General chemistry the essential concepts 6th edition 2

cha75632_ch11_363-398.indd Page 378 378 CHAPTER 11 10/27/09 5:00:18 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 Introduction to Organic Chemistry Properties and Reactions of Alkynes The simplest alkyne is ethyne, better known as acetylene (C2H2) The structure and bonding of C2H2 were discussed in Section 10.5 Acetylene is a colorless gas (b.p 284°C) prepared in the laboratory by the reaction between calcium carbide and water: CaC2 (s) 2H2O(l) ¡ C2H2 (g) Ca(OH) (aq) Industrially, it is prepared by the thermal decomposition of ethylene at about 1100°C: C2H4 (g) ¡ C2H2 (g) H2 (g) Acetylene has many important uses in industry Because of its high heat of combustion 2C2H2 (g) 5O2 (g) ¡ 4CO2 (g) 2H2O(l) The reaction of calcium carbide with water produces acetylene, a flammable gas DH° 22599.2 kJ/mol acetylene burned in an “oxyacetylene torch” gives an extremely hot flame (about 3000°C) Thus, oxyacetylene torches are used to weld metals (see p 200) Acetylene is unstable and has a tendency to decompose: C2H2 (g) ¡ 2C(s) H2 (g) In the presence of a suitable catalyst or when the gas is kept under pressure, this reaction can occur with explosive violence To be transported safely, it must be dissolved in an inert organic solvent such as acetone at moderate pressure In the liquid state, acetylene is very sensitive to shock and is highly explosive Being an unsaturated hydrocarbon, acetylene can be hydrogenated to yield ethylene: C2H2 (g) H2 (g) ¡ C2H4 (g) It undergoes these addition reactions with hydrogen halides and halogens: CHqCH(g) HX(g) ¡ CH2“CHX(g) CHqCH(g) X2 (g) ¡ CHX“CHX(g) CHqCH(g) 2X2 (g) ¡ CHX2OCHX2 (l) Methylacetylene (propyne), CH3OCqCOH, is the next member in the alkyne family It undergoes reactions similar to those of acetylene The addition reactions of propyne also obey Markovnikov’s rule: H 3C CH OCqCOH ϩ HBr 888n Propyne Can you account for Markovnikov’s rule in this molecule? propyne H G D CPC D G Br H 2-bromopropene R EVIEW OF CONCEPTS How could an alkene and an alkyne be distinguished by using only a hydrogenation reaction? cha75632_ch11_363-398.indd Page 379 9/16/09 9:16:34 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 379 11.3 Aromatic Hydrocarbons 11.3 Aromatic Hydrocarbons Benzene (C6H6) is the parent compound of this large family of organic substances As we saw in Section 9.8, the properties of benzene are best represented by both of the following resonance structures (p 304): mn Benzene 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 carbon-hydrogen bonds, and the CCC and HCC angles are all 120° Therefore, each carbon atom is sp2-hybridized; it forms three sigma bonds with two adjacent carbon atoms and a hydrogen atom (Figure 11.14) 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 351, 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 11.15) In the ethylene molecule, the overlap of the two 2pz orbitals gives rise to a bonding and an antibonding molecular orbital, which are localized over the two C atoms The interaction of the 2pz orbitals in benzene, however, leads to the formation of 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 An electron micrograph of benzene molecules, which shows clearly the ring structure 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 H C H C C C H Top view H C Side view C H H Figure 11.14 The sigma bond framework of the benzene molecule Each C atom is sp2-hybridized and forms sigma bonds with two adjacent C atoms and another sigma bond with an H atom (a) (b) Figure 11.15 (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 cha75632_ch11_363-398.indd Page 380 9/16/09 9:16:41 PM user-s180 380 CHAPTER 11 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 Introduction to Organic Chemistry 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 As we will see shortly, electron delocalization imparts extra stability to aromatic hydrocarbons 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 Nomenclature of Aromatic Compounds The naming of monosubstituted benzenes, that is, benzenes in which one H atom has been replaced by another atom or a group of atoms, is quite straightforward, as shown next: CH2CH3 A ethylbenzene Cl A NH2 A chlorobenzene NO2 A aminobenzene (aniline) nitrobenzene If more than one substituent is present, we must indicate the location of the second group relative to the first The systematic way to accomplish this is to number the carbon atoms as follows: Three different dibromobenzenes are possible: Br A Br Br A Br A E H Br 1,2-dibromobenzene (o-dibromobenzene) 1,3-dibromobenzene (m-dibromobenzene) A Br 1,4-dibromobenzene (p-dibromobenzene) The prefixes o- (ortho-), m- (meta-), and p- (para-) are also used to denote the relative positions of the two substituted groups, as just shown for the dibromobenzenes Compounds in which the two substituted groups are different are named accordingly Thus, NO2 A H Br is named 3-bromonitrobenzene, or m-bromonitrobenzene cha75632_ch11_363-398.indd Page 381 9/16/09 9:16:49 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 11.3 Aromatic Hydrocarbons 381 Finally we note that the group containing benzene minus a hydrogen atom (C6H5) is called the phenyl group Thus, the following molecule is called 2-phenylpropane: This compound is also called isopropylbenzene (see Table 11.2) A CH3OCHOCH3 Properties and Reactions of Aromatic Compounds Benzene is a colorless, flammable liquid obtained chiefly from petroleum and coal tar Perhaps the most remarkable chemical property of benzene is its relative inertness Although it has the same empirical formula as acetylene (CH) and a high degree of unsaturation, it is much less reactive than either ethylene or acetylene The stability of benzene is the result of electron delocalization In fact, benzene can be hydrogenated, but only with difficulty The following reaction is carried out at significantly higher temperatures and pressures than are similar reactions for the alkenes: H H A EH H H H H GD H G DH HO O Pt ϩ 3H2 8888n catalyst OH HO G E HH D H H DG H A H H H cyclohexane We saw earlier that alkenes react readily with halogens and hydrogen halides to form addition products, because the pi bond in CPC can be broken more easily The most common reaction of halogens with benzene is substitution For example, H H E H H A H E A H HH FeBr3 ϩ Br2 8888n catalyst Br A H EH E H HH H A H ϩ HBr bromobenzene Note that if the reaction were addition, electron delocalization would be destroyed in the product H H A H H E A H Br D H O OBr G H and the molecule would not have the aromatic characteristic of chemical unreactivity A catalyst is a substance that can speed up the rate of a reaction without itself being used up More on this topic in Chapter 14 cha75632_ch11_363-398.indd Page 382 9/16/09 9:16:57 PM user-s180 382 CHAPTER 11 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 Introduction to Organic Chemistry Figure 11.16 Some polycyclic aromatic hydrocarbons Compounds denoted by * are potent carcinogens An enormous number of such compounds exist in nature Naphthalene Anthracene Benz(a)anthracene* Phenanthrene Naphthacene Dibenz(a,h)anthracene* Benzo(a)pyrene Alkyl groups can be introduced into the ring system by allowing benzene to react with an alkyl halide using AlCl3 as the catalyst: CH2CH3 A AlCl ϩ CH3CH2Cl 8888n catalyst ethyl chloride ϩ HCl ethylbenzene An enormously large number of compounds can be generated from substances in which benzene rings are fused together Some of these polycyclic aromatic hydrocarbons are shown in Figure 11.16 The best known of these compounds is naphthalene, which is used in mothballs These and many other similar compounds are present in coal tar Some of the compounds with several rings are powerful carcinogens—they can cause cancer in humans and other animals R EVIEW OF CONCEPTS Benzene has sp2-hybridized carbon atoms and multiple bonds However, unlike ethylene, geometric isomerism is not possible in benzene Explain 11.4 Chemistry of the Functional Groups We now examine some organic functional groups, groups that are responsible for most of the reactions of the parent compounds In particular, we focus on oxygen-containing and nitrogen-containing compounds Alcohols All alcohols contain the hydroxyl functional group, OOH Some common alcohols are shown in Figure 11.17 Ethyl alcohol, or ethanol, is by far the best known It is produced biologically by the fermentation of sugar or starch In the absence of oxygen the enzymes present in bacterial cultures or yeast catalyze the reaction enzymes C6H12O6 (aq) O¡ 2CH3CH2OH(aq) 2CO2 (g) C2H5OH ethanol cha75632_ch11_363-398.indd Page 383 9/16/09 9:17:01 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 11.4 Chemistry of the Functional Groups H A HOCOOH A H H H A A HOCOC OOH A A H H H H H A A A HOC OCOC OH A A A H OH H Methanol (methyl alcohol) Ethanol (ethyl alcohol) 2-Propanol (isopropyl alcohol) OH Figure 11.17 Common alcohols Note that all the compounds contain the OH group The properties of phenol are quite different from those of the aliphatic alcohols H H A A H O CO CO H A A OH OH Phenol Ethylene glycol This process gives off energy, which microorganisms, in turn, use for growth and other functions Commercially, ethanol is prepared by an addition reaction in which water is combined with ethylene at about 280°C and 300 atm: H SO CH2“CH2 (g) H2O(g) O¡ CH3CH2OH(g) Ethanol has countless applications as a solvent for organic chemicals and as a starting compound for the manufacture of dyes, synthetic drugs, cosmetics, and explosives It is also a constituent of