447 10.7 Molecular Orbital Configurations The Carbon Molecule (C2) The carbon atom has the electron configuration 1s22s22p2; thus, there are 12 electrons in the C2 molecule Referring to Figures 10.26 and 10.27, we place the last four electrons in the p2py and p2pz orbitals Therefore, C2 has the electron configuration 2 w 2 (s1s ) (sw 1s ) (s2s ) (s2s ) (p2py ) (p2pz ) Its bond order is 2, and the molecule has no unpaired electrons Again, diamagnetic C2 molecules have been detected in the vapor state Note that the double bonds in C2 are both pi bonds because of the four electrons in the two pi molecular orbitals In most other molecules, a double bond is made up of a sigma bond and a pi bond The Oxygen Molecule (O2) The ground-state electron configuration of O is 1s22s22p4; thus, there are 16 electrons in O2 Using the order of increasing energies of the molecular orbitals discussed above, we write the ground-state electron configuration of O2 as 2 2 w w w (s1s ) (sw 1s ) (s2s ) (s2s ) (s2px ) (p2py ) (p2pz ) (p2py ) (p2pz ) w According to Hund’s rule, the last two electrons enter the pw 2py and p2pz orbitals with parallel spins Ignoring the s1s and s2s orbitals (because their net effects on bonding are zero), we calculate the bond order of O2 using Equation (10.2): bond order 12 (6 2) Therefore, the O2 molecule has a bond order of and oxygen is paramagnetic, a prediction that corresponds to experimental observations Table 10.5 summarizes the general properties of the stable diatomic molecules of the second period TABLE 10.5 Properties of Homonuclear Diatomic Molecules of the Second-Period Elements* Li2 B2 C2 N2 O2 F2 w 2px w 2p x h h hg hg w w 2py, 2pz hg hg hg hg hg 2py, 2pz w w 2py, 2pz 2px h h hg hg hg hg hg hg 2px hg hg hg hg hg w 2s hg hg hg hg hg hg 2s 267 104.6 159 288.7 131 627.6 110 941.4 121 498.7 142 156.9 2py, 2pz w 2s 2s Bond order Bond length (pm) Bond enthalpy (kJ/mol) Magnetic properties Diamagnetic Paramagnetic Diamagnetic Diamagnetic Paramagnetic Diamagnetic *For simplicity the s1s and sw 1s orbitals are omitted These two orbitals hold a total of four electrons Remember that for O2 and F2, s2px is lower in energy than p2py and p2pz 448 Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals Example 10.6 shows how MO theory can help predict molecular properties of ions EXAMPLE 10.6 The N12 ion can be prepared by bombarding the N2 molecule with fast-moving electrons Predict the following properties of N12 : (a) electron configuration, (b) bond order, (c) magnetic properties, and (d) bond length relative to the bond length of N2 (is it longer or shorter?) Strategy From Table 10.5 we can deduce the properties of ions generated from the homonuclear molecules How does the stability of a molecule depend on the number of electrons in bonding and antibonding molecular orbitals? From what molecular orbital is an electron removed to form the N12 ion from N2? What properties determine whether a species is diamagnetic or paramagnetic? Solution From Table 10.5 we can deduce the properties of ions generated from the homonuclear diatomic molecules (a) Because N12 has one fewer electron than N2, its electron configuration is 2 w 2 (s1s ) (sw 1s ) (s2s ) (s2s ) (p2py ) (p2pz ) (s2px ) (b) The bond order of N12 is found by using Equation (10.2): bond order 12 (9 4) 2.5 (c) N21 has one unpaired electron, so it is paramagnetic (d) Because the electrons in the bonding molecular orbitals are responsible for holding the atoms together, N12 should have a weaker and, therefore, longer bond than N2 (In fact, the bond length of N12 is 112 pm, compared with 110 pm for N2.) Check Because an electron is removed from a bonding molecular orbital, we expect Similar problems: 10.57, 10.58 the bond order to decrease The N12 ion has an odd number of electrons (13), so it should be paramagnetic Practice Exercise Which of the following species has a longer bond length: F2 or F22 ? 10.8 Delocalized Molecular Orbitals So far we have discussed chemical bonding only in terms of electron pairs However, the properties of a molecule cannot always be explained accurately by a single structure A case in point is the O3 molecule, discussed in Section 9.8 There we overcame the dilemma by introducing the concept of resonance In this section we will tackle the problem in another way—by applying the molecular orbital approach As in Section 9.8, we will use the benzene molecule and the carbonate ion as examples Note that in discussing the bonding of polyatomic molecules or ions, it is convenient to determine first the hybridization state of the atoms present (a valence bond approach), followed by the formation of appropriate molecular orbitals The Benzene Molecule Benzene (C6H6) is a planar hexagonal molecule with carbon atoms situated at the six corners All carbon-carbon bonds are equal in length and strength, as are all carbonhydrogen bonds, and the CCC and HCC angles are all 120° Therefore, each carbon 449 10.8 Delocalized Molecular Orbitals atom is sp2-hybridized; it forms three sigma bonds with two adjacent carbon atoms and a hydrogen atom (Figure 10.28) This arrangement leaves an unhybridized 2pz orbital on each carbon atom, perpendicular to the plane of the benzene molecule, or benzene ring, as it is often called So far the description resembles the configuration of ethylene (C2H4), discussed in Section 10.5, except that in this case there are six unhybridized 2pz orbitals in a cyclic arrangement Because of their similar shape and orientation, each 2pz orbital overlaps two others, one on each adjacent carbon atom According to the rules listed on p 443, the interaction of six 2pz orbitals leads to the formation of six pi molecular orbitals, of which three are bonding and three antibonding A benzene molecule in the ground state therefore has six electrons in the three pi bonding molecular orbitals, two electrons with paired spins in each orbital (Figure 10.29) Unlike the pi bonding molecular orbitals in ethylene, those in benzene form delocalized molecular orbitals, which are not confined between two adjacent bonding atoms, but actually extend over three or more atoms Therefore, electrons residing in any of these orbitals are free to move around the benzene ring For this reason, the structure of benzene is sometimes represented as in which the circle indicates that the pi bonds between carbon atoms are not confined to individual pairs of atoms; rather, the pi electron densities are evenly distributed throughout the benzene molecule The carbon and hydrogen atoms are not shown in the simplified diagram We can now state that each carbon-to-carbon linkage in benzene contains a sigma bond and a “partial” pi bond The bond order between any two adjacent carbon atoms is therefore between and Thus, molecular orbital theory offers an alternative to the resonance approach, which is based on valence bond theory (The resonance structures of benzene are shown on p 387.) H C H H C C C C H C H H Figure 10.28 The sigma bond framework in the benzene molecule Each carbon atom is sp2-hybridized and forms sigma bonds with two adjacent carbon atoms and another sigma bond with a hydrogen atom Electrostatic potential map of benzene shows the electron density (red color) above and below the plane of the molecule For simplicity, only the framework of the molecule is shown The Carbonate Ion Cyclic compounds like benzene are not the only ones with delocalized molecular orbitals Let’s look at bonding in the carbonate ion (CO22 ) VSEPR predicts a trigonal planar geometry for the carbonate ion, like that for BF3 The planar structure of the carbonate ion can be explained by assuming that the carbon atom is sp2-hybridized The C atom forms sigma bonds with three O atoms Thus, the unhybridized 2pz orbital of the C atom can simultaneously overlap the 2pz orbitals of all three O atoms Figure 10.29 Top view (a) Side view (b) (a) The six 2pz orbitals on the carbon atoms in benzene (b) The delocalized molecular orbital formed by the overlap of the 2pz orbitals The delocalized molecular orbital possesses pi symmetry and lies above and below the plane of the benzene ring Actually, these 2pz orbitals can combine in six different ways to yield three bonding molecular orbitals and three antibonding molecular orbitals The one shown here is the most stable CHEMISTRY in Action Buckyball, Anyone? I n 1985 chemists at Rice University in Texas used a highpowered laser to vaporize graphite in an effort to create unusual molecules believed to exist in interstellar space Mass spectrometry revealed that one of the products was an unknown species with the formula C60 Because of its size and the fact that it is pure carbon, this molecule has an exotic shape, which the researchers worked out using paper, scissors, and tape Subsequent spectroscopic and X-ray measurements confirmed that C60 is shaped like a hollow sphere with a carbon atom at each of the 60 vertices Geometrically, buckyball (short for “buckminsterfullerene”) is the most symmetrical molecule known In spite of its unique features, however, its bonding scheme is straightforward Each carbon is sp2-hybridized, and there are extensive delocalized molecular orbitals over the entire structure The discovery of buckyball generated tremendous interest within the scientific community Here was a new allotrope of carbon with an intriguing geometry and unknown properties to investigate Since 1985 chemists have created a whole class of fullerenes, with 70, 76, and even larger numbers of carbon atoms Moreover, buckyball has been found to be a natural component of soot Buckyball and its heavier members represent a whole new concept in molecular architecture with far-reaching implications For example, buckyball has been prepared with a helium atom trapped in its cage Buckyball also reacts with potassium to give K3C60, which acts as a superconductor at 18 K It is also possible to attach transition metals to buckyball These derivatives show promise as catalysts Because of its unique shape, buckyball can be used as a lubricant One fascinating discovery, made in 1991 by Japanese scientists, was the identification of structural relatives of buckyball These molecules are hundreds of nanometers long with a tubular shape and an internal cavity about 15 nm in diameter Dubbed “buckytubes” or “nanotubes” (because of their size), 450 The geometry of a buckyball C60 (left) resembles a soccer ball (right) Scientists arrived at this structure by fitting together paper cutouts of enough hexagons and pentagons to accommodate 60 carbon atoms at the points where they intersect these molecules have two distinctly different structures One is a single sheet of graphite that is capped at both ends with a kind of truncated buckyball The other is a scroll-like tube having anywhere from to 30 graphitelike layers Nanotubes are many times stronger than steel wires of similar dimensions Numerous potential applications have been proposed for them, including conducting and high-strength materials, hydrogen storage media, molecular sensors, semiconductor devices, and molecular probes The study of these materials has created a new field called nanotechnology, so called because scientists can manipulate materials on a molecular scale to create useful devices In the first biological application of buckyball, chemists at the University of California at San Francisco and Santa Barbara made a discovery in 1993 that could help in designing drugs to treat AIDS The human immunodeficiency virus (HIV) that causes AIDS reproduces by synthesizing a long protein chain, which is cut into smaller segments by an enzyme called HIV-protease One way to stop AIDS, then, might (Figure 10.30) The result is a delocalized molecular orbital that extends over all four nuclei in such a way that the electron densities (and hence the bond orders) in the carbon-to-oxygen bonds are all the same Molecular orbital theory therefore provides an acceptable alternative explanation of the properties of the carbonate ion as compared with the resonance structures of the ion shown on p 387 We should note that molecules with delocalized molecular orbitals are generally more stable than those containing molecular orbitals extending over only two atoms For example, the benzene molecule, which contains delocalized molecular orbitals, is chemically less reactive (and hence more stable) than molecules containing “localized” CPC bonds, such as ethylene 335 pm Computer-generated model of the binding of a buckyball derivative to the site of HIV-protease that normally attaches to a protein needed for the reproduction of HIV The buckyball structure (purple color) fits tightly into the active site, thus preventing the enzyme from carrying out its function Graphite is made up of layers of six-membered rings of carbon The structure of a buckytube that consists of a single layer of carbon atoms Note that the truncated buckyball “cap,” which has been separated from the rest of the buckytube in this view, has a different structure than the graphitelike