General Chemistry Principles, Patterns, and Applications, 2011

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c. (CH 3 ) 3 N + BCl 3 → 24.4 Common Classes of Organic Reactions L E A R N I N G O B JE C T I V E 1. To become familiar with the common classes of organic reactions. Certain patterns are encountered repeatedly in organic reactions, many reflecting the interactions of nucleophiles and electrophiles. In this section, we discuss five common types of organic reactions: substitution reactions, elimination reactions, addition reactions, radical reactions, and oxidation–reduction reactions. You have encountered many of these types of reactions previously, such as the formation of peptides by the elimination of water, the oxidation– reduction reactions that generate voltage in batteries, and chain reactions that involve organic radicals. (For more information on peptide formation, see Chapter 12 "Solids", Section 12.8 "Polymeric Solids". For more information on batteries, see Chapter 19 "Electrochemistry". For more information on radicals, see Chapter 14 "Chemical Kinetics", Section 14.6 "Reaction Rates—A Microscopic View".) In this section, we expand our discussion to include some of the mechanisms behind these reactions. Substitution In a substitution reaction, one atom or a group of atoms in a substance is replaced by another atom or group of atoms from another substance. A typical substitution reaction is reacting the hydroxide ion with methyl chloride: Equation 24.1 CH 3 Cl + OH − → CH 3 OH + Cl − Methyl chloride has a polar C–Cl bond, with the carbon atom having a partial positive charge. In Equation 24.1, the electronegative Cl atom is replaced by another electronegative species that is a stronger nucleophile, in this case OH − . Reactions of this sort are called nucleophilic substitution reactions. For this type of reaction to occur, the nucleophilic reactant must possess a pair of electrons and have a greater affinity for the electropositive carbon atom than the original substituent. One type of nucleophilic substitution reaction is shown in Equation 24.1. It proceeds by a mechanism in which the lone pair of electrons on the entering nucleophile (OH − ) attacks the partially positively charged carbon atom of the polar C–Cl bond, causing the C–Cl bond to weaken and break: Figure 24.12 Saylor URL: http://www.saylor.org/books Saylor.org 2238
the Pattern Note In nucleophilic substitution reactions, the nucleophile must possess a pair of electrons and have a greater affinity for the electropositive species than the original substituent. The convention for writing such a mechanism is to draw arrows showing the direction of electron flow— that is, from the electron-rich center (the nucleophile) to the electron-poor center (the electrophile). The intermediate species, enclosed by square brackets, represents a transient arrangement of atoms that is only postulated to exist. If the atom under attack (in this case, the partially positively charged carbon atom) had –CH3groups bonded to it rather than H atoms, the bulky methyl groups would interfere with the attack by OH − , making the reaction sterically hindered. The reaction would then proceed in two discrete steps in a second type of substitution reaction: the C–Cl bond would break, forming the (CH3)3C + carbocation (the electrophile), which would then react with hydroxide (the nucleophile) in a separate step to give the product, (CH3)3COH. Mustard gas. An example of a nucleophilic substitution reaction involves the chemical warfare agent known as mustard gas [(ClCH2CH2)2S], which caused about 400,000 casualties during World War I. Mustard gas is toxic because it contains a chloride that can be displaced by nucleophilic amino groups in proteins, thereby allowing the molecule to irreversibly bond to a protein. Because the other product of the reaction is HCl, mustard gas causes severe burns to mucous membranes in the respiratory tract. If mustard gas reacts with DNA (deoxyribonucleic acid), cross-linking of the DNA strands through sulfur occurs, which results in coding errors, the inhibition of replication, and disruption of other DNA functions. If mustard gas reacts with RNA (ribonucleic acid), protein synthesis is altered (see Section 24.6 "The Molecules of Life"). Elimination Saylor URL: http://www.saylor.org/books Saylor.org 2239
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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
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Bonds Broken (kJ/mol) Bonds Formed
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DHrxn » å(bond energies of bonds
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. Cl-Cl, I-I c. O-O, Se-Se d. S-S,
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atom. Electron-rich (negatively cha
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In the absence of a field (a), the
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moment by writing an arrow above th
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A The charge on each atom is given
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e. Na 2 S f. SiO 2 g. LiBr 5. If th
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. Draw Lewis electron structures fo
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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 2156 and 2157:
(Crystal field splitting energy als
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 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
Page 2350 and 2351:
Half-Reaction E° (V) Nd 3+ + 3e
Page 2352 and 2353:
Half-Reaction E° (V) U 3+ + 3e −
Page 2354 and 2355:
10 1.2281 40 7.3814 70 31.176 100 1
Page 2356 and 2357:
Chapter 32 Appendix H: Periodic Tab
Page 2358 and 2359:
List of Elements Name Symbol Atomic
Page 2360 and 2361:
List of Elements Name Symbol Atomic
Page 2362 and 2363:
Chapter 33 Appendix I: Experimental
Page 2364 and 2365:
Chapter 34 Art Credits 34.1 Molecul
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General Chemistry Principles, Patterns, and Applications, 2011

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