alcoholic beverages Ethanol is the only nontoxic (more properly, the least toxic) of the straight-chain alcohols; our bodies produce an enzyme, called alcohol dehydrogenase, which helps metabolize ethanol by oxidizing it to acetaldehyde: alcohol CH3CH2OH OOO ¡ CH3CHO H2 dehydrogenase acetaldehyde This equation is a simplified version of what actually takes place; the H atoms are taken up by other molecules, so that no H2 gas is evolved Ethanol can also be oxidized by inorganic oxidizing agents, such as acidified potassium dichromate, to acetic acid: 3CH3CH2OH 2K2Cr2O7 8H2SO4 ¡ 3CH3COOH 2Cr2 (SO4 ) orange-yellow green 2K2SO4 11H2O This reaction has been employed by law enforcement agencies to test drivers suspected of being drunk A sample of the driver’s breath is drawn into a device called a breath analyzer, where it is reacted with an acidic potassium dichromate solution From the color change (orange-yellow to green) it is possible to determine the alcohol content in the driver’s blood Ethanol is called an aliphatic alcohol because it is derived from an alkane (ethane) The simplest aliphatic alcohol is methanol, CH3OH Called wood alcohol, it was prepared at one time by the dry distillation of wood It is now synthesized industrially by the reaction of carbon monoxide and molecular hydrogen at high temperatures and pressures: Fe2O3 CO(g) 2H2 (g) O ¡ CH3OH(l) catalyst methanol 383 Left: A K 2Cr2O7 solution Right: A Cr2(SO4)3 solution cha75632_ch11_363-398.indd Page 384 384 CHAPTER 11 10/27/09 5:00:32 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 Introduction to Organic Chemistry Methanol is highly toxic Ingestion of only a few milliliters can cause nausea and blindness Ethanol intended for industrial use is often mixed with methanol to prevent people from drinking it Ethanol containing methanol or other toxic substances is called denatured alcohol The alcohols are very weakly acidic; they not react with strong bases, such as NaOH The alkali metals react with alcohols to produce hydrogen: 2CH3OH 2Na ¡ 2CH3ONa H2 sodium methoxide However, the reaction is much less violent than that between Na and water: 2H2O 2Na ¡ 2NaOH H2 Alcohols react more slowly with sodium metal than water does Two other familiar aliphatic alcohols are 2-propanol (or isopropyl alcohol), commonly known as rubbing alcohol, and ethylene glycol, which is used as an antifreeze Most alcohols—especially those with low molar masses—are highly flammable Ethers Ethers contain the ROOOR9 linkage, where R and R9 are a hydrocarbon (aliphatic or aromatic) group They are formed by the reaction between an alkoxide (containing the RO2 ion) and an alkyl halide: NaOCH3 CH3Br sodium methoxide CH3OCH3 methyl bromide ¡ CH3OCH3 NaBr dimethyl ether Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric acid at 140°C C2H5OH C2H5OH ¡ C2H5OC2H5 H2O This reaction is an example of a condensation reaction, which is characterized by the joining of two molecules and the elimination of a small molecule, usually water Like alcohols, ethers are extremely flammable When left standing in air, they have a tendency to slowly form explosive peroxides: CH3 A C2H5OC2H5 ϩ O2 88n C2H5OOCOOOOOH A diethyl ether H 1-ethyoxyethyl hydroperoxide Peroxides contain the OOOOO linkage; the simplest peroxide is hydrogen peroxide, H2O2 Diethyl ether, commonly known as “ether,” was used as an anesthetic for many years It produces unconsciousness by depressing the activity of the central nervous system The major disadvantages of diethyl ether are its irritating effects on the respiratory system and the occurrence of postanesthetic nausea and vomiting “Neothyl,” or methyl propyl ether, CH3OCH2CH2CH3, is currently favored as an anesthetic because it is relatively free of side effects cha75632_ch11_363-398.indd Page 385 9/16/09 9:17:08 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 11.4 Chemistry of the Functional Groups 385 Aldehydes and Ketones Under mild oxidation conditions, it is possible to convert alcohols to aldehydes and ketones: CH3OH ϩ 12 O2 88n H2CPO ϩ H2O formaldehyde H3C C2H5OH ϩ O2 88n H G D CPO ϩ H2O acetaldehyde H H3C A G CPO ϩ H2O CH3OCOCH3 ϩ O2 88n D A H3C OH CH3CHO acetone The functional group in these compounds is the carbonyl group, H ECPO In an aldehyde at least one hydrogen atom is bonded to the carbon in the carbonyl group In a ketone, the carbon atom in the carbonyl group is bonded to two hydrocarbon groups The simplest aldehyde, formaldehyde (H2CPO) has a tendency to polymerize; that is, the individual molecules join together to form a compound of high molar mass This action gives off much heat and is often explosive, so formaldehyde is usually prepared and stored in aqueous solution (to reduce the concentration) This rather disagreeable-smelling liquid is used as a starting material in the polymer industry and in the laboratory as a preservative for animal specimens Interestingly, the higher molar mass aldehydes, such as cinnamic aldehyde OCHPCHOC H D M Cinnamic aldehyde gives cinnamon its characteristic aroma O have a pleasant odor and are used in the manufacture of perfumes Ketones generally are less reactive than aldehydes The simplest ketone is acetone, a pleasant-smelling liquid that is used mainly as a solvent for organic compounds and nail polish remover Carboxylic Acids Under appropriate conditions both alcohols and aldehydes can be oxidized to carboxylic acids, acids that contain the carboxyl group, OCOOH: CH3CH2OH O2 ¡ CH3COOH H2O CH3CHO 12O2 ¡ CH3COOH These reactions occur so readily, in fact, that wine must be protected from atmospheric oxygen while in storage Otherwise, it would soon turn to vinegar due to the formation of acetic acid Figure 11.18 shows the structure of some of the common carboxylic acids Carboxylic acids are widely distributed in nature; they are found in both the plant and animal kingdoms All protein molecules are made of amino acids, a special kind of carboxylic acid containing an amino group (ONH2) and a carboxyl group (OCOOH) CH3COOH cha75632_ch11_363-398.indd Page 386 9/16/09 9:17:13 PM user-s180 386 CHAPTER 11 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 Introduction to Organic Chemistry Figure 11.18 Some common carboxylic acids Note that they all contain the COOH group (Glycine is one of the amino acids found in proteins.) O B HOCOOH H O A B HOC OCOOH A H H H H O A A A B HO COC OC OC OOH A A A H H H Formic acid Acetic acid Butyric acid O B COOH Benzoic acid H H O A A B NO COC OOH A A H H O B C OOH A C OOH B O O H OH H O B A A A B HOO COC OC OC OCOOH A A A H C H J G O OH Glycine Oxalic acid Citric acid Unlike the inorganic acids HCl, HNO3, and H2SO4, carboxylic acids are usually weak They react with alcohols to form pleasant-smelling esters: O B CH3COOH ϩ HOCH2CH3 88n CH3OCOOOCH2CH3 ϩ H2O This is a condensation reaction acetic acid ethanol ethyl acetate Other common reactions of carboxylic acids are neutralization CH3COOH NaOH ¡ CH3COONa H2O and formation of acid halides, such as acetyl chloride CH3COOH PCl5 ¡ CH3COCl HCl POCl3 acetyl chloride phosphoryl chloride Acid halides are reactive compounds used as intermediates in the preparation of many other organic compounds Esters Esters have the general formula R9COOR, in which R9 can be H, an alkyl, or an aromatic hydrocarbon group and R is an alkyl or an aromatic hydrocarbon group Esters are used in the manufacture of perfumes and as flavoring agents in the confectionery and soft-drink industries Many fruits owe their characteristic smell and flavor to the presence of esters For example, bananas contain isopentyl acetate [CH3COOCH2CH2CH(CH3)2], oranges contain octyl acetate (CH3COOC8H17), and apples contain methyl butyrate (CH3CH2CH2COOCH3) The functional group in esters is OCOOR In the presence of an acid catalyst, such as HCl, esters undergo a reaction with water (a hydrolysis reaction) to regenerate a carboxylic acid and an alcohol For example, in acid solution, ethyl acetate is converted to acetic acid: The odor of fruits is mainly due to the ester compounds in them CH3COOC2H5 H2O Δ CH3COOH C2H5OH ethyl acetate acetic acid ethanol However, this reaction does not go to completion because the reverse reaction, that is, the formation of an ester from an alcohol and an acid, also occurs to an appreciable cha75632_ch11_363-398.indd Page 387 9/16/09 9:17:18 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-11 11.4 Chemistry of the Functional Groups 387 Figure 11.19 Oil (a) (b) (c) The cleansing action of soap The soap molecule is represented by a polar head and zigzag hydrocarbon tail An oily spot (a) can be removed by soap (b) because the nonpolar tail dissolves in the oil, and (c) the entire system becomes soluble in water because the exterior portion is now ionic extent On the other hand, when the hydrolysis reaction is run in aqueous NaOH solution, ethyl acetate is converted to sodium acetate, which does not react with ethanol, so this reaction goes to completion from left to right: CH3COOC2H5 NaOH ¡ CH3COO Na 1 C2H5OH ethyl acetate sodium acetate ethanol The term saponification (meaning soapmaking) was originally used to describe the reaction between an ester and sodium hydroxide to yield soap (sodium stearate): C17H35COOC2H5 NaOH ¡ C17H35COO Na 1 C2H5OH ethyl stearate sodium stearate Saponification is now a general term for alkaline hydrolysis of any type of ester Soaps are characterized by a long nonpolar hydrocarbon chain and a polar head (the OCOO2 group) The hydrocarbon chain is readily soluble in oily substances, while the ionic carboxylate group (OCOO2) remains outside the oily nonpolar surface Figure 