cylindrical portion of the tube Chemists have devised ways to open the cap in order to place other molecules inside the tube The buckyball compound itself is not a suitable drug for use against AIDS because of potential side effects and delivery difficulties, but it does provide a model for the development of such drugs be to inactivate the enzyme When the chemists reacted a watersoluble derivative of buckyball with HIV-protease, they found that it binds to the portion of the enzyme that would ordinarily cleave the reproductive protein, thereby preventing the HIV virus from reproducing Consequently the virus could no longer infect the human cells they had grown in the laboratory O O O O C C O O Figure 10.30 Bonding in the carbonate ion The carbon atom forms three sigma bonds with the three oxygen atoms In addition, the 2pz orbitals of the carbon and oxygen atoms overlap to form delocalized molecular orbitals, so that there is also a partial pi bond between the carbon atom and each of the three oxygen atoms 451 452 Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals Review of Concepts Describe the bonding in the nitrate ion (NO2 ) in terms of resonance structures and delocalized molecular orbitals Key Equations m Q r (10.1) bond order Expressing dipole moment in terms of charge (Q) and distance of separation (r) between charges number of electrons number of electrons a b (10.2) in antibonding MOs in bonding MOs Summary of Facts and Concepts The VSEPR model for predicting molecular geometry is based on the assumption that valence-shell electron pairs repel one another and tend to stay as far apart as possible According to the VSEPR model, molecular geometry can be predicted from the number of bonding electron pairs and lone pairs Lone pairs repel other pairs more forcefully than bonding pairs and thus distort bond angles from the ideal geometry Dipole moment is a measure of the charge separation in molecules containing atoms of different electronegativities The dipole moment of a molecule is the resultant of whatever bond moments are present Information about molecular geometry can be obtained from dipole moment measurements There are two quantum mechanical explanations for covalent bond formation: valence bond theory and molecular orbital theory In valence bond theory, hybridized atomic orbitals are formed by the combination and rearrangement of orbitals from the same atom The hybridized orbitals are all of equal energy and electron density, and the number of hybridized orbitals is equal to the number of pure atomic orbitals that combine Valence-shell expansion can be explained by assuming hybridization of s, p, and d orbitals In sp hybridization, the two hybrid orbitals lie in a straight line; in sp2 hybridization, the three hybrid orbitals are directed toward the corners of an equilateral triangle; in sp3 hybridization, the four hybrid orbitals are directed toward the corners of a tetrahedron; in sp3d hybridization, the five hybrid orbitals are directed toward the corners of a trigonal bipyramid; in sp3d2 hybridization, the six hybrid orbitals are directed toward the corners of an octahedron Media Player Chapter Summary In an sp2-hybridized atom (for example, carbon), the one unhybridized p orbital can form a pi bond with another p orbital A carbon-carbon double bond consists of a sigma bond and a pi bond In an sp-hybridized carbon atom, the two unhybridized p orbitals can form two pi bonds with two p orbitals on another atom (or atoms) A carbon-carbon triple bond consists of one sigma bond and two pi bonds Molecular orbital theory describes bonding in terms of the combination and rearrangement of atomic orbitals to form orbitals that are associated with the molecule as a whole Bonding molecular orbitals increase electron density between the nuclei and are lower in energy than individual atomic orbitals Antibonding molecular orbitals have a region of zero electron density between the nuclei, and an energy level higher than that of the individual atomic orbitals 10 We write electron configurations for molecular orbitals as we for atomic orbitals, filling in electrons in the order of increasing energy levels The number of molecular orbitals always equals the number of atomic orbitals that were combined The Pauli exclusion principle and Hund’s rule govern the filling of molecular orbitals 11 Molecules are stable if the number of electrons in bonding molecular orbitals is greater than that in antibonding molecular orbitals 12 Delocalized molecular orbitals, in which electrons are free to move around a whole molecule or group of atoms, are formed by electrons in p orbitals of adjacent atoms Delocalized molecular orbitals are an alternative to resonance structures in explaining observed molecular properties Questions and Problems 453 Key Words Antibonding molecular orbital, p 440 Bond order, p 444 Bonding molecular orbital, p 440 Delocalized molecular orbital, p 449 Dipole moment (m), p 420 Homonuclear diatomic molecule, p 445 Hybrid orbital, p 428 Hybridization, p 428 Molecular orbital, p 440 Nonpolar molecule, p 421 Pi bond (p bond), p 437 Pi molecular orbital, p 443 Polar molecule, p 421 Sigma bond (s bond), p 437 Sigma molecular orbital, p 441 Valence shell, p 410 Valence-shell electron-pair repulsion (VSEPR) model, p 410 Electronic Homework Problems The following problems are available at www.aris.mhhe.com if assigned by your instructor as electronic homework Quantum Tutor problems are also available at the same site ARIS Problems 10.7, 10.8, 10.9, 10.10, 10.12, 10.14, 10.21, 10.24, 10.33, 10.35, 10.36, 10.38, 10.41, 10.54, 10.55, 10.58, 10.60, 10.66, 10.69, 10.70, 10.73, 10.74, 10.76, 10.78, 10.81, 10.82, 10.85, 10.89, 10.99, 10.101, 10.104, 10.105, 10.109 Quantum Tutor Problems 10.7, 10.8, 10.9, 10.10, 10.11, 10.12, 10.14, 10.70, 10.73, 10.74, 10.75, 10.79, 10.81, 10.99, 10.109 Questions and Problems Molecular Geometry 10.8 Review Questions 10.1 10.2 10.3 10.4 10.5 10.6 How is the geometry of a molecule defined and why is the study of molecular geometry important? Sketch the shape of a linear triatomic molecule, a trigonal planar molecule containing four atoms, a tetrahedral molecule, a trigonal bipyramidal molecule, and an octahedral molecule Give the bond angles in each case How many atoms are directly bonded to the central atom in a tetrahedral molecule, a trigonal bipyramidal molecule, and an octahedral molecule? Discuss the basic features of the VSEPR model Explain why the magnitude of repulsion decreases in the following order: lone pair-lone pair lone pairbonding pair bonding pair-bonding pair In the trigonal bipyramidal arrangement, why does a lone pair occupy an equatorial position rather than an axial position? The geometry of CH4 could be square planar, with the four H atoms at the corners of a square and the C atom at the center of the square Sketch this geometry and compare its stability with that of a tetrahedral CH4 molecule Problems 10.7 Predict the geometries of the following species using the VSEPR method: (a) PCl3, (b) CHCl3, (c) SiH4, (d) TeCl4 10.9 10.10 10.11 10.12 10.13 10.14 Predict the geometries of the following species: (a) AlCl3, (b) ZnCl2, (c) ZnCl22 Predict the geometry of the following molecules and ion using the VSEPR model: (a) CBr4, (b) BCl3, (c) NF3, (d) H2Se, (e) NO2 Predict the geometry of the following molecules and ion using the VSEPR model: (a) CH3I, (b) ClF3, (c) H2S, (d) SO3, (e) SO22 Predict the geometry of the following molecules using the VSEPR method: (a) HgBr2, (b) N2O (arrangement of atoms is NNO), (c) SCN2 (arrangement of atoms is SCN) Predict the geometries of the following ions: (a) NH14 , 22 2 (b) NH2 , (c) CO3 , (d) ICl2 , (e) ICl4 , (f) AlH , 22 (g) SnCl5 , (h) H3O , (i) BeF , Describe the geometry around each of the three central atoms in the CH3COOH molecule Which of the following species are tetrahedral? SiCl4, SeF4, XeF4, CI4, CdCl2− Dipole Moments Review Questions 10.15 Define dipole moment What are the units and symbol for dipole moment? 10.16 What is the relationship between the dipole moment and the bond moment? How is it possible for a molecule to have bond moments and yet be nonpolar? 454 Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals 10.17 Explain why an atom cannot have a permanent dipole moment 10.18 The bonds in beryllium hydride (BeH2) molecules are polar, and yet the dipole moment of the molecule is zero Explain Problems 10.19 Referring to Table 10.3, arrange the following molecules in order of increasing dipole moment: H2O, H2S, H2Te, H2Se 10.20 The dipole moments of the hydrogen halides decrease from HF to HI (see Table 10.3) Explain this trend 10.21 List the following molecules in order of increasing dipole moment: H2O, CBr4, H2S, HF, NH3, CO2 10.22 Does the molecule OCS have a higher or lower dipole moment than CS2? 10.23 Which of the following molecules has a higher dipole moment? Br H H Br G D CPC D G ECl (a) 10.31 Describe the bonding scheme of the AsH3 molecule in terms of hybridization 10.32 What is the hybridization state of Si in SiH4 and in H3Si—SiH3? 10.33 Describe the change in hybridization (if any) of the Al atom in the following reaction: AlCl3 Cl2 ¡ AlCl2 10.34 Consider the reaction Br G D CPC G D H H BF3 NH3 ¡ F3BONH3 (b) 10.35 10.24 Arrange the following compounds in order of increasing dipole moment: Cl A Problems Br (a) ClH 2p orbitals of an atom hybridize to give two hybridized orbitals? 10.29 What is the angle between the following two hybrid orbitals on the same atom? (a) sp and sp hybrid orbitals, (b) sp2 and sp2 hybrid orbitals, (c) sp3 and sp3 hybrid orbitals 10.30 How would you distinguish between a sigma bond and a pi bond? Cl A Cl A A Cl A Cl A Cl (b) (c) (d) ECl ClH 10.36 ECl Valence Bond Theory Review Questions 10.25 What is valence bond theory? How does it differ from the Lewis concept of chemical bonding? 10.26 Use valence bond theory to explain the bonding in Cl2 and HCl Show how the atomic orbitals overlap when a bond is formed 10.27 Draw a potential energy curve for the bond formation in F2 Hybridization Review Questions 10.28 (a) What is the hybridization of atomic orbitals? Why is it impossible for an isolated atom to exist in the hybridized state? (b) How does a hybrid orbital differ from a pure atomic orbital? Can two 10.37 10.38 10.39 10.40 10.41 Describe the changes in hybridization (if any) of the B and N atoms as a result of this reaction What hybrid orbitals are used by nitrogen atoms in the following species? (a) NH3, (b) H2NONH2, (c) NO2 What are the hybrid orbitals of the carbon atoms in the following molecules? (a) H3COCH3 (b) H3COCHPCH2 (c) CH3OCqCOCH2OH (d) CH3CHPO (e) CH3COOH Specify which hybrid orbitals are used by carbon atoms in the following species: (a) CO, (b) CO2, (c) CN2 What is the hybridization state of the central N atom in the azide ion, N32? (Arrangement of atoms: NNN.) The allene molecule H2CPCPCH2 is linear (the three C atoms lie on a straight line) What are the hybridization states of the carbon atoms? Draw diagrams to show the formation of sigma bonds and pi bonds in allene Describe the hybridization of phosphorus in PF5 How many sigma bonds and pi bonds are there in each of the following molecules? H H H Cl A A G D H 3COCPCOCqCOH CPC ClOCOCl D G A A H H H H (a) (b) (c) Questions and Problems 10.42 How many pi bonds and sigma bonds are there in the tetracyanoethylene molecule? NqC NqC CqN G D CPC D G CqN 10.43 Give the formula of a cation comprised of iodine and fluorine in which the iodine atom is sp3d-hybridized 10.44 Give the formula of an anion comprised of iodine and fluorine in which the iodine atom is sp3d 2-hybridized Molecular Orbital Theory Review Questions 10.45 What is molecular orbital theory? How does it differ from valence bond theory? 10.46 Define the following terms: bonding molecular orbital, antibonding molecular orbital, pi molecular orbital, sigma molecular orbital 10.47 Sketch the shapes of the following molecular orbitw als: s 1s, s w 1s, p 2p , and p 2p How their energies compare? 10.48 Explain the significance of bond order Can bond order be used for quantitative comparisons of the strengths of chemical bonds? Problems 10.49 Explain in molecular orbital terms the changes in HOH internuclear distance that occur as the molec21 ular H2 is ionized first to H1 and then to H2 10.50 The formation of H2 from two H atoms is an energetically favorable process Yet statistically there is less than a 100 percent chance that any two H atoms will undergo the reaction Apart from energy considerations, how would you account for this observation based on the electron spins in the two H atoms? 10.51 Draw a molecular orbital energy level diagram for each of the following species: He2, HHe, He12 Compare their relative stabilities in terms of bond orders (Treat HHe as a diatomic molecule with three electrons.) 