CHAPTER 1 Electronic Structure and Covalent Bonding 1. The mass number = the number of protons + the number of neutrons The atomic number = the number of protons. All isotopes of a specific element have the same atomic number; the atomic number of oxygen is 8. Therefore: The isotope of oxygen with a mass number of 16 has 8 protons and 8 neutrons. The isotope of oxygen with a mass number of 17 has 8 protons and 9 neutrons. The isotope of oxygen with a mass number of 18 has 8 protons and 10 neutrons. 2. a, Carbon has 4 valence electrons. ¢. Oxygen has 6 valence electrons. b. Nitrogen has 5 valence electrons. d. ‘Fluorine has 7 valence electrons. 3. Atoms in the same column of the periodic table have the same number of valence electrons. Potassium (K) is in the same column as lithium and sodium. Therefore potassium, like lithium and sodium, has one valence electron. 4. a. Nitrogen has 2 core electrons and 5 valence electrons. Phosphorus has 10 core electrons and 5 valence electrons. b. Oxygen has 2 core electrons and 6 valence electrons. Sulfur has 10 core electrons and 6 valence electrons. 5. We have determined (in Problem 2) that fluorine has 7 valence electrons. Fluorine, chlorine, bromine, and iodine are all in the same column of the periodic table. Therefore, chlorine, bromine, and iodine each have 7 valence electrons. 6. The polarity of a bond can be determined by the difference in the electronegativities (given in the text in Table 1.2 on page 9) of the atoms sharing the bonding electrons. For example in part a, the difference in electronegativity between H and C is 0.4 (2.5 ~ 2.1 = 0.4), whereas the difference in electronegativity between Cl and C is 0.5 (3.0 - 2. ).5). Therefore, because Cl and C have the greater difference in electronegativity, the bond between them is more polar. a. Cl—CHy © HOF b. H—OH 4. Cl—CHs10. i. Chapter 1 ‘As stated in the previous problem, the polarity of a bond can be determined by the difference in the electronegativities of the atoms sharing the bonding electrons. ‘a. KCI has the most polar bond; the difference in electronegativity between the bonding atoms is 0.22 (3.0 - 0.8 = 2.2), whereas it is 1.8 for LiBr, 1.6 for Nal, and 0 for Ch. b. Cl; has the least polar bond because the two chlorine atoms share the bonding electrons equally. To answer this question, compare the electronegativities of the two atoms sharing the bonding electrons using Table 1.2. (Notice that if the atoms being compared are in the same horizontal row of the periodic chart, the atom on the right is the more electronegative; if the atoms being compared are in the same column, the one closer to the top of the column is the more electro- negative.) ab ae a & & a. HOH b. HyxC—Nih, ¢. HO—Br a. a a. LiH and HF are polar (they have a red end and a blue end). b. Because the hydrogen of HF is blue, we know that HF has the most positively charged hydrogen. By answering this question you will see that a formal charge is a bookkeeping device. It does not necessarily tell you which atom has the greatest electron density or is the most elec- tron deficient. a, oxygen ©. oxygen b. oxygen (it is more red) d. hydrogen (it is the most blue) Notice that in hydroxide ion, the atom with the formal negative charge is the atom with the greater electron density. In the hydronium ion, however, the atom with the formal positive charge is not the most electron deficient atom.13. 14, 15. 16. 17. b. b. (CH;CH,NH) CH;NHCH3 CH3CHCH3CI Chapter 1 ©. CH;CH,OH e. CH;CH,CE 4. cHOCH, f. HONK, i ¢. CH;COCH;CH3 it 4. CHACHACNCH:CHs cH oN d. CandH C2He is possible: CHyCH has that molecular formula. CoH; is not possible C3Hy is not possible C3Hg is possible: CHsCH2CH; has that molecular formula. C4Hio is possible: CH;CH2CH2CH; has that molecular formula. 318. 19, 20. 