11.19 shows the action of soap Amines Amines are organic bases that have the general formula R3N, in which one of the R groups must be an alkyl group or an aromatic hydrocarbon group Like ammonia, amines are weak Brønsted bases that react with water as follows: RNH2 H2O ¡ RNH13 OH2 Like all bases, the amines form salts when allowed to react with acids: CH3NH2 HCl ¡ CH3NH13 Cl2 methylamine methylammonium chloride These salts are usually colorless, odorless solids that are soluble in water Many of the aromatic amines are carcinogenic Summary of Functional Groups Table 11.4 summarizes the common functional groups, including the CPC and CqC groups Organic compounds commonly contain more than one functional group Generally, the reactivity of a compound is determined by the number and types of functional groups in its makeup CH3NH2 cha75632_ndx_I1-I12.indd Page I-2 12/3/09 3:49:03 PM user-s180 I-2 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Atomic mass unit (amu), 61 Atomic number (Z ), 36, 252 Atomic nucleus, 34 Atomic orbitals, 226, 228 electron assignment to, 228, 233 energies of, 231 hybrid, (see Hybrid orbitals) relationship between quantum numbers and, 226 Atomic radius, 258 Atomic theory See Atom Atomic weight See Atomic mass Aufbau principle, 239 Autoionization of water, 546 Automotive emission, 496 Average atomic mass, 61 Average bond enthalpies, 310 Avogadro, Amedeo, 63, 145 Avogadro’s law, 146 Avogadro’s number (NA), 63 Axial position, 324 B Balancing equations, 76, 662, 729 equilibrium constant and, 520 nuclear reactions, 729 redox reactions, 662 Ball-and-stick model, 41 Balmer series, 221 Barium, 270 Barium hydroxide [Ba(OH)2], 107, 126, 552 Barium sulfate (BaSO4), 606 Barometer, 139 Bartlett, Neil, 275 Base (in DNA), 774 Base(s), 51, 545 Arrhenius, 105 Brønsted, 105, 545 general properties of, 105 ionization constant of, 566 Lewis, 581 properties of, 105 strength, 552, 566 Base ionization constants (Kb), 566 relationship between acid ionization constants and, 569 Base pairs, 774 Base strength, 552, 566 Basic oxides, 277, 579 Batteries, 680 dry cell, 680 fuel cell, 683 lead storage, 681 lithium-ion, 682 mercury, 681 Bauxite, 693 Becquerel, Antoine, 33 Belt of stability, 732 Benzene (C6H6), 304, 379 bonding in, 304, 379 electron micrograph of, 379 resonance in, 304 structure of, 304 Benzoic acid, 386, 556 Beryllium, 270 Beryllium chloride (BeCl2), 321, 338 Beryllium hydride (BeH2), 306, 342 Beta (b) particles, 33 Beta (b) pleated sheet, 770 Beta (b) rays See Beta particles Bidentate ligands, 709 Bimolecular reaction, 490 Binary compounds, 45 Biological effects of radiation, 753 Body-centered cubic cell (bcc), 412 Bohr model, 218 Bohr, Niels D., 219 Boiling point, 423 and intermolecular forces, 424 vapor pressure and, 424 Boiling-point elevation, 449 Boltzmann equation, 632 Boltzmann, Ludwig, 157, 632 Bomb calorimeter, 192 Bond(s) coordinate covalent, 306 in coordination compounds, 708 covalent, see Covalent bond double, see Double bond enthalpy, 309 hydrogen, see Hydrogen bond ionic, 287 length, 293 in metals, 419 multiple, 293, 345 pi (p), 345 polar covalent, 294 sigma (s), 345 triple, see Triple bonds Bond angles, 322, 341 Bond enthalpies, 309, 311 (table) Bond length, 293 Bond moments, dipole, 331 Bond order, 352 Bond polarity, 294 Bonding molecular orbital, 349 Bonding pairs, 321 Boric acid, 581 Born, Max, 289 Born-Haber cycle, 289 Boron, 271 Boron trifluoride (BF3), 306, 339, 581 Boundary surface diagrams, 229 Boyle, Robert, 141 Boyle’s law, 143 Breath analyzer, 383 Breeder reactors, 747 Bromine, 118, 274 Bromine-formic acid reaction, 469 Brønsted acid, 105, 545 Brønsted acid-base theory, 105, 545 Brønsted base, 105, 545 Brønsted, Johannes, 105 Buffer solutions, 591 Buffering capacity, 592 Buret, 9, 125 C Calcium, 270 Calcium carbide (CaC2), 378 Calcium carbonate (CaCO3), 518, 590, 644 Calcium oxide (CaO; quicklime), 644 Calcium phosphate [Ca3(PO4)2], 607 Calorimeter, 191 constant-pressure bomb, 194 constant-volume bomb, 192 Calorimetry, 191 Cancer, 754 See also Carcinogenicity Capillary action, 407 Capsaicin, 363 Carbides, 45 Carbon, 272 allotropes of, 41, 197 atomic mass of, 61 Carbon dioxide (CO2) acidic properties, 579, 582 bond moments of, 332 enthalpy of formation of, 198 as Lewis acid, 582 Lewis structure of, 293 phase diagram of, 427 photosynthesis and, 751 solid (dry ice), 428 solubility of, 446 Carbon-12, 63 Carbon-14, 738 Carbon-14 dating, 738 Carbon monoxide combustion of, 190 enthalpy of formation, 199 Carbon tetrachloride (CCl4), 371 Carbonate ion, 304 Carbonic acid (H2CO3), 562 formation of, 579, 582 ionization constants, 563 Carbonyl group, 385 Carboxyl group, 385 Carboxylic acids, 385 Carcinogenicity of amines, 387 of polycyclic aromatic hydrocarbons, 382 of radiation, 754 Carothers, Wallace, 765 Catalysis, 493 air pollution reduction by, 496 enzyme, 497 heterogeneous, 494 homogeneous, 497 Catalysts, 493 in catalytic converters, 496 effects of, on equilibrium, 531 enzymes as, 497 heterogeneous, 494 homogeneous, 497 Catalytic converters, 496 Catalytic rate constant, 493 Catalytic reforming, 397 Cathode, 666 Cathode ray(s), 32 Cathode ray tube, 32 Cathodic protection, 687 Cations, 40 electron configuration of, 255 hydrolysis of, 573, 575 identification of, in solutions, 617 nomenclature of, 46 (table) radius of, 259 Caustic soda See Sodium hydroxide cha75632_ndx_I1-I12.indd Page I-3 11/20/09 5:16:59 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Cell diagram, 666 Cell potential, 666 Cell voltage, 666 See also Electromotive force Celsius temperature scale, 11, 144 Cesium, 269 Chadwick, James, 35 Chain reaction, nuclear, 744 Chargaff’s rule, 774 Charge-to-mass ratio (e/m), 32 Charles, Jacques, 144 Charles’ law (Charles’ and Gay-Lussac’s law), 145 Chelating agents, 709 Chemical analysis gravimetric analysis, 122 qualitative analysis, 617 Chemical energy, 177 Chemical equations, 75 See Balancing equations Chemical equilibrium, 100, 511 Chemical formulas, 41 empirical, 42, 72 molecular, 41 74 structural, 42, 365 Chemical kinetics, 467 Chemical properties, Chemical reactions, 75 acid-base, 105, 108, 597 addition, 375, 762 of alkanes, 371 of alkenes, 374 of alkynes, 378 of aromatic compounds, 381 bimolecular, 490 combination, 114 combustion, 114 condensation, 384, 765 Dalton’s definition of, 30 displacement, 114 first-order, 475 half, 110 half-cell, 666 metathesis, 100 neutralization, 108, 124, 597 nuclear reactions compared with, 729 oxidation-reduction See Oxidationreduction reactions precipitation, 100, 611 rate of See Rate of reaction redox, 109 second-order, 480 spontaneous, 629 substitution, 381 termolecular, 490 unimolecular, 490 Chemistry, Chernobyl, 747 Chiral drugs, 391 Chiral molecules, 389 Chirality, 389 Chloric acid, 50 Chlorine, 274 Chloroform, (CHCl3), 371 Chlorous acid (HClO2), 50 Chromium, 239 Chromosomes, 754 Cinnamic aldehyde, 385 Cisplatin, 722 Cis-trans isomers of alkenes, 373 of coordination compounds, 713 Clausius-Clapeyron equation, 421 Closed system, 178 Closest packing, 413 Cohesion, 407 Colligative properties, 447 of electrolyte solutions, 457 of nonelectrolyte solutions, 447 Collision theory, 484 Color of indicators, 605 of transition metal ions, 716 wavelength and, 214, 717 Color wheel, 717 Combination reaction, 114 Combustion of acetylene, 200, 378 of alkanes, 371 of carbon monoxide, 190 of hydrogen, 7, 178 of methane, 187 of sulfur, 114, 181 Combustion reaction, 114 Common-ion effect solubility and, 613 Complex ion(s), 614 magnetic properties of, 718 solubility equilibria and, 614 See also Coordination compounds Complex ion formation, 615 Compounds, aromatic See Aromatic hydrocarbons coordination See Coordination compounds in Dalton’s theory, 30 inorganic See Inorganic compounds ionic See Ionic compounds molecular, 47 organic, 52, 364 Concentration, 118, 440 chemical equilibria and changes in, 527 effects of, on emf, 676 Concentration cells, 679 Concentration of solution, 118, 440 Concentration units, 118, 440 compared, 441 molality, 440 molarity, 118, 440 mole fraction, 154, 447 percent by mass, 440 Condensation, 420 Condensation reactions, 384, 765 Conductivity, metallic, 419 Conformation, 367 Conjugate acid, 545 Conjugate acid-base pair, 545, 569 Conjugate base, 545 Constant-pressure calorimeter, 194 Constant-volume bomb calorimeter, 192 Constructive interference, 349 Control rods, 746 Cooperativity, 772 Coordinate covalent bonds, 306 I-3 Coordination compounds, 707 bonding in, 715 color, 716 geometry of, 713 in living system, 721 magnetic properties of, 718 naming, 710 oxidation state, 710 reactions of, 721 Coordination number, 412, 708 Copolymers, 764 Copper, 241 corrosion of, 686 electron configuration of, 241 purification of, 693 Copper carbonate (CuCO3; patina), 686 Copper hydroxide, 607 Copper-zinc galvanic cells, 665 Core atomic, See Nucleus noble gas, 239 nuclear reactor, 746 Corrosion, 685 of iron, 685 Coulomb (C), 33, 673 Coulomb’s law, 289 Coupled reaction, 652 Covalent bond, 292 coordinate, 306 polar, 294 Covalent compounds, 292 Covalent crystals, 418 Cracking process, 375 Crenation, 454 Crick, Francis, 774 Critical mass, 744 Critical pressure (Pc ), 424, 425 (table) Critical temperature (Tc), 424, 425 (table) Crude oil, 366 Cryolite, 693 Crystal(s), 417 covalent, 418 ionic, 417 metallic, 419 molecular, 418 Crystal field splitting, 716 Crystal field theory, 715 Crystal structure, 410 Crystalline solids, 410 Crystallization, 437 Cubic close-packed (ccp), 414 Cubic unit cell, 412 Curie, (Ci), 753 Curie, Marie, 33 Cycloalkanes, 372 Cyclobutane, 372 Cyclohexane, 372 Cyclotron, 741 