General Chemistry Principles, Patterns, and Applications, 2011

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(Crystal field splitting energy also applies to tetrahedral complexes: Δt.) It is important to note that the splitting of the d orbitals in a crystal field does not change the total energy of the five d orbitals: the two eg orbitals increase in energy by 0.6Δo, whereas the three t2gorbitals decrease in energy by 0.4Δo. Thus the total change in energy is 2(0.6Δo) + 3(−0.4Δo) = 0. Note the Pattern Crystal field splitting does not change the total energy of the d orbitals. Thus far, we have considered only the effect of repulsive electrostatic interactions between electrons in the d orbitals and the six negatively charged ligands, which increases the total energy of the system and splits the d orbitals. Interactions between the positively charged metal ion and the ligands results in a net stabilization of the system, which decreases the energy of all five d orbitals without affecting their splitting (as shown at the far right in part (a) in Figure 23.10 "An Octahedral Arrangement of Six Negative Charges around a Metal Ion Causes the Five "). Electronic Structures of Metal Complexes We can use the d-orbital energy-level diagram in Figure 23.10 "An Octahedral Arrangement of Six Negative Charges around a Metal Ion Causes the Five " to predict electronic structures and some of the properties of transition-metal complexes. We start with the Ti 3+ ion, which contains a single d electron, and proceed across the first row of the transition metals by adding a single electron at a time. We place additional electrons in the lowest-energy orbital available, while keeping their spins parallel as required by Hund’s rule. As shown in Figure 23.11 "The Possible Electron Configurations for Octahedral ", for d 1 – d 3 systems—such as [Ti(H2O)6] 3+ , [V(H2O)6] 3+ , and [Cr(H2O)6] 3+ , respectively—the electrons successively occupy the three degenerate t2g orbitals with their spins parallel, giving one, two, and three unpaired electrons, respectively. We can summarize this for the complex [Cr(H2O)6] 3+ , for example, by saying that the chromium ion has a d 3 electron configuration or, more succinctly, Cr 3+ is a d 3 ion. Figure 23.11 The Possible Electron Configurations for Octahedral dn Transition-Metal Complexes (n = 1–10) Saylor URL: http://www.saylor.org/books Saylor.org 2156
Two different configurations are possible for octahedral complexes of metals with d 4 ,d 5 , d 6 , and d 7 configurations; the magnitude of Δo determines which configuration is observed. When we reach the d 4 configuration, there are two possible choices for the fourth electron: it can occupy either one of the empty eg orbitals or one of the singly occupiedt2g orbitals. Recall from Chapter 6 "The Structure of Atoms" that placing an electron in an already occupied orbital results in electrostatic repulsions that increase the energy of the system; this increase in energy is called the spinpairing energy (P). If Δo is less than P, then the lowest-energy arrangement has the fourth electron in one of the emptyeg orbitals. Because this arrangement results in four unpaired electrons, it is called ahighspin configuration, and a complex with this electron configuration, such as the [Cr(H2O)6] 2+ ion, is called a high-spin complex. Conversely, if Δo is greater than P, then the lowest-energy arrangement has the fourth electron in one of the occupied t2gorbitals. Because this arrangement results in only two unpaired electrons, it is called alow-spin configuration, and a complex with this electron configuration, such as the [Mn(CN)6] 3− ion, is called a low-spin complex. Similarly, metal ions with the d 5 , d 6 , or d 7 electron configurations can be either high spin or low spin, depending on the magnitude of Δo. In contrast, only one arrangement of d electrons is possible for metal ions with d 8 –d 10 electron configurations. For example, the [Ni(H2O)6] 2+ ion is d 8 with two unpaired electrons, the [Cu(H2O)6] 2+ ion is d 9 with one unpaired electron, and the [Zn(H2O)6] 2+ ion is d 10 with no unpaired electrons. Note the Pattern If Δo is less than the spin-pairing energy, a high-spin configuration results. Conversely, if Δo is greater, a low-spin configuration forms. Factors That Affect the Magnitude of Δ o The magnitude of Δo dictates whether a complex with four, five, six, or seven delectrons is high spin or low spin, which affects its magnetic properties, structure, and reactivity. Large values of Δo (i.e., Δo > P) yield a low-spin complex, whereas small values of Δo (i.e., Δo < P) produce a high-spin complex. As we noted, the Saylor URL: http://www.saylor.org/books Saylor.org 2157
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This text was adapted by The Saylor
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third, it provides a review for tho
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Chapter 1 Introduction to Chemistry
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accounting for only 0.0000001% of E
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eginning scientist who intends to s
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elements by mass. Thus sodium chlor
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Strategy: Refer to the definitions
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Chemists study the structures, phys
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kerosene, diesel fuel, and lubricat
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Solution: a. A Tea is a solution of
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centimeter (g/cm 3 ). As mass incre
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contrast, the mass of sample E is s
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e. the sensitivity of the volume to
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15. Classify each statement as an e
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8. Gold has a density of 19.30 g/cm
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know to be carbon dioxide, is the s
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as did the first. But what was the
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. Ratios of 3.0 and 2.0 give 1.8 g
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Summary The ancient Greeks first pr
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1. Electrons and protons have elect
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well before he was run over by a ho
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In a single famous experiment, howe
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The dates in parentheses are the ye
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C O N C E PTUAL P R OBLEMS 1. Descr
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As described in Section 1.7 "Introd
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In with 8 neutrons and 6 protons. T
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Solution: A The element with 82 pro
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the isotopes. Because most elements
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The mass of an atom is a weighted a
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2. Determine the number of protons,
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The elements are arranged in a peri
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exhibit manic-depressive, or bipola
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f. nickel g. potassium h. radon i.
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10. Based on their locations in the
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emoved, minimize inadvertent contam
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supplements. Second, as shown in Fi
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Measurement Instruments of Measurem
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Base Quantity Unit Name Abbreviatio
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g. 2002.080 h. 0.01020 Solution a.
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( 6 .0 22 × 1 0 23 ) ( 6 . 42 × 1
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f. infinite (rule 5) S K I L L BUIL
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In the worked examples in this text
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The deviations are 1.125 g − 1.11
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Please be sure you are familiar wit
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Isotope Percent Abundance (%) Atomi
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2.1 Chemical Compounds L E A R N I
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Compounds that consist primarily of
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a. Nitrous oxide, also called “la
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Figure 2.3 The Three-Dimensional St
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group or as a water molecule in whi
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Answer: a. CHCl 3 a. N 2H 4 b. C 4H
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Figure 2.6 The Effect of Charge and
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Predict the charge on the most comm
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(a) The positively and negatively c
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1. The structural formula for chlor
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ANSWERS 5. a. 27 b. 38 c. 54 d. 28
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Asked for: empirical formula for bi
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Formula NH4 + CH3NH3 + OH − O2 2
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. A The potassium cation is K + , a
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d. H 2 S e. NaC 2 H 3 O 2 4. Genera
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. B 2 H 6 c. C 6 H 12 O 6 d. P 4 O
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1. Place the ions in their proper o
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more oxygen atoms ends in -ate, and
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Write the systematic name (and the
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Compounds and Covalent Molecular Su
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2− h. C 2 O 4 3. Name each anion.
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A N S W E R 1. a. rubidium bromide
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a. sodium hydroxide b. calcium cyan
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. Prefixes derived from Greek stems
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a. A Because sulfur is to the left
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in Chapter 7 "The Periodic Table an
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Name Number of Carbon Atoms Molecul
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groups are on the same side of the
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alkane, the alkene, or the alkyne.
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c. 2-butyne d. cyclooctene Given: n
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c. HC≡C(CH 2) 4CH 3 d. e. The gen
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ends of the chain connected to form
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e. 7. For each structural formula,
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. neptunium(IV) oxide c. iron(II) s
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e. 2.5 Acids and Bases LEARNING OBJ
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Figure 2.20 The Relationship betwee
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Figure 2.21 Some Common Carboxylic
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Common acids and the polyatomic ani
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f. H 2 SO 4 7. Draw the structure o
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4. Name each compound. a. H 2 SO 4
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chemicals are either fertilizers (a
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accomplish this transformation is c
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years was tetraethyllead [(C2H5)4Pb
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(from the Latin vitrum, meaning “
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(K2O). The usual source of potassiu
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7. ♦ Sodamide, or sodium amide, i
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As you learned in Chapter 1 "Introd
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E X A M P L E 2 Calculate the formu
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12—is also arbitrary. The importa
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chemists to calculate the mass of a
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mass of ethylene glycol (g) molar m
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a. 1.71 g b. 0.721 g Summary The mo
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. c. d. e. 5. Calculate the molar m
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a. b. 8. Calculate the number of mo
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Substance Mass (g) Number of Moles
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We could also calculate the mass pe
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Determining the Empirical Formula o
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possible. To obtain whole numbers,
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Because there are two phosphorus at
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A Use the masses and molar masses o
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lood. At this point, we cannot know
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C Multiply each subscript in the em
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The empirical formula of a substanc
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15. Calculate the mass percentage o
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2. Salicylic acid is used to make a
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23. a. 27.6 mg C and 1.98 mg H b. 5
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sides. Equation 3.9 and Equation 3.