21. Chapter 1 H HH H a nett ene bhhada h in H H H nH H H H b. Hee ant—b—_bb ten a boebn hon wo ween hk 4 4 4 The two carbon-carbon bonds form as a result of sp>— sp’ overlap. Each of the eight carbon-hydrogen bonds form as a result of sp°—s overlap. la and 1b are solved in the text. 2a. 2b. Because carbon forms only single bonds, it uses sp” orbitals. Because the four sp* orbitals of carbon orient themselves to get as far away from each other as possible, the bond angles are all 109.5°. a Qa Vv oN all the bond angles are 109.5° 3a. Ho 3b. Because carbon forms a triple bond, it uses sp orbitals; one sp orbital forms a 7 bond with hydro- gen and the other sp orbital forms a o bond with nitrogen. Carbon’s two remaining p orbitals form the two 7 bonds to nitrogen. Because carbon is sp hybridized, the H-C-N bond angle is 180°. H-C=N the bond angle is 180° CH, with no lone pairs has bond angles of 109.5°. H,0 with 2 lone pairs has bond angles of 104.5°. The bond angle decreases as the number of lone pairs increases because a lone pair is more dif- fuse than a bonding pair. Therefore, H;O° with 1 lone pair has bond angles in between those of methane and water; its bond angles will be greater than 104.5° and less than 109.5°.22. 23. 24. 25. 26. 27. 28. Chapter} 5 The hydrogens of the ammonium ion are the bluest atoms. Therefore, they have the least electron density. In other words, they have the most positive (least negative) electrostatic potential. Water is the most polar—it has a deep red area and the most intense blue area. Methane is the least polar—it is all the same color with no red or blue areas. We have seen that the carbon atom in the methyl carbanion is sp* hybridized. Because carbon has one lone pair, its bond angle should be about 107.3°, the same as the observed bond angle in NHs, another molecule with an sp” hybridized central atom and one lone pair. Bonding electrons in shells farther from the nucleus form longer bonds; they also form weaker bonds due to poorer overlap of the bonding orbitals. Therefore: a. relative lengths of the bonds in the halogens are: Br: > Ch, relative strengths of the bonds are: Cl > Brz b.. relative lengths: HBr > HCI > HF relative strengths: HF > HCl > HBr Notice that the shorter bond is the stronger bond a. 1. C—Br 2. C—C 3. H—Cl bo. CHa 2. C—H 3. H-H We know the obond is stronger than a zrbond because the c’bond in ethane has a bond dissocia- tion energy of 90 kcal/mol, whereas the bond dissociation energy of the double bond (+ 2) in ethene is 174 kcal/mol, which is less than twice as strong. Because the o bond is stronger, we know that it has more effective orbital-orbital overlap. 3 ODO BN a. Hy sp Pop Pg ("ep ” Cn (ar a be Robt ae ew pO Hes SOL SE (Oo ; eo PR cH eS OcHCHy PA _ IN eae} te Np &®) te ee Me Ng? sn6 Chapter 1 29, a, 109.5° b. 107.3° cc. 109.5° d. 104.5°* +104.5° is the correct prediction based on the bond angle in water. However, the bond angle is actually somewhat larger (111.7°) because the bond opens up to minimize the interaction between the electron clouds of the relatively bulky CH groups. 30. a. The single-bonded carbon and the single-bonded oxygen use sp’ orbitals. Each hydrogen uses an s orbital. sp>-s overlap ‘| UC. ‘\"H we OH op3.s overlap sp°-sp3 overlap the H-C-H and H-C-O bond angles are ~109.5° the C-O-H bond angle is ~104.5° b. The single-bonded nitrogen and the single-bonded oxygen use sp° orbitals. Each hydrogen uses an s orbital. sp?-s overlap wh Sy H » 7 OE ss ovetap sp?-sp? overlap the H-N-H and H-N-O bond angles are ~107.3° the N-O-H bond angle is ~104.5° ¢. The double-bonded carbon and the double-bonded oxygen use sp” orbitals. The remaining p orbital on C and the remaining p orbital on O form a zrbond. The single-bonded oxygen uses sp’ orbitals. Each hydrogen uses an s orbital. the o bond is formed by sp?-sp? overlap the 1 bond is formed by p-p overlap ps overlap iS H ‘OH (OE aps overap sp?-sp? overlap the O-C-O and H-C-O bond angles are ~120° the C-O-H bond angle is ~104.5° d. Each triple-bonded nitrogen uses sp orbitals. The remaining two p orbitals on each N form sbonds. Because the compound has only two atoms, there are no bond angles. the o bond is formed by sp-sp overlap {each 1 bond is formed by p-p overlap31. 32. 33. 34. 35. 36. 37. 38. Chapter! 7 a4 b. 5 «8 a. 2 a. sp’, 107.3° c. sp’, 107.3° e. sp’, 120° B sp, 180° b. sp’, 109.5° dsp’, 109.5° f. sp’, 120° h. sp°, 107.3° If you need help, see the answer to Problem 8. & & & & 8 be B a ROB b. HyC—cL ©. HjC—MgBr 4. H,N—On a. CH3CH2CH3 b. CH;CH=CH) ¢. CH;C=CCH; or CH;CH)>C=CH a. 109.5° b. 104.5° ce. 120° d, 180° formal charge = the number of valence electrons ~ (the number of lone-pair electrons + 1/2 the number of bonding electrons) a. formal charge = 6 — (6 + 1)=6-7 b. formal charge = 6 —(5 + 1)=6-6=0 ¢. formal charge = 5 -(4+2)=5-6=-1 we H 4, formal charge = 4 - (2+2)=4-4=0 H—C—H Is 25 2p 2y 2. 