Cytochromes, 722 Cytosine, 775 D d Orbitals, 230 and crystal-field theory, 715 hybridization of, 344 Dacron, 765 cha75632_ndx_I1-I12.indd Page I-4 11/20/09 5:16:59 PM user-s180 I-4 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Dalton, John, 30 Dalton’s atomic theory, 30 Dalton’s law of partial pressures, 153 Daniell cell, 666 Dating, radionuclear, 738 Dative bond, 306 Davisson, Clinton, 224 de Broglie, Louis, 223 de Broglie’s hypothesis, 223 Debye (D), 331 Debye, Peter J., 331 Decay series See Radioactive decay series Decomposition reaction, 114 Definite proportions, law of, 30 Delocalized molecular orbital, 379 Democritus, 30 Denaturant, 772 Denatured alcohol, 384 Denatured proteins, 772 Density, 10 See also Electron density gas, 150 nuclear, 731 water, 409 Deoxyhemoglobin, 722, 771 Deoxyribonucleic acid (DNA) See DNA Deposition, 426 Derived SI units, 10 Destructive interference, 349 Deuterium, 36 Deuterium oxide, (D2O; heavy water), 746 Deviation from ideal gas behavior, 164 Dextrorotatory isomers, 391 Diagonal relationship, 268 Diagonal rule, 671 Diamagnetism, 234, 718 Diamond as allotrope of carbon, 41, 197, 418 entropy of, 634 structure of, 418 Diatomic molecules, 39 Dichloroethylene, 332, 373 Dichromate ion, 662 Diethyl ether, 384, 423 Diffusion, 162 Dihedral angle, 368 Dilution of solutions, 120 Dimensional analysis, 18, 80 Dinitrogen pentoxide (N2O5), 273, 476, 579 Dinitrogen tetroxide (N2O4), 511, 529 Dipeptide, 652, 767 Dipolar ion, 767 Dipole moments (m), 331 Dipole-dipole forces, 401 Dipole-induced dipole, 402 Dipositive ions, 260 Diprotic acids, 106, 562 ionization constant of, 563 Disintegration See Nuclear disintegration Dispersion forces, 403 Displacement reactions, 114 Distribution of molecular speed, 160 DNA (deoxyribonucleic acid), 774 binding to cisplatin, 723 electron micrograph, 774 structure of, 776 Donor atom, 708 Double bonds, 293, 345 Doubling time, 747 Downs cell, 687 Dry cell batteries, 680 Dry ice, 428 Dynamic equilibrium, 100, 420 Dynamite, 176 E Earth age of, 740 composition of, Eclipsed conformation, 367 EDTA (ethylenediaminetetraacetate) structure of, 709 treatment of metal poisoning with, 709 Effective nuclear charge (Zeff), 257 Effusion, 163 Einstein, Albert, 216 Einstein’s mass-energy equation, 31, 734 Elastomers (synthetic rubber), 764 Electrocatalysts, 684 Electrochemical series, 117 Electrochemistry, 662 Electrode(s) anode, 666 cathode, 666 Electrode potential See Standard reduction potential Electrolysis, 687 of aqueous sodium chloride, 689 metal purification by, 693 of molten sodium chloride, 687 quantitative aspects of, 691 of water, 688 Electrolyte(s), 98 strong, 98 weak, 98 Electrolyte solutions, colligative properties of, 457 Electrolytic cells, 687 Electromagnetic radiation, 213 Electromagnetic wave, 213 Electrometallurgy, 693 Electromotive force (emf), 666 effects of concentration on, 676 standard, 668 Electron, 32 charge-to-mass ratio of, 32 nonbonding See Lone pairs probability distribution of, 226 valence, 254 Electron affinity, 266, 266 (table) Electron capture, 733 Electron charge cloud, 226 Electron configuration, 233, 239 anions, 255 Aufbau principle and, 239 cations, 255 diamagnetism and paramagnetism in, 234 of diatomic molecules, 353, 356 electron assignment to orbitals in, 233 ground state, 233, 240 Hund’s rule and, 236 Pauli exclusion principle and, 233 Electron density, 226 Electron probability, 226 Electron spin, 228, 234 in coordination compounds, 718 Hund’s rule and, 236 Pauli exclusion principle and, 233, 718 Electron density, 226 Electron probability, 226 Electron spin quantum number (ms), 228 Electron subshell, 227 Electron-dot symbols, 286 Electronegativity, 294 Elementary particles, 36, 729 Elementary steps, 489 Elements, abundance, atomic radii of, 257 classification of, 38, 253 in Earth’s crust, electron affinity in, 266 electronegativity of, 294 essential, ground state electron configurations of, 233, 240 ionization energies of, 263 (table) periodic and group properties of, 268 representative, 253 symbols of, (table), A-9 transuranium See Transuranium elements Emf See Electromotive force Emission spectra, 218 Empirical formula, 42 determination of, 72 Enantiomers, 389, 714 End point, 603 Endothermic process, 179 Energy, 177 See also Free energy chemical, 177 crystal field splitting, 716 ionization, 262 kinetic See Kinetic energy law of conservation of, 177 mass-energy conversion, 734 nuclear binding See Nuclear binding energy potential See Potential energy solar See Solar radiation thermal See Heat unit of, 158 See also Free energy Energy changes See also Enthalpy; Free energy in chemical reactions, 186 and first law of thermodynamics, 180 Enthalpy (H), 186 standard, 197 Enthalpy of reaction (DHrxn), 186 Entropy (S), 630 absolute, 639 and Boltzmann equation, 632 changes, 632, 636, 638 and microstate, 631 phase transition, 646 of reaction (DSrxn), 636 standard, 633 Enzyme(s), 497 alcohol dehydrogenase, 383 catalysis of, 497 hexokinase, 498 lock-and-key model of, 497 cha75632_ndx_I1-I12.indd Page I-5 12/3/09 3:49:18 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Enzyme-substrate intermediate (ES), 498 Equation See also Chemical Equations Arrhenius, 484 balancing, 76, 662, 729 Clausius-Clapeyron, 421 Einstein’s, 31, 734 Henderson-Hasselbach, 595 ideal gas, 147 ionic, 103 molecular, 102 Nernst, 676 net ionic, 103 nuclear, 729 redox, 662 Schrödinger, 225 thermochemical, 188 van der Waals, 165 Equatorial position, 324 Equilibrium, 100, 420, 511, 647 Equilibrium constant; Solubility Equilibria catalyst effect on, 531 and concentration changes, 527 dynamic, 100, 420 free energy and, 647 heterogeneous, 518 homogeneous, 514 and Le Chatelier’s principle See Le Chatelier’s principle liquid-solid, 424 liquid-vapor, 420 solid-vapor, 426 and temperature changes, 530 volume and pressure changes and, 529 Equilibrium constant; Solubility equilibria Equilibrium constant (K), 513, 648 See also Ionization constants balanced equation and, 520 and equilibrium concentration calculations, 523 in heterogeneous equilibrium, 518 in homogeneous equilibrium, 514 and law of mass action, 513 reaction direction and, 521 Equilibrium vapor pressure, 421 Equivalence point, 125, 598, 600, 602 Escape velocity, 162 Essential elements, Ester, 386 Ethane (C2H6), 78 conformational analysis of, 367 Ethanol (C2H5OH), 73, 382 Ether, 384 Ethyl acetate (CH3COOC2H5), 386, 497 Ethyl group (C2H5), 369 Ethyl stearate, 387 Ethylene (C2H4), 373 bonding in, 293, 345 in polymerization, 377 Ethylene glycol [CH2(OH)CH2(OH)], 383, 451 Ethylenediamine, 708 Ethylenediaminetetraacetate See EDTA Evaporation See Vaporization Excess reagent, 83 Excited level (excited state), 220 Exothermic processes, 179 Expanded octet, 307, 344 Exponential notation See Scientific notation Extensive properties, F f Orbitals, 230 Face-centered cubic unit cell ( fcc), 412 Factor-label method See Dimensional analysis Fahrenheit temperature scale, 12 Family of elements, 38 Faraday constant (F ), 673 Faraday, Michael, 673 Fat, 375, 397 Fermentation, 382 First ionization energy, 262 First law of thermodynamics, 180 First-order reactions, 475 Fission reactions, 743 Fission reactors, 745 Flame test, 619 Fluorine, 274 mass defect of, 734 nuclear stability, 733 oxidation number of, 112, 296 Fluorite, 417 Force, 138 adhesive, 407 cohesive, 407 dispersion, 403 intermolecular See Intermolecular forces unit of, 138 van der Waals, 401 Formal charge, 300 Formaldehyde (CH2O), 385 bonding in, 347 Formation constant (Kf), 615 Formic acid (HCOOH), 386, 469 Formula mass, 68 Formulas See Chemical formulas Free energy (G), 641 chemical equilibria and, 647 and electrical work, 673 in phase transition, 646 spontaneity and, 642 standard free energy change, 642 temperature and, 644 Freezing point, 424 Freezing-point depression, 450 Frequency (n), 212 Frequency factor (A), 485 Fuel cell, 683 Functional groups, 52, 364, 382, 388 (table) Fusion entropy and, 633, 646 molar heat of, 426 (table) nuclear, 748 G Gallium, 252, 271 Galvanic cells, 665 Galvanized iron, 687 Gamma (g) rays, 34 I-5 Gas(es), 137 Avogadro’s law, 146 Boyle’s law, 143 Charles’ law, 145 Dalton’s law of partial pressure of, 153 density of, 151 emission spectrum of, 218 kinetic molecular theory of, 158 monatomic, 137 noble See Noble gases pressure of, 138 properties of, 137 solubility of, 445 stoichiometry, 151 Gas constant (R), 147 units of, 143, A-1 van der Waals, 165 (table) Gay-Lussac, Joseph, 144 Geiger counter, 752 Geiger, Hans, 35 Genetic effects of radiation, 754 Geometric isomers, 373, 713 Geometric shapes of orbitals, 229, 230, 337 Germer, Lester, 224 Gibbs, Josiah W., 641 Gibbs free energy See Free energy Glass electrode, 679 Glucose (C6H12O6), 382 Glutamic acid, 768, 771 Glycerol, 407 Glycine, 386, 768 Goodyear, Charles, 764 Gram (g), 10 Graham’s law of diffusion, 162 Graphite, allotrope of carbon, 41, 197, 418 entropy of, 634 structure of, 418 Gravimetric analysis, 122 Ground state (ground level), 219 Group (periodic), 38 Guanine, 774 H H2 Lewis structure of, 291 potential energy of, 335 Haber, Fritz, 289, 495 Haber process, 494 Half-cell potential See Standard reduction potential Half-cell reactions, 666 Half-life, 478 of carbon-14, 738 of cobalt-60, 479, 750 of first-order reactions, 478 of iodine-131, 751 of plutonium-239, 747 second-order reactions, 481 of sodium-24, 479, 751 of technetium-99, 752 of tritium, 741 of uranium-238, 739 zero-order reactions, 483 Half-reaction, 110 Half-reaction method, 662 cha75632_ndx_I1-I12.indd Page I-6 11/20/09 5:17:00 PM user-s180 I-6 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Halide, 