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Construct a table showing how to in
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Equation 3.11 C 7 H 16 (l) + O 2 (g
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Given: reactants and product Asked
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4. What information can be obtained
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A balanced chemical equation gives
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mass of CO 2 = 1 .51 mol CO 2 × 44
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The volatility and toxicity of merc
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4. Convert the number of moles of p
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B We need to calculate the number o
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Given: masses of reactants and prod
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The stoichiometry of a reaction des
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e. 10.648 g of Ba 3 (PO 4 ) 2 f. 5.
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13. Under the proper conditions, am
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2 PaI 5 (s) → Δ 2 Pa(s) + 5I 2 (
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c. 0.923 kg K 3 PO 4 d. 0.458 kg Ni
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Familiarity with a few basic types
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equal the total of electrons gained
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oxidation state of oxygen is determ
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. Note that (NH 4) 2SO 4 is an ioni
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oxidant + reductant → oxidation
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The following reactions have import
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Using Table 3.1 "Basic Types of Che
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eduction reaction, one atom must lo
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N U M E R I C A L PR O BL E M S Ple
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8. For each redox reaction, determi
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15. The reaction of X 4 (orange) wi
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. Na, +1; Cl, −1 c. O, −2; C, +
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. Each year since the mid-1970s, sc
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Note the important chemical species
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Equation 3.37 CCl 3 F(g) → light
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hole was first observed until about
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then we would have a potential cata
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chemistry. Before proceeding to the
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Because many measurements are repor
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Skill Builder ES5 provides practice
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9. Ritalin is a mild central nervou
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20. You have obtained a 720 mg samp
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Equation 1: ___ + O 2 → ___ + ___
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11. ♦ Lead sulfide and hydrogen p
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20. 21. 3Al(s) + 3NH 4 ClO 4 (s)
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The reaction of mercury(II) acetate
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to have a net charge of zero, the p
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that contain ions conduct electrici
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Figure 4.5 The Difference between S
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B If the compound is ionic and diss
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d. butanol e. pentanoic acid 10. Pr
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d. ammonium chloride e. propanoic a
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The units of molarity are therefore
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Figure 4.7 Preparation of 250 mL of
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Exercise Another solution commonly
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In determining the volume of stock
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a. Sodium hydroxide is an ionic com
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Solution concentrations are typical
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Compound Mass (g) Moles Concentrati
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and either the masses of solid reac
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US states, a blood alcohol level of
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In Example 7 and Example 8, the ide
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Either the masses or the volumes of
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By eliminating the spectator ions,
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that kind of prediction is to attem
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Rule 6 most carbonate (CO3 2− ) a
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Cl − ions. The possible products
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pattern of metallic silver granules
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arsenite (NaAsO 2), the active ingr
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A N S W E R 1. 3.75 g Ag 2 CrO 4 ;
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Because of the limitations of the A
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In contrast, only a fraction of the
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Exercise Classify each compound as
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Note the Pattern Acid plus base yie
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A Write the balanced chemical equat
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H + ions. For example, a 1.0 M OH
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Tools have been developed that make
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. hydrobromic acid c. methylamine d
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10. A 25.00 mL sample of a 0.9005 M
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c. 1.42 × 10 −3 mol HBr 16. 17.
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on a huge scale to supply the energ
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Equation 4.53 Al(OH) 3 (s) + 3H + (
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The number of electrons lost in the
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5. Write the oxidation and reductio
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contains two protons, in this case,
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Consequently, it has been speculate
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When using the activity series to p
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. A strip of zinc is placed in an a
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d. Cl 2 (aq) → ClO − 3 (aq) + C
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E X A M P L E 2 0 The calcium salt
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Glutathione is a low-molecular-weig
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The structure of vitamin C (ascorbi
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1. The titration procedure is an ap
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4. 5. a. titration of Ba(OH) 2 with
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log 10a = alog 10 = (10a) = a The s
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c. 1000 × 0.010 d. 200 × 3000 e.
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When PbCl 2 is dissolved in hot wat
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8. Calcium hydroxide and calcium ca
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1. 0.106 M acetaminophen; acetamino
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1. To understand the concept of ene
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Energy, Heat, and Work One definiti
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To demonstrate, let’s calculate t
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1 cal = 4.184J exactly 1 J = 0.2390
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f. the energy emitted by a cellular
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8. [3] As you will learn in Chapter
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The change in elevation between sta
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(a) Initially, the system (a copper
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Reversing a reaction or a process c
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Possible sources of the approximate
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E X A M P L E 3 When carbon is burn
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Equation 5.23 elements ® compound
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Use to identify the standard state
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Using , we write Equation 5.29 DHor
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The combustion of fats such as palm
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Physical changes, such as melting o
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definition of enthalpy : H= E + PV
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3. Based on the following energy di
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16. The following table lists value
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3. −20.3 kJ 4. −34.3 kJ/mol Cl
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Compound Specific Heat [J/(g·°C)]
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Passive solar system. During the da
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Exercise (a) If a 14.0 g chunk of g
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A Calculate the mass of the solutio
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ather than the enthalpy change (ΔH
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K E Y E QU A T I ON S relationship
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7. A solution is made by dissolving
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Because of their different chemical
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A Write balanced chemical equations
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the food for protein, carbohydrate,
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A Convert mass and height to SI uni
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1. Determine the amount of energy a
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In general, it is more efficient to
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Table 5.7 Properties of Different T
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A Write a balanced chemical equatio
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Most of Earth’s carbon is found i
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14.4°C. Even small increases, howe
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4. The structure of coal is quite d
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Figure 5.25 A Comparison of the Fah
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Now suppose you wish to report the
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3. Many biochemical processes occur
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d. How many kilojoules of energy ar
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stable compounds, and why carbon an
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are used in such diverse applicatio
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As you will soon see, the energy of
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1. What are the characteristics of
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developed in 1873 by James Clerk Ma
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attempt to assassinate Hitler, and
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the assumption that radiant energy
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. What is the energy in joules of a
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1. a. 4.59 × 10 −31 J/photon, ra
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In 1913, a Danish physicist, Niels
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Figure 6.11 The Emission of Light b
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Figure 6.12 Electron Transitions Re
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Bohr’s model of the hydrogen atom
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the form of a continuous emission s
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chambers explode in stages. (b) The
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process produces a cascade of photo
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1. Using a Bohr model and the trans
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Equation 6.14 m = Ec2 = hnc2 = hlc
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Higher-energy vibrations (overtones
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The Heisenberg Uncertainty Principl
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Einstein’s relationship between m
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N U M E R I C A L P R O B L E M S 1
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energy. Thus each wave function is
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(a) The density of the dots shows e
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B For each allowed value of l, calc
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nucleus) and decreases steadily wit
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difference between the two models i
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and y axis (2py), respectively. Not
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6.26 "The Five Equivalent 3", the p
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electron. When more than one electr
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Because of the effects of shielding
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probabilities in space that is ofte
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would be the energy of the photon?
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9. A p orbital is found to have one
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In a magnetic field, an electron ha
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The Aufbau Principle We construct t
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At oxygen, with Z = 8 and eight ele
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Hund’s rule tells us that the rem
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Solution: By placing the electrons
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The electron configurations of the
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Asked for: valence electron configu
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1. How many magnetic quantum number
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f. palladium g. bismuth h. europium
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1. For a 4p subshell, n = 4 and l =
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joules of a mole of photons emitted
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Wavelength (nm) Color of Light 622-
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13. A new element is believed to ha
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Newlands’s table had no logical p
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masses 44, 68, 72, and 100, in the
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Despite its usefulness, Mendeleev
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3. How did Moseley’s contribution
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definite than those images suggest.
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Covalent atomic radii can be determ
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greater the effective nuclear charg
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A These elements are not all in the
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Gray circles indicate the sizes of
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Source: R. D. Shannon, “Revised e
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12. How is an isoelectronic series
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Ionization Energies Because atoms d
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There is a decrease in ionization e
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Given: three elements Asked for: el
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Consequently, ionization energies g
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The darkness of the shading inside
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Equation 7.6 E(g)+e−→E−(g) en
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Figure 7.13 Electron Affinities (in
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electron repulsions in a dianion ar
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found in the upper right corner of
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Pauling won two Nobel Prizes, one f
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one of the most fundamental we can
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The general trends for the first io
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4. Most of the first row transition
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a. As, Bi, and N b. O, F, and Ar c.
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however, because the I 3 values cor
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We have said that elements with the
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plaster of Paris. Magnesium and ber
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Group 14 The group 14 elements stra
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In contrast to the layered structur
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H3PO4. Antimony and bismuth are rel
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an ns 2 np 5 valence electron confi
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welding and in the manufacture of r
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Strategy: A Based on the conductivi
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1. Of the group 1 elements, which w
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7. In an attempt to explore the che
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three np 3 electrons; and −3, due
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and iodine as iodide (I − ) and i
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When people who exercise vigorously
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Given: element and data in Table 1.
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containing Zn 2+ ? Why or why not?
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covalent compounds that dissolve in
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where the electrostatic repulsions
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Exercise Calculate the amount of en
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At r < r 0 , the energy of the syst
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Substance U (kJ/mol) MgI2 2293 NaOH
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lowest lattice energy, and GaP, wit
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and a thermochemical cycle called t
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Source: Data from CRC Handbook of C
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Equation 8.7 may be used as a tool
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Thus U for BaO is slightly more tha
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Ionic compounds have strong electro
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"Selected Enthalpies of Sublimation
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atom. An exception to the octet rul
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Electron-electron and proton-proton
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We can illustrate the formation of
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2. Each hydrogen atom (group 1) has
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Adding three lone pairs each to oxy
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Elements may form multiple bonds to
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formal charge = ( ) valence e - fre
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If an atom in a molecule or ion has
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sulfur has a formal charge of +1. C
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2. Carbon has 4 valence electrons,
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Three carbon atoms now have an octe
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a. volatility. b. melting point. c.