38 3px Py Hye 4s aca HW HH NN WH HH 1st 20? 2p6 30? aps as? boc Hoh WW A WW 1st 2st ape a? ape ear HN WW A RW 1st 268 ape 30? ap6 ame fH hot dt 12 262 29639. 40. 41. 42, 43. 44, Chapter 1 “d” is the only one written correctly a. CH3CH2CH3 ¢. (CH3)3CCH3 e. CH3CH2CH3 b. CHy d. (CH3)yCHCH2CH3 f. CH3CH2CH2CH3 a. C—F>C—O>C—N ¢ H—O>H—N>H—C b. C—Cl>C—Br>C—I d. C—N>C—H>C—C ° It a Hoe eoa H i H H if e. H-¢-e-0—-4 f. ana ne H HH-C-HH = HH-C—HH Notice that none of the atoms in “e” has a formal charge. at if it me a. Bere b. oe c Boone a. mn HOH HH HOH HH H The lone pair in ammonia causes the molecule to be polar; the red indicates the negative end and the blue indicates the positive end. When the lone pair is protonated to form the ammonium ion, the charge distribution in the molecule becomes symmetrical and the bond angles become larger. (The H-N-H bond angle changes from 107.3° to 109.5°.)45. 47. ~ 48. Chapter! 9 sp » se a. CH;CH=CH) . CHjCH,OH @. CHyCH=NCH oe 1 i i ! J Db. CH,CCH; d. CH,C=N f. CH3OCH CH; a. The open arrow points to the shorter of the two indicated bonds in each compound. For 1, 2, and 3: a triple bond is shorter than a double bond which is shorter than a single bond. 9 sp sp sp? sp? | =| 1. CHyCH=CHC=CH 2, CHsCCH,OH 3. CHsNHCH,CH;N=CHCH; 5? sp sp Dp sp? sp sp* sp sp? sp? sp" sp If the central atom is sp’ hybridized, the molecule will have tetrahedral bond angles. Therefore, the following have tetrahedral bond angles, although, because of lone pairs, some of the bond angles will be a little less than a “pure” tetrahedral bond angle of 109.5°. HO -H30° — NH3_-*NHy_— CH In an alkene, six atoms are in the same plane: the two sp” carbons and the two atoms that are bonded to each of the two sp” carbons. The other atoms in the molecule will not be in the same plane with these six atoms. Oca - sc ow ou, N / oe Cy H ‘CH,CH3 ro Cc no yes If you put stars next to the six atoms that lie in a plane in each molecule, you might be able to see more clearly whether the indicated atoms lie in the same plane. cH; ty A tH of A A _ CH, Vad Ved « co ASS ASN le le y Ste ¥ ‘HCH x OH x OH10 49. 50. 51. 52. Chapter 1 AIL3 carbons are sp° hybridized. All the bond angles are 109.5°. H+ H- b. w” Coxe. 120° 4. 1207 \ I Nw os? All 4 carbons are sp* hybridzed, All the bond angles are 120°. The bond between oxygen and sodium is ionic. All the other bonds are covalent. Thus, sodium methoxide has 4 covalent bonds. ‘a. An H-H bond is formed by s—s overlap. A C—C bond is formed by sp*—sp* overlap. Because an s orbital is closer to the nucleus than is an sp’ orbital, an H—H bond is shorter than a C—C bond. b. A C—H bond is formed by sp’—s overlap. Therefore, a C—H bond will be longer than an H--H bond (0.74A) but shorter than a C—C bond (1.54 A). Because the triple-bonded carbons are sp hybridized, the bond angle indicated by the arrow needs to be close to 180° if the compound is to be a stable compound; it is impossible to have a 180° bond angle in a six-membered ring. (Try to make a molecular model.) DChapter! 11 Chapter 1 Practice Test ‘What is the hybridization of the carbon atom in each of the following? cu, cH, Hy Draw the Lewis structure for H2COs. Which compound has larger bond angles, H30° or "NH? Which bond is more polar? a. C—OorC—N b. C—ClorC—F Give the structure of a compound that contains five carbons, two of which are sp” hybridized and three of which are sp° hybridized. a. What orbitals do carbon's electrons occupy before promotion? 'b. What orbitals do carbon's electrons occupy after promotion but prior to hybridization? ¢. What orbitals do carbon's electrons occupy after hybridization? Indicate whether each of the following statements is true or false: a. Api bond is stronger than a sigma bond. T OF b. A triple bond is shorter than a double bond. T F ¢. The oxygen-hydrogen bonds in water are formed by the overlap of an sp? orbital of oxygen with an s orbital of hydrogen. T OF d. A double bond is stronger than a single bond. T F €. A tetrahedral carbon has bond angles of 107.5°. T OF For each of the following compounds indicate the hybridization of the atom to which the arrow is pointing: CH;OCH; CH;CH=CH, ANSWERS TO ALL THE PRACTICE TESTS CAN BE FOUND AT THE END OF THE. SOLUTIONS MANUAL