275 Hall process, 693 Halogen(s), 39, 274 displacement, 114 electronegativity of, 294 oxoacids, 50 properties of, 275 Halogenation of alkanes, 371 Heat, 178, 184 of fusion, 426 of neutralization, 194 of solution, 438 of sublimation, 426 of vaporization, 421 Heat capacity (C), 191 Heat content See Enthalpy Heavy water See Deuterium oxide Heavy water reactor, 746 Heisenberg uncertainty principle, 225 Heisenberg, Werner, 225 Helium, 275 boiling point of, 403 escape velocity of, 162 formation of, 737 intermolecular forces in, 403 ionization energy of, 263 Heme group, 722, 772 Hemoglobin, 446, 722, 772 Hemolysis, 454 Henderson-Hasselbach equation, 595 Henry’s law, 445 Hertz (Hz), 213 Hess’s law, 199 Heterogeneous catalysis, 494 Heterogeneous equilibria, 518 Heterogeneous mixture, Hexagonal close-packed (hcp), 414 Hexamethylenediamine, 765 Hexokinase, 498 High-spin complexes, 718 Hindenburg, 179 Hiroshima, 745 Homogeneous catalysis, 497 Homogeneous equilibria, 514 Homogeneous mixture, Homonuclear diatomic molecule, 353 Homopolymers, 762 Hund’s rule, 236, 718 Hybrid orbitals, 337, 341 (table) of molecules with double and triple bonds, 345 sp, 338, 347 sp , 339, 345 sp3, 336 sp3d, 344 sp3d2, 344 Hybridization, 337 Hydrate, 52 Hydration, 99 of ions, 99, 402 of protons, 106, 545 Hydrocarbons, 52, 364 aliphatic, 364 aromatic, 364, 379 saturated, 364 unsaturated, 375 Hydrochloric acid (HCl), 105, 551 in acid-base titrations, 126, 597, 602 as monoprotic acid, 106, 551 Hydrocyanic acid (HCN), 553, 556 Hydrofluoric acid (HF), 556 ionization constant of, 556 as weak acid, 551 Hydrogen, 269 atomic orbitals of, 226 combustion of, 7, 178 displacement of, 114 isotopes of, 36 oxidation number of, 112 properties of, 269 Hydrogen atom Bohr’s theory of, 218 emission spectrum of, 218 energy of, 219 Schrödinger equation and, 225 Hydrogen bomb, 749 Hydrogen bond, 405, 409, 771, 774 Hydrogen displacement reaction, 114 Hydrogen fluoride (HF), 294, 331 Hydrogen halides, acid strength of, 570 dipole moments of, 333 Hydrogen ion hydrated, 106, 545 pH and concentration of, 548 Hydrogen molecule bonding in, 291, 334, 352 combustion of, 7, 178 Lewis structure, 291 Hydrogen peroxide (H2O2), 42 decomposition of, 470, 491 oxidation number in, 296 percent composition by mass of, 70 Hydrogen sulfide (H2S) as diprotic acid, 563 in qualitative analysis, 618 Hydrogenation, 375 Hydrogen-oxygen fuel cell, 683 Hydrohalic acids, 49, 570 Hydrolysis alkaline (saponification), 387 ATP, 652, 767 of esters, 386, 497 metal ion, 575 salt, 573 Hydrometer, 682 Hydronium ion, 106, 545 Hydroxides alkali metal, 107, 552 alkaline earth metal, 107, 552 amphoteric, 617 Hydroxyapatite [Ca5(PO4)3OH], 606 Hydroxyl groups (OH groups), 382 Hypertonic solution, 453 Hypochlorous acid, 50 Hypothesis, Hypotonic solution, 453 I Ibuprofen, 391 Ice, 409 Ice-water equilibrium, 424 Ideal gas, 147 Ideal gas equation, 147 Ideal solution, 449 Incomplete octet, 306 Indicators, 125, 603 Induced dipole, 402 Inert complex, 721 Inorganic compounds, 44 Instantaneous rate, 470 Intensive properties, Intermediates, 490 Intermolecular forces, 401 dipole-dipole forces, 401 dispersion forces, 403 ion-dipole forces, 401 van der Waals forces, 401 Internal energy (U), 180 International System of Units (SI units), International Union of Pure and Applied Chemistry (IUPAC), 38, 368 Intramolecular forces, 401 Iodine, 274 sublimation of, 426 Iodine-131, 751 Iodine number, 398 Ion, 39 dipositive, 260 electron configuration of, 255 hydrated, 99, 402 monatomic, 40 polyatomic, 40 spectator, 103 transition metal, 256, 706 tripositive, 260 unipositive, 260 Ion pairs, 457 Ion product constant, 547 Ion-dipole forces, 401 Ion-induced dipole, 401 Ionic bond, 287 Ionic compounds, 40 formula of, 43 nomenclature, 45 Ionic crystals, 417 Ionic equation, 103 Ionic radius, 259 Ionic solids, 417 Ionization constants See also Acid ionization constants; Base ionization constants of bases, 566 of diprotic and polyprotic acids, 562 of monoprotic acid, 555 Ionization energy, 262, 263 (table) Ionizing radiation, 754 Ion-product constant of water (Kw), 546 Iron corrosion of, 685 galvanized, 687 Iron thiocyanate, 527 Isoelectronic ions, 256 Isolated system, 178 Isolation method, 473 Isomer(s) enantiomers, 389, 714 geometric, 373, 713 of polymers, 763 structural, 365 cha75632_ndx_I1-I12.indd Page I-7 11/20/09 5:17:00 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Isomerism See Isomer(s) Isomerization, 373 Isoprene, 763 Isopropanol (rubbing alcohol), 384 Isotactic polymers, 763 Isotonic solution, 453 Isotopes, 36 applications of, 750 J Joule (J), 158 K Kekulé, August, 304 Kelvin, Lord (William Thomson), 144 Kelvin temperature scale, 11, 144 Ketones, 385 Kidney stone, 611 Kilogram (kg), 10 Kinetic energy, 158 Kinetic lability, 721 Kinetic molecular theory of gases, 158 liquids and solids in, 400 Kinetics See Chemical kinetics Krypton, 275 L Labile complex, 721 Lanthanide series See Rare earth series Large hadron collider (LHC), 728 Latex, 764 Lattice energy, 289, 291 (table) Lattice point, 410 Law(s), Avogadro’s, 146 Boyle’s, 143 Charles’, 145 of conservation of energy, 177 of conservation of mass, 31 Dalton’s, of partial pressures, 153 of definite proportions, 30 first law of thermodynamics, 180 Henry’s, 445 Hess’s, 199 of mass action, 513 of multiple proportions, 31 of octaves, 252 Raoult’s, 447 rate, 472 second law of thermodynamics, 635 third law of thermodynamics, 639 Le Chatelier, Henri, 527 Le Chatelier’s principle, 527 acid ionization and, 555 chemical equilibrium and, 527 common-ion effect and, 613 solubility equilibria and, 613 Lead poisoning, treatment of, 709 Lead storage batteries, 681 Leclanche cell, 680 Length, SI base unit of, Levorotatory isomers, 391 Lewis acid, 581 Lewis acid-base theory, 581 Lewis base, 581 Lewis dot symbols, 286 Lewis, Gilbert, 286, 581 Lewis structures, 292 formal charge and, 300 octet rule and, 292 and resonance concept, 303 Lexan, 761 Ligands, 707, 708 (table) strong-field, 718 weak-field, 718 Light absorption of, and crystal field theory, 716 electromagnetic theory of, 213 particle-wave duality of, 216 plane-polarized, 390 speed of, 213 Light water reactors, 745 Limiting reagents, 83 Line spectra, 219 Linear molecule, 321, 346 Liquid(s), 400 properties of, 407 solutions of liquids in, 437 solutions of solids in, 437 surface tension in, 407 viscosity of, 407 Liquid-solid equilibrium, 424 Liquid-vapor equilibrium, 420 Liter (L), 10 Lithium, 269 Lithium-ion battery, 682 Litmus, 105 Lock-and-key theory, 497 Logarithm, A-6 London forces See Dispersion forces London, Fritz, 403 Lone pairs, 292 Low-spin complexes, 718 Lucite (Plexiglas; polymethyl methacrylate), 762 M Macromolecules See Polymers Macroscopic properties, Magic number, 731 Magnesium, 270 cathodic protection with, 687 Magnetic confinement, 749 Magnetic field electron spin and, 228, 234, 718 Magnetic quantum number (ml), 227 Magnetism of complex ions, 718 diamagnetism, 234, 718 paramagnetism, 234, 718 Main group elements, 253 Manganese dioxide (MnO2), 156, 493 Manometer, 140 Many-electron atoms, 226 Marsden, Ernest, 34 Marsh gas See Methane Mass, atomic See Atomic mass I-7 critical, 744 defect, 734 electron, 32 molar, 63, 150, 455 molecular, 66 percent composition by See Percent composition by mass SI base unit of, of subatomic particles, 36 subcritical, 744 Mass action, law of, 513 Mass defect, 734 Mass number (A), 36 Mass spectrometer, 68 Mass-energy conversion, 734 Matter, classification of, Maxwell, James, 157 Maxwell speed distribution, 160 Mean square speed, 160 Mechanical work, 182 Melting, entropy and, 646 Melting point, 424 Membrane potential, 680 Mendeleev, Dmitri, 252 Mercury batteries, 681 Mercury oxide (HgO), 179, 630 Messenger RNA, 776 Metabolism, 652 Metal(s), 38, 254, 269 alkali See Alkali metal(s) alkaline earth See Alkaline earth metal(s) bonding in, 419 corrosion See Corrosion displacement reactions, 116 in ionic compounds, 45 properties of, 38, 253, 269 Metal ion: electron configurations, 255 hydrolysis of, 575 radii, 259 Metallic bonds, 419 Metallic crystals, 419 Metallic elements, 38, 254, 269 Metalloids, 38 Metathesis reaction, 100 Meter, Methane (CH4), 364 bonding in, 336 combustion of, 371 molecular geometry of, 323, 336 Methanol (CH3OH), 327, 383 Methyl chloride, 371 Methyl group (CH3), 369 Methyl radical, 371 Methylene chloride (CH2Cl2), 371 Metric unit, Meyer, Lothar, 252 Microscopic properties, Microwaves, 214 Millikan, Robert, 33 Miscible liquids, 439 Mixture, heterogeneous, homogeneous, racemic, 391 Moderator, 746 cha75632_ndx_I1-I12.indd Page I-8 11/20/09 5:17:00 PM user-s180 I-8 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Molal boiling-point elevation constant, 450 Molal freezing-point depression constant, 451 Molality (m), 440 Molar concentration, 118 Molar heat of fusion 426, 426 (table) sublimation, 426 of vaporization, 421, 422 (table) Molar mass, 63, 150, 455 Molar solubility, 608 Molar volume, 147 Molarity (M), 118, 440 Mole, 62 Mole fraction (X), 154, 447 Mole method, 80 Molecular compounds, 47 Molecular crystals, 418 Molecular equation, 102 Molecular formula, 41, 74 Molecular geometry, 321 See also Hybrid orbitals; Valence-shell electron-pair repulsion model of coordinating compounds, 713 of cycloalkanes, 372 Molecular mass, 66 Molecular models, 41 Molecular orbital configuration, 351 Molecular orbital theory, 349 Molecular orbitals, 349 antibonding, 349 bonding, 349 Molecular rotation, 634 Molecular shapes See Molecular geometry Molecular speed, 160 distribution of, 160 root-mean-square, 160 Molecular