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h. NH 4 + . 8. Draw Lewis electron
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2. Draw the most likely structure f
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7. a. 11 b. 8 c. 8 d. 8 e. 14 f. 8
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. Sr is the reductant; Br is the ox
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There are three equivalent resonanc
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The octet rule is based on the fact
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Note the Pattern Electron-deficient
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General exceptions to the octet rul
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As you learned in Chapter 4 "Reacti
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dioxide to give the bicarbonate ion
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1. In each reaction, identify the L
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Compound Bond Order Bond Length (pm
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Figure 8.11 The Strength of Covalen
Page 748 and 749:
Bonds Broken (kJ/mol) Bonds Formed
Page 750 and 751:
DHrxn » å(bond energies of bonds
Page 752 and 753:
. Cl-Cl, I-I c. O-O, Se-Se d. S-S,
Page 754 and 755:
atom. Electron-rich (negatively cha
Page 756 and 757:
In the absence of a field (a), the
Page 758 and 759:
moment by writing an arrow above th
Page 760 and 761:
A The charge on each atom is given
Page 762 and 763:
e. Na 2 S f. SiO 2 g. LiBr 5. If th
Page 764 and 765:
. Draw Lewis electron structures fo
Page 766 and 767:
Chapter 9 Molecular Geometry and Co
Page 768 and 769:
We can use the VSEPR model to predi
Page 770 and 771:
*Lone pairs are shown using a dashe
Page 772 and 773:
(Figure 9.2 "Geometries for Species
Page 774 and 775:
AX 2 E: SO 2 1. The central atom, s
Page 776 and 777:
Four Electron Groups One of the lim
Page 778 and 779:
structure of PCl5 is 2 n. There are
Page 780 and 781:
The three lone pairs of electrons h
Page 782 and 783:
AX 4 E 2 : ICl 4 − 1. The central
Page 784 and 785:
2. B There are five bonding groups
Page 786 and 787:
3. The structure with the lowest en
Page 788 and 789:
We predict that all four nonhydroge
Page 790 and 791:
(a) In CO2, the C-O bond dipoles ar
Page 792 and 793:
of zero: Exercise Which molecule(s)
Page 794 and 795:
a. CH3Cl b. PCl3 c. CO d. SF6 e. IF
Page 796 and 797:
lone pairs of electrons. a. HCl b.
Page 798 and 799:
c. d. e. four electron groups, bent
Page 800 and 801:
14. SF6: The S-F bonds are quite po
Page 802 and 803:
forms between the two hydrogen atom
Page 804 and 805:
Figure 9.11 Three Different Ways to
Page 806 and 807:
The position of the atomic nucleus
Page 808 and 809:
Figure 9.14 A Hypothetical Stepwise
Page 810 and 811:
Combining one ns and three np atomi
Page 812 and 813:
3s and 3p valence subshells, can be
Page 814 and 815:
Given: three chemical species Asked
Page 816 and 817:
would have to be sp 3 d hybridized.
Page 818 and 819:
4. Draw the molecular structure, in
Page 820 and 821:
. sp 3 , pyramidal c. sp 2 , trigon
Page 822 and 823:
1s atomic orbitals on the two hydro
Page 824 and 825:
these orbitals are shown in the ene
Page 826 and 827:
calculated bond order to predict th
Page 828 and 829:
A Two He 1s atomic orbitals combine
Page 830 and 831:
(a) For alkali metal diatomic molec
Page 832 and 833:
C Calculate the bond order and pred
Page 834 and 835:
Overlap of atomic orbital lobes wit
Page 836 and 837:
Although many combinations of atomi
Page 838 and 839:
Bond Orders in Selected Gas-Phase M
Page 840 and 841:
Unlike earlier diagrams, only the m
Page 842 and 843:
Each sulfur atom contributes 6 vale
Page 844 and 845:
Recently, however, nitric oxide has
Page 846 and 847:
The hydrogen 1s atomic orbital inte
Page 848 and 849:
computed molecular orbitals extend
Page 850 and 851:
Molecular orbital theory is able to
Page 852 and 853:
25. How does electron screening aff
Page 854 and 855:
oxidation or a reduction to improve
Page 856 and 857:
a. Adding an electron to an antibon
Page 858 and 859:
1. To explain resonance structures
Page 860 and 861:
The two 2p orbitals on each carbon
Page 862 and 863:
σ-bonding framework: Carbon and ox
Page 864 and 865:
With a molecular orbital approach t
Page 866 and 867:
The σ bonds and lone pairs account
Page 868 and 869:
Figure 9.37 π Bonding in 1,3-Butad
Page 870 and 871:
in dim light. Once again, a molecul
Page 872 and 873:
3. ♦ Saccharin is an artificial s
Page 874 and 875:
Chapter 10 Gases In Chapter 6 "The
Page 876 and 877:
gases (group 18) are monatomic gase
Page 878 and 879:
While gases have a wide array of us
Page 880 and 881:
2. Determine whether the melting po
Page 882 and 883:
is heated, the increased kinetic en
Page 884 and 885:
a. 3.27 × 10 4 Pa (4.74 lb/in. 2 )
Page 886 and 887:
Each square meter of Earth’s surf
Page 888 and 889:
Mercury barometers have been used t
Page 890 and 891:
If the tube is open to the atmosphe
Page 892 and 893:
another unit of pressure: 1 atmosph
Page 894 and 895:
6. If you constructed a manometer t
Page 896 and 897:
(a) Initially the gas is at a press
Page 898 and 899:
10.8 "The Relationship between Volu
Page 900 and 901:
Note the Pattern For a sample of ga
Page 902 and 903:
4. Use Boyle’s law to explain why
Page 904 and 905:
V = ( constant)(nTP) By convention,
Page 906 and 907:
Equation 10.17 V = nRTP = ( constan
Page 908 and 909:
C Equate the ratios of those terms
Page 910 and 911:
Initial V 0.406 L n 0.025 mol 0.406
Page 912 and 913:
Thus all the quantities except V 2
Page 914 and 915:
M = dRTP Exercise Radon (Rn) is a r
Page 916 and 917:
density, 58 g/L. The major constitu
Page 918 and 919:
7. Given the following information
Page 920 and 921:
6. Calculate the volume in liters o
Page 922 and 923:
a. 0.21 g HI; b. 840 g H 2 S; c. 0.
Page 924 and 925:
The total pressure of a mixture of
Page 926 and 927:
The composition of a gas mixture ca
Page 928 and 929:
P A X A PCO2 PH 2O (28 mmHg) 0.031
Page 930 and 931:
Elevation (km) Pressure in Summer (
Page 932 and 933:
moles O2 = (9250 mol H 2SO4) (1.5 m
Page 934 and 935:
Temperatures"). As shown in Figure
Page 936 and 937:
A 1.00 g sample of zinc metal is ad
Page 938 and 939:
. 604 mL O 2 5. Percent composition
Page 940 and 941:
The square root of v2¯¯¯ is the
Page 942 and 943:
Figure 10.14 The Distributions of M
Page 944 and 945:
Solution: a. Increasing the tempera
Page 946 and 947:
ut in this experiment, two cotton b
Page 948 and 949:
During World War II, scientists wor
Page 950 and 951:
KE¯¯¯¯¯¯=12M1v2rms1=12M2v2rms
Page 952 and 953:
other gas molecules and with the wa
Page 954 and 955:
Root mean square speed vrms = v21+
Page 956 and 957:
1. To recognize the differences bet
Page 958 and 959:
Because the molecules of an ideal g
Page 960 and 961:
Gas a (L 2·atm)/mol2 ) b (L/mol) A
Page 962 and 963:
P = nRTV - nb - an2V 2 = (7.05 mol)
Page 964 and 965:
volume of the gaseous molecules and
Page 966 and 967:
are drawn using a “best-fit” ap
Page 968 and 969:
It is important to remember that wh
Page 970 and 971:
Absorbance (400 nm) PO4 3− (mol/L
Page 972 and 973:
10.10 End-of-Chapter Material A P P
Page 974 and 975:
a. Your lab is in Denver, Colorado,
Page 976 and 977:
a. A 50.0 L reaction vessel is char
Page 978 and 979:
Density The molecules of a liquid a
Page 980 and 981:
The kinetic molecular description o
Page 982 and 983:
Repulsive Dipole-Dipole Interaction
Page 984 and 985:
Table 11.2 Relationships between th
Page 986 and 987:
Substance Molar Mass (g/mol) Meltin
Page 988 and 989:
whereas He boils at −269°C. The
Page 990 and 991:
Determine the intermolecular forces
Page 992 and 993:
the other. In contrast, each oxygen
Page 994 and 995:
Exercise Considering CH 3CO 2H, (CH
Page 996 and 997:
more polarizable than smaller ones
Page 998 and 999:
17. Do you expect the boiling point
Page 1000 and 1001:
it only has one O-H bond with an H
Page 1002 and 1003:
The same phenomenon holds molecules
Page 1004 and 1005:
for water, then the liquid in the c
Page 1006 and 1007:
Motor oils and other lubricants dem
Page 1008 and 1009:
2. How is the environment of molecu
Page 1010 and 1011:
8. Cohesive forces are the intermol
Page 1012 and 1013:
Nearly all of us have heated a pan
Page 1014 and 1015:
(a) When a liquid is introduced int
Page 1016 and 1017:
evaporate more slowly. Although the
Page 1018 and 1019:
ln(P2P1) = -DHvapR(1T 2 -1T1) Conve
Page 1020 and 1021:
oils at a temperature greater than
Page 1022 and 1023:
pressure above the liquid. Molecule
Page 1024 and 1025:
3. The ΔH vap of carbon tetrachlor
Page 1026 and 1027:
and vice versa). We use dry ice, wh
Page 1028 and 1029:
The direct conversion of a solid to
Page 1030 and 1031:
This plot of temperature shows what
Page 1032 and 1033:
This plot of temperature shows what
Page 1034 and 1035:
Suppose you are overtaken by a bliz
Page 1036 and 1037:
8. Why do substances with high enth
Page 1038 and 1039:
enough energy to overcome the inter
Page 1040 and 1041:
N U M E R I C AL PROBLEMS 1. The de
Page 1042 and 1043:
5. 45.0 kJ/mol 7. 488 kJ 9. 32.6 kJ
Page 1044 and 1045:
for a sample of benzene in Figure 1
Page 1046 and 1047:
useful in catalytic processes such
Page 1048 and 1049:
corresponds to the solid phase, whe
Page 1050 and 1051:
the solid phase. Along this line, t
Page 1052 and 1053:
satisfying, it is incorrect, as we
Page 1054 and 1055:
Given: phase diagram, temperature,
Page 1056 and 1057:
upon their relative densities. For
Page 1058 and 1059:
In the nematic phase, only the long
Page 1060 and 1061:
Applying a voltage to selected segm
Page 1062 and 1063:
d. sodium decanoate {Na[CH 3(CH 2)
Page 1064 and 1065:
T O PI C S Natural Logarithms Cal
Page 1066 and 1067:
20.50.026 Solution: a. ln(22 × 18.
Page 1068 and 1069:
c. Using the Clausius-Clapeyron equ
Page 1070 and 1071:
Deformation of the ionic crystal ca
Page 1072 and 1073:
in amorphous form if the liquid pha
Page 1074 and 1075:
. impurities in the liquid from whi
Page 1076 and 1077:
Crystalline solids have regular ord
Page 1078 and 1079:
Figure 12.2 Unit Cells in Two Dimen
Page 1080 and 1081:
Figure 12.4 The General Features of
Page 1082 and 1083:
entirely within a unit cell, such a
Page 1084 and 1085:
The arrangement of the atoms in a s
Page 1086 and 1087:
Figure 12.7 Close-Packed Structures
Page 1088 and 1089:
N U M E R I C A L PR O BL E M S 1.
Page 1090 and 1091:
within a unit cell is required to a
Page 1092 and 1093:
The most common structure based on
Page 1094 and 1095:
Figure 12.11 The Zinc Blende Struct
Page 1096 and 1097:
Two equivalent views are shown: (a)
Page 1098 and 1099:
determined accurately and routinely
Page 1100 and 1101:
More complex structures are possibl
Page 1102 and 1103:
What is the empirical formula of th
Page 1104 and 1105:
10. 11. Mg: 17.2°, Zn: 18.2°, Ni:
Page 1106 and 1107:
Name of Steel Typical Composition*
Page 1108 and 1109:
Figure 12.17 The Role of Dislocatio
Page 1110 and 1111:
Memory Metal The compound NiTi, pop
Page 1112 and 1113:
Sr 2+ (ionic radius = 118 pm) subst
Page 1114 and 1115:
Figure 12.18 The Two Most Common De
Page 1116 and 1117:
metals, lanthanides, and actinides,
Page 1118 and 1119:
6. Substitutional impurities are of
Page 1120 and 1121:
c. Without defects, the mass is 0.1
Page 1122 and 1123:
Self-healing rubber is an example o
Page 1124 and 1125:
strong covalent (C-C or Si-Si) or p
Page 1126 and 1127:
thus producing high electrical cond
Page 1128 and 1129:
A Locate the component element(s) i
Page 1130 and 1131:
5. Suppose you want to synthesize a
Page 1132 and 1133:
If the distance between the metal a
Page 1134 and 1135:
completely populated), so they do n
Page 1136 and 1137:
Insulators In contrast to metals, e
Page 1138 and 1139:
Figure 12.25 A Comparison of the Ke
Page 1140 and 1141:
The conductivity of the metal (tung
Page 1142 and 1143:
amounts of desired impurities and a
Page 1144 and 1145:
a. Predict the electrical propertie
Page 1146 and 1147:
7. Carbon is an insulator, and sili
Page 1148 and 1149:
The superconducting transition temp
Page 1150 and 1151:
superconducting at temperatures as
Page 1152 and 1153:
Compound Tc (K) YBa2Cu3O7−x 95 Bi
Page 1154 and 1155:
Formation", polymerization is the p
Page 1156 and 1157:
Many of the synthetic polymers we u
Page 1158 and 1159:
strong, and impact resistant. Its p
Page 1160 and 1161:
percentage of iron in wings and fus
Page 1162 and 1163:
SiCl4 s ( ) + 4CH 3CH 2OH ( l) + 4N
Page 1164 and 1165:
Figure 12.34 Some Possible Arrangem
Page 1166 and 1167:
Determine under what conditions the
Page 1168 and 1169:
a. Explain why the emitted light sh
Page 1170 and 1171:
9. A polymerization reaction is use
Page 1172 and 1173:
L E A R N I N G O B JE C T I V E 1.
Page 1174 and 1175:
Solvation can be an exothermic or e
Page 1176 and 1177:
All spontaneous processes with ΔH
Page 1178 and 1179:
The first substance, LiCl, is an io
Page 1180 and 1181:
The magnitude of the changes in bot
Page 1182 and 1183:
the molecule or ion happens to coll
Page 1184 and 1185:
sodium halides increase from NaI to
Page 1186 and 1187:
Gas Solubility (M) × 10 −4 Xe 50
Page 1188 and 1189:
Low-molecular-mass hydrocarbons wit
Page 1190 and 1191:
Exercise Identify the most importan
Page 1192 and 1193:
E X A M P L E 3 The following subst
Page 1194 and 1195:
solution has two or more phases tha
Page 1196 and 1197:
(a) The potassium complex of the cr
Page 1198 and 1199:
a. cyclohexane or methanol b. I 2 o
Page 1200 and 1201:
A N S W E R S 1. 2. 3. 4. 5. 6. 7.
Page 1202 and 1203:
a. A The molarity is the number of
Page 1204 and 1205:
E X A M P L E 5 Several years ago,
Page 1206 and 1207:
Unit Definition Application percent
Page 1208 and 1209:
d. MEtOH = (0.686 mol100 mL) \ (100
Page 1210 and 1211:
1. Complete the following table for
Page 1212 and 1213:
2Fe(s) + 3Br 2 (aq) → 2FeBr 3 (aq
Page 1214 and 1215:
1. To understand the relationship a
Page 1216 and 1217:
process (ΔHsoln < 0). Conversely,
Page 1218 and 1219:
"Energy Sources and the Environment
Page 1220 and 1221:
the Henry’s law constants for sol
Page 1222 and 1223:
CO2 = kPO2 = (1.27 ´10 - 3 M / atm
Page 1224 and 1225:
2. The solubility of O 2 in 100 g o
Page 1226 and 1227:
(CH3CO2Na) and 50 g of KBr, we can
Page 1228 and 1229:
ut calcium carbonate (CaCO3) is qui
Page 1230 and 1231:
Properties of Liquids".) (b) Increa
Page 1232 and 1233:
The Henry’s law constant for O 2
Page 1234 and 1235:
pump. Filling the flask with nitrog
Page 1236 and 1237:
Solubility may increase or decrease
Page 1238 and 1239:
decrease with increasing temperatur
Page 1240 and 1241:
External pressure has very little e
Page 1242 and 1243:
Note the Pattern Gases that react w
Page 1244 and 1245:
CONCEP TUAL PROBLEMS 1. Use the kin
Page 1246 and 1247:
Page 1248 and 1249:
to tissues. In a common inherited d
Page 1250 and 1251:
(a) Soaps and detergents, which con
Page 1252 and 1253:
hydrophobic tails attached to a hyd
Page 1254 and 1255:
must be better.” Instead of using
Page 1256 and 1257:
Chemical Kinetics The gases, liquid
Page 1258 and 1259:
At 180°C, however, a completely di
Page 1260 and 1261:
Factors that influence the reaction
Page 1262 and 1263:
The progress of a simple reaction (
Page 1264 and 1265:
Time (h) [Aspirin] (M) [Salicylic A
Page 1266 and 1267:
depend on the total volume of the s
Page 1268 and 1269:
A Using the equations in Example 1,
Page 1270 and 1271:
eactants ([R]) after a given amount
Page 1272 and 1273:
eaction rate of the hydrolysis reac
Page 1274 and 1275:
C Because the reaction rate is inde
Page 1276 and 1277:
5. During the hydrolysis reaction A
Page 1278 and 1279:
eaction order are described in this
Page 1280 and 1281:
This graph shows the concentrations
Page 1282 and 1283:
In a first-order reaction, the reac
Page 1284 and 1285:
The rate law and reaction order of
Page 1286 and 1287:
Data for the reaction at 320°C are
Page 1288 and 1289:
A Having been given the initial con
Page 1290 and 1291:
synthesis of drugs. Like the first-
Page 1292 and 1293:
At high temperatures, nitrogen diox
Page 1294 and 1295:
1[NO2]3600 = 1[NO2]0 + kt = 10.056
Page 1296 and 1297:
8.5 ´10 - 3 M / min34 ´10 - 3 M /
Page 1298 and 1299:
The peroxydisulfate ion (S 2O 8 2
Page 1300 and 1301:
C 3 H 7 Br + S 2 O 3 2− → C 3 H
Page 1302 and 1303:
These plots show the decomposition
Page 1304 and 1305:
E X AM P L E 9 Dinitrogen pentoxide
Page 1306 and 1307:
second order in C 4H 6; rate = k[C
Page 1308 and 1309:
Time (s) Pressure (mmHg) 0 348 400
Page 1310 and 1311:
experimentally. (To understand why,
Page 1312 and 1313:
Rate-determining step. The phenomen
Page 1314 and 1315:
This mechanism is consistent with t
Page 1316 and 1317:
CH3· + CH3· → H3CCH3 Cl· + Cl
Page 1318 and 1319:
3. Nitramide (O 2 NNH 2 ) decompose
Page 1320 and 1321:
The reaction rate, not the rate con
Page 1322 and 1323:
The diagram shows how the energy of
Page 1324 and 1325:
Most collisions of NO and O3 molecu
Page 1326 and 1327:
The frequency factor is used to con
Page 1328 and 1329:
B If the activation energy of a rea
Page 1330 and 1331:
K E Y T A K E A W A Y For a chemic
Page 1332 and 1333:
6. The reaction rate at 25°C is 1.
Page 1334 and 1335:
An example of heterogeneous catalys
Page 1336 and 1337:
Commercial Process Catalyst Reactan
Page 1338 and 1339:
6. An area of intensive chemical re
Page 1340 and 1341:
substrate concentrations, the plot
Page 1342 and 1343:
9. ♦ L-Aspartic acid is an amino
Page 1344 and 1345:
13. Figure 14.27 "Hydrogenation of
Page 1346 and 1347:
the ratio of the reaction rate of t
Page 1348 and 1349:
Chemical Equilibrium In Chapter 14
Page 1350 and 1351:
(a) Initially, this idealized syste
Page 1352 and 1353:
Given: three reaction systems Asked
Page 1354 and 1355:
1. To know the relationship between
Page 1356 and 1357:
K = [ C]c[ D]d[ A]a[ B]b where K is
Page 1358 and 1359:
corresponds to an essentially irrev
Page 1360 and 1361:
Use the value of the equilibrium co
Page 1362 and 1363:
K¢¢ = [N2O4]1/ 2[NO2] The values
Page 1364 and 1365:
where K is the equilibrium constant
Page 1366 and 1367:
Incorporating all the constant valu
Page 1368 and 1369:
Note the Pattern The concentrations
Page 1370 and 1371:
18S8( s) +O2( g) SO2( g) K1= 4.4 ´
Page 1372 and 1373:
A more complex example of this type
Page 1374 and 1375:
chemical equation for the reaction,
Page 1376 and 1377:
D We sum the numbers in the [NOCl]
Page 1378 and 1379:
The water-gas shift reaction is imp
Page 1380 and 1381:
K = 54 at 425°C. If 0.172 M H 2 an
Page 1382 and 1383:
In many situations it is not necess
Page 1384 and 1385:
100% to completion. When we solve t
Page 1386 and 1387:
quantities or concentrations of the
Page 1388 and 1389:
the reaction quotient is defined as
Page 1390 and 1391:
Saylor URL: http://www.saylor.org/b
Page 1392 and 1393:
Because K = 2.4 × 10 −4 , we see
Page 1394 and 1395:
Initially the concentration of CO2(
Page 1396 and 1397:
concentration of either HI or NH3,
Page 1398 and 1399:
a. Because HgO(s) and Hg(l) are pur
Page 1400 and 1401:
a. K = [CH 4][H 2S]2[CS2][H 2]4; ]
Page 1402 and 1403:
1. To predict the effects of stress
Page 1404 and 1405:
and the system will once again be a
Page 1406 and 1407:
Exercise For each equilibrium syste
Page 1408 and 1409:
c. 2NO2( g) 2NO( g) +O2( g) Given:
Page 1410 and 1411:
Increasing the temperature (adding
Page 1412 and 1413:
eaction with an unfavorable equilib
Page 1414 and 1415:
the magnitudes of the two equilibri
Page 1416 and 1417:
CH4 O2 CO2 H2O Q K remove water 0.6
Page 1418 and 1419:
eaction mixture to NH3, as is done
Page 1420 and 1421:
Controlling the amount of product f
Page 1422 and 1423:
3. What effect does a catalyst have
Page 1424 and 1425:
Thus we can obtain the solutions to
Page 1426 and 1427:
3. ♦ Phosphorus pentachloride, an
Page 1428 and 1429:
ecycling industry as well as in the
Page 1430 and 1431:
c. Would an increase in pressure fa
Page 1432 and 1433:
7. 8. 9. a. 10. 11. 1. K = [CO2]4[S
Page 1434 and 1435:
definition you use. In practice, ch
Page 1436 and 1437:
In pure water, the concentrations o
Page 1438 and 1439:
As pH decreases, [H + ] and the aci
Page 1440 and 1441:
Equation 16.10: [H + ] = 10 −pH D
Page 1442 and 1443:
a. household bleach (11.4) b. milk
Page 1444 and 1445:
ase. Once again, we have two conjug
Page 1446 and 1447:
As we noted earlier, the concentrat
Page 1448 and 1449:
CN - ( aq) + H2O( l) OH - ( aq) + H
Page 1450 and 1451:
In an acid-base reaction, the proto
Page 1452 and 1453:
You will notice in Table 16.2 "Valu
Page 1454 and 1455:
The hydrogen sulfate ion (HSO4 −
Page 1456 and 1457:
a. H2O( l) + HS -( aq) OH -( aq) +
Page 1458 and 1459:
25°C is 5.13 or 3.12, respectively
Page 1460 and 1461:
The contours show the electron dens
Page 1462 and 1463:
B In contrast, SO 4 2− is the con
Page 1464 and 1465:
c. C3H 7NO2( aq) +OH - ( aq) C3H6NO
Page 1466 and 1467:
2. Arrange these bases in order of
Page 1468 and 1469:
The same trend is predicted by anal
Page 1470 and 1471:
These electrostatic potential maps
Page 1472 and 1473:
causes electrons to be drawn from o
Page 1474 and 1475:
Given: series of compounds Asked fo
Page 1476 and 1477:
Inductive effects and charge deloca
Page 1478 and 1479:
Equation 16.38 CCH 3CO2H = [CH 3CO2
Page 1480 and 1481:
+(+0.0042 M ) = 0.0042 M[H +]f = [H
Page 1482 and 1483:
H2O( l) + NH 3( aq) NH 4 + ( aq) +O
Page 1484 and 1485:
Ka = [H+][HCO2-][HCO2H] = (1.00 ´1
Page 1486 and 1487:
B To calculate the pH, we need to d
Page 1488 and 1489:
As shown here for benzoic acid (C6H
Page 1490 and 1491:
f. percent ionized = [PhCO2-]CPhCO2
Page 1492 and 1493:
Equation 16.48 acidbasesumHA H + +A
Page 1494 and 1495:
e determined, as can the pH of the
Page 1496 and 1497:
8. The pK a of Cl 3 CCO 2 H is 0.64
Page 1498 and 1499:
50.00 mL of distilled water, the pH
Page 1500 and 1501:
As shown in part (b) in Figure 16.1
Page 1502 and 1503:
of the titration. Note also that th
Page 1504 and 1505:
All problems of this type must be s
Page 1506 and 1507:
C If excess acetate is present afte
Page 1508 and 1509:
weaker (its pKa or pKb becomes larg
Page 1510 and 1511:
The curve for the titration of 25.0
Page 1512 and 1513:
B The equilibrium between the weak
Page 1514 and 1515:
Red cabbage juice contains a mixtur
Page 1516 and 1517:
The graph shows the results obtaine
Page 1518 and 1519:
3. The pK a values of phenol red, b
Page 1520 and 1521:
. A volume of 5.0 mL of 2.55 M NaOH
Page 1522 and 1523:
A N S W E R S 1. 2. 3. 43 mL 4. 5.