10.52 Arrange the following species in order of increasing stability: Li2, Li1 , Li2 Justify your choice with a molecular orbital energy level diagram 10.53 Use molecular orbital theory to explain why the Be2 molecule does not exist 10.54 Which of these species has a longer bond, B2 or B12 ? Explain in terms of molecular orbital theory 10.55 Acetylene (C2H2) has a tendency to lose two protons (H1) and form the carbide ion (C222), which is present in a number of ionic compounds, such as CaC2 and MgC2 Describe the bonding scheme in the C222 ion in terms of molecular orbital theory Compare the bond order in C222 with that in C2 455 10.56 Compare the Lewis and molecular orbital treatments of the oxygen molecule 10.57 Explain why the bond order of N2 is greater than that of N12 , but the bond order of O2 is less than that of O12 10.58 Compare the relative stability of the following species and indicate their magnetic properties (that is, diamagnetic or paramagnetic): O2, O12 , O22 (superoxide ion), O22 (peroxide ion) 10.59 Use molecular orbital theory to compare the relative stabilities of F2 and F 10.60 A single bond is almost always a sigma bond, and a double bond is almost always made up of a sigma bond and a pi bond There are very few exceptions to this rule Show that the B2 and C2 molecules are examples of the exceptions Delocalized Molecular Orbitals Review Questions 10.61 How does a delocalized molecular orbital differ from a molecular orbital such as that found in H2 or C2H4? What you think are the minimum conditions (for example, number of atoms and types of orbitals) for forming a delocalized molecular orbital? 10.62 In Chapter we saw that the resonance concept is useful for dealing with species such as the benzene molecule and the carbonate ion How does molecular orbital theory deal with these species? Problems 10.63 Both ethylene (C2H4) and benzene (C6H6) contain the CPC bond The reactivity of ethylene is greater than that of benzene For example, ethylene readily reacts with molecular bromine, whereas benzene is normally quite inert toward molecular bromine and many other compounds Explain this difference in reactivity 10.64 Explain why the symbol on the left is a better representation of benzene molecules than that on the right 10.65 Determine which of these molecules has a more delocalized orbital and justify your choice (Hint: Both molecules contain two benzene rings In naphthalene, the two rings are fused together In biphenyl, the two rings are joined by a single bond, around which the two rings can rotate.) 456 Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals 10.66 Nitryl fluoride (FNO2) is very reactive chemically The fluorine and oxygen atoms are bonded to the nitrogen atom (a) Write a Lewis structure for FNO2 (b) Indicate the hybridization of the nitrogen atom (c) Describe the bonding in terms of molecular orbital theory Where would you expect delocalized molecular orbitals to form? 10.67 Describe the bonding in the nitrate ion NO2 in terms of delocalized molecular orbitals 10.68 What is the state of hybridization of the central O atom in O3? Describe the bonding in O3 in terms of delocalized molecular orbitals dipole moment (d) SiH2 Planar or pyramidal shape? (e) Br2CH2 Polar or nonpolar molecule? 10.80 Which of the following molecules and ions are lin1 ear? ICl2 , IF , OF2, SnI2, CdBr2 10.81 Draw the Lewis structure for the BeCl 22 ion Predict its geometry and describe the hybridization state of the Be atom 10.82 The N2F2 molecule can exist in either of the following two forms: F Additional Problems 10.69 Which of the following species is not likely to have a tetrahedral shape? (a) SiBr4, (b) NF1 , (c) SF4, 2 (d) BeCl 22 , (e) BF , (f) AlCl 10.70 Draw the Lewis structure of mercury(II) bromide Is this molecule linear or bent? How would you establish its geometry? 10.71 Sketch the bond moments and resultant dipole moments for the following molecules: H2O, PCl3, XeF4, PCl5, SF6 10.72 Although both carbon and silicon are in Group 4A, very few SiPSi bonds are known Account for the instability of silicon-to-silicon double bonds in general (Hint: Compare the atomic radii of C and Si in Figure 8.5 What effect would the larger size have on pi bond formation?) 10.73 Predict the geometry of sulfur dichloride (SCl2) and the hybridization of the sulfur atom 10.74 Antimony pentafluoride, SbF5, reacts with XeF4 and XeF6 to form ionic compounds, XeF31SbF 62 and XeF1 SbF Describe the geometries of the cations and anion in these two compounds 10.75 Draw Lewis structures and give the other information requested for the following molecules: (a) BF3 Shape: planar or nonplanar? (b) ClO2 Shape: planar or nonplanar? (c) H2O Show the direction of the resultant dipole moment (d) OF2 Polar or nonpolar molecule? (e) NO2 Estimate the ONO bond angle 10.76 Predict the bond angles for the following molecules: (a) BeCl2, (b) BCl3, (c) CCl4, (d) CH3Cl, (e) Hg2Cl2 (arrangement of atoms: ClHgHgCl), (f ) SnCl2, (g) H2O2, (h) SnH4 10.77 Briefly compare the VSEPR and hybridization approaches to the study of molecular geometry 10.78 Describe the hybridization state of arsenic in arsenic pentafluoride (AsF5) 10.79 Draw Lewis structures and give the other information requested for the following: (a) SO3 Polar or nonpolar molecule? (b) PF3 Polar or nonpolar molecule? (c) F3SiH Show the direction of the resultant D NPN D F F G D NPN F (a) What is the hybridization of N in the molecule? (b) Which structure has a dipole moment? 10.83 Cyclopropane (C3H6) has the shape of a triangle in which a C atom is bonded to two H atoms and two other C atoms at each corner Cubane (C8H8) has the shape of a cube in which a C atom is bonded to one H atom and three other C atoms at each corner (a) Draw Lewis structures of these molecules (b) Compare the CCC angles in these molecules with those predicted for an sp3-hybridized C atom (c) Would you expect these molecules to be easy to make? 10.84 The compound 1,2-dichloroethane (C2H4Cl2) is nonpolar, while cis-dichloroethylene (C2H2Cl2) has a dipole moment: Cl Cl A A HOCOCOH A A H H 1,2-dichloroethane Cl G D CPC D G Cl H H cis-dichloroethylene The reason for the difference is that groups connected by a single bond can rotate with respect to each other, but no rotation occurs when a double bond connects the groups On the basis of bonding considerations, explain why rotation occurs in 1,2dichloroethane but not in cis-dichloroethylene 10.85 Does the following molecule have a dipole moment? Cl H H G D CPCPC D G Cl (Hint: See the answer to Problem 10.39.) 10.86 So-called greenhouse gases, which contribute to global warming, have a dipole moment or can be bent or distorted into shapes that have a dipole moment Which of the following gases are greenhouse gases? N2, O2, O3, CO, CO2, NO2, N2O, CH4, CFCl3 10.87 The bond angle of SO2 is very close to 1208, even though there is a lone pair on S Explain Credits Karp, Photographer; figure 16.10, 16.11, 16.12 (all): © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 753 (top left): © Jody Dole/Getty Images; p 753 (top right): © Scientific American, March 1970, Vol 222, No 3, p 88 Photo by A.R Terepka; figure 16.13 (all): © McGraw-Hill Higher Education, Inc./Stephen Frisch, Photographer; p 767 (both): © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer CHAPTER 17 Opener: © Corbis/Vol 188; figure 17.4: © E.R Degginger/Color-Pic; figure 17.5: © NASA; p 776: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 17.8: NOAA; figure 17.9: © NASA; figure 17.10: © E.R Degginger/Color-Pic; p 780: © Roger Ressmeyer/Corbis Images; figure 17.20 (left): © NYC Parks Photo Archive/Fundamental Photographs; figure 17.20 (right): © Kristen Brochmann/Fundamental Photographs; figure 17.22: © Owen Franken; figure 17.24: © Owen Franken; p 789: © James A Sugar/ Corbis Images; p 790: © Barth Falkenberg/ Stock Boston; figure 17.26: © Stan Ries/Index Stock Imagery/Photolibrary; figure 17.29: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer CHAPTER 18 Opener: © National Lime Association; p 803: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 805: © Matthias K Gebbert/University of Maryland, Baltimore County/Dept of Mathematics and Statistics; p 807: © McGraw-Hill Higher Education, Inc./ Ken Karp, Photographer; p 815: United States Postal Service; p 820–821: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer CHAPTER 19 Opener: © Nathan S Lewis, California Institute of Technology; figure 19.2: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 860: © AP/Wide World Photos; p 861: © Derek Lovely; figure 19.12: © NASA; figure 19.13a: © E.R Degginger/Color-Pic; figure 19.13b: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 19.13c: © Donald Dietz/Stock Boston; figure 19.15: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 19.18: © McGrawHill Higher Education, Inc./Stephen Frisch, Photographer; p 878, p 880, p 882 (both): © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer C-3 CHAPTER 20 CHAPTER 23 Opener: © James L Dye; figure 20.2: © Lamont-Doherty/Dr Bruce Heezen; figure 20.5: © Jeff Smith; figure 20.7: Courtesy, Copper Development Association; figure 20.13: © Wards Natural Science Establishment; figure 20.14: © Aronson Photo/Stock Boston; figure 20.15: © Wards Natural Science Establishment; figure 20.16: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 20.17: © Wards Natural Science Establishment; figure 20.19: © E.R Degginger/ Color-Pic; p 906 (both): © Courtesy of Aluminum Company of America Opener: Jeff Hester, Arizona State University and NASA, Image produced by AURA/STSci; p 988: Courtesy, Allen Mills, UC Riverside; figure 23.5: © Fermi Lab; figure 23.11: © Toby Talbot/AP Images; figure 23.12: © Marvin Lazarus/Photo Researchers; figure 23.13: © Los Alamos National Laboratories; p 1006: From Meshik, A.P et.al.: The Workings of An Ancient Nuclear Reactor.” Scientific American November 2005; 293(5) Photo appeared on pages 8283 Photo by Franỗois GauthierLafaye; p 1007 (top): © U.S Department of Energy/Photo Researchers; p 1007 (bottom): © NASA; figure 23.15: © Lawrence Livermore National Labs; figure 23.16: © U.S Navy Photo/Department of Defense; figure 23.17 (both): © SIU/Visuals Unlimited; p 1012: © Alexander Tsiaras/Photo Researchers; p 1014: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 1015: Courtesy Prof Otto K Harling, Dr Peter J Binns, Dr Kent J Riley, MIT/Harvard BNCT Group; p 1023: Christ and His Disciples at Emmaus by Han van Meegeren/Museum Boijmans Van Beunuingen, Rotterdam CHAPTER 21 Opener: © NASA; p 918: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 21.5: © Courtesy General Electric Research and Development Center; figure 21.6: © David Tejada/Tejada Photography, Inc.; p 923: © Jeff Smith; figure 21.7: © McGrawHill Higher Education, Inc./Ken Karp, Photographer; figure 21.8: © O’Keefe/PhotoLink/ Photodisc/Getty Images; p 931 (left): © Bob Daemmrich/Daemmrich Photography; p 931 (right): © Jeff Roberson; p 934: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 21.14: © L.V Bergman/The Bergman Collection; p 938: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 21.18: © Charles Beck/Vulcan Materials Company; figure 21.20: © Jim Brandenburg CHAPTER 22 Opener: © Al Lemme/Fritz Goro; figure 22.4 (Sc), (Ti), (V), (Cr), (Mn), (Fe), (Co), (Ni): © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 22.4 (Cu): © L.V Bergman/The Bergman Collection; figure 22.5, 22.6: © Wards Natural Science Establishment; p 965: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 22.15: © Joel Gordon 1979; figure 22.20: © McGrawHill Higher Education, Inc./Ken Karp, Photographer; p 975: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 978: Courtesy of the author; p 984: Unidentified Noblewoman Artist unknown Oil on panel 19th Century Courtesy, Mead Art Museum, Amherst College, Amherst, Massachusetts Gift of David Willis AC 1995.63 CHAPTER 24 Opener: © Jean Miele/Corbis; figure 24.1: © J H Robinson/Photo Researchers; p 1036: © Steve Gschmeissner/SPL/Photo Researchers; p 1037: © E.R Degginger/Color-Pic; p 1038: © Laura Stern & John Pinston, Courtesy of Laura Stern/U.S Geological Survey; p 1039: © IBM Corporation-Almaden Research Center; p 1043: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 1045: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; p 1047: © Biophoto/ Photo Researchers; p 1049: © Courtesy of American Petroleum Institute; p 1058: © AP/ Wide World Photos; p 1059: © Ed Bock/ Corbis Images CHAPTER 25 Opener, p 1063, figure 25.2: © McGraw-Hill Higher Education, Inc./Ken Karp, Photographer; figure 25.4: © Charles Weckler/Image Bank/ Getty Images; p 1066: © Richard Hutchings/ Photo Researchers; figure 25.7: E R Degginger/ Color-Pic; p 1077: © Lawrence Berkeley Laboratory A Absolute entropy, 807, 813 Absolute temperature scale, 19, 183 Absolute zero, 183 Absorption spectrum, 559, 969 Acceptor impurity, 896 Accuracy, 26 Acetaldehyde (CH3CHO), 1044 Acetic acid (CH3COOH), 123, 660, 727, 1045 ionization constant of, 671 titrations of, 727 Acetic acid-sodium acetate system, 714, 718 Acetone (CH3COCH3), 1044 Acetyl chloride (CH3COCl), 1045 Acetylene (C2H2), 1037 bonding in, 375, 438 