture

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    Basic Concepts of Chemistry 6 1.31 (a) solid iron (b) liquid water (c) water vapor 1.32 (a) water vapor, helium (b) liquid water, solid aluminum (c) brass 1.33 The three liquids will be layered, with hexane floating on top of water, which in turn floats on top of the perfluorohexane. HDPE will lie at the top of the water layer. PVC will lie on top of the perfluorohexane layer. Teflon will sink to the bottom of the perfluorohexane layer. 1.34 Melting point. Sugar melts around 160-186 °C while salt melts at 800 °C. 1.35 HDPE will float in liquids with a density higher than 0.97 g/mL, ethylene glycol, water, acetic acid, and glycerol. 1.36 The sample's density and melting point could be compared with that of silver to prove whether or not the sample is silver. 1.37 Milk is mostly water. When water freezes its volume increases (its density decreases). When the milk froze, the increase in volume was so great that it pushed out of the bottle. 1.38 The mass of the object is determined and then the volume is determined by submersion in a known volume of liquid. The increase in volume would be equal to the volume of the irregularly shaped object. The density could be calculated by dividing its mass by its volume. 1.39 If too much sugar is excreted, the density of urine will increase. If too much water is excreted, the density of urine will decrease. 1.40 One could check for an odor, check the boiling or freezing point, or determine the density. If the density is approximately 1 g/cm 3 at room temperature, the liquid could be water. If it boils at about 100 °C and freezes at about 0 °C, that would be consistent with water. To check for the presence of salt, boil the liquid away. If a substance remains, it could be salt, but further testing would be required.

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    Chapter 1 7 1.41 (a) Solid potassium reacts with liquid water to produce gaseous hydrogen and a homogeneous mixture of potassium hydroxide in liquid water. (b) The reaction is a chemical change. (c) Potassium and water are reactants, hydrogen and potassium hydroxide are products. (d) Among the qualitative observations are (i) the reaction is violent; and (ii) heat and light (a purple flame) are produced. 1.42 Least dense liquid: water Most dense liquid: mercury Medium density: carbon tetrachloride 1.43 Any balloon filled with a gas having a density less than 1.12 g/L will float in air. Helium and neon balloons will float. 1.44 A copper-colored metal could be copper, but it may also be an alloy of copper, for example, brass or bronze. Testing the material’s density and melting temperature would be one way to find out if it is copper. 1.45 Physical change 1.46 (a) Mass CHCl 3 = 10.0 mL · 1.492 g/mL = 14.9 g Mass CHBr 3 = 5.0 mL · 2.890 g/mL = 14 g Mass of solution = 14.9 g + 14 g = 29 g Density = mass of solution/volume of solution = 29 g/15.0 mL = 1.9 g/mL (b) Mass of solution = 2.07 g/mL · 20.0 mL = 41.4 g Also, mass of solution = mass CHCl 3 + mass CHBr 3 Let X = volume CHCl 3 and (20.0 mL − X) = volume CHBr 3 Then, mass of solution = (1.492 g/mL)X + (2.890 g/mL)(20.0 mL – X) = 41.4 g X = 11.7 mL CHCl 3 (20.0 – X) = 8.3 mL CHBr 3 To obtain 20.0 mL of solution with d = 2.07 g/cm 3 , mix 11.7 mL CHCl 3 and 8.3 mL CHBr 3 .

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    Basic Concepts of Chemistry 8 1.47 (a) Au, Cu, Ag (b) (1 K/1 °C)(1064 °C + 273 °C) = 1337 K (c) Gold is not the most dense element. Iridium is the most dense element. (d) 0.75 × 5.58 g = 4.2 g (e) 56 × 10 6 couples × (1 ring/person) × (6.15 mg/ring) × (1 g/1000 mg) = 3.4 × 10 5 g 3.4 × 10 5 g × 1 troy ounce/31.1 g × $1620/troy ounce = $ 1.8 × 10 7