Page 1524 and 1525:
changed; the ionization constant Ka
Page 1526 and 1527:
HCO2H ( aq) H + ( aq) + HCO2 -( aq)
Page 1528 and 1529:
A buffer maintains a relatively con
Page 1530 and 1531:
Solution: a. According to the Hende
Page 1532 and 1533:
[HCO2 − ] [H + ] [HCO2H] initial
Page 1534 and 1535:
lower the final pH to 1.32 instead
Page 1536 and 1537:
Adding Equation 16.63 and Equation
Page 1538 and 1539:
K E Y T A K E A W A Y The common i
Page 1540 and 1541:
d. Buffer; the NaOH neutralizes onl
Page 1542 and 1543:
To understand how buffers work, let
Page 1544 and 1545:
The initial concentrations, the cha
Page 1546 and 1547:
If the equilibrium constant for the
Page 1548 and 1549:
constant expression provides an eas
Page 1550 and 1551:
Answer: a. 4.08 b. 9.68 The Henders
Page 1552 and 1553:
[HCO2H] [OH − ] [HCO2 − ] initi
Page 1554 and 1555:
weak acid; at the upper right, the
Page 1556 and 1557:
According to Equation 16.65, adding
Page 1558 and 1559:
d. mixing 100 mL of 0.1 M hydrofluo
Page 1560 and 1561:
d. What is the final pH if 10.00 mL
Page 1562 and 1563:
5. ♦ Fluoroacetic acid is a poiso
Page 1564 and 1565:
calcium phosphate, one of the two m
Page 1566 and 1567:
B Convert the solubility of the sal
Page 1568 and 1569:
Asked for: molar concentration and
Page 1570 and 1571:
If Q is less than Ksp, the solution
Page 1572 and 1573:
continue to precipitate until the s
Page 1574 and 1575:
The equilibrium constant for a diss
Page 1576 and 1577:
c. iron(II) carbonate d. silver pho
Page 1578 and 1579:
19. Use the data in Chapter 26 "App
Page 1580 and 1581:
Page 1582 and 1583:
magnitude of attractive electrostat
Page 1584 and 1585:
Ion-pair formation, the incomplete
Page 1586 and 1587:
[Cu(NH3)4(H2O)2] 2+ complex ion is
Page 1588 and 1589:
The value of x indicates that our a
Page 1590 and 1591:
a. in pure water b. in 1.0 M KCl so
Page 1592 and 1593:
detergents prevents the magnesium a
Page 1594 and 1595:
Figure 17.5 An MRI Image of the Hea
Page 1596 and 1597:
Equation 17.13 MA s ( ) M + ( aq) +
Page 1598 and 1599:
(HO 2CCO 2H), which is a weak dipro
Page 1600 and 1601:
table. Oxides of metallic elements
Page 1602 and 1603:
elements are acidic oxides, which e
Page 1604 and 1605:
H 2S aq ( ) H + ( aq) + HS - ( aq)H
Page 1606 and 1607:
Substituting the desired oxalate co
Page 1608 and 1609:
2. 3. No; both metal ions will prec
Page 1610 and 1611:
in Chapter 6 "The Structure of Atom
Page 1612 and 1613:
sample of AuCl, what is the solubil
Page 1614 and 1615:
7. No; these cations would precipit
Page 1616 and 1617:
absorbing heat—the flow of therma
Page 1618 and 1619:
Using a frictionless piston, if the
Page 1620 and 1621:
the engine chamber and the expandin
Page 1622 and 1623:
Answer: −0.500 L·atm, or −50.7
Page 1624 and 1625:
. How much work is done if the pers
Page 1626 and 1627:
useful work is not fixed, as discus
Page 1628 and 1629:
Equation 18.10 qp = DE + PDVconstan
Page 1630 and 1631:
For reactions that result in a net
Page 1632 and 1633:
. Assuming the heat capacity of the
Page 1634 and 1635:
at a value between the initial temp
Page 1636 and 1637:
for a Sample of Four Gas Molecules
Page 1638 and 1639:
structure of water, leading to an i
Page 1640 and 1641:
can continue indefinitely. In contr
Page 1642 and 1643:
In the initial state (top), the tem
Page 1644 and 1645:
In this case, ΔSfus = (6.01 kJ/mol
Page 1646 and 1647:
a. What is ΔS for this process? b.
Page 1648 and 1649:
. irreversible c. reversible d. irr
Page 1650 and 1651:
only system that meets this criteri
Page 1652 and 1653:
Substance S° [J/(mol·K)] CH3OH 12
Page 1654 and 1655:
To calculate ΔS° for a chemical r
Page 1656 and 1657:
Thus we can use a combination of he
Page 1658 and 1659:
Entropy changes can be calculated u
Page 1660 and 1661:
c. 114.5 J/K d. −173.2 J/K 4. 5.
Page 1662 and 1663:
What about processes for which ΔG
Page 1664 and 1665:
"Temperature Dependence of Δ" show
Page 1666 and 1667:
Device Energy Conversion Approximat
Page 1668 and 1669:
Calculate the standard free-energy
Page 1670 and 1671:
Calculate ΔG° for the reaction of
Page 1672 and 1673:
thermodynamically spontaneous, but
Page 1674 and 1675:
free energy of formation (DG f ), i
Page 1676 and 1677:
3. Nitrogen fixation is the process
Page 1678 and 1679:
5. 919 K 6. 7. MgCO 3 : ΔG° = 63
Page 1680 and 1681:
Because the free-energy change for
Page 1682 and 1683:
Solution: In Example 10, we used ta
Page 1684 and 1685:
ln K1ln K2 = -DH°RT1+ DS°R = -DH
Page 1686 and 1687:
N U M E R I C A L PR O BL E M S 1.
Page 1688 and 1689:
. What is the equilibrium constant
Page 1690 and 1691:
Table 18.4 The Relationship between
Page 1692 and 1693:
Even at 1000°C, ΔG is very positi
Page 1694 and 1695:
B We can find the corresponding val
Page 1696 and 1697:
Because cells are open systems, the
Page 1698 and 1699:
information on respiration, see Cha
Page 1700 and 1701:
Figure 18.19 NAD + and Its Reduced
Page 1702 and 1703:
Thus any reaction that involves the
Page 1704 and 1705:
An average 70 kg adult stores about
Page 1706 and 1707:
A living cell is a system that is n
Page 1708 and 1709:
a. standard enthalpy of combustion
Page 1710 and 1711:
c. What is K? d. This reaction requ
Page 1712 and 1713:
a. aerobic conversion b. −268 kJ
Page 1714 and 1715:
Equation 19.1 Zn(s) + Br 2 (aq) →
Page 1716 and 1717:
To illustrate the basic principles
Page 1718 and 1719:
electric current can flow from the
Page 1720 and 1721:
Answer: − a. MnO (aq) + 4 (aq) +
Page 1722 and 1723:
The solution concentrations were no
Page 1724 and 1725:
c. Which electrode is negatively ch
Page 1726 and 1727:
19.2 Standard Potentials L E A R N
Page 1728 and 1729:
an electrochemical reaction and the
Page 1730 and 1731:
The SHE consists of platinum wire t
Page 1732 and 1733:
E° values do not depend on the sto
Page 1734 and 1735:
6H 2 O(l) + 2Al(s) + 2OH − (aq)
Page 1736 and 1737:
In acidic solution, the redox react
Page 1738 and 1739:
Equation 19.40 Zn(s)∣ Zn 2+ (aq,
Page 1740 and 1741:
When using a galvanic cell to measu
Page 1742 and 1743:
The voltage E′ is a constant that
Page 1744 and 1745:
C O N C E PTUAL P R OBLEMS 1. Is a
Page 1746 and 1747:
c. Fe 3+ (aq) + Cd(s) → Fe 2+ (aq
Page 1748 and 1749:
1. To know how to predict the relat
Page 1750 and 1751:
significantly greater ΔHhydration
Page 1752 and 1753:
Answer: a. Ag + (aq); H 2O 2(aq) b.
Page 1754 and 1755:
The oxidative and reductive strengt
Page 1756 and 1757:
phenomenon of electrolysis and laid
Page 1758 and 1759:
Use the data in Table 19.2 "Standar
Page 1760 and 1761:
Thus E°cell is directly proportion
Page 1762 and 1763:
ΔG = ΔG° + RT ln Q We also know
Page 1764 and 1765:
Applying the Nernst equation to a s
Page 1766 and 1767:
As the reaction progresses, the con
Page 1768 and 1769:
Ecell = 0 V - (0.0591 V1)log([Ag+]d
Page 1770 and 1771:
Another use for the Nernst equation
Page 1772 and 1773:
measure the solubility product of a
Page 1774 and 1775:
9. 10. N U M E R I C A L PR O BL E
Page 1776 and 1777:
g. Is the reduction of Mn 3+ (aq) t
Page 1778 and 1779:
c. What conditions can be changed t
Page 1780 and 1781:
graphite, and starch (part (a) in F
Page 1782 and 1783:
caused by the solid electrolyte, on
Page 1784 and 1785:
anode: Cd(s) + 2OH − (aq) → Cd(
Page 1786 and 1787:
When an external voltage in excess
Page 1788 and 1789:
called an alkaline battery when ada
Page 1790 and 1791:
deoxygenated water will not rust—
Page 1792 and 1793:
Holes in a protective coating allow
Page 1794 and 1795:
(Figure 19.20 "The Use of a Sacrifi
Page 1796 and 1797:
a. Not unless you plan to sell the
Page 1798 and 1799:
(a) When compartments that contain
Page 1800 and 1801:
The electrolysis of a molten mixtur
Page 1802 and 1803:
Equation 19.111 anode : 2H2O l Equa
Page 1804 and 1805:
control its electrical conductivity
Page 1806 and 1807:
Summary In electrolysis, an externa
Page 1808 and 1809:
19.8 End-of-Chapter Material A P P
Page 1810 and 1811:
when Cr(II) is oxidized to Cr(III)
Page 1812 and 1813:
Metal E versus Ag/AgCl (V) Monel [N
Page 1814 and 1815:
9. 10. 11. 12. 13. 14. 15. 16. 17.