properties and reactions of, 1037 Acetylsalicylic acid (aspirin), 671, 698 Achiral molecules, 966 Acid(s), 65, 129, 660 Arrhenius, 130 Brønsted, 130, 660 diprotic, 131, 681 general properties of, 130 ionization constants of See Ionization constants Lewis, 697 monoprotic, 131, 671 polyprotic, 131, 685 strength of, 666, 685 strong and weak, defined, 666 triprotic, 131, 685 Acid ionization constants (Ka), 671 of diprotic and polyprotic acids, 683 of monoprotic acids, 671 relation between base ionization constants and, 680 Acid paper, 710 Acid rain, 695, 785 Acid strength, 666, 685 Acid-base indicators, 154, 732, 734 (table) Acid-base properties, 130 of hydroxides, 696 of oxides, 695 of salt solutions, 689 of water, 661 Acid-base reactions, 133, 153, 723 Acid-base theory Arrhenius, 130 Brønsted, 130 Lewis, 697 Acid-base titrations, 153, 723 Acidic oxides, 353, 695 Actinide series, 309 Activated complex, 583 Activation energy (Ea), 583, 974 Active site, 600 Active transport, 698 Activity, 621, 664 Activity series, 142 Actual yield, 106 Addition reactions, 599, 1035, 1062 Adenine, 827, 1076 Adenosine diphosphate, 827 Adenosine triphosphate, 827 Adhesion, 469 Adiabatic process, 239 Adipic acid, 1067 Aerosols, 541, 779, 790 AIDS, 451 Air, composition of, 770 Air pollution carbon monoxide and, 793 radon and, 791 smog and, 789 sulfur dioxide and, 786 Alcohol(s), 1042 condensation reactions of, 1043 denatured, 1043 oxidation of, 1042 Alcohol dehydrogenase, 1042 Aldehydes, 1044 Aliphatic alcohols, 1042 Aliphatic hydrocarbons See Alkanes Alkali metal(s), 53, 345, 897 coinage metals compared with, 352 electronegativity, 897 group trends of, 345 ionization energy, 897 properties of, 345, 897 reactions of, with oxygen, 346, 898 Alkali metal hydroxides, 667, 900 Alkaline earth metal(s), 53, 346, 902 properties of, 346, 901 Alkaline earth metal hydroxides, 667 amphoterism of, 696 Alkanes (aliphatic hydrocarbons), 68, 1026 nomenclature of, 1028 optical isomerism of substituted, 1032 reactions of, 1031 Alkenes (olefins), 1033 geometric isomers of, 1035 nomenclature of, 1034 properties and reactions of, 1034 Alkyl group, 1029 Alkyl halides, 1032 Alkynes, 1037 Allotropes, 55, 253 carbon, 55, 253, 449, 902 oxygen, 55, 932 phosphorus, 928 sulfur, 936 tin, 488 Alloys, 886 Alpha helix, 1069 Alpha (a) particles, 46 Alpha (a) rays See Alpha particles Alum, 905 Aluminum, 348, 903 metallurgy of, 903 recovery of, 906 Aluminum chloride (AlCl3), 692, 904 Aluminum hydride (AlH3), 905, 916 Aluminum hydroxide [Al(OH)3], 696, 905 Aluminum oxide (Al2O3), 348, 903 Aluminum sulfate [Al2(SO4)3)], 710 Amalgams, 871, 887 Amide group, 1069 Amide ion, 668, 925 Amines, 1046 Amino acids, 1068, 1070 (table) Aminobenzene (aniline), 1046 Ammonia (NH3), 925 as base, 132 in fertilizers, 108 ionization constant of, 678 ion product, 925 as Lewis base, 697 molecular geometry, 414, 429 preparation of, 596, 646 solubility of, 525 as solvent, 899 Ammonium chloride (NH4Cl), 691 Ammonium ion, 61, 132 Ammonium nitrate (NH4NO3), 108, 931 Amorphous solids, 486 Ampere (A), 869 Amphoteric hydroxide, 696, 754 Amphoteric oxides, 353, 695 Amplitude of wave, 276 Anaerobic organism, 1026 Analytical chemistry See Chemical analysis Angstrom (Å), 47 Angular momentum quantum number (l), 295 Anhydrous compounds, 67 Aniline (aminobenzene), 1046 Anions, 54 containing metal atoms, 963 electron configuration of, 329 hydrolysis, 690 names of, 61, 963 radius of, 333 Anode, 44, 842 sacrificial, 865 Antacids, 698 Antibonding molecular orbitals, 440 Antifreeze, 532 Antiknocking agent, 1048 Antitumor agents, 978 Aqua ligand, 963 Aqua regia, 927 Aqueous solution, 122 Argon, 351, 355 Aristotle, 42 Aromatic hydrocarbons, 1039 nomenclature of, 1039 properties and reactions of, 1040 Arrhenius, Svante, 130 Arrhenius acid-base theory, 130 Arrhenius equation, 583 Arsenic, 170, 1085 Art forgery, 1022 Artificial radioactivity, 999 Artificial snow, 239 Ascorbic acid See Vitamin C Aspirin (acetylsalicylic acid), 671, 698 Astatine, 350 Aston, Francis, 88 Atactic polymers, 1063 Atmospheric composition, 770 Atmospheric pollution See air pollution Atmospheric pressure, 176 boiling point and, 498 freezing point and, 498 standard, 177 Atom, 43 Dalton’s theory of, 42 emission spectrum of, 286 Greek theories of, 42 Rutherford’s model of, 46 structure of, 48 Thomson’s model of, 46 Atomic bomb, 50, 1003 Atomic mass, 80 Atomic mass unit (amu), 80 Atomic nucleus, 47 Atomic number (Z ), 49, 325 Atomic orbitals, 294, 297 electron assignment to, 305 energies of, 299 hybrid See Hybrid orbitals relationship between quantum numbers and, 295 Atomic radii, 331 Atomic theory See Atom I-1 I-2 Index Atomic weight See Atomic mass Aufbau principle, 307 Aurora borealis, 773 Autoionization of water, 661 Automotive emissions, 597, 789 Average atomic mass, 80 Average bond enthalpies, 394 Avogadro, Amedeo, 82, 184 Avogadro’s law, 184 Avogadro’s number, 82 Axial position, 413 B Bacteria fuel cell, 861 Balancing equations, 96, 838 equilibrium constant and, 628 nuclear reactions, 988 redox reactions, 838 Ball-and-stick model, 55 Balmer series, 286 Band theory, 894 Barium, 346, 902 Barium hydroxide [Ba(OH)2], 132, 667 Barium sulfate (BaSO4), 735 Barometer, 177 Bartlett, Neil, 352 Base(s), 67, 130, 660 Arrhenius, 130 Brønsted, 130, 660 general properties of, 130 ionization constant of, 678 Lewis, 697 strength of, 667 Base ionization constants (Kb), 678 relationship between acid ionization constants and, 680 Base pairs, 1077 Base strength, 667 Basic oxides, 353, 695 Basic oxygen process, 890 Batteries, 857 dry cell, 857 fuel cell, 860 lead storage, 858 mercury, 857 lithium ion, 859 Bauxite, 903 Becquerel, Antoine, 46 Belt of stability, 991 Benzene (C6H6), 1039 bonding in, 387, 448 electron micrograph of, 1039 structure of, 387, 448, 1039 Benzoic acid, 689, 1045 Beryl, 886 Beryllium, 346, 901 Beryllium chloride (BeCl2), 410, 430 Beryllium hydride (BeH2), 389 Beta (b) particles, 46 Beta pleated sheet, 1072 Beta (b) rays See Beta particles Bidentate ligands, 960 Big Bang theory, 10 Bimolecular reaction, 588 Binary compounds, 59 Binary hydrides, 916 Binding energy See Nuclear binding energy Biological effects of radiation, 1012 Biological nitrogen fixation, 771 Biosphere II, 226 Blast furnace, 889 Blood oxygen in, 525, 645, 724 pH of, 724 Body-centered cubic cell (bcc), 475 Bohr, Niels, 283 Bohr model, 283 Boiler scale, 129 Boiling point, 493 and intermolecular forces, 493 pressure and, 493, 498 vapor pressure and, 493 Boiling-point elevation, 531 Boltzmann, Ludwig, 202 Boltzmann constant, 805 Boltzmann equation, 805 Bomb calorimeter, 247 Bombardier beetle, 257 Bond(s) coordinate covalent, 390 of coordination compounds, 967 covalent See Covalent bonds dative, 390 double See Double bonds electronegativity and, 377 enthalpy, 394 hydrogen See Hydrogen bond ionic, 367, 369 length, 376 in metals, 485, 894 multiple, 375 pi, 437 polar covalent, 377 sigma, 437 single See Single bond in solids, 482 triple See Triple bonds Bond angles, 411, 415 Bond enthalpy, 394, 395 (table) Bond length, 376 Bond moments, dipole, 420 Bond order, 444 Bond polarity, 377 Bond strength, acid strength and, 685 Bonding molecular orbitals, 440 Bonding pairs, 410, 413 Boric acid, 697 Born, Max, 370 Born-Haber cycle, 369 Boron, 347 Boron neutron capture therapy, 1015 Boron trifluoride (BF3), 389, 430, 697 Bose, Satyendra, 210 Bose-Einstein condensate, 210 Boundary surface diagrams, 298 Boyle, Robert, 179 Boyle’s law, 179 Bragg, Sir William L., 481 Bragg, William H., 481 Bragg equation, 480 Brass, 514 Breathalyzer, 146 Breeder reactors, 1005 Bromine, 144, 350, 945 Bromine-formic acid reaction, 559 Brønsted, Johannes N., 130 Brønsted acid, 130, 660 Brønsted base, 130, 660 Brønsted acid-base theory, 130, 660 Buckminsterfullerine See Buckyball Buckyball, 449 Buffer solutions, 717 Buret, 16, 154 Butadiene, 1065 C Calcite See Calcium carbonate Calcium, 346, 902 Calcium carbide (CaC2), 921, 1037 Calcium carbonate (CaCO3), 753, 787, 902 decomposition of, 624, 818 production of iron, 889 sulfur dioxide removal with, 787 Calcium hydroxide [Ca(OH)2; slaked lime], 903 Calcium oxide (CaO; quicklime), 367, 787, 903 Calcium phosphate, 753, 930 Calorie, 251 Calorimeter constant-pressure, 249 constant-volume bomb, 247 Calorimetry, 245 Cancer, 1015 See also Carcinogenicity Capillary action, 469 Carbides, 921, 1037 Carbon, 348, 920 allotropes of, 55, 253, 449, 920 See also Diamond; Graphite atomic mass of, 80 in inorganic compounds, 59 phase diagram of, 920 in steelmaking, 891 Carbon cycle, 781 Carbon dioxide (CO2), 922 acidic properties, 696 bond moments of, 421 climate and, 781 enthalpy of formation of, 254 indoor pollutant, 793 phase diagram of, 499 photosynthesis and, 594, 783 solid (dry ice), 499 solubility of, 525, 526 toxicity of, 526 Carbon disulfide (CS2), 938 Carbon-12, 80 Carbon-14, 580, 998 Carbon-14 dating, 580, 998 Carbon monoxide (CO), 922 enthalpy of formation, 255 from automotive emissions, 597, 789 hemoglobin affinity for, 793 indoor pollutant, 793 metal purification with, 892 toxicity of, 793 Carbon tetrachloride (CCl4), 376, 1031 Carbonate ion, 382, 387, 449 Carbonic acid (H2CO3), 627, 681, 699 formation, 699, 724 ionization constants, 683 Carbonic anhydrase, 724, 753 Carbonyl group, 1044 Carborundum, 921 Carboxyhemoglobin, 793 Carboxyl group, 1044 Carboxylic acids, 1044 acid strength, 688 Carcinogenicity of amines, 1046 of ethylene dibromide, 945 of polycyclic aromatic hydrocarbons, 1041 of radiation, 1015 Carothers, Wallace, 1067 Cast (pig) iron, 890 Catalysis, 594 air pollution reduction by, 597 enzyme, 599 heterogeneous, 595 homogeneous, 598 Catalysts, 594 in catalytic converters, 597 effects of, on equilibrium, 643 enzymes as, 599 heterogeneous, 595 homogeneous, 598 Natta-Ziegler, 1064 Catalytic converters, 597 Catalytic rate constant (kc), 595 Catenation, 920, 1026 Cathode, 44, 842 Cathode ray(s), 44 Cathode ray tube, 44 Cathodic protection, 865 Cations, 54 electron configuration of, 329 hydrolysis of, 691 identification of, 754 ionic radius of, 333 nomenclature of, 61 Caustic soda See Sodium hydroxide Cell diagram, 843 Cell potential, 843 Cell voltage, 843 See also Electromotive force Cellulose, 710 Celsius temperature scale, 19 Cementite, 891 Cesium, 345 Chadwick, James, 48 Chain reaction, nuclear, 1002 Chalcopyrite (CuFeS2), 958 Chalk, 902 Chargaff, E., 1076 Chargaff’s rule, 1076 Charge cloud (electron charge cloud), 294 Charge-to-mass ratio (e/m), 44 Charles, Jacques, 182 Charles’s law (Charles’s and Gay-Lussac’s law), 183 Index Chelating agents, 961 Chemical analysis See also Qualitative analysis; Quantitative analysis with coordination compounds, 975 Chemical energy, 230 Chemical equations, 94 balanced See Balancing equations free elements in, 329 interpretation of, 95 Chemical equilibrium, 124, 616 Chemical formulas, 55 empirical, 56, 92 molecular, 55 structural, 56 Chemical kinetics, 558 Chemical properties, 15 Chemical reactions, 94 acid-base, 133, 153, 723 addition, 599, 1035, 1062 of alkanes, 1031 of alkenes, 1034 of alkynes, 1037 of aromatic compounds, 1040 bimolecular, 588 combination, 139 combustion, 141 condensation, 1042, 1067, 1068 of coordination compounds, 973 Dalton’s definition of, 42 decomposition, 141 displacement, 141 disproportionation, 144 first-order, 570 gases in, 194 half, 135 half-cell, 842 metathesis, 124 neutralization, 133, 153, 723 nuclear reactions compared with, 988 oxidation-reduction See Oxidation-reduction reactions precipitation, 124, 741 rate of See Rate of reaction second-order, 577 spontaneous, 802, 816 substitution, 1040 termolecular, 588 thermite, 904 unimolecular, 588 zero-order, 579, 601 Chemistry, Chernobyl, 1007 Chile saltpeter (NaNO3), 900 Chiral molecules, 960, 1032 Chlor-alkali process, 941 Chlorine, 350, 939 preparation of, 941 uses of, 944 Chlorine monoxide (ClO), 776 Chlorofluorohydrocarbons (CFCs), 776 Chloroform, (CHCl3), 1032 Chlorophyll, 952, 977 Chlorous acid (HClO2), 66, 944 Cholesterol, 1047 Chromium, 309, 954 Chromosomes, 1015 Cinnamic aldehyde, 1044 Cisplatin, 978 Cis-trans isomers of alkenes, 1035 of coordination compounds, 965 Clapeyron, Benoit, 491 Clausius, Rudolf, 491 Clausius-Clapeyron equation, 491 Climate carbon dioxide and, 781 effects of water on, 471 Closed system, 231 Closest packing, 470 Cloud seeding, 945 Coal, 920 Coal gasification, 923 Cohesion, 469 Coinage metals, 352 Coke, 888 Colligative properties of electrolyte solutions, 539 of nonelectrolyte solutions, 526 Collision theory, 582 Colloids, 541 Color of chlorophyll, 952 of glass, 488 of indicators, 734 of transition metal ions, 969 wavelength and, 278, 969 Color wheel, 969 Combination reaction, 139 Combustion, 141 of acetylene, 256, 1037 of alkanes, 1031 of hydrogen, 15, 232 of methane, 242, 1031 of sulfur, 139, 234 Common ion effect acid-base equilibria and, 714 solubility and, 744 Complex ion(s), 749, 959 magnetic properties of, 971 solubility equilibria and, 749 See also Coordination compounds Complex ion formation, 749 Compounds, 12 anhydrous, 