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    Let’s Review 9 Let’s Review The Tools of Quantitative Chemistry I NSTRUCTOR ’ S N OTES This section reviews a wide range of mathematical topics that will be needed by the student in the course, so mastery of this material should be stressed. The need for accurate measurement of physical quantities and the correct recording of this information can be characterized as necessary for reasons of safety using medical (drug dosage) and engineering examples (material composition and properties). Mistakes in this area can mean the difference between life and death. A pre-quiz selected from the Study Questions at the end of this section could help establish what degree of review is needed for your students. S UGGESTED D EMONSTRATIONS 1. Units of Measurement  Add a few drop of bromcresol green to a 2-L flask before the lecture. On filling with water during lecture, the water becomes blue. When the flask is almost full, it is topped off with dilute HCl, and the solution turns yellow. Next, the water is poured into an ordinary 1-L flask or beaker that already contains some dilute base, and the solution turns blue again. This is then poured into a graduated cylinder containing some phenolphthalein. We use this sequence to comment on the relative accuracies of the different types of glassware. We take some containers such as soda cans so students can connect metric units with familiar objects.  A weighed piece of fruit or some other solid gives some meaning to mass expressed in grams.  Earley, C. W. “A Simple Demonstration for Introducing the Metric System to Introductory Chemistry Classes,” Journal of Chemical Education 1999 , 76 , 1215. 2. Demonstrations Using Significant Figures  Kirksey, H. G. “Significant Figures: A Classroom Demonstration,” Journal of Chemical Education 1992 , 69 , 497.  Abel, K. B.; Hemmerlin, W. M. “Significant Figures,” Journal of Chemical Education 1990 , 67 , 213.

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    The Tools of Quantitative Chemistry 10 S OLUTIONS TO S TUDY Q UESTIONS LR.1 (25 °C + 273.15 °C) 1 K 1 C  = 298 K LR.2 (5.5  10 3 °C + 273.15 °C) 1 K 1 C  = 5.8  10 3 K LR.3 (a) 289 K (b) 97 °C (c) 310 K LR.4 (a) –196 °C (b) 336 K (c) 1177 °C LR.5 42.195 km · 1000 m 1 km = 4.2195  10 4 m 42.195 km · 0.62137 miles 1 km = 26.219 miles LR.6 19 cm · 10 mm 1 cm = 190 mm 19 cm · 1 m 100 cm = 0.19 m LR.7 2.5 cm  2.1 cm = 5.3 cm 2 5.3 cm 2 · 2 1 m 100 cm       = 5.3  10 –4 m 2 LR.8 2 2 2 11.8 cm Area = r = = 109 cm 2         2 2 –2 2 1 m 109 cm = 1.09 10 m 100 cm         LR.9 250. mL · 3 1 cm 1 mL = 250. cm 3 250. mL · 3 1 L 10 mL = 0.250 L 250. mL · 3 1 cm 1 mL · 3 1 m 100 cm       = 2.50  10 –4 m 3 250. mL · 3 1 L 10 mL · 3 1 dm 1 L = 0.250 dm 3

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    Let’s Review 11 LR.10 1.5 L · 3 10 mL 1 L = 1.5  10 3 mL 1.5 L · 3 10 mL 1 L · 3 1 cm 1 mL = 1.5  10 3 cm 3 1.5  10 3 cm 3 · 3 1 dm 10 cm       = 1.5 dm 3 LR.11 2.52 kg · 3 10 g 1 kg = 2.52  10 3 g LR.12 2.265 g · 3 1 kg 10 g = 2.265  10 –3 kg 2.265 g · 3 10 mg 1 g = 2.265  10 3 mg LR.13 500. mL · 3 1 cm 1 mL · 3 1.11 g 1 cm = 555 g LR.14 3 1 cm 2.365 g 10.5 g  = 0.225 cm 3 LR.15 density = 2.361 g (2.35 cm 1.34 cm 0.105 cm)   = 7.14 g/cm 3 The metal is (c) Zinc LR.16 600 g H 2 O · 3 1 cm 0.995 g = 600 cm 3 600 g Pb · 3 1 cm 11.35 g = 50 cm 3 Given equal masses the less dense substance (water) will have a greater volume. LR.17 1200 Cal · 3 10 cal 1 Cal · 4.184 J 1 cal = 5.0  10 6 J LR.18 1670 kJ · 3 10 J 1 kJ · 1 cal 4.184 J · 3 1 Cal 10 cal = 399 Cal LR.19 170 kcal · 3 10 cal 1 kcal · 4.184 J 1 cal · 3 1 kJ 10 J = 710 kJ The food product with 170 kcal per serving has a greater energy content per serving.