Page 1816 and 1817:
living organisms is 1.3 × 10 −12
Page 1818 and 1819:
The relationship between the number
Page 1820 and 1821:
hypothesis that the nucleus contain
Page 1822 and 1823:
with 114 protons and 184 neutrons m
Page 1824 and 1825:
3. Give the number of protons, the
Page 1826 and 1827:
Chapter 20 Nuclear Chemistry Until
Page 1828 and 1829:
living organisms is 1.3 × 10 −12
Page 1830 and 1831:
Figure 20.1 Competing Interactions
Page 1832 and 1833:
numbers 2, 8, 20, 50, 82, and 126.
Page 1834 and 1835:
f. This nuclide has an atomic numbe
Page 1836 and 1837:
5. Isotopes with magic numbers of p
Page 1838 and 1839:
starting material. As we shall see,
Page 1840 and 1841:
Similarly, the lower left subscript
Page 1842 and 1843:
R88226a ® R86222n +a24 Because nuc
Page 1844 and 1845:
The atomic numbers of the parent an
Page 1846 and 1847:
a. A We know the identities of the
Page 1848 and 1849:
a proton and an electron. The elect
Page 1850 and 1851:
The first successful nuclear transm
Page 1852 and 1853:
number of the target is 27, so the
Page 1854 and 1855:
Data source: T. R. England and B. F
Page 1856 and 1857:
charge. Six different kinds of nucl
Page 1858 and 1859:
8. Which types of nuclear decay rea
Page 1860 and 1861:
c. a. Ra ® R86220n +a 208 Tl → 8
Page 1862 and 1863:
a. An unknown element emits γ rays
Page 1864 and 1865:
ays, their interaction with matter
Page 1866 and 1867:
the rem (roentgen equivalent in man
Page 1868 and 1869:
By far the most important source of
Page 1870 and 1871:
adiation dose per year = 2.87 ´10
Page 1872 and 1873:
Studies on fruit flies show a linea
Page 1874 and 1875:
1. 2. 3. Ionizing radiation is high
Page 1876 and 1877:
Equation 20.29 DE = (Dm)c2 we can r
Page 1878 and 1879:
A Using particle and isotope masses
Page 1880 and 1881:
smooth curve but exhibits sharp pea
Page 1882 and 1883:
Nuclear Fission and Fusion First di
Page 1884 and 1885:
Figure 20.18 Nuclear Fusion In a nu
Page 1886 and 1887:
DE = (-0.188386 amu)(931 MeV / amu)
Page 1888 and 1889:
a. 4. a. P91234a ® ?+ b -10 b. R88
Page 1890 and 1891:
. The formation of lead-206 by alph
Page 1892 and 1893:
an uncontrolled nuclear chain react
Page 1894 and 1895:
neutrons, slowing them to increase
Page 1896 and 1897:
eactor to produce twice as much fis
Page 1898 and 1899:
or the kidneys, which are almost in
Page 1900 and 1901:
shown in Figure 20.25 "Using Radiat
Page 1902 and 1903:
1. Neutron flow is regulated by usi
Page 1904 and 1905:
some examples are Ru and Ir. You ma
Page 1906 and 1907:
heavier elements such as carbon and
Page 1908 and 1909:
concentration of neutrons is so gre
Page 1910 and 1911:
4. During the lifetime of a star, d
Page 1912 and 1913:
Neglecting the fission products, wr
Page 1914 and 1915:
12. 130 W 13. Saylor URL: http://ww
Page 1916 and 1917:
to lose electrons in chemical react
Page 1918 and 1919:
C to C bonds are common for carbon,
Page 1920 and 1921:
c. predict which element differs th
Page 1922 and 1923:
C O N C E PTUAL P R OBLEMS 1. List
Page 1924 and 1925:
S T R U C T U R E A N D R E A C T I
Page 1926 and 1927:
Urey won the Nobel Prize in Chemist
Page 1928 and 1929:
Because of its 1s 1 electron config
Page 1930 and 1931:
Hydrogen gas can also be generated
Page 1932 and 1933:
g. Pd h. Al 6. Which has the higher
Page 1934 and 1935:
8. Seawater contains 3.5% dissolved
Page 1936 and 1937:
sulfuric acid to dissolve the desir
Page 1938 and 1939:
product of reaction with Lithium So
Page 1940 and 1941:
Equation 21.10 4KO 2 (s) + 2CO 2 (g
Page 1942 and 1943:
stoichiometry and color of intercal
Page 1944 and 1945:
"Solutions", crown ethers are cycli
Page 1946 and 1947:
Figure 21.11 Alkali Metal-Liquid Am
Page 1948 and 1949:
esponsible for transmitting nerve i
Page 1950 and 1951:
d. Li 3N(s) + KCl(s) → Given: rea
Page 1952 and 1953:
to form ionic halides; the heavier
Page 1954 and 1955:
3. Sodium metal is prepared by elec
Page 1956 and 1957:
The alkaline earth metals are produ
Page 1958 and 1959:
One major difference between the gr
Page 1960 and 1961:
The reaction in Equation 21.27 is t
Page 1962 and 1963:
Organometallic Compounds Containing
Page 1964 and 1965:
whereas that of BaCO 3 is almost tw
Page 1966 and 1967:
must appear in the products, and bo
Page 1968 and 1969:
1. Beryllium iodide reacts vigorous
Page 1970 and 1971:
Page 1972 and 1973:
containing structural materials. No
Page 1974 and 1975:
Because the health of cells depends
Page 1976 and 1977:
Summary Covalent hydrides in which
Page 1978 and 1979:
2. Ultrahigh-purity tritium, which
Page 1980 and 1981:
cell. The Na + , K + , Mg 2+ , and
Page 1982 and 1983:
1. To understand the trends in prop
Page 1984 and 1985:
group 13 elements, only aluminum is
Page 1986 and 1987:
Property Boron Aluminum* Gallium In
Page 1988 and 1989:
Unlike metallic solids, elemental b
Page 1990 and 1991:
(a) The hydrogen-bridged dimer B2H6
Page 1992 and 1993:
oxidized to H + and O 2 will be red
Page 1994 and 1995:
in dilute acid, but Al2O3 and Ga2O3
Page 1996 and 1997:
Because Al is a main group element
Page 1998 and 1999:
7. Because the B-N unit is isoelect
Page 2000 and 2001:
d. B 2 H 6 (g) + 2(C 2 H 5 ) 2 S(g)
Page 2002 and 2003:
d. 16Ga(l) + 3S 8 (s) → 8Ga 2 S 3
Page 2004 and 2005:
The most common sources of diamonds
Page 2006 and 2007:
stoichiometry as those of carbon, h
Page 2008 and 2009:
laboratory, fullerenes have been fo
Page 2010 and 2011:
temperatures with electropositive m
Page 2012 and 2013:
Predict the products of the reactio
Page 2014 and 2015:
Silicon has relatively low-energy,
Page 2016 and 2017:
The cavities normally contain hydra
Page 2018 and 2019:
The structure of a linear silicone
Page 2020 and 2021:
character increases. Silicates cont
Page 2022 and 2023:
22.3 The Elements of Group 15 (The
Page 2024 and 2025:
about 0.1% of Earth’s crust, is m
Page 2026 and 2027:
Note the Pattern Because neutral co
Page 2028 and 2029:
About 10% of the ammonia produced a
Page 2030 and 2031:
to handle. A third allotrope of pho
Page 2032 and 2033:
The heavier pnicogens form sulfides
Page 2034 and 2035:
states. The stability of the +5 oxi
Page 2036 and 2037:
A N S W E R S 1. 2. 3. 4. 5. NaNO 2
Page 2038 and 2039:
photosensitive, selenium is also us
Page 2040 and 2041:
selenium) have similar properties b
Page 2042 and 2043:
covalent compounds in which the bon
Page 2044 and 2045:
Because most of the heavier chalcog
Page 2046 and 2047:
contain C=S or C=Se bonds and have
Page 2048 and 2049:
Summary Because the electronegativi
Page 2050 and 2051:
4. 5. CrO 3 < Al 2 O 3 < Sc 2 O 3 <
Page 2052 and 2053:
the Cl2 produced annually; organobr
Page 2054 and 2055:
Oxidative strength decreases down g
Page 2056 and 2057:
covalent character of the halide du
Page 2058 and 2059:
a. When the reactants have the same
Page 2060 and 2061:
2. 3. 4. 5. Ionic character decreas
Page 2062 and 2063:
was the first of the noble gases to
Page 2064 and 2065:
Property Helium Neon Argon Krypton
Page 2066 and 2067:
Xe(g) + 2F 2 (g) → XeF 4 (s) The
Page 2068 and 2069:
Based on the position of radon in t
Page 2070 and 2071:
2. Write a balanced chemical equati
Page 2072 and 2073:
d. the reactivity of elemental C an
Page 2074 and 2075:
20. Zeolites have become increasing
Page 2076 and 2077:
Chapter 23 The d-Block Elements Cha
Page 2078 and 2079:
Because of the lanthanide contracti
Page 2080 and 2081:
Due to a small increase in successi
Page 2082 and 2083:
Sc Ti V Cr Mn Fe Co Ni Cu Zn V V V
Page 2084 and 2085:
Most transition-metal compounds are
Page 2086 and 2087:
The group 3 metals react with nonme
Page 2088 and 2089:
Each titanium atom is surrounded by
Page 2090 and 2091:
molybdenum produced annually is use
Page 2092 and 2093:
engines. Because tungsten itself ha
Page 2094 and 2095:
discovered until the 19th century.