vibration, 634 Molecular weight See Molecular mass Molecularity, 490 Molecules, 39 chemical formulas and, 41 chiral, 389 diatomic, 39 linear, 321, 338, 346 nonpolar, 332 odd-electron, 307 planar, 323, 346 polar, 332 polyatomic, 39 Monatomic gases, 137 Monatomic ions, 40 Monodentate ligands, 709 Monomers, 762, 766 (table) Monoprotic acids, 106, 555 Moseley, Henry, 252 Multiple bonds, 293, 345 Multiple proportions, law of, 31 Mutagen, 391 Myoglobin, 722 N N2 See Nitrogen Nagasaki, 745 Naming compounds See Nomenclature Naphthalene (C10H8), 382 Natural gas, 365 Natural radioactivity, 736 Natural polymers, 762, 767 Neon, 69, 275 Neoprene (polychloroprene), 764 Neothyl, 384 Neptunium, 742, 747 Nernst equation, 676 Nernst, Walther 676 Net ionic equation, 103 Neutralization reactions, 108, 124, 597 Neutron, 35, 729, 744 Neutrons-to-protons ratio, 731 Newlands, John, 252 Newman projection, 367 Newton (N), 138 Newton, Sir Isaac, 138 Newton’s second law of motion, 138 Nitric acid (HNO3), 106 Ostwald process in production of, 495 as strong acid, 551 Nitric oxide (NO), 307 Nitrogen, 273 bond enthalpy, 311 bonding in, 293, 356 electronegativity of, 294 Lewis structure of, 293 Nitrogen dioxide (NO2), 137, 511, 529 Nitrogen pentoxide (N2O5), 273, 476, 579 Noble gas core, 239 Noble (rare) gases, 39, 275 Node, 223, 350 Nomenclature of acids, 49 of acids and their conjugate bases, 553 (table), 556, 563 of alkanes, 368 of alkenes, 374 of alkynes, 377 of anions, 45, 46 (table), 711 of aromatic compounds, 380 of bases, 51 of cations, 46 (table) of coordination compounds, 710 of ionic compounds, 45 of molecular compounds, 47 of oxoacids, 50 (table) of oxoanions, 50 (table) of simple acids, 50 (table) of transuranium elements, 742 Nonbonding electrons, 292 Nonelectrolyte, 98 Nonelectrolyte solutions, colligative properties of, 447 Nonideal gas behavior, 164 Nonmetal, 38, 254 Nonmetallic elements, 38, 254 Nonpolar molecule, 332 Nonspontaneous reactions, 629 Nonvolatile solutes, 447 Nuclear binding energy, 733 nuclear stability and, 735 per nucleon, 735 of uranium, 744 Nuclear chain reaction, 744 Nuclear chemistry, 729 Nuclear decay series, 737 Nuclear disintegration, 731 Nuclear energy from fission reactors, 745 from fusion reactors, 748 hazards of, 747 Nuclear equation balancing, 729 Nuclear fission, 743 reactors, 745 Nuclear fusion, 748 Nuclear reactions, 729 compared with chemical reactions, 729 and decay series, 737 fission, 743 fusion, 748 moderator of, 746 nature of, 729 by transmutation, 729, 740 Nuclear reactors, 745 breeder, 747 fission, 746 fusion, 748 heavy water, 746 light water, 745 thermal pollution and, 746 Nuclear stability, 731 Nuclear transmutation, 729, 740 Nuclear wastes, 748 Nucleic acids, 774 Nucleons, 733 Nucleotide, 774 Nucleus, 34 density of, 731 Nylon (polyhexamethylene adipamide), 765 Nylon rope trick, 765 O O2 See Oxygen electron configuration, 355 paramagnetism, 349 solubility, 445 O3 See Ozone Octahedral complex, 715 Octahedron, 324 Octane number, 397 Octaves, law of, 252 Octet rule, 292 exceptions to, 305 Odd-electron molecules, 307 Oil, hydrogenated, 375 Olefins See Alkenes Open system, 178 Opsin, 374 Orbital diagram, 232 Orbitals See Atomic orbitals; Hybrid orbitals; Molecular orbitals Organic chemistry, 364 Organic compounds, 52, 364 Organic polymers See Polymer(s) Orientation factor, 488 Osmosis, 453 Osmotic pressure (p), 453 Ostwald process, 495 Overlap in hybridization of atomic orbitals, 336 in valence bond theory, 334 cha75632_ndx_I1-I12.indd Page I-9 11/20/09 5:17:00 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Overvoltage, 689 Oxalic acid, 528 Oxidation numbers (oxidation state), 111 assignment of, 111, 296 and electronegativity, 296 of halogens, 113 of metals in coordination compounds, 710 of nonmetallic elements, 113 of transition elements, 113, 706 Oxidation reactions, 110 Oxidation states See oxidation numbers Oxidation-reduction reactions (redox reactions), 109 balancing, 662 oxidation numbers and See Oxidation numbers spontaneous, 673 Oxides, 274, 277, 579 acidic, 277, 579 amphoteric, 277, 579 basic, 277, 579 Oxide ion, 274, 553 Oxidizing agent, 111 Oxoacid, 49, 571 Oxoanion, 50 Oxyacetylene torch, 200, 378 Oxygen, 274 alkali metal reactions with, 270 allotropes of, 41, 197 electronegativity of, 294 oxidation number of, 112, 296 solubility in blood, 446 Oxygen-hydrogen fuel cell, 683 Oxygen-propane fuel cell, 684 Oxyhemoglobin, 722, 771 Ozone, 41, 510 formal charges in, 300 hole, 466 resonance structure of, 303 P p Orbitals, 229 Packing spheres, 411 Paramagnetism, 234, 718 Partial pressure, 153 Dalton’s law of, 153 Particle accelerators, 741 Particle theory of light, 216 Particle-wave duality, 223 Pascal (Pa), 138 Passivation, 686 Patina, 687 Pauli, Wolfgang, 233 Pauli exclusion principle, 233, 718 Pauling, Linus, 294, 770 Penetrating power, 235 Pentane (C5H12), 366 Peptide bond, 767 Percent composition by mass, 70 Percent ionic character, 295 Percent ionization, 561 Percent by mass, 440 Percent yield, 86 Perchloric acid (HClO4 ), 50, 553 Period, 38 Periodic group, 38 Periodic table, 38 atomic radii trends in, 257 electron affinity trends in, 266 electronegativity trends in, 295 families in, 38 groups in, 38 historical development of, 252 ionization energy trends in, 263 modern, 255 periods of, 38 Permanganate ion, as oxidizing agent, 663 Peroxide, 270 pH, 548 of acid-base titrations, 598 of buffer solutions, 595 pH meter, 549, 597 Phase, 414 Phase changes, 420 effects of pressure on, 427 and entropy, 646 liquid-solid, 424 liquid-vapor, 420 solid-vapor, 426 Phase diagrams, 427 Phenolphthalein, 125, 604 Phenyl group, 381 Phosphoric acid (H3PO4), 106, 550, 579 ionization constants of, 563 Phosphorus, 273 allotropes of, 273 Phosphorus(V) oxide (P4O10), 273, 579 Phosphorus pentachloride (PCl5), 323 Photoelectric effect, 216 Photons, 216 Photosynthesis, 751 carbon dioxide and, 751 isotope applications to, 751 Physical equilibrium, 511 Physical properties, Pi (p) bond, 345 Pi (p) molecular orbital, 350 Pipet, pKa, 595 Planck, Max, 212 Planck constant (h), 215 Plane-polarized light, 389 Plasma, 749 Platinum as catalyst, 375, 496 as electrocatalyst, 667, 684 therapeutic uses of complexes of, 722 Plato, 30 Plutonium-239, 747 pOH, 549 Polar covalent bonds, 294 Polar molecules, 332 Polarimeter, 390 Polarizability, 402 Polaroid film, 391 Pollution See Thermal pollution Polyatomic ions, 40 Polyatomic molecules, 39 Polychloroprene (neoprene), 764 Poly-cis-isoprene, 763 Polycyclic aromatic hydrocarbons, 382 Polydentate ligands, 709 Polyester, 765 I-9 Polyethylene, 377 Polymer(s), 377, 762 Polymerization by addition, 377, 762 by condensation, 765, 767 Polypeptide, 770 Polypropene, 763 Polyprotic acids, 106, 562 Polytetrafluoroethylene (Teflon), 766 Polyunsaturated hydrocarbons, 375 Poly(vinyl chloride), 762 Positron, 730 Potassium, 269 Potassium chlorate (KClO3), 77, 155, 493 Potassium dichromate (K2Cr2O7), 383, 662 Potassium hydrogen phthalate, 125 Potassium superoxide (KO2), 270 Potential See Standard reduction potential Potential energy, 177 Precipitate, 100 Precipitation reaction, 100, 611 Precision, 17 Prefixes nomenclature, 47 (table) SI unit, (table) Pressure, 138 atmospheric See Atmospheric pressure chemical equilibrium and changes in, 529 critical, 424 gas, 138 osmotic, 453 partial, 153 phase changes and, 427 SI unit, 138 vapor See Vapor pressure Pressure-volume relationship of gas, 141 Primary structure, 771 Principal quantum number (n), 220, 227 Probability, in electron distribution, 226, 229 Problem solving, 20, 80, 557 Product, 76 Propane, 365, 684 Propane-oxygen fuel cell, 684 Properties chemical, extensive, intensive, macroscopic, microscopic, physical, Propene, 377, 763 Protein, 767 denatured, 772 structure of, 770 Proton, 34, 729 Proust, Joseph, 30 Purine, 774 Pyrimidine, 774 Q Quadratic equaton, 558, A-7 Qualitative, Qualitative analysis, 617 Quanta, 212 Quantitative, cha75632_ndx_I1-I12.indd Page I-10 11/20/09 5:17:01 PM user-s180 I-10 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Quantitative analysis, 124 See also Acid-base titrations gravimetric, 122 Quantum, 215 Quantum corral, 211 Quantum mechanics, 226 Quantum numbers, 226 angular momentum, 227 electron spin, 228 magnetic, 227 principal, 220, 227 Quantum theory, 212 Quartz crystalline, 419 melting point of, 419 R Racemic mixture, 391 Rad (radiation absorbed dose), 753 Radiant energy, 177 Radiation, 31, 213 biological effect of, 754 electromagnetic, 213 ionizing, 754 Radiation damage genetic, 754 somatic, 754 Radiation dose, 753 Radical, 307, 371, 754 Radioactive decay series, 737 Radioactive isotopes, 750 Radioactive waste disposal, 748 Radioactivity, 33, 736 artificial, 740 biological effects of, 753 natural, 736 nuclear stability and, 731 Radiocarbon dating, 738 Radiotracers, 751 Radium, 29, 270 Radius atomic, 258 ionic, 259 Radon, 274 Raoult’s law, 447 Rare earth series, 241 Rare gases See Noble gases Rate constant, 472 Rate of reaction, 467 between bromine and formic acid, 469 dependence of, on activation energy and temperature, 485 and stoichiometry, 467 Rate-determining step, 491 Rate law, 472 See also Reaction order Rays alpha, 33 beta, 33 gamma, 34 RBE (relative biological effectiveness), 753 Reactants, 76 Reaction See Chemical reactions; Nuclear reactions; Thermonuclear reactions Reaction mechanisms, 489 elementary steps, 489 and molecularity of reaction, 490 Reaction order, 472 determination of, 473 first-order, 475 second-order, 480 zero-order, 482 Reaction quotient (Q ), 522, 647, 650, 676 Reaction rate, 467 Reactors See Nuclear reactors Reagents, limiting, 