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    The Tools of Quantitative Chemistry 12 LR.20 130 Calories × 4.184 J/cal × 1000 cal/Calorie = 5.4 × 10 5 J = 5.4 × 10 2 kJ. The juice provides more total energy. 5.4 × 10 2 kJ/335 mL = 1.6 kJ/mL 630 kJ/295 mL = 2.1 kJ/mL. The juice provides more energy per milliliter. LR.21 (a) Method A average = 2.2 + 2.3 + 2.7 + 2.4 4 = 2.4 g/cm 3 Method B average = 2.703 + 2.701 + 2.705 + 5.881 4 = 3.480 g/cm 3 For method B the reading of 5.811 can be excluded because it is more than twice as large as all other readings. Using only the first three readings, average = 2.703 g/cm 3 . (b) Method A: Percent error = 2.4 – 2.702 100 % 2.702  = 10 % Method B: Percent error = 2.703 – 2.702 100 % 2.702  = 0.04 % (omitting data point) (c) Method A: Standard deviation = 2 2 2 2 0.2 + 0.1 + 0.3 + 0 3 = 0.2 g/cm 3 Method B: Standard deviation = 2 2 2 0 + 0.002 + 0.002 2 = 0.002 g/cm 3 (omitting data point) (d) Before excluding a data point for B, method A is more accurate and more precise. After excluding the fourth data point for B, this method gives a more accurate and more precise result. LR.22 (a) Student A: Average = 135 °C Percent error = 135 – 135 100 % 135  = 0 % Student B: Average = 138 °C Percent error = 138 – 135 100 % 135  = 2 % (b) Student B is more precise; Student A is more accurate LR.23 (a) 5.4  10 –2 g (2 significant figures) (c) 7.92  10 –4 g (3 significant figures) (b) 5.462  10 3 g (4 significant figures) (d) 1.6  10 3 mL (2 significant figures) LR.24 (a) 1623 (4 significant figures) (c) 0.0632 (3 significant figures) (b) 0.000257 (3 significant figures) (d) 3404 (4 significant figures) LR.25 (a) 9.44  10 –3 (c) 11.9 (b) 5.694  10 3 (d) 0.122 LR.26 (a) 2.44  10 8 (c) 0.133 (b) 4.85  10 –2 (d) 0.0286

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    Let’s Review 13 LR.27 y = 0.1637x + 0.0958 0 1 2 3 4 5 6 7 0 20 40 Number of kernels slope = 0.1637 g/kernel The slope represents the average mass of a kernel. Using the straight-line equation, mass = (0.1637 g/kernel)(20 kernels) + 0.0958 g = 3.370 g 20.88 g = (0.1637 g/kernel)(number of kernels) + 0.0958 g number of kernels = 127 LR.28 (a) 0.21 (b) 5.6 (c) slope = 5.6 – 4.0 0.30 – 0.21 = 18; intercept = 0.20 (d) y = 18 x + 0.20 = (18)(1.0) + 0.20 = 18 LR.29 (a) slope = 20.00 – 4.00 0.00 – 4.00 = –4.00, intercept = 20.00, y = –4.00 x + 20.00 (b) y = –4.00 x + 20.00 = (–4.00)(6.0) + 20.00 = –4.00 LR.30 (a) y = 4E-05x - 0.0416 0 1 2 3 4 5 6 7 0.E+00 1.E+05 2.E+05 1/speed (b) y = 4.0  10 –5 x – 0.0416 y-intercept = –0.0416 LR.31 C = 0.0823 LR.32 n = 1.63 LR.33 T = 295

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