67 aromatic See Aromatic hydrocarbons coordination See Coordination compounds in Dalton’s theory, 42 inorganic, 59 ionic, 53, 57, 369 molecular, 62 nonstoichiometric, 916 organic, 59, 68, 1026 Concentration, 147, 517 chemical equilibria and changes in, 638 effects on emf, 853 Concentration cells, 856 Concentration of solution, 147, 517 Concentration units, 147, 517 compared, 519 molality, 518 molarity, 147, 518 mole fraction, 198, 518 percent by mass, 517 Condensation, 490 Condensation reactions, 1042, 1067, 1068 Conduction band, 894 Conductivity of metals, 485, 894 of nonmetallic elements, 895 Conductor, 895 Conjugate acid, 660 Conjugate acid-base pair, 660, 680 Conjugate base, 660 Constant-pressure calorimeter, 249 Constant-volume bomb calorimeter, 247 Constructive interference, 441, 481 Contact process, 938 Control rods, 1004 Cooling curve, 496 Cooperativity, 1075 Coordinate covalent bonds, 390, 697 Coordination compounds, 959 applications of, 974 bonding in, 967 in living systems, 976 magnetic properties, 971 naming, 962 oxidation number, 961 reactions of, 973 stereochemistry of, 964 Coordination number, 475, 960 Coordination theory of Werner, 959 Copolymer, 1065 Copper, 958 corrosion of, 864 electron configuration of, 309 ionization energy of, 352 metallurgy of, 958 purification of, 892 Copper carbonate (CuCO3; patina), 864 Copper sulfate (CuSO4 ), 67 Core atomic See Nucleus noble gas, 307 nuclear reactor, 1004 Core electrons, 327 Corona, 320 Corrosion, 862 Corundum (Al2O3), 903 Coulomb (C), 849, 870 Coulomb, Charles, 369 Coulomb’s law, 369, 990 Coupled reactions, 825 Covalent bonds, 374 coordinate, 390 polar, 377 Covalent compounds, 374 Covalent crystals, 484 Covalent hydrides, 916 Cracking process, 1035 Crenation, 536 Crick, Francis, 1077 Critical mass, 1002 I-3 Critical pressure (Pc ), 494 Critical temperature (Tc), 494, 495 (table) Crown ether, 884 Crude oil, 1048 Cryolite (Na3AlF6), 904 Crystal(s), 485 covalent, 484 ionic, 482 metallic, 485 molecular, 484 X-ray diffraction by, 480 Crystal field splitting, 968 Crystal field theory, 968 Crystal structure, 472 Crystalline solids, 472 Crystallization, 514 fractional, 522 Cubic close-packed (ccp) structure, 477 Cubic unit cell, 474 Curie, (Ci), 1012 Curie, Marie, 46 Curie, Pierre, 46 Cyanide, 921 Cycloalkanes, 1033 Cyclohexane, 1033 Cyclotron, 1000 Cytochrome c, 977 Cytochrome oxidase, 921 Cytosine, 1077 D d Orbitals, 298, 968 and crystal field theory, 968 hybridization of, 435 Dacron, 1067 Dalton (atomic mass unit), 80 Dalton, John, 42 Dalton’s atomic theory, 42 Dalton’s law of partial pressures, 197 Daniell cell, 842 Data, Dating, radionuclear, 580, 998 with Prussian Blue, 984 Dative bonds, 390 Davisson, Clinton, 291 de Broglie, Louis, 288 de Broglie’s hypothesis, 288 Debye (D), 420 Debye, Peter J., 420 Decay series See Radioactive decay series Decomposition reactions, 141 Definite proportions, law of, 43 Delocalized molecular orbitals, 448 of benzene, 448 of carbonate ion, 449 of metals, 485, 894 Democritus, 42 Denaturant, 1076 Denatured alcohol, 1043 Denatured proteins, 766, 1076 Denitrification, 771 Density, 15 gas, 191 of nucleus, 990 water, 472 I-4 Index Dental amalgam, 871 Deoxyhemoglobin, 976, 1075 Deoxyribonucleic acid (DNA) See DNA Deposition, 497 Derived SI units, 18 Desalination, 541 Destructive interference, 441 Detergents, 975 Deuterium, 50, 917 Deuterium oxide, (D2O; heavy water), 917, 1004 Deviation from ideal gas behavior, 211 Dextrorotatory isomers, 966 Diagonal relationship, 344, 696, 916 Diagonal rule, 847 Diamagnetism, 303 Diamond as allotrope of carbon, 55, 253, 920 entropy of, 807 structure of, 484 synthetic, 921 Diaphragm cell, 941 Diatomic molecules, 53 heteronuclear, 783 homonuclear, 445, 783 Dichloroethylene, 422, 1035 Dichromate ion, 157, 838 Diethyl ether, 1043 Diffusion, gaseous, 208 Dilution of solutions, 149 Dimensional analysis, 27 Dimethylglyoxine, 975 Dinitrogen pentoxide (N2O5), 572 Dinitrogen tetroxide (N2O4), 616, 642 Dinosaurs, 38 Dipeptide, 1068 Dipolar ion, 1068 Dipole moments (m), 420, 422 (table) Dipole-dipole forces, 463 Dipole-induced dipole, 464 Dipositive ions, 333 Diprotic acids, 131, 681 ionization constant of, 683 Dispersion forces, 465 Displacement reactions, 141 Disproportionation reactions, 144 Distillation desalination by, 541 fractional, 529, 1048 metal purification by, 892 Distribution, 804 DNA (deoxyribonucleic acid), 1076 cisplatin binding to, 978 electron micrograph, 1077 fingerprinting by, 1083 structure of, 1078 Dolomite, 901 Donor atom, 960 Donor impurity, 895 Doping, 895 Double bonds, 375, 437 Doubling time, 1005 Downs cell, 866 Dry cell batteries, 859 Dry ice, 68, 499 Dynamic equilibrium, 490 E Earth age of, 998 composition of, 52 (table) EDTA (ethylenediaminetetraacetate), 960 treatment of metal poisoning with, 961 Effective nuclear charge, 330 Efficiency, 815 Effusion, gaseous, 209 Egg formation, 753 hard boiling, 500, 766 Einstein, Albert, 43, 210, 280, 993 Einstein’s mass-energy equation, 993 Einstein’s relativity theory, 993, 1001 Elastomers (synthetic rubber), 1065 Electrical work, 849 Electrocatalysts, 860 Electrochemical series, 142 Electrochemistry, 841 Electrode(s), 842 anode, 842 cathode, 842 Electrode potential See Standard reduction potential Electrolysis, 866 of aqueous sodium chloride, 867 metal purification by, 892 of molten sodium chloride, 866 quantitative aspects of, 869 of water, 866 Electrolyte(s), 122 strong, 122 weak, 122 Electrolyte solutions, colligative properties of, 534 Electrolytic cell, 866 Electromagnetic radiation, 277 Electromagnetic wave, 277 Electromotive force (emf), 843 effects of concentration on, 852 standard, 843 Electron(s), 44 charge-to-mass ratio of, 44 nonbonding See Lone pairs probability distribution of, 298 valence, 327 Electron affinity, 341, 342 (table) Electron capture, 992 Electron charge, 44 Electron charge cloud, 294 Electron configuration, 301 anions, 329 Aufbau principle and, 307 cations, 329 diamagnetism and paramagnetism in, 302 electron assignment to orbitals in, 301 ground state, 301, 308 Hund’s rule and, 304 and molecular orbitals, 443 Pauli exclusion principle and, 302 and shielding effect, 303 Electron density, 294 Electron microscope, 292 Electron probability, 294, 298 Electron spin, 296, 302 in coordination compounds, 971 Hund’s rule and, 304 Pauli exclusion principle and, 302 Electron spin quantum number (ms), 296 Electron subshell, 295 Electron-dot symbols, 366 Electronegativity, 377 Elementary particles, 988 Elementary steps, 588 Elements, 11 abundance, 52 atomic radii of, 331 classification of, 51, 326 derivation of names and symbols, A-1 electron affinity of, 341 electronegativity of, 377 essential, 52 ground state electron configurations of, 301 (table), 327 ionization energies of, 338 (table) periodic and group properties of, 344 representative, 326 symbols of, 12 (table) transuranium See Transuranium elements Emf See Electromotive force Emission spectra, 280 Empirical formula, 56, 92 Emulsion, 541 Enantiomers, 966 End point, 732 Endothermic process, 232 Energy, 230 chemical, 230 crystal field splitting, 968 of hydrogen atom, 284 ionization, 337 kinetic See Kinetic energy lattice See Lattice energy law of conservation of, 230 mass-energy conversion, 993 molecular orbital energy level diagram, 441 nuclear binding See Nuclear binding energy potential See Potential energy solar See Solar radiation thermal See Heat unit of, 202 Energy changes in chemical reactions, 241 and first law of thermodynamics, 234 Enthalpy (H ), 240 and Born-Haber cycle, 369 standard, 253 Enthalpy of reaction, 241 Enthalpy of solution, 258 Entropy (S), 803 absolute, 807, 813 changes, 805 and microstate, 804 phase transition, 820 standard, 807 Environmental pollution acid rain, 695, 785 Freon, 776 nuclear wastes, 1006 sulfur dioxide, 695 thermal, 523, 1004 Enzyme(s), 599 alcohol dehydrogenase, 1042 carbonic anhydrase, 724, 753 catalysis of, 599 cytochrome oxidase, 921 hexokinase, 600 HIV-protease, 451 lock-and-key model of, 600 Enzyme-substrate intermediate (ES), 601 Equation Arrhenius, 583 Boltzmann, 805 chemical, 94 Clausius-Clapeyron, 491 Einstein, 993 Henderson-Hasselbach, 715 ideal gas, 185 ionic, 127 molecular, 126 Nernst, 853 net ionic, 127 nuclear, 988 redox, 838 Schrödinger, 293 thermochemical, 242 van der Waals, 212 Equatorial position, 413 Equilibrium, 124, 617 catalyst effect on, 643 and chemical kinetics, 630 and concentration changes, 638 dynamic, 490 free energy and, 821 heterogeneous, 624 homogeneous, 619 liquid-solid, 495 liquid-vapor, 489 multiple, 627 solid-vapor, 497 and temperature changes, 642 volume and pressure changes and, 640 Equilibrium constant (K), 618, 821 balanced equation and, 628 and equilibrium concentration calculations, 634 in heterogeneous equilibrium, 624 in homogeneous equilibrium, 619 and law of mass action, 618 in multiple equilibria, 627 units, 621 Equilibrium vapor pressure, 490 Index Equivalence point in acid-base titrations, 154, 723 in redox titrations, 156 Erythrocytes See red blood cells Escape velocity, 208 Essential elements, 52 Esters, 1045 Ethane (C2H6), 1027 Ethanol (C2H5OH), 92, 1042 Ethers, 1043 Ethyl acetate (CH3COOC2H5), 598, 1046 Ethyl group (C2H5), 1029 Ethylene (C2H4), 1033 bonding in, 375, 437 in polymerization, 1063 Ethylene dibromide, 945 Ethylene glycol [CH2(OH)CH2(OH)], 532, 1043 Ethylenediamine, 960 Ethylenediaminetetraacetate See EDTA Eutrophication, 975 Evaporation See Vaporization Excess reagent, 103 Excited level (excited state), 285 Exothermic processes, 232 Expanded octet, 390 Expanded valence shell, 390, 436 Explosives, 901, 931, 1003 Exponential notation See Scientific notation Extensive properties, 15 F f Orbitals, 298, 309 Face-centered cubic unit cell (fcc), 475, 477 Factor label method, 27 Farenheit temperature scale See Temperature scales Family of elements, 51 Faraday, Michael, 849, 1039 Faraday constant (F ), 849 Femtochemistry, 593 Fermentation, 781, 1042 Ferromagnetic substances, 887 Fertilizers, 108 Fingerprints, 1058 First law of thermodynamics, 233 First-order reactions, 570 Fischer, Emil, 600 Fission reactions, 1001 Fission reactors, 1003 Flame test, 755 Flotation method, 886 Fluorapatite, 108 Fluoridation, 944 Fluorine, 350, 939 fluoridation with, 944 mass defect of, 992 oxidation number of, 140, 380 preparation of, 940 uses, 944 Fluorite (CaF2), 482, 902 Flux, 889 Food irradiation, 1014 Force, 176 adhesive, 469 dispersion, 465 intermolecular See Intermolecular forces intramolecular, 463 unit of, 176 van der Waals, 463 Formal charge, 384 Formaldehyde (CH2O), 439, 793, 1044 Formation constant (Kf), 749, 750 (table) Formic acid (HCOOH), 559, 671, 1045 Formula mass, 87 Formulas See Chemical formulas Fossil fuels, 918, 1048 Fractional crystallization, 522 Fractional distillation, 529, 1049 Fractional precipitation, 742 Fractionating column, 529, 1049 Francium, 337 Frasch, Herman, 935 Frasch process, 935 Fraunhofer, Josef, 320 Free energy (G), 815 chemical equilibria and, 821 and electrical work, 849 in phase transition, 820 spontaneity and, 816 standard free energy of reaction, 816 temperature and, 818 Free radicals, 1013, 1031 Freezing, desalination by, 541 Freezing point, 495 Freezing-point depression, 532 Freons, 776, 943 Frequency (n), 276 Frequency factor (A), 583 Fresh water, 541 Fuel, fossil See Fossil fuels Fuel cell, 862 Fuel value, 251 Functional groups, 68, 1026, 1047 (table) Fusion entropy and, 820 molar heat of, 496 (table) nuclear, 1007 effusion of See Effusion emission spectrum of, 280 kinetic molecular theory of, 203 monatomic, 172 noble See Noble gases pressure of, 175 solubility of, 523, 524, 526 Gas constant (R), 185 units of, 185, A-7 van der Waals, 213 (table) Gasoline, 1048 antiknocking agents in, 1048 Gastric juice, 698 Gauge pressure, 272 Gay-Lussac, Joseph, 182 Geiger, Hans, 47 Geiger counter, 1012 Genetic effects of radiation, 1015 Geobacter, 861 Geometric isomer(s), 965, 1035 Geometric shapes of orbitals, 298, 433 Gerlach, Walther, 296 Germer, Lester, 291 Gibbs, Josiah, 815 Gibbs free energy See Free energy Glass, 486, 489 (table) Glass electrode, 855 Glucose (C6H12O6), 710, 1042 Glutamic acid, 1070, 1074 Glycerol, 470 Glycine, 1070 Gold extraction of, 921 ionization energy of, 352 oxidation of, 927 Goodyear, Charles, 1065 Gram (g), 17 Graham, Thomas, 208 Graham’s law of diffusion, 208 Graphite, 55, 253, 484, 920 as covalent crystal, 484 entropy of, 807 Gravimetric analysis, 151 Greenhouse effect, 781 Ground state (ground level), 285 Group (periodic), 51 Guanine, 1077 Guldberg, Cato, 618 Gunpowder, 901 Gypsum (CaSO4 ? 