83 Red cabbage, 604 Red phosphorus, 273 Redox equation, 662 Redox reactions See Oxidation-reduction reactions Reducing agent, 111 Reduction potential See Standard reduction potential Reduction reaction, 110 Relative biological effectiveness (RBE), 753 Relativity theory, 734, 741 Rem (roentgen equivalent for man), 753 Representative (main group) elements, 253 Residue, 770 Resonance, 303 Resonance structure, 303 Retinal, 374 Reversible denaturation, 773 Reversible reaction, 100 Ribonucleic acid See RNA Ribosomal RNA, 776 RNA, 774 Rocks age determination of, 739 Rhodopsin, 374 Röntgen, Wilhelm, 33 Root-mean-square speed, 160 Rotation about bonds, 373, 770 molecular, 634 of plane-polarized light, 389 Rotational motion, 634 Rubber (polyisopropene), 763 natural, 763 structure, 763 synthetic, 764 vulcanization, 764 Rubbing (isopropanol) alcohol, 384 Rust, 685 Rutherford, Ernest, 34, 252, 740 Rydberg constant (RH), 219 S s Orbitals, 228 Sacrificial anode, 687 Salt(s), 108 hydrolysis of, 573 Salt bridge, 666 Salt hydrolysis, 573 Salt solutions, acid-base properties of, 573 Saponification, 387 Saturated hydrocarbons, 364 See also Alkanes Saturated solutions, 437 SBR (styrene-butadiene rubber), 764 Scattering experiment, 34 Schrödinger, Erwin, 225 Schrödinger equation, 225 Scientific method, Scientific notation, 14 Second law of thermodynamics, 635 Second-order reaction, 480 Secondary valence, 707 Seed crystals, 437 Semipermeable membrane, 452 SHE (standard hydrogen electrode), 668 Shell, 227 Shielding constant, 257 Shielding effect, 235, 257 Shroud of Turin, 738 SI units (International System of Units), Sickle cell anemia, 771 Sigma (s) bonds, 345 Sigma (s) molecular orbital, 349 Significant figures, 15, A-6 Silicon, 272 Silk, 771 Silver corrosion of, 686 Silver bromide (AgBr), 609 Silver chloride (AgCl) gravimetric analysis of, 123 solubility and, 606 Simple cubic cell (scc), 412 Simplest formula, 42, 72 Single bond, 293 Skeletal structure, 367 Slow (thermal) neutrons, 743 Soap, 387 Sodium, 269 production of, 687 reaction with water, 114, 189 Sodium acetate (CH3COONa), 437, 573, 591 Sodium acetate-acetic acid system, 591 Sodium chloride (NaCl), 43 electrolysis of aqueous, 689 electrolysis of molten, 687 melting ice with, 450 structure of, 43, 418 Sodium hydroxide (NaOH), 552 in saponification, 387 in titrations, 126, 597, 599 Sodium stearate, 387 Solar energy, 177 Solar radiation as energy source, 172 Solids See also Crystals bonding in, 416 characteristic properties of, 400 (table) solutions of, in liquids, 437 temperature and solubility of, 443 Solid-liquid equilibrium, 424 Solid-vapor equilibrium, 426 Solubility, 101, 438, 608 common-ion effect and, 613 gas, 444 molar, 608 and pressure, 445 rules of, 101 and temperature, 443 Solubility equilibria, 606 common-ion effect and, 613 complex ions and, 614 cha75632_ndx_I1-I12.indd Page I-11 11/20/09 5:17:01 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Solubility product, 606, 607 (table) molar solubility and, 608 qualitative analysis of, 617 Solutes, 98 nonvolatile, 447 volatile, 448 Solution, 98, 437 concentration units, 118, 440 dilution of, 120 electrolyte, colligative properties of, 457 heat of, 438 ideal, 449 isotonic, hypertonic, and hypotonic, 453 nonelectrolyte, colligative properties of, 447 saturated, 437 standard, 124 supersaturated, 437 types of, 437 unsaturated, 437 Solution process, 437 Solution stoichiometry, 122, 597 Solvation, 439 Solvent, 98 Somatic effects of radiation, 754 Sorensen, Soren, 548 sp Hybridization, 338, 346 sp2 Hybridization, 339, 345 sp3 Hybridization, 336 sp3d Hybridization, 344 sp3d2 Hybridization, 344 Space-filling model, 41 Specific heat (s), 191 Spectator ions, 103 Spectrochemical series, 718 Spectrum absorption, 470, 717 emission, 218 visible See Visible spectrum Speed of electromagnetic waves, 213 of light, 213 Maxwell speed distribution, 160 Spin See Electron spin Spontaneous processes, 629 Square planar complex, 720 Stability belt of, 732 nuclear, 731 Stability constant See Formation constant Stable nucleus, 731 Staggered conformation, 368 Stalactites, 606 Stalagmites, 606 Standard atmospheric pressure, 139 Standard emf, 668 o Standard enthalpy of formation (DHf ), 197, A-2 o Standard enthalpy of reaction (DHrxn), 198 ° Standard entropy (S ), 633, A-2 Standard entropy of reaction (DSorxn), 636 Standard free energy of formation (DG of), 642, A-2 Standard free energy of reaction o ), 642 (DGrxn Standard hydrogen electrode (SHE), 668 Standard reduction potential, 667, 670 (table) of transition metals, 706 Standard solution, 124 Standard state, 197, 642 Standard temperature and pressure, (STP), 147 Standing waves, 223 State excited, 220 ground, 219 oxidation See Oxidation numbers standard, 197, 642 thermodynamic, 180 State functions, 180 State of a system, 180 Staudinger, Hermann, 762 Steam engine, 628 Stereoisomers, 713 Stock solution, 120 Stoichiometric amounts, 83 Stoichiometry, 80 actual, theoretical, and percentage yields in, 86 and gas reactions, 151 rate of reaction and, 467 STP (standard temperature and pressure), 147 Straight-chain alkanes, 366 Strength of acids and bases, 105, 551, 570 Strong acids, 105, 551 Strong bases, 105, 552 Strong-field ligands, 718 Strontium, 270 Strontium-90, 271, 743 Structural formula, 42, 365 Structural isomers, 365 Styrene-butadiene rubber (SBR), 764 Subatomic particles, 36, 729 Sublimation, 426 Subshell, 227 Substance, Substituted alkanes, chirality of, 389 Substitution reactions, 381 Substrates, 497 Subunits, 721, 771 Subcritical mass, 741 Sulfur, 274 combustion of, 114, 181 in vulcanization process, 764 Sulfur dioxide (SO2) geometry of, 325 Lewis structure of, 325 Sulfur hexafluoride (SF6), 324, 344, 424 Sulfur tetrafluoride (SF4), 326 Sulfur trioxide (SO3), 274, 579 Sulfuric acid (H2SO4) in batteries, 682 as diprotic acid, 106, 551 ionization constant of, 563 as strong acid, 551 Sun nuclear fusion in, 748 See also Solar radiation Superoxide ion, 112, 754 Supersaturated solution, 437 I-11 Surface tension, 407 Surroundings, 178, 638 Syndiotactic polymers, 763 Synthetic rubbers (elastomers), 764 System, 178 closed, 178 isolated, 178 open, 178 state of, 179 T Technetium-99, 752 Teflon (polytetrafluoroethylene), 762 Temperature chemical equilibria and changes, 530 chemical reactions and, 485 critical, 424 and rate of reaction, 485 solubility and, 443 and water vapor pressure, 156 (table) Temperature scales Celsius, 11, 144 Farenheit, 11 Kelvin, 11, 144 Temporary dipole, 403 Termites, 365 Termolecular reactions, 490 Ternary compound, 45 Tetrahedral complex, 720 Tetrahedron, 323 Thalidomide, 391 Theoretical yield, 86 Theory, Therapeutic chelating agents, 722 Thermal energy, 177 Thermal motion, 159 Thermal (slow) neutrons, 743 Thermal pollution, 444, 746 Thermochemical equation, 188 Thermochemistry, 178 Thermodynamics, 179, 629 first law of, 180 and living system, 651 second law of, 635 third law of, 639 Thermonuclear bomb, 749 Thermonuclear reactions, 748 Thiosulfate ions, 751 Third law of thermodynamics, 639 Thomson, G P., 224 Thomson, Joseph, 32 Three Mile Island nuclear reactor, 747 Thymine, 774 Thyroid gland, 751 Time SI unit of, Titration, 124, 597 strong acid vs strong base, 597 strong acid vs weak base, 602 weak acid vs strong base, 599 Titration curve, 598, 600, 603 TNT, 176 Tokamak, 749 Toluene, 448 Torr, 139 Torricelli, Evangelista, 139 cha75632_ndx_I1-I12.indd Page I-12 11/20/09 5:17:01 PM user-s180 I-12 /Volumes/MHDQ-New/MHDQ144/MHDQ144-ndx Index Toxicity of carbon tetrachloride, 372 of chloroform, 372 of gases, 137 of methanol, 384 of plutonium-239, 747 of strontium-90, 271 Tracers, 751 Trans isomers See Cis-trans isomers Transfer RNA, 776 Transition metal(s), 239, 704 electron configuration, 239, 705 oxidation numbers of, 113, 706 Transition state, 484 Translational motion, 633 Transmutation, nuclear, 729, 740 Transpiration, 454 Transuranium elements, 742 (table), 743 Trigonal bipyramid, 324 Tripeptide, 770 Triple bonds, 293, 345 Triple point, 427 Tripositive ion, 260 Triprotic acid, 106, 562 Tritium, 37, 741 U Ultraviolet (UV), 214 Uncertainty principle, 225 Unimolecular reaction, 490 Unipositive ion, 260 Unit cell, 410 Unit, SI, Unsaturated hydrocarbons, 375 Unsaturated solution, 437 Unshared electron pairs, 292 Uracil, 774 Uranium fission product of, 743 isotopes of, 37, 747 Uranium decay series, 737 Uranium oxide (U3O8), 746 Uranium-235, 37, 743, 744 Uranium-238, 37 in breeder reactor, 747 dating with, 739 decay of, 737 V Valence bond theory, 334 Valence electrons, 254 Valence shell, 321 Valence shell expansion, 344 Valence-shell electron-pair repulsion (VSEPR) model, 321 and molecules in which central atom has no lone pairs, 321 and molecules in which central atom has one or more lone pairs, 324 Valine, 769, 771 van der Waals constants, 165 (table) van der Waals equation, 165 van der Waals forces, 401 van der Waals, Johannes, 164 van’t Hoff factor, 457 Vapor, 137 Vapor pressure, 156, 421 Vaporization (evaporation), 420 entropy and, 646 molar heat of, 421, 422 (table) Vapor-pressure lowering, 447 Vector, 332 Vibrational motion, 634 Viscosity, 407 Visible spectrum, 214, 717 Vision, 374 Vitamin C See Ascorbic acid Volatile solute, 448 Volt, 666 Voltaic cell, 665 Volume, 10 chemical equilibria and changes in, 529 SI unit of, 10 Volume-temperature relation of gases, 144 Volumetric flask, 8, 119 VSEPR See Valence-shell electron-pair repulsion model Vulcanization, 764 Water vapor, pressure of, 156 (table) Watson, James, 774 Wave function, 225 Wave mechanics, 226 Wavelength, 212 color and, 214, 716 radiation and, 214 