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The coulombic attraction is directly proportional to the charge on each ion (Equation 1) so the ions with the higher charges will give the greater
3 + 2 − a , O . coulombic attraction. The answer is therefore (b) G
+ The Li+ ion is smaller than the R ion (58 vs 149 pm). Because the b
lattice energy is related to the coulombic attraction between the ions, it will be inversely proportional to the distance between the ions (see Equation 2). Hence the larger rubidium ion will have the lower lattice energy for a given anion. 2.5 2.7 (a) 5; (b) 4; (c) 7; (d) 3
1 0 2 5 1 0 2
A r ] 3 d 4 s ; K r ] 4 d ; A r ] 3 d 4 s (a) [Ar]; (b) [ (c) [ (d) [
1 41 02
1 0 1 0 X e ] 4 f5 d 6 s ; X e ] 4 f5 d (a) [ (b) [ (c) [ (d) [ A r ] 3 d ; A r ] 3 d ;
1 4 1 0
K r ] 4 d 5 s ; (a) [ same; In+ and Sn2+ lose 5p valence electrons. (b) none 1 0 K r ] 4 d ; Pd (c) [
1 0 2 2 + 2 + 2 + 2 + (a) C (d) N o ; (b) F e ; (c) M o ; b
2.13 2.15 2.17
3 + 3 + 3 + 3 + (a) C o ; (b) F e ; (c) R u ; (d) M o
(a) 4s; (b) 3p; (c) 3p; (d) 4s
(a) −1; (b) −2; (c) +1; (d) +3 (+1 sometimes observed); (e) +2
(a) 3; (b) 6; (c) 6; (d) 2 K r ] 4 d 5 s ; K r ] 4 d ;no unpaired (a) [ no unpaired electrons; (b) [
1 0 2 1 0 1 4 4 X e ] 4 f 5 d ; electrons; (c) [ four unpaired electrons; (d) [Kr]; no 8 unpaired electrons; (e) [ A r ] 3 d ;two unpaired electrons
(a) 3p; (b) 5s; (c) 5p; (d) 4d (a) +7; (b) −1; (c) [Ne] for +7, [Ar] for −1; (d) electrons are lost or added to give noble-gas configuration.
2.29 2.31 2.33
g A s ; n S l H ; T e ; iF (a) M (b) I (c) A (d) H (e) B 3 2 2 3; 3 2 3 i O ; b O ; l O (a) B (b) P (c) T 2 3 2 2 3
Cl Cl C Cl Cl
O Cl C Cl
F F N F
E must be a member of the nitrogen family and since it is a third period element E must be phosphorous (P) . of the 11 electrons remaining. these must come from E.39 C H O C O H O H The structure has a total of 32 electrons. 6 come from the oxygen.37 O (a) H C H (b) H H C H H (c) H N H 2.35 H (a) H B H H H (b) Br O (c) N H 2. This leaves 5 electrons unaccounted for. of these.2. Therefore. 21 are accounted for by the chlorines (3 Cl’s × 7 valence electrons each).
41 H (a) H N H H 2.2.45 Cl O N O O Cl N O 2.47 0 +1 + (a) N O (b) N 0 N 0 -1 +1 (c) C O (d) C -1 C -1 -2 -1 0 - (e) C N .43 H H C C H C H C C C C H H C C C C H H C C C H H H H C C C H H C C C C H H C C C C H H C C C H H ( Cl K b K ) K P 3_ ( c ) Na Cl O H H C C H C H C C C H C C C C H H C C C C H H H H H C C H C C C C H H C C C C H H C C C C H H H 2.
. 0 . . . all of the atoms have formal charges of 0. . +1 S O ..2. in the second structure..53 (a) In the first structure.. lower energy . lower energy .. . 0 O . .49 2. and the other F is +1. .51 H -1 10 -1 (a) O . -1 . 0 1- ... . .. . . whereas. O .. in the second . O H O .. whereas... -1 -1 . . +1 -1 (b) O . one F is 0. . S -1 +2 O S H O ... .. 2.. . Xe is −1.. O .. ... O ...... the formal charges at Xe and F are 0... 0 S O H O ...... .... . . 10 O .. (b) In the first structure. ... 0 1-1 . . The first structure is favored on the basis of formal charges.