2H2O), 902, 935 G H Gallium, 324 Galvanic cells, 841 Galvanized iron, 865 Gamma (g) rays, 46 Gamow, George, 10 Gangue, 886 Gas(es), 13, 172 Avogadro’s law, 184 Boyle’s law, 179 Charles’s law, 183 in chemical reactions, 194 Dalton’s law of partial pressure of, 197 density of, 191 diffusion of See Diffusion H2 See also Hydrogen; Hydrogen atom Lewis structure of, 374 molecular orbitals of, 441 potential energy of, 426 Haber, Fritz, 370, 590 Haber process, 596, 646 Hair, 1084 Half-cell potential See Standard reduction potential Half-cell reactions, 842 Half-life, 337, 575 of carbon-14, 580 of cobalt-60, 575, 1009 of first-order reactions, 575 I-5 of francium-223, 337 of iodine-125, 1011 of iodine-131, 1011 of plutonium-239, 1007 of potassium-40, 998 of radon-222, 791 of second-order reactions, 578 of sodium-24, 575, 1011 of technetium-99, 1012 of tritium, 917, 1000 of uranium-238, 998 of zero-order reactions, 580 Half-reaction, 135 Halic acids, 686, 943 Halides, 351, 942 alkali metal, lattice energy and, 372 alkyl, 1032 hydrogen See Hydrogen halides phosphorus, 929 solubility of, 125 Hall, Charles, 903 Hall process, 903 Halogen(s), 53, 350, 939 displacement of, 143 electronegativity, 939 industrial and biological roles of, 944 ionization energy, 939 oxoacids, 65, 943 preparation of, 940 properties of, 940 Halogenation of alkanes, 1031 Hard water, 129 Heat, 231, 238 of dilution, 260 of fusion, 496 of hydration, 259 of solution, 258 of vaporization, 490 Heat capacity (C), 246 Heat content See Enthalpy Heat engine, 814 Heating curve, 496 Heavy water See Deuterium oxide Heavy water reactor, 1004 Heisenberg, Werner, 293 Heisenberg uncertainty principle, 293 Helium, 351 boiling point of, 465 discovery of, 320 escape velocity of, 208 formation of, 995 intermolecular forces in, 465 ionization energy of, 338 primordial, 10 Hematite (Fe2O3), 957 Heme group, 976, 1075 Hemoglobin (Hb) binding of oxygen, 525, 645, 976, 1075 as buffer, 724 carbon monoxide affinity for, 793 production of, 645 structure of, 976, 1073 Hemolysis, 535 Henderson-Hasselbach equation, 715 Henry, William, 524 I-6 Index Henry’s law, 524, 526 Hertz (Hz), 277 Hess, Germain H., 255 Hess’s law, 255, 259, 371 Heterogeneous catalysis, 595 Heterogeneous equilibria, 624 Heterogeneous mixture, 11 Heteronuclear diatomic molecules, 783 Hexagonal close-packed (hcp) structure, 477 Hexamethylenediamine, 1067 Hexokinase, 600 High-spin complexes, 971 High-temperature superconductor, 486 Hindenburg, 232 Hiroshima, 1003 HIV, 450 Homogeneous catalysis, 598 Homogeneous equilibria, 619 Homogeneous mixture, 11 Homonuclear diatomic molecules, 445, 783 Homopolymers, 1063 Human immunodeficiency virus See HIV Hund, Fredrick, 304 Hund’s rule, 304, 443, 447, 971 Hybrid orbitals, 428, 433 (table) of molecules with double and triple bonds, 437 sp, 430, 438 sp2, 430, 437 sp3, 428 sp3d, 436 sp3d2, 435 Hybridization, 428 Hydrate, 67, 1038 Hydration, 123, 259 heat of, 259 of ions, 123, 259, 806 of protons, 131, 660 Hydrazine (N2H4), 925 Hydrides binary, 916 covalent, 916 interstitial, 916 ionic, 916 phosphorus, 928 Hydrocarbons, 68, 1026 aliphatic See Alkanes alkynes See Alkynes aromatic See Aromatic hydrocarbons cycloalkanes, 1033 saturated, 1026 unsaturated, 1033, 1037, 1039 Hydrochloric acid (HCl), 131, 686 in acid-base titrations, 723, 730 as monoprotic acid, 131 preparation of, 942 Hydrocyanic acid (HCN), 671, 921 Hydrofluoric acid (HF) ionization constant of, 671 as weak acid, 672 Hydrogen, 345, 914 atomic orbitals of, 297 combustion of, 15, 232 displacement of, 141 isotopes of, 50, 917 metallic, 919 oxidation number of, 138 preparation of, 915 properties of, 345, 915 Hydrogen atom Bohr’s theory of, 282 emission spectrum of, 283 energy of, 284 Schrödinger equation and, 293 Hydrogen bomb, 1009 Hydrogen bond 467, 1069, 1072 Hydrogen bromide (HBr), 943 Hydrogen chloride (HCl), 943 Hydrogen cyanide (HCN), 175, 921 Hydrogen economy, 918 Hydrogen fluoride (HF), 377, 420, 943 Hydrogen halides, 942 acid strength of, 685 dipole moments of, 422 Hydrogen iodide (HI), 943 kinetics of formation, 590 Hydrogen ion hydrated, 131, 660 pH and concentration, 664 Hydrogen molecule (H2) combustion, 15, 232 Lewis structure, 374 molecular orbital, 441 Hydrogen peroxide (H2O2), 933 decomposition of, 144, 562, 590 disproportionation, 144 as oxidizing agent, 933 percent composition by mass of, 89 as reducing agent, 933 Hydrogen sulfide (H2S), 936 as diprotic acid, 681 preparation of, 936 in qualitative analysis, 755 Hydrogenation, 918 Hydrogen-oxygen fuel cell, 862, 919 Hydrohalic acids, 686, 942 Hydrolysis alkaline (saponification; base hydrolysis), 1046 of anions, 690, 723 of esters, 592, 1046 metal ion, 692 salt, 689 Hydrometer, 859 Hydronium ion (H3O1), 131, 660 Hydrophilic interaction, 541 Hydrophobic interaction, 541, 1074 Hydroxides alkali metal, 667, 696, 900 alkaline earth metal, 667, 696 amphoteric, 696 Hydroxyapatite, 735, 903 Hydroxyl groups (OH groups), 1042 Hydroxyl radical, 779, 786, 1013 Hypertonic solution, 535 Hypochlorous acid, 65, 943 Hypothesis, Hypotonic solution, 535 I Ice, 471 ICE method, 634 Ice skating, 500 Ice-water equilibrium, 495 Ideal gas, 185 Ideal gas equation, 185 Ideal solution, 529 Impurities acceptor, 896 donor, 895 Incomplete octet, 389 Indicators See acid-base indicators Induced dipole, 464 Inert complexes, 974 Infrared active, 783 Initial rate, 566 Inorganic compounds, 59 Instantaneous rate, 560 Insulators, 895 Intensive properties, 15 Interference of waves, 441, 481 Intermediates, 588 Intermolecular forces, 174, 463 dipole-dipole forces, 463 dispersion forces, 465 ion-dipole forces, 463 ion-induced dipole, 464 van der Waals forces, 463 Internal energy, 234 International System of Units (SI units), 16 International Union of Pure and Applied Chemistry See IUPAC Interstitial hydrides, 916 Intramolecular forces, 463 Iodine, 350, 939 nuclear stability of, 994 preparation of, 144, 942 sublimation of, 497 uses of, 945 Iodine-131, 1011 Ion(s), 54 dipositive, 333 electron configuration of, 329 hydrated, 123, 259 hydrolysis, 689 monatomic, 54 polyatomic, 54 separation of, by fractional precipitation, 742 spectator, 127 transition metal, 60, 955, 970 tripositive, 333 unipositive, 333 Ion pairs, 539 Ion product constant, 662 Ion-dipole forces, 463 Ion-electron method, 838 Ion-induced dipole, 464 Ionic bond, 367, 369, 379 Ionic compounds, 53, 57 nomenclature, 59 Ionic crystals, 482 Ionic equation, 127 Ionic hydrides, 916 Ionic radii, 333 Ionic solids (ionic crystals), 482 Ionization constants of bases, 679 of diprotic and polyprotic acids, 683 of monoprotic acid, 671 Ionization energy, 337, 338 (table) Ionizing radiation, 1013 Ion-product constant of water (Kw), 662 Ionosphere, 773 Iridium, 38 Iron, 957 corrosion of, 862 ferromagnetic properties of, 887 galvanized, 865 metallurgy of, 888 Iron sulfide (FeS), 767 Isoelectronic ions, 330 Isolated system, 231 Isomer(s) geometric, 965, 1035 optical, 965, 1032 of polymers, 1063 structural, 1025 Isomerism See Isomer(s) Isoprene, 1064 Isopropanol, 1043 Isotactic polymers, 1063 Isotonic solution, 535 Isotopes, 49, 917, 1010 applications of, 594, 974, 1010, 1011 IUPAC, 51, 327, 1029 J Jeffreys, Alec, 1083 Joule (J), 202 Joule, James Prescott, 202 Jupiter, 208, 919 K Kekulé, August, 387, 1039 Kelvin, Lord (William Thomson), 183 Kelvin temperature scale, 19, 183 Keratin, 1084 Ketones, 1044 Kilogram (kg), 17 Kinetic energy, 203, 230 Kinetic isotope effect, 916 Kinetic molecular theory of gases, 203 liquids and solids in, 462 Kinetics See Chemical kinetics Krypton, 351 L Labile complexes, 974 Lachrymator, 789 Lake Nyos, 526 Lanthanide series See Rare earth series Index Laser, 288, 1009 Lattice energy (U), 259, 369, 372 (table) of alkali metal halides, 372 and Born-Haber cycle, 369 and chemical formulas, 372 Lattice point, 473 Laue, Max von, 480 Laughing gas (nitrous oxide), 68, 926 Law, Law(s) Avogadro’s, 184 Boyle’s, 179 Charles’, 183 of conservation of energy, 230 of conservation of mass, 43 Coulomb’s, 369, 990 Dalton’s, of partial pressures, 197 of definite proportions, 43 first law of thermodynamics, 233 Graham’s, of diffusion, 208 Henry’s, 524, 526 Hess’s, 255, 259, 371 of mass action, 618 of multiple proportions, 43 of octaves, 324 Raoult’s, 527 rate, 565 second law of thermodynamics, 808 third law of thermodynamics, 812 Le Chatelier, Henri L., 638 Le Chatelier’s principle, 638 acid ionization and, 677, 732 chemical equilibrium and, 638 common ion effect and, 714, 744 and eggshell formation, 753 emf and, 856 solubility equilibria and, 744 Lead, 348 tetraethyl, 1049 tetramethyl, 1049 treatment of, 961 Lead-206, 998 Lead chamber process, 599 Lead storage batteries, 858 Leclanché cell, 857 Length, SI base unit of, 18 Levorotatory isomers, 966 Lewis acid, 697 Lewis base, 697 Lewis acid-base theory, 697 Lewis dot symbols, 366 Lewis, Gilbert N., 366 Lewis structures, 375 formal charge and, 384 octet rule and, 375 and resonance concept, 386 Lexan, 1060 Libby, Willard F., 581 Ligands, 959, 960 (table) strong-field, 971 weak-field, 971 Light absorption of, and crystal field theory, 969 electromagnetic theory of, 277 particle-wave duality of, 280 plane-polarized, 960 speed of, 277 Light water reactors, 1003 Lime, 787, 903 Limestone See Calcium carbonate Liming, 785, 903 Limiting reagents, 103 Line spectra, 283 Linear molecule, 411, 430 Liquid(s), 13, 469 properties of, 462 (table) solutions of liquids in, 514 solutions of solids in, 514 surface tension in, 469 viscosity of, 470 Liquid crystals, 501 Liquid-solid equilibrium, 495 Liquid-vapor equilibrium, 489 Liter (L), 18 Lithium, 345 Lithium deuteride (LiD), 1009 Lithium fluoride (LiF), 367 Lithium oxide (Li2O), 346 Litmus, 130 Living systems coordination compounds in, 976 thermodynamics of, 825 Lock-and-key theory, 600 Logarithm, A-13 London forces See Dispersion forces London, Fritz, 464 Lone pairs, 374 Low-spin complexes, 971 Lucite (Plexiglas; polymethyl methacrylate), 1066 M Macromolecules See Polymers Macroscopic properties, 16 Magic number, 990 Magnesium, 158, 346, 901 band theory of, 894 cathodic protection with, 865 combustion, 135 preparation, 158 Magnesium hydroxide [Mg(OH)2], 158, 699, 746, 902 Magnesium nitride (Mg3N2), 902 Magnesium oxide (MgO), 135, 902 Magnetic confinement, 1008 Magnetic field of electromagnetic waves, 277 electron spin and, 296, 302 Magnetic quantum number (ml), 295 Magnetism, 302 of complex ions, 971 diamagnetism, 302, 971 ferromagnetism, 887 paramagnetism, 295, 440, 971 of transition metals, 971 Magnetite (Fe3O4), 957 Main group elements, 326 Manganese dioxide (MnO2), 200, 594 Manganese nodules, 887 Manometer, 178 Many-electron atoms, 294 Marble, 902 Markovnikov, Vladimir, 1035 Markovnikov’s rule, 1035 Marsden, Ernest, 47 Marsh, James, 170 Marsh gas See methane Marsh test, 170 Martian Climate Orbiter, 21 Mass, 15 atomic See Atomic mass critical, 1002 defect, 992 electron, 44 formula, 87 molar, 82, 192, 536 molecular, 85 percent composition by See Percent composition by mass SI base unit of, 17 of subatomic particles, 49 subcritical, 1002 Mass action, law of, 618 Mass defect, 992 Mass number (A), 49 Mass spectrometer, 88 Mass-energy conversion, 43, 993 Matter, 10 classification of, 13 conservation of, 43 Maxwell, James, 202 Maxwell speed distribution, 205 Mean square speed, 204 Mechanical work, 235 Melting, entropy and, 820 Melting point, 495 of alkali metal halides, 372 of alkali metals, 337 of diamond, 484 of francium, 337 pressure and, 498 of quartz, 484 Membrane potential, 856 Mendeleev, Dmitri, 344 Mercury in almalgam, 871, 887 in barometers, 177 mineral extraction with, 887 Mercury batteries, 857 Mercury oxide (HgO), 141, 232, 803 Mesosphere, 773 Metabolism, 826 Metal(s), 51, 485, 851 alkali See Alkali metal(s) alkaline earth See Alkaline earth metal(s) bonding in, 485, 894 coinage, 352 displacement reactions, 142 corrosion See Corrosion in ionic compounds, 61 occurrence of, 886 preparation of, 886 properties of, 50, 878 purification of, 892 Metal hydrides, 910 Metal ion electron configurations, 329 hydrolysis of, 692 radii, 333 I-7 Metallic bonds, 485, 894 Metallic crystals, 485 Metallic elements, 51, 886, 954 See also Metal(s) Metalloids, 51 Metallurgy, 886 coordination compounds in, 892, 922 pyrometallurgy, 888 Metathesis reaction, 124 Meter, 18 Methane (CH4), 1026 combustion of, 242, 1021 hydrate, 1038 molecular geometry of, 412, 429 Methanol (CH3OH), 417, 1043 Methyl acetate, 592 Methyl chloride, 1031 Methyl group, 1029 Methyl radical, 1032 Methyl propyl ether (neothyl), 1044 Methylene chloride, 1031 Methyl-tert-butyl ether (MTBE), 1049 Metric unit, 16 Meyer, Lothar, 324 Microscopic properties, 16 Microstate, 804 Microwave oven, 424 Microwaves, 278, 424 Milk of magnesia, 699, 746, 902 Millikan, Robert, 44 Mineral, 886 (table) Miscible liquids, 516 Mixture, 11 gas, law of partial pressures and, 197 heterogeneous, 11 homogeneous, 11 racemic, 960 Moderator, 1003 Molal boiling-point elevation constant, 531 Molal freezing-point depression constant, 532 Molality (m), 518 Molar concentration, 147 Molar heat of fusion, 496 (table) sublimation, 497 of vaporization, 490, 492 (table) Molar mass, 82, 192, 536 Molar solubility, 737 Molarity (M ), 147, 518 Mole, 81 Mole fraction (X ), 198, 518 Mole method, 99 Molecular compounds, 62 Molecular crystals, 484 Molecular equation, 126 Molecular formula, 55, 93 Molecular geometry, 410 of coordinating compounds, 964 of cycloalkanes, 1033 Molecular mass, 85 