Wave-particle duality, 222 Waves, 212 electromagnetic, 213 frequency, 212 interference, 349 length, 212 properties of, 212 standing, 223 Weak acids defined, 105, 551 ionization constants of, 555, 556, 563 Weak bases defined, 105, 552 ionization constants of, 566, 567 Weak-field ligands, 718 Weight, atomic See Atomic mass molecular See Molecular mass percentage, composition by See Percentage composition White phosphorus, 273 Wood alcohol See Methanol Work, 177, 182 electrical, 673 free energy and, 673 and gas expansion, 182 W X rays, 33 periodic table and, 252 X-ray diffraction, 410 Xenon, 275 Waste disposal, radioactive waste, 748 Water acid-base properties of, 546 autoionization of, 546 boiling point of, 424 density of, 409 dipole moment, 333 electrolysis of, 688 geometry of, 326 hydrogen bonds in, 405, 409 ion product constant, 547 Lewis structure, 292 as moderator, 746 phase diagram of, 427 specific heat of, 191, 408 structure of, 326, 409 surface tension of, 407 vapor pressure of, 156 (table) viscosity of, 407 X Y Yields actual, 86 percent, 86 theoretical, 86 Z Zero electron density (node), 223, 350 Zero-order reactions, 482 Zinc in batteries, 680 cathodic protection with, 687 Zincblende, 417 44.96 39 Calcium 40.08 38 Potassium 39.10 37 (223) 5B 6B 7B 8B 10 11 1B 12 2B (227) Actinium (257) Rutherfordium Rf 104 178.5 Hafnium 72 Hf 91.22 Zirconium 40 Zr 47.88 Titanium 22 Ti Protactinium (231) Thorium 232.0 238.0 Uranium U 92 Pa 91 Th 90 144.2 140.9 Neodymium Praseodymium 60 Nd (262) Bohrium Bh 107 186.2 Rhenium 75 Re (98) Technetium 43 Tc 54.94 Manganese 25 Mn Cerium 59 Pr (263) Seaborgium Sg 106 183.9 Tungsten 74 W 95.94 Molybdenum 42 Mo 52.00 Chromium 24 Cr 140.1 58 Ce (260) Dubnium Db 105 180.9 Tantalum 73 Ta 92.91 Niobium 41 Nb 50.94 Vanadium V 23 (237) Neptunium 93 Np (147) Promethium 61 Pm (265) Hassium Hs 108 190.2 Osmium 76 Os 101.1 Ruthenium 44 Ru 55.85 Iron 26 Fe (242) Plutonium 94 Pu 150.4 Samarium 62 Sm (266) Meitnerium Mt 109 192.2 Iridium Ir 77 102.9 Rhodium 45 Rh 58.93 Cobalt 27 Co (243) Americium 95 Am 152.0 Europium 63 Eu (269) Darmstadtium Ds 110 195.1 Platinum 78 Pt 106.4 Palladium 46 Pd 58.69 Nickel 28 Ni (247) Curium 96 Cm 157.3 Gadolinium 64 Gd (272) Roentgenium Rg 111 197.0 Gold 79 Au 107.9 Silver 47 Ag 63.55 Copper 29 Cu (247) Berkelium 97 Bk 158.9 Terbium 65 Tb 112 200.6 Mercury 80 Hg 112.4 Cadmium 48 Cd 65.39 Zinc 30 Zn (249) Californium 98 Cf 162.5 Dysprosium 66 Dy 113 204.4 Thallium 81 Tl 114.8 Indium 49 In 69.72 Gallium 31 Ga 26.98 Aluminum (254) Einsteinium 99 Es 164.9 Holmium 67 Ho 114 207.2 Lead 82 Pb 118.7 Tin 50 Sn 72.59 Germanium 32 Ge 28.09 Silicon Si 14 12.01 Carbon C 14 4A (253) Fermium 100 Fm 167.3 Erbium 68 Er 115 209.0 Bismuth 83 Bi 121.8 Antimony 51 Sb 74.92 Arsenic 33 As 30.97 Phosphorus P 15 14.01 Nitrogen N 15 5A (256) Mendelevium 101 Md 168.9 Thulium 69 Tm 116 (210) Polonium 84 Po 127.6 Tellurium 52 Te 78.96 Selenium 34 Se 32.07 Sulfur S 16 16.00 Oxygen O 16 6A (254) Nobelium No 102 173.0 Ytterbium 70 Yb (117) (210) Astatine 85 At 126.9 Iodine I 53 79.90 Bromine 35 Br 35.45 Chlorine 17 Cl 19.00 Fluorine F 17 7A Lr (257) Lawrencium 103 175.0 Lutetium 71 Lu 118 (222) Radon 86 Rn 131.3 Xenon 54 Xe 83.80 Krypton 36 Kr 39.95 Argon 18 Ar 20.18 Neon 10 Ne 4.003 Helium He 18 8A The 1–18 group designation has been recommended by the International Union of Pure and Applied Chemistry (IUPAC) but is not yet in wide use In this text we use the standard U.S notation for group numbers (1A–8A and 1B–8B) No names have been assigned for elements 112–116 and 118 Element 117 has not yet been synthesized Nonmetals Metalloids Metals Radium (226) Francium Ac 89 Ra 88 Fr 87 138.9 Lanthanum Barium 137.3 Cesium 132.9 La 57 Ba 56 Cs 55 87.62 Yttrium 88.91 Strontium Y 85.47 Sr Rubidium Rb Scandium 21 Sc 20 19 Ca 24.31 K Magnesium Sodium 22.99 Al 13 Mg 12 11 Na Boron 10.81 B 13 3A 9.012 4B Atomic mass Beryllium 3B Carbon 12.01 Atomic number Lithium Be 2A C 6.941 Li 1.008 Hydrogen H 1 1A cha75632_ep.indd Page 10/14/09 6:26:03 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-EndPaper cha75632_ep.indd Page 10/14/09 6:26:05 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-EndPaper List of the Elements with Their Symbols and Atomic Masses* Element Actinium Aluminum Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Bohrium Boron Bromine Cadmium Calcium Californium Carbon Cerium Cesium Chlorine Chromium Cobalt Copper Curium Darmstadtium Dubnium Dysprosium Einsteinium Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Hassium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese Meitnerium Symbol Atomic Number Atomic Mass† Ac Al Am Sb Ar As At Ba Bk Be Bi Bh B Br Cd Ca Cf C Ce Cs Cl Cr Co Cu Cm Ds Db Dy Es Er Eu Fm F Fr Gd Ga Ge Au Hf Hs He Ho H In I Ir Fe Kr La Lr Pb Li Lu Mg Mn Mt 89 13 95 51 18 33 85 56 97 83 107 35 48 20 98 58 55 17 24 27 29 96 110 105 66 99 68 63 100 87 64 31 32 79 72 108 67 49 53 77 26 36 57 103 82 71 12 25 109 (227) 26.98 (243) 121.8 39.95 74.92 (210) 137.3 (247) 9.012 209.0 (262) 10.81 79.90 112.4 40.08 (249) 12.01 140.1 132.9 35.45 52.00 58.93 63.55 (247) (269) (260) 162.5 (254) 167.3 152.0 (253) 19.00 (223) 157.3 69.72 72.59 197.0 178.5 (265) 4.003 164.9 1.008 114.8 126.9 192.2 55.85 83.80 138.9 (257) 207.2 6.941 175.0 24.31 54.94 (266) Element Mendelevium Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium Potassium Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Roentgenium Rubidium Ruthenium Rutherfordium Samarium Scandium Seaborgium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium Symbol Atomic Number Atomic Mass† Md Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rg Rb Ru Rf Sm Sc Sg Se Si Ag Na Sr S Ta Tc Te Tb Tl Th Tm Sn Ti W U V Xe Yb Y Zn Zr 101 80 42 60 10 93 28 41 102 76 46 15 78 94 84 19 59 61 91 88 86 75 45 111 37 44 104 62 21 106 34 14 47 11 38 16 73 43 52 65 81 90 69 50 22 74 92 23 54 70 39 30 40 (256) 200.6 95.94 144.2 20.18 (237) 58.69 92.91 14.01 (253) 190.2 16.00 106.4 30.97 195.1 (242) (210) 39.10 140.9 (147) (231) (226) (222) 186.2 102.9 (272) 85.47 101.1 (257) 150.4 44.96 (263) 78.96 28.09 107.9 22.99 87.62 32.07 180.9 (99) 127.6 158.9 204.4 232.0 168.9 118.7 47.88 183.9 238.0 50.94 131.3 173.0 88.91 65.39 91.22 *All atomic masses have four significant figures These values are recommended by the Committee on Teaching of Chemistry, International Union of Pure and Applied Chemistry † Approximate values of atomic masses for radioactive elements are given in parentheses cha75632_ep.indd Page 10/14/09 6:26:06 PM user-s180 /Volumes/MHDQ-New/MHDQ144/MHDQ144-EndPaper Fundamental Constants 6.0221415 1023 1.60217653 10219 C 9.1093826 10228 g 96,485.3383 C/mol e2 8.314 J/K ? mol (0.08206 L ? atm/K ? mol) 6.6260693 10234 J ? s 1.672621 10224 g 1.67492728 10224 g 2.99792458 108 m/s Avogadro’s number Electron charge (e) Electron mass Faraday constant (F) Gas constant (R) Planck’s constant (h) Proton mass Neutron mass Speed of light in vacuum Useful Conversion Factors and Relationships lb 453.6 g in 2.54 cm (exactly) mi 1.609 km km 0.6215 mi pm 10212 m 10210 cm gal 3.785 L quarts atm 760 mmHg 760 torr 101,325 N/m2 101,325 Pa cal 4.184 J (exactly) L ? atm 101.325 J J51C31V 5°C ?°C (°F 32°F) 9°F 9°F (°C) (32°F) ?°F 5°C 1K b ?K (°C 273.15°C) a 1°C 1 1 1 1 1 Color Codes for Molecular Models H B C N O F P S Cl Br I cha75632_ep.indd Page 10/21/09 7:14:05 PM user-s176 /Volumes/MHDQ-New/MHDQ144/MHDQ144-EndPaper Some Prefixes Used with SI Units tera (T) giga (G) mega (M) kilo (k) deci (d) 1012 109 106 103 1021 centi (c) milli (m) micro (m) nano (n) pico (p) 1022 1023 1026 1029 10212 Index of Important Figures and Tables Acid-base indicators Amino acids Atomic radii Bond enthalpies Critical temperatures of substances Electron affinities of the elements Electron configurations of the elements Electronegativities of the elements Formation constants of complex ions Homonuclear diatomic molecules of the second-period elements Hybrid orbitals Ionic radii Ionization constants of bases Ionization constants of diprotic and polyprotic acids Ionization constants of monoprotic acids Ionization energies of the elements Molar heats of fusion Molar heats of vaporization Molecular geometry (central atom has no lone pairs) Molecular geometry (central atom has one or more lone pairs) Names of anions containing metal atoms Names of common inorganic cations and anions Names of common ligands Naming ionic and molecular compounds Organic functional groups Oxidation numbers of the elements Qualitative analysis flowchart Solubility product constants Solubility rules Specific heats of common substances Standard enthalpies of formation of elements and compounds Standard entropies of elements and compounds Standard free energies of formation of elements and compounds Standard reduction potentials van der Waals constants Water vapor pressure at various temperatures 605 768 258 311 425 266 240 294 616 356 341 261 567 563 556 263 426 422 322 328 711 46 711 49 388 113 618 607 101 191 A-2 A-2 A-2 670 165 156 ... 21 411 kJ/mol 2C2H2 (g) 5O2 (g) ¡ 4CO2 (g) 2H2O(l) DH° 22 599 kJ/mol H2 (g) 12O2 (g) ¡ H2O(l) DH° 22 85.8 kJ/mol calculate the heat of hydrogenation for acetylene: C2H2 (g) H2 (g) ¡ C2H4 (g) 11.49... DHvap 26 .0 kJ/mol The data are P1 401 mmHg    C2H5OC2H5 P2 ? T1 18°C 29 1 K      T2 29 °C 3 02 K From Equation ( 12. 4) we have ln 26 ,000 J/mol 29 1 K 3 02 K 401 c d P2 8.314 J/K ? mol (29 1 K) (3 02 K)... Diethyl ether (C2H5OC2H5) Ethanol (C2H5OH) Tc(°C) 1 32. 4 21 86 Pc(atm) 111.5 6.3 28 8.9 47.9 31.0 73.0 1 92. 6 35.6 24 3 63.0 Mercury (Hg) 14 62 Methane (CH4) 28 3.0 45.6 Molecular hydrogen (H2) 22 39.9 12. 8