Page 2096 and 2097:
The groups 8-10 metals form a range
Page 2098 and 2099:
dissolves in the 3:1 HCl:HNO3 mixtu
Page 2100 and 2101:
Refer to the periodic trends in thi
Page 2102 and 2103:
adius ratio causes extensive polari
Page 2104 and 2105:
4. Most of the transition metals ca
Page 2106 and 2107: 1. 2. 3. 4. 5. 6. 7. 8. 9. Pt 10+ ,
Page 2108 and 2109: 2FeTiO 3 (s) + 6C(s) + 7Cl 2 (g)
Page 2110 and 2111: on sulfuric acid production, see Ch
Page 2112 and 2113: Group Element Z Valence Electron Co
Page 2114 and 2115: All three group 7 elements have sev
Page 2116 and 2117: nickel uses the same alloy. In cont
Page 2118 and 2119: old. Copper is almost as ancient, w
Page 2120 and 2121: atteries. Large amounts of mercury
Page 2122 and 2123: chlorine. The most likely combinati
Page 2124 and 2125: group 8 metals in their highest oxi
Page 2126 and 2127: 9. Pt 10+ , Ir 9+ , and Ni 10+ . Be
Page 2128 and 2129: Equation 23.5 PbS s ( ) + O2( g) ®
Page 2130 and 2131: WO3( s) +3H2( g)- ® DW ( s) +3H2O(
Page 2132 and 2133: 2. 3. VCl4 l ( ) +2H 2( g)VCl4( l)
Page 2134 and 2135: present. For example, Werner’s da
Page 2136 and 2137: MA 4B 2 complexes with each of the
Page 2138 and 2139: Coordination Number 2 Although it i
Page 2140 and 2141: This coordination number is by far
Page 2142 and 2143: ases are hard acids, whereas metal
Page 2144 and 2145: Experimentally, it is observed that
Page 2146 and 2147: Isomers that contain the same numbe
Page 2148 and 2149: Octahedral complexes also exhibit c
Page 2150 and 2151: In addition, two structures are pos
Page 2152 and 2153: 2. Can a tetrahedral MA 2 B 2 compl
Page 2154 and 2155: ligands like CO, CFT enables chemis
Page 2158 and 2159: magnitude of Δo depends on three f
Page 2160 and 2161: Note the Pattern The largest Δos a
Page 2162 and 2163: spin d 6 complexes, which accounts
Page 2164 and 2165: energy is not the same for all five
Page 2166 and 2167: D In a high-spin octahedral d 6 com
Page 2168 and 2169: line represents the behavior predic
Page 2170 and 2171: Figure 23.16 The Jahn-Teller Effect
Page 2172 and 2173: Values of the lattice energies for
Page 2174 and 2175: 4. The ionic radii of V 2+ , Fe 2+
Page 2176 and 2177: Consequently, most microorganisms s
Page 2178 and 2179: A schematic drawing of the structur
Page 2180 and 2181: (−0.20 to −0.50 V) potentials,
Page 2182 and 2183: lue copper protein. Moreover, the r
Page 2184 and 2185: In a cytochrome c, the heme iron is
Page 2186 and 2187: transport system is available to pr
Page 2188 and 2189: (a) The Fe 2+ ion in deoxymyoglobin
Page 2190 and 2191: electron density is so great that t
Page 2192 and 2193: Although hemocyanin and hemerythrin
Page 2194 and 2195: The active site of carbonic anhydra
Page 2196 and 2197: In the conversion of ethylene glyco
Page 2198 and 2199: 2. Gout is a painful disorder cause
Page 2200 and 2201: these complexes is octahedral; in t
Page 2202 and 2203: (carboxylate-bridged copper dimers)
Page 2204 and 2205: Figure 24.1 Major Classes of Organi
Page 2206 and 2207:
positions of groups attached to an
Page 2208 and 2209:
Figure 24.3 Carbon-Carbon Bonding i
Page 2210 and 2211:
Figure 24.5 Potential Energy Plot a
Page 2212 and 2213:
Structural Isomers Unlike conformat
Page 2214 and 2215:
E X A M P L E 2 Draw all the struct
Page 2216 and 2217:
superimposed on its mirror image, a
Page 2218 and 2219:
E X A M P L E 3 Draw the cis and tr
Page 2220 and 2221:
. 1-methyl-3-chlorocyclopentane Ans
Page 2222 and 2223:
Although enantiomers have identical
Page 2224 and 2225:
physical and chemical properties, w
Page 2226 and 2227:
pregnancy, but unfortunately only t
Page 2228 and 2229:
A N S W E R S 1. sp 3 ; it is a σ
Page 2230 and 2231:
a. Draw the structures of the enant
Page 2232 and 2233:
24.3 Reactivity of Organic Molecule
Page 2234 and 2235:
Adding one electron to a carbocatio
Page 2236 and 2237:
c. The (CH 3) 3C + cation contains
Page 2238 and 2239:
c. (CH 3 ) 3 N + BCl 3 → 24.4 Com
Page 2240 and 2241:
Some reactions involve the removal,
Page 2242 and 2243:
Equation 24.6 Br ×+ Br ×CH 3CH 2
Page 2244 and 2245:
a. The CN − ion of KCN is a poten
Page 2246 and 2247:
2. Sketch the mechanism for the nuc
Page 2248 and 2249:
the solid state. It is therefore se
Page 2250 and 2251:
Saylor URL: http://www.saylor.org/b
Page 2252 and 2253:
Alkenes and alkynes are most often
Page 2254 and 2255:
carbocation formed in the first ste
Page 2256 and 2257:
Oxygen- and Nitrogen-Containing Fun
Page 2258 and 2259:
In compounds containing a carbonyl
Page 2260 and 2261:
Containing Functional Groups"), and
Page 2262 and 2263:
Compounds that contain the carboxyl
Page 2264 and 2265:
protonate the doubly bonded oxygen
Page 2266 and 2267:
the two substituents on the amide n
Page 2268 and 2269:
onded to one hydrogen and two alkyl
Page 2270 and 2271:
Given: reactants Asked for: product
Page 2272 and 2273:
substitution reaction. Alcohols und
Page 2274 and 2275:
A N S W E R S 1. 2. 3. 4. 5. (c) an
Page 2276 and 2277:
1. To understand the general proper
Page 2278 and 2279:
In contrast, the radicals formed du
Page 2280 and 2281:
Alkenes and alkynes are most often
Page 2282 and 2283:
The carbocation formed in the first
Page 2284 and 2285:
contain the carbonyl functional gro
Page 2286 and 2287:
Figure 24.17 Some Familiar Aldehyde
Page 2288 and 2289:
Containing Functional Groups"), and
Page 2290 and 2291:
Compounds that contain the carboxyl
Page 2292 and 2293:
protonate the doubly bonded oxygen
Page 2294 and 2295:
the two substituents on the amide n
Page 2296 and 2297:
molecular masses. Primary amines te
Page 2298 and 2299:
Solution: a. The proton on the carb
Page 2300 and 2301:
density. An alcohol is often prepar
Page 2302 and 2303:
15. What factors determine the reac
Page 2304 and 2305:
24.6 The Molecules of Life L E A R
Page 2306 and 2307:
In solution, simple sugars exist pr
Page 2308 and 2309:
Because carbohydrates have a carbon
Page 2310 and 2311:
Given: Fischer projection of a suga
Page 2312 and 2313:
The double bonds of unsaturated fat
Page 2314 and 2315:
Nucleic Acids Nucleic acids are the
Page 2316 and 2317:
untreated, it produces severe brain
Page 2318 and 2319:
2. Cyclohexanecarboxylic acid is a
Page 2320 and 2321:
Both glyceraldehyde and glyceric ac
Page 2322 and 2323:
1. The first staggered conformation
Page 2324 and 2325:
Substance ΔHf° (kJ/mol) ΔGf° (k
Page 2326 and 2327:
Page 2328 and 2329:
Page 2330 and 2331:
Page 2332 and 2333:
Page 2334 and 2335:
Page 2336 and 2337:
Compound Name Compound Formula K sp
Page 2338 and 2339:
Compound Name Compound Formula K sp
Page 2340 and 2341:
Name Formula K a1 pKa1 K a2 pKa2 K
Page 2342 and 2343:
Chapter 27 Appendix C: Dissociation
Page 2344 and 2345:
Name Formula K a1 pKa1 K a2 pKa2 K
Page 2346 and 2347:
Chapter 29 Appendix E: Standard Red
Page 2348 and 2349:
Half-Reaction E° (V) Cu 2+ + 2e
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Half-Reaction E° (V) Nd 3+ + 3e
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Half-Reaction E° (V) U 3+ + 3e −
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10 1.2281 40 7.3814 70 31.176 100 1
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Chapter 32 Appendix H: Periodic Tab
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List of Elements Name Symbol Atomic
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List of Elements Name Symbol Atomic
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Chapter 33 Appendix I: Experimental
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Chapter 34 Art Credits 34.1 Molecul
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General Chemistry Principles, Patterns, and Applications, 2011

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