Molecular models, 55 Molecular orbital theory, 440 I-8 Index Molecular orbitals, 440 bonding and antibonding, 440 configurations of, 443 delocalized, 448 energy level diagram of, 441, 442, 444, 445, 446 Molecular rotation, 806 Molecular shapes See Molecular geometry Molecular speed, 205 distribution of, 205 root-mean-square, 206 Molecular vibration, 783, 806 Molecular weight See Molecular mass Molecularity, 588 Molecules, 53 chemical formulas and, 55 chiral, 960, 1032 diatomic, 53 linear, 411, 430 nonpolar, 421 odd-electron, 390 planar, 412, 430, 437 polar, 421 polyatomic, 53 Monatomic gases, 174 Monatomic ions, 54 Mond, Ludwig, 892 Mond process, 892 Monodentate ligands, 960 Monomers, 1062, 1066 (table) Monoprotic acids, 131, 671 Moseley, Henry, 325 Most probable speed, 205 Multiple bonds, 375, 437 Multiple equilibria, 627 Multiple proportions, law of, 43 Myoglobin, 976 N N2 See Nitrogen n -type semiconductors, 895 Nagasaki, 1003 Naming compounds See Nomenclature Naphthalene (C10H8), 1041 Napoleon, 170, 488 Natta, Giulio, 1064 Natural gas, 1026 Natural polymers, 1064, 1067 Negative deviation, 529 Neon, 88, 351 Neoprene (polychloroprene), 1065 Neothyl, 1044 Neptunium, 1005 Nernst, Walter, 853 Nernst equation, 853 Net ionic equation, 127 Neutralization reactions, 133, 153, 723 Neutron, 48, 988 Neutron activation analysis, 171 Newlands, John, 324 Newton (N), 21, 176 Newton, Sir Isaac, 176 Newton’s second law of motion, 9, 21, 176 Nickel, 955 chemical analysis of, 975 extraction of, 892 Nitric acid (HNO3), 668, 927 Oswald process in production of, 597 as oxidizing agent, 926 as strong acid, 668 structure of, 382 Nitric oxide (NO), 393, 926 Nitride ion, 924 Nitrogen, 349, 924 bonding in, 375, 447 common compounds of, 924 (table) preparation of, 924 Nitrogen cycle, 770 Nitrogen dioxide (NO2), 616, 642, 926 in smog formation, 789 Nitrogen fixation, 771 Nitrogen narcosis, 203 Nitrogen pentoxide (N2O5), 572 Nitroglycerin, 393 Nitrous oxide N2O (laughing gas), 68, 926 Noble gas core, 307 Noble gases, 53, 351, 355 Node, 289, 441 Noguchi, Thomas, 554 Nomenclature of acids, 65 of acids and their conjugate bases, 668 (table) of alkanes, 1028 of alkenes, 1034 of alkynes, 1037 of anions, 61 (table), 963 (table) of aromatic compounds, 1039 of bases, 67 of cations, 61 (table) of common compounds, 68 (table) of coordination compounds, 962 of inorganic compounds, 59, 64 of molecular compounds, 62, 64 of oxoacids, 66 (table) of oxoanions 66 (table) of simple acids 65 (table) Nonbonding electrons, 374 Nonelectrolyte(s), 122 Nonelectrolyte solutions, colligative properties of, 526 Nonideal gas behavior, 211 Nonmetal, 51, 914 Nonmetallic elements, 51, 914 Nonmetallic oxides, 353, 932 Nonpolar molecule, 421 Nonspontaneous reactions, 802 Nonstoichiometric compounds, 916 Nonvolatile solutes, 527 Nuclear binding energy, 992 nuclear stability and, 993 per nucleon, 994 of uranium, 1002 Nuclear chain reaction, 1002 Nuclear chemistry, 988 Nuclear decay series, 996 Nuclear energy from fission reactors, 1003 from fusion reactors, 1008 hazards of, 1005 Nuclear equation, 988 Nuclear fission, 1001 reactions, 1001 reactors, 1003 Nuclear fusion, 1007 Nuclear reactions, 988 balancing, 988 and decay series, 995 fission, 1001 fusion, 1007 moderator of, 1003 nature of, 988 by transmutation, 988, 999 Nuclear reactors, 1003, 1008 breeder, 1005 fission, 1003 fusion, 1008 heavy water, 1004 light water, 1003 natural, 1006 thermal pollution and, 1004 Nuclear stability, 990 Nuclear transmutation, 988, 999 Nuclear wastes, 1007 Nucleic acids, 1076 Nucleons, 992 Nucleotide, 1077 Nucleus, 47 density of, 990 radius of, 990 Nylon (polyhexamethylene adipamide), 1067 Nylon rope trick, 1067 O O2 See also Oxygen preparation of, 932 properties of, 932 solubility, 523, 525 O3 See Ozone Octahedron, 412 Octane number, 1048 Octaves, law of, 324 Octet rule, 375 exceptions to, 389 Odd-electron molecules, 390 Oil as fossil fuel, 918, 1048 in ore preparation, 886 Oil, hydrogenated, 599, 918 Olefins See Alkenes Oleum, 938 Open system, 231 Optical isomers, 965, 1032 Orbitals See Atomic orbitals; Hybrid orbitals; Molecular orbitals Ores, 886 preparation of, 886 roasting of, 786, 887 Organic chemistry, 1026 Organic compounds, 59, 68, 1026 Organic polymers See Polymers Orientation factor, 587 Orthoclase See Phosphoric acid Osmosis, 534 Osmotic pressure (p), 534 Ostwald, Wilhelm, 597 Ostwald process, 597 Otto cycle, 1048 Overlap in hybridization of atomic orbitals, 428 in molecular orbitals, 440 in valence bond theory, 426 Overvoltage, 868 Oxalic acid, 638 Oxidation numbers, 136 assignment of, 138, 380 of halogens, 140 of metals in coordination compounds, 956 of nonmetallic elements, 140 of transition elements, 140, 956 Oxidation reactions, 135 Oxidation states See Oxidation numbers Oxidation-reduction reactions (redox reactions), 135 balancing equations of, 838 quantitative aspects of, 156 spontaneous, 849 Oxides acidic, 353, 695, 932 amphoteric, 353, 695, 933 basic, 353, 695, 933 Oxidizing agent, 136 Oxoacid, 65, 686, 943 Oxoanion, 66 Oxyacetylene torch, 256, 1037 Oxygen, 350, 932 alkali metal reactions with, 346, 897 allotropes of, 53, 932 in blood, 525, 645, 724 hemoglobin and, 525, 645, 724, 976, 1075 molecular orbital theory of, 440, 447 oxidation number of, 140, 380 paramagnetism, 440 and photosynthesis, 594, 771 preparation of, 932 Oxygen cycle, 771 Oxygen-hydrogen fuel cell, 862 Oxygen-propane fuel cell, 862 Oxyhemoglobin, 525, 645, 724, 976, 1075 Ozone, 55, 934 depletion of, 775 preparation of, 934 properties of, 934 resonance structure of, 386 in smog formation, 789 P p Orbitals, 298 P4, structure of, 928 p-type semiconductors, 896 Packing efficiency, 476 Palladium, 917 Index Paramagnetism, 303, 440, 971 Partial pressure, 196 Dalton’s law of, 197 Particle accelerators, 1000 Particle theory of light, 280 Particle-wave duality, 280, 288 Pascal (Pa), 176 Pascal, Blaise, 176 Passivation, 864 Patina, 864 Pauli, Wolfgang, 302 Pauli exclusion principle, 302, 441, 443 Pauling, Linus, 377, 1069, 1074 Penetrating power, 303 Pentane (C5H12), 1027 Peptide bond, 1068 Percent composition by mass, 89, 517 Percent composition by weight See Percent composition by mass Percent hydrolysis, 690 Percent ionic character, 379 Percent ionization, 677 Percent yield, 106 Perchloric acid (HClO4), 66, 668, 687, 943 Perhalic acids, 943 Period, 51 Periodic group, 51 Periodic table, 51, 324 atomic radii trends in, 333 electron affinity trends in, 342 electronegativity trends in, 378 families in, 51 groups in, 51 historical development of, 324 ionization energy trends in, 339 periods of, 51 Permanent wave, 1084 Permanganate ion, as oxidizing agent, 157 Peroxide, 346, 932, 1043 Peroxyacetyl nitrate (PAN), 789 Petroleum, 1048 pH, 663 of acid-base titrations, 710 of acid rain, 783 blood, 724 of buffer solutions, 718 common ion effect on, 714 solubility equilibria and, 746 pH meter, 664, 723, 855 Phase, 462 Phase changes, 489 effects of pressure on, 498 and entropy, 820 liquid-solid, 495 liquid-vapor, 489 solid-vapor, 497 Phase diagrams, 498, 499, 531, 920 Phenolphthalein, 154, 733 Phenyl group, 1040 Phosphate buffer, 722 Phosphate rocks, 108, 927 Phosphine, 928 Phosphoric acid (H3PO4), 131, 685, 930 ionization constant of, 683 Phosphorus, 349, 927 allotropes of, 928 in fertilizers, 109 Phosphorus acid (H3PO3), 930 Phosphorus(V) oxide (P4O10), 929 Phosphorus(III) oxide (P4O6), 929 Phosphorus pentachloride (PCl5), 929 Phosphorus trichloride (PCl3), 929 Photochemical smog, 789 Photodissociation, 775 Photoelectric effect, 280 Photons, 280 Photosynthesis, 594, 770, 1010 carbon dioxide and, 594, 783 chlorophyll in, 977 isotope applications to, 594, 1010 oxygen and, 594, 771 Physical equilibrium, 616 Physical properties, 14 Pi (p) bond, 437 Pi (p) molecular orbitals, 443 Pig (cast) iron, 890 Pipet, 16 pKa, 715 Planck, Max, 276, 279 Planck constant (h), 279 Plane-polarized light, 966 Plants in carbon cycle, 781 osmotic pressure in, 536 Plasma, 1008 Platinum as catalyst, 597, 790 as electrocatalyst, 860 therapeutic uses of complexes of, 978 Plato, 42 Plutonium-239, 1005 pOH, 664 Polar bonds, 377 Polar covalent bonds, 377 Polar molecules, 421 Polar ozone hole, 777 Polar solvent, 123 Polarimeter, 966 Polarizability, 464 Polaroid film, 966 Pollution See Environmental pollution Polyatomic ions, 54 Polyatomic molecules, 53 Polychloroprene (neoprene), 1065 Poly-cis-isoprene, 1064 Polycyclic aromatic hydrocarbons, 1041 Polydentate ligands, 960 Polyester, 1067 Polyethylene, 1063 Polyisopropene See Rubber Polymer(s), 1062, 1066 (table) Polymerization by addition, 1062 by condensation, 1067, 1068 Polypeptide, 1068 Polypropenes, 1063 Polyprotic acids, 131, 685 Polytetrafluoroethylene (Teflon), 944, 1063 Poly(vinyl chloride), 1063 Porphine, 976 Porphyrins, 976 Positive deviation, 529 Positron, 988, 989 Potassium, 345, 898 Potassium-40, 998 Potassium chlorate (KClO3), 200, 594 Potassium dichromate (K2Cr2O7), 146, 157, 838 Potassium hydrogen phthalate, 153 Potassium hydroxide (KOH), 900 Potassium nitrate (KNO3), 900 Potassium permanganate (KMnO4), 157, 839 Potassium superoxide (KO2), 345, 899 Potential See Standard reduction potential Potential energy, 230 Precipitate, 124 Precipitation reaction, 124, 741 ion separation by fractional, 742 Precision, 27 Prefixes nomenclature, 63 (table) SI unit, 17 (table) Pressure, 175 atmospheric See Atmospheric pressure chemical equilibrium and changes in, 640 critical, 494 gas, 175 osmotic, 534 partial, 196 phase changes and, 498 SI unit, 175 vapor See Vapor pressure Pressure cookers, 500 Pressure-volume relationship of gas, 179 Primary pollutant, 789 Primary structure, 1072 Primary valence, 959 Principal quantum number (n), 284, 295 Probability, in electron distribution, 294, 298 Problem solving, 28, 83, 634 Product, 95 Propane, 1027 Propane-oxygen fuel cell, 862 Propene, 1035 Properties chemical, 15 extensive, 15 intensive, 15 macroscopic, 16 microscopic, 16 physical, 14 Propyne (methylacetylene), 1037 Protein, 1067 denatured, 766, 1076 structure of, 1069 Protium, 917 Proton, 47, 988 Proust, Joseph, 43 I-9 Prussian blue, 984 Pyrex glass, 489 Pyrite, 935 Pyrometallurgy, 888 Q Quadratic equation, 673, A-14 Qualitative analysis, 754 Qualitative data, Quantitative analysis, 151 See also Acid-base titrations gravimetric, 151 of redox reactions, 156 Quantitative data, Quantum, 279 Quantum mechanics, 293 Quantum numbers, 294 angular momentum, 295 electron spin, 296 magnetic, 295 principal, 284, 295 Quantum theory, 276 Quartz crystalline, 484 melting point of, 484 structure of, 488 Quaternary structure, 1072 Quicklime (See Calcium oxide) R Racemic mixture, 960 Rad, 1012 Radiant energy, 230 Radiation, 44 biological effect of, 1012 climate and, 781 electromagnetic, 277 ionizing, 1013 solar See also Solar radiation Radiation dose, 1012 Radicals, 392, 1013, 1032 Radioactive decay series, 995 Radioactive isotopes, 1010 Radioactive waste disposal, 1007 Radioactivity, 45 artificial, 999 biological effects of, 1012 natural, 995 nuclear stability and, 990 Radiocarbon dating, 580, 998 Radiotracers, 1010 Radium, 1012, 1022 Radius atomic, 331 ionic, 333 nuclear, 990 Radon, 351, 355, 791 Ramsay, Sir William, 355 Raoult, Francois, 527 Raoult’s law, 527 Rare earth series, 309 Rate constant, 561 Rate-determining step, 589 Rate law, 565 Rate of reaction, 558 and stoichiometry, 563 I-10 Index Rays alpha, 46 beta, 46 gamma, 46 RBE (relative biological effectiveness), 1013 Reactants, 95 Reaction See Chemical reactions; Nuclear reactions Reaction mechanisms, 588 elementary steps, 588 experimental study, 592 and molecularity of reaction, 588 Reaction order, 566 determination of, 566 first-order, 570 second-order, 577 zero order, 579, 601 Reaction quotient (Q), 632, 737, 821, 852 Reaction rate, 558 Reaction yield, 106 Reactors See Nuclear reactors Red blood cells (erythrocytes), 724, 1075 Red cabbage, 734 Red phosphorus, 928 Redox reactions See Oxidationreduction reactions Redox titration, 156 Reducing agent, 136 Reduction potential See Standard reduction potential Reduction reaction, 135 electrolytic, 888 of minerals, 888 Refining of metals, 892 Relative biological effectiveness (RBE), 1013 Relativity, theory of, 993, 1001 Rem, 1013 Representative (main group) elements, 326 Residue, 1068 Resonance, 387 Resonance structure, 387 Reverse osmosis, 542 Reversible reaction, 124 Reversible renaturation, 1076 Ribonucleic acid See RNA RNA, 1076 Roasting of ores, 786, 791 Rocks age determination of, 998 phosphate, 109, 927 Röntgen, Wilhelm, 45 Root-mean-square speed, 206 Rotation about bonds, 1035 molecular, 806 of plane-polarized light, 966 Rotational motion, 806 Rubber (poly-cis-isopropene), 1064 natural, 1064 structure, 826, 1064 synthetic, 1065 thermodynamics of, 826 vulcanization, 1065 Rubbing (isopropyl) alcohol, 1043 Ruby laser, 286 Rust, 8, 862 Rutherford, Ernest, 47, 325, 999 Rydberg, Johannes, 284 Rydberg constant (RH), 284 S s Orbitals, 297 S8, structure of, 936 Sacrificial anode, 865 Salt(s), 133 hydrolysis of, 689 Salt