(b) There is one Lewis stucture that obeys the octet rule: - O H S O O The formal charge at sulfur can be reduced to 0 by including one double bond contribution. 2. its placement near an oxygen atom makes it less likely for that oxygen atom to donate a lone pair to an adjacent atom. unlike the sulfite ion. one O atom has a formal charge of +1 and the other O has a formal charge of −1.55 (a) The sulfite ion has one Lewis structure that obeys the octet rule: -2 O S O O and three with an expanded octet: -2 -2 -2 O S O O O S O O O S O O The structures with expanded octets have lower formal charges. which has three resonance forms. The first structure is thus preferred. the presence of the hydrogen ion restricts the electrons to the oxygen atom to which it is attached. - O H S O O O H S O O Notice that.structure. Because H is electropositive. This change gives rise to two expanded octet structures. .
.. .. . O Cl O O . ... O .. ..... ... O . O .57 Radicals are species with an unpaired electron.. . ..... . The formal charge at Cl can be reduced to 0 by including three doublebond contributions... . . .... O . . . 2. . O ... O . . .. . . . Cl O O . O ... . . there are two resonance forms.. O .. .(c) The perchlorate ion has one Lewis structure that obeys the octet rule: O .. . . For the nitrite ion.... . O . . both of which obey the octet rule: O N O O N O .. O .. thereby giving rise to four resonance forms. Cl O .. Cl O .. therefore only (b) and (c) are radicals since they have an odd number of electrons while (a) and (d) have an even number of electrons allowing Lewis structures to be drawn with all electrons paired. . .... .. . .. O ..... .. Cl O ...
61 + (a) Cl I Cl I has 2 bonding pairs and 2 lone pairs - Cl I has 4 bonding pairs and 2 lone pairs (b) Cl I Cl Cl I has 3 bonding pairs and 2 lone pairs (c) Cl Cl I Cl Cl I has 5 bonding pairs and 1 lone pair (d) Cl Cl I Cl Cl . therefore (a) and (c) are radicals.2.59 The Lewis Structures are (a) Cl O (b) Cl O O Cl O (c) O N O Cl Radicals are species with an unpaired electron. 2.
65 (a) F O Xe F F 2 lone pairs (b) F Xe F F (c) F F O Xe F F 2 lone pairs 1 lone pair 2. .7) < Br (3.67 2.0) In (1.6) (a) The bond in HCl would be more ionic. The electronegativity difference is greater between H and Cl then between H and I. making the HCl bond more ionic. F (b) The bonds in C 4 would be more ionic.1) < Se (2.2.0) < Sb (2.0) < Cl (3. making the C—F bonds more ionic.71 I (2.69 2.8) < Sn (2.2) < F (4.63 (a) F F F S F F F 10 electrons F (b) F Xe 12 electrons (c) F F F As F F F (d) Cl Cl Cl Te Cl 12 electrons 10 electrons 2. The electronegativity difference is greater between C and F than between C and H.
the bond is an average of three Lewis structures in which the bond is double in one form and single in two of the forms. In the sulfite ion. Because these S—O bonds would have a substantial amount of single bond character. 2. we expect the bond length to be longest in carbonate. In carbonate.73 + 2 + 2 + <S <B . 116 pm. 2 − S O O (b) S O 2~ S 3 3 > O Similar arguments can be used for these molecules as in part (a). We would thus expect the bond order to be approximately 1. The ionic radii for these species are 140 pm. there are three Lewis structures that have a zero formal charge at S. 196 pm. more highly charged cations have greater R b r e polarizing power. Each has one S —O double bond and two S—O single bonds. In S 2 O and S 3.3.75 2− 3− <N <C O l− < B r−. respectively. whereas the C—O bonds would be more ionic. they would be O O expected to be longer than those in S 2 or S 3. 2. so the C—S bonds would be expected to be almost completely covalent. Because the bond length is inversely related to the number of bonds between the atoms. 27 pm. The ionic radii are 149 pm. however. 2. the Lewis structures with the lowest formal charge at S have double bonds between S and each O.(c) C and S have nearly identical electronegativities. the polarizability increases as the ion gets larger and less electronegative. smaller. This is consistent with O O the experimental data that show the S—O bond lengths in S 2 and S 3 . 171 pm. In CO there is a triple O bond and in C 2 the C—O bonds are double bonds. 181 pm. respectively.77 2 − C O (a) C O 2 > CO 3 > 2 − C O 3 will have the longest C—O bond length.