bridge, 842 Salt hydrolysis, 689 Saltpeter (KNO3), 900 Saponification, 1046 Saturated hydrocarbons, 1026 See also Alkanes Saturated solutions, 514 SBR (styrene-butadiene rubber), 1065 Scanning electron microscope, 292 Scattering experiment, 47 Schrödinger, Erwin, 293 Schrödinger equation, 293 Scientific method, 8, 10 Scientific notation, 22 Scuba diving, 202 Seawater composition of 541 (table) desalination of, 541 Second law of motion, 9, 21, 176 Second law of thermodynamics, 808 Secondary pollutant, 789 Secondary structure, 1072 Secondary valence, 959 Second-order reactions, 577 Seed crystals, 514 Semiconductors, 895 Semipermeable membrane, 534 SHE (standard hydrogen electrode), 843 Shell, 295 Shielding constant, 330 Shielding effect, 303, 331 Shroud of Turin, 580 SI units (International System of Units), 16 Sickle cell anemia, 292, 1074 Sigma (s) bonds, 437 Sigma (s) molecular orbital, 441 Significant figures, 23, 665, A-13 Silica glass See Quartz Silicon, 348 doping of, 895 purification of, 893 Silicon carbide (SiC; carborundum), 921 Silicon dioxide (SiO2), 484, 488 Silk, 1072 Silver corrosion of, 864 extraction of, 921 ionization energy of, 352 Silver bromide (AgBr), 739, 945 Silver chloride (AgCl) fractional precipitation of, 742 gravimetric analysis of, 152 solubility and, 735 Silver iodide (AgI), 945 Simple cubic cell (scc), 475 Simplest formula, 56, 92 Single bond, 375 Slag, 889 Slaked lime [calcium hydroxide, Ca(OH)2], 902 Smelting of ores, 786, 887 Smog, 789 Snowmaking, 239 Soap, 544 Soda ash (sodium carbonate, Na2CO3), 900 Soda lime glass, 489 Sodium, 345, 898 production of, 866 reaction with water, 141 Sodium acetate (CH3COONa), 514, 714, 718 Sodium acetate-acetic acid system, 714, 718 Sodium bicarbonate (NaHCO3), 68 Sodium carbonate (Na2CO3; soda ash), 900 Sodium chloride (NaCl), 57, 373, 376, 899 electrolysis of aqueous, 867 electrolysis of molten, 866 melting ice with, 532 structure of, 57 Sodium fluoride, 944 Sodium hydroxide (NaOH; caustic soda), 900 in saponification, 1046 in titrations, 153, 723 Sodium nitrate (NaNO3), 900 Sodium peroxide, 346 Sodium stearate, 544 Sodium tripolyphosphate, 975 Soft water, 129 Solar energy, 230 Solar radiation as energy source, 230 in hydrogen preparation, 919 oxygen balance and, 776 ozone protecting from, 775 Solder, 514 Solids characteristic properties of, 13, 469 solutions of, in liquids, 514 temperature and solubility of, 522 See also Crystal(s) Solid-vapor equilibrium, 497 Solubility, 125, 737 common ion effect and, 744 gas, 523, 524, 526 molar, 737 rules of, 125 and temperature, 521 Solubility equilibria, 735 common ion effect and, 744 complex ions and, 749 in fractional precipitation, 742 pH and, 746 Solubility product, 735, 736 (table) molar solubility and, 740 (table) qualitative analysis of, 754 Solutes, 122 nonvolatile, 527 volatile, 528 Solution(s), 122 concentration units, 147, 517 dilution of, 149 electrolyte, colligative properties of, 539 heat of, 258 ideal, 529 isotonic, hypertonic, and hypotonic, 535 nonelectrolyte, colligative properties of, 526 saturated, 514 standard, 153 stock, 149 supersaturated, 514 types of, 514 unsaturated, 514 Solution process, 515 Solution stoichiometry, 151, 153, 156, 723 Solvation, 516 Solvay, Ernest, 900 Solvay process, 900 Solvent, 122 Somatic effects of radiation, 1015 Sorensen, Soren P., 663 sp Hybridization, 430, 438 sp2 Hybridization, 430, 437 sp3 Hybridization, 428 sp3d Hybridization, 436 sp3d2 Hybridization, 435 Space shuttle glow, 775 Space-filling model, 55 Specific heat (s), 246 Spectator ions, 127 Spectrochemical series, 970 Spectrum absorption, 559, 969 emission, 280 visible See Visible spectrum Speed of electromagnetic waves, 277 of light, 277 Maxwell speed distribution, 205 Root-mean-square, 206 Spin See Electron spin Spontaneous processes, 802, 816 Square planar complex, 973 Stability belt of, 991 nuclear, 991 Stability constant See Formation constant Stable nucleus, 991 Stainless steel, 890 Stalactites, 712 Stalagmites, 712 Standard atmospheric pressure, 177 Standard cell potential, 843 Index Standard electrode potential, 843 See also Standard reduction potential Standard emf, 843 Standard enthalpy of formation (DH°f ), 252, A-8 Standard enthalpy of reaction, 253 Standard entropies (So), 807, A-8 Standard entropy of reaction, 809 Standard free energy of formation (DG°f ), 816, A-8 Standard free energy of reaction, 816 Standard hydrogen electrode, (SHE), 843 Standard reduction potential, 843, 846 (table) of transition elements, 955 Standard solution, 153 Standard state, 252, 816 Standard temperature and pressure, (STP), 186 Standing waves, 288 State excited, 285 ground, 285 oxidation See Oxidation numbers standard, 252, 816 thermodynamic, 233 State functions, 233 State of a system, 233 Staudinger, Hermann, 1062 Steel, 890 Stereoisomers, 964, 1035, 1063 Stern, Otto, 296 Stock, Alfred, 60 Stock solution, 149 Stock system, 60 Stoichiometric amounts, 103 Stoichiometry, 99 actual, theoretical, and percentage yields in, 106 and gas reactions, 194 rate of reaction and, 563 Stone leprosy, 785 STP (standard temperature and pressure), 186 Straight-chain alkanes, 68, 1027 Stratosphere, 773 Strength of acids and bases, 66, 685 molecular structure and acid, 685 Strong acids, 666 Strong bases, 667 Strong-field ligands, 971 Strontium, 347 Strontium-90, 347 Structural formula, 55 Structural isomers, 1025 Structure, acid strength and, 685 Strutt, John William (Lord Rayleigh), 355 Styrene-butadiene rubber (SBR), 1065 Subatomic particles, 41, 49, 988 Subcritical mass, 1002 Sublimation, 497 Subshell, 295 Substance, 11 Substituted alkanes, optical isomerism of, 1032 Substitution reactions, 1040 Substrates, 600 Subunits, 976, 1073 Sulfur, 350, 935 allotropes of, 936 combustion of, 139, 234 common compounds of, 936 deposits at volcanic sites, 780 extraction by Frasch process, 935 in vulcanization process, 1065 Sulfur dioxide (SO2), 937 in acid rain, 785 Lewis structure of, 414 Sulfur hexafluoride (SF6), 390, 413, 435, 494, 938 Sulfur tetrafluoride (SF4), 413 Sulfur trioxide (SO3), 786, 937 Sulfuric acid (H2SO4), 937 in batteries, 858 as diprotic acid, 131, 681, 937 heat of dilution, 260 as oxidizing agent, 938 production of, 937 as strong acid, 666 Sun See also Solar radiation emission spectrum of, 320, 782 nuclear fusion in, 1007 Superconductors, 6, 486 Supercooling, 497 Superoxide ion, 346, 932 Supersaturated solution, 514 Surface tension, 469 Surroundings, 231, 811 Syndiotactic polymers, 1063 Syngas, 923 Synthetic rubbers (elastomers), 1065 System closed, 231 defined, 231 isolated, 231 open, 233 state of, 227 T Technetium-99, 1012 Teflon (polytetrafluoroethylene), 944, 1063 Temperature chemical equilibria and changes, 642 critical, 494 and rate of reaction, 583 solubility and, 521 and water vapor pressure, 200 (table) Temperature scales Celsius, 19, 183 Farenheit, 19 Kelvin, 19, 183 Temporary dipole, 465 Termites, 1026 Termolecular reactions, 588 Ternary compound, 60 Tertiary structure, 1072 Tetracarbonylnickel [Ni(CO4)], 892 Tetraethyllead [(C2H5)4Pb], 1049 Tetrahedral complex, 973 Tetrahedron, 412 Theoretical yield, 106 Theory, Therapeutic chelating agents, 978 Thermal energy, 230 Thermal motion, 204 Thermal (slow) neutrons, 1001 Thermal pollution, 523, 1004 Thermite reaction, 904 Thermochemical equation, 242 Thermochemistry, 228, 231 Thermodynamic efficiency, 815, 862 Thermodynamics, 233, 800 first law of, 233 in living systems, 825 second law of, 808 third law of, 812 Thermonuclear bomb, 1009 Thermonuclear reactions, 1007 Thermosphere, 773 Thioacetamide, 937 Thiosulfate ions, 1010 Third law of thermodynamics, 812 Thomson, George, 291 Thomson, Joseph, 44, 46 Thorium-232, 1005 Three Mile Island nuclear reactor, 1007 Threshold frequency, 280 Thymine, 1077 Thyroid gland, 1011 Thyroxine, 945 Time SI unit of, 17 Tin, 348, 488 Tincture of iodine, 945 Titanium dioxide, 710 Titanium(III) chloride (TiCl3), 1064 Titration acid-base, 153, 723 redox, 156 Titration curve, 726, 728, 731 Tokamak, 1008 Toluene, 529 Tooth decay, 871 Torr, 177 Torricelli, Evangelista, 177 Toxicity of arsenic, 170, 1085 of carbon dioxide, 526, 793 of carbon monoxide, 793 of carbon tetrachloride, 1032 of chloroform, 1032 of cyanide, 921 of deuterium oxide, 916 of formaldehyde, 793 of gases, 175 of hydrogen sulfide, 937 of methanol, 1043 of ozone, 789, 934 of plutonium-239, 1007 of radon-222, 791 of smog, 789 of strontium-90, 347 I-11 of sulfur dioxide, 937 of tetracarbonylnickel, 892 of white phosphorus, 928 Tracers, 1010 Trans isomers see Cis-trans isomers Transition metal(s), 60, 309, 954 electron configuration, 330, 954 oxidation numbers of, 140, 956 properties of, 954 Transition metal oxides, 696 Transition state, 583 Translational motion, 806 Transmutation, nuclear, 988, 999 Transpiration, 536 Transuranium elements 1000 (table) Triethylaluminum [Al(C2H5)3], 1064 Trigonal bipyramid, 412 Trinitrotoluene (TNT), 1003 Triple bonds, 375, 438 Triple point, 498 Tripolyphosphate, 975 Tripositive ion, 333 Triprotic acid, 131, 685 Tritium, 50, 917, 1000 Trona, 900 Troposphere, 771 Tungsten, 888 Tyndall, John, 541 Tyndall effect, 541 Tyvek, 1063 U Uncertainty principle, 293 Unimolecular reaction, 588 Unipositive ion, 333 Unit, SI, 16 Unit cells, 473 Unsaturated hydrocarbons, 1033 Unsaturated solutions, 514 Unshared electron pairs, 374 Uranium fission product of, 1002 isotopes of, 50 Uranium decay series, 995 Uranium oxide (U3O8), 1004 Uranium-235, 50, 1001, 1002, 1003 Uranium-238, 50 abundance of, 1005 dating with, 998 decay of, 996 Urea in fertilizer, 109 preparation of, 109, 1025 treatment of sickle-cell anemia, 1075 V Valence, 959 Valence band, 894 Valence bond theory, 424 Valence electrons, 327 Valence shell, 410 Valence shell expansion, 436 I-12 Index Valence-shell electron-pair repulsion (VSEPR) model, 410 and molecules in which central atom has no lone pairs, 410 and molecules in which central atom has one or more lone pairs, 413 Valine, 1074 Van der Waals, Johannes, 212 Van der Waals constants 213 (table) Van der Waals equation, 212 Van der Waals forces, 463 Van Meegeren, Han, 1022 Vanadium oxide (V2O5), 937 van’t Hoff, Jacobus, 534 van’t Hoff factor, 539 Vapor, 175 Vapor pressure, 200, 490 Vaporization (evaporation), 490 entropy and, 805 molar heat of, 490, 492 (table) Vapor-pressure lowering, 527 Vector, 420 Vermeer, Jan, 1022 Vibrational motion, 782, 806 Viscosity, 470 Visible spectrum, 278, 969 Vision, 1036 Vitamin C, 671 Volatile solutes, 528 Volcanoes, 780 Volt, 849 Voltage, 842 See also Electromotive force Voltaic (galvanic) cell, 841 Voltmeter, 842 Volume, 15 chemical equilibria and changes in, 640 constant, 247 SI unit of, 18 Volumetric flask, 16, 147 VSEPR See Valence-shell electron-pair repulsion model Vulcanization, 1065 W Waage, Peter, 618 Waste disposal, radioactive waste, 1007 Water acid-base properties of, 661 autoionization of, 661 density of, 472 dipole moment of, 422 electrolysis of, 866 fluoridation of, 944 hard, 129 hydrogen bonds in, 471 ion product constant of, 662 as moderator, 1003 phase diagram of, 499 soft, 129 specific heat of, 246, 471 structure of, 471 surface tension of, 469 vapor pressure of, 200 (table) vibrational motions, 782, 806 viscosity of, 470 Water gas, 914 Water vapor, pressure of 200 (table) Watson, James, 1077 Watt, 907 Wave function, 293 Wave mechanics, 294 Wavelength, 276 color and, 278, 969 radiation and, 278 Wave-particle duality, 280, 288 Waves, 276 amplitude, 276 electromagnetic, 277 frequency, 276 interference, 441, 451 length, 276 properties of, 276 standing, 288 Weak acids defined, 667 ionization constants of, 671, 683 strong base reactions with, 727 Weak bases defined, 668 ionization constants of, 678 strong acid reactions with, 730 Weak-field ligands, 971 Weight, 17 atomic See Atomic mass molecular See Molecular mass percentage, composition by See Percentage composition by mass Werner, Alfred, 959 White lead [Pb3(OH)2(CO3)2], 1022 White phosphorus, 928 Wohler, F., 1025 Wood alcohol See Methanol Wood’s metal, 555 Work, 230, 235 electrical, 849 free energy and, 849 and gas expansion, 236 X X rays, 45 diffraction of, 480 periodic table and, 325 Xenon, 351 Y Yields actual, 106 percent, 106 theoretical, 106 Z Zero electron density (node), 289, 441 Zero-order reactions, 579, 601 Ziegler, Karl, 1064 Zincblende, 482 Zinc in batteries, 857 cathodic protection with, 865 Zinc sulfide (ZnS), 44 Zone refining, 893 ... (a) (b) Figure 11.15 The seven types of unit cells Angle a is defined by edges b and c, angle b by edges a and c, and angle g by edges a and b b a α β c γ Simple cubic a=b=c α = β = γ = 90° Tetragonal... (a) A corner atom in any cell is shared by eight unit cells (b) An edge atom is shared by four unit cells (c) A facecentered atom in a cubic cell is shared by two unit cells Closest Packing Clearly... transdichloroethylene shown on p 422 can be interconverted by heating or irradiation (a) Starting with cis-dichloroethylene, show that rotating the CPC bond by 1808 will break only the pi bond but will leave