3 pm. The C—N bonds are single bonds and so one might expect the bond distance to be the sum of the single bond C radius and the single bond N radius (77 plus 75 pm) which is 152 pm. This is the experimentally found value. . The experimental value is 123. 127 ppm. The C—N bond in the last molecule 3 2 would. because the C atom is involved in a multiple bond. (b) The C—O bonds in carbon dioxide are double bonds. 2. H N H H N H (c) C >C > HCN 3 2 2 H N H The C—N bond in HCN is a triple bond.0 pm.2 − to be 143 pm. so the N—N single bond in hydrazine would be expected to be ca. its radius is actually smaller. be expected to be the longest. The experimental value is 145 pm. 127 pm. O Thus we predict the CRO in C 2 to be ca. which is 2 × (60 pm) or 120 pm. Bond distance increases with size going down Group 14/IV. 2 H N H and in C it is a single bond. which is close to the experimental value of 133 pm. therefore. (d) The N —N bond is a double bond so we expect the bond distance to be two times the double bond covalent radius of N.81 (a) 77 pm + 72 pm = 149 pm (b) 111 pm + 72 pm = 183 pm (c) 141 pm + 72 pm = 213 pm. The sum of that radius (67 pm) and the N single bond radius gives 142 pm. whereas those in S O 3 range from about 145 pm to 152 pm depending on the compound. However. The covalent radius for doubly bonded carbon is 67 pm and that of O is 60 pm. 150 pm.79 (a) The covalent radius of N is 75 pm. 2. in C it is a double bond. The experimental bond length is 116. (c) The C—O bond is a double bond so it would be expected to be the same as in (b).
87 (a) Br O (c) C -1 C -1 -2 O CH3 C O CH3 O C O .2.83 +1 -1 +1 -1 +1 +1 N N N N N +1 +1 N -1 N N N N N N N N N 2.85 (a) -1 0 O -1 -2 O C O C O O -2 C O 0 C O 0 -2 0 O O C O C O O O C O C O O -2 -1 0 (b) 2.
(b) H H C C CH3 O H H C C CH3 O (c) CH3 O C H N CH3 O C H N 2. whereas N 2 has a triple bond and O 2 a double bond.91 (a) . All bonds in P4 and S 8 are single bonds. unlike the small N and O atoms.89 P and S are larger atoms that are less able to form multiple bonds to themselves. 2.
(b) N N N N N N + suitable resonance form .
9847) is obtained between lattice energy and (1 − d*/d)/d. Since oxygen is gaining electrons on going from H2O2 to H2O it is undergoing reduction. respectively. A better fit (R2 = 0. are 0 0 0 H O O H H O H Note that all atom have formal charges of zero. A possible explanation is that .72 × 10-3 2.95 (a) MI Li NaI KI RbI CsI d(M–I).9731) exists between lattice energy and d(M–I). (c) There is not close agreement between the estimated (683 kJ∙mol-1) and experimental (886 kJ∙mol-1) lattice energies. (b) The Lewis structures for hydrogen peroxide and water. on the other hand is undergoing oxidation: the oxidation number of carbon changes from +2/3 to +1 on conversion from ascorbic acid to C6H8O6 which means it is losing elecctrons.93 (a) In H2O2. oxidation numbers are far more useful in determining whether a material has been oxidized or reduced. hydrogen peroxide. suggesting that there is no driving force for this conversion based solely on formal charges. the estimated AgI lattice energy is 683 kJ∙mol-1. Ascorbic acid (C6H8O6).61 × 10-3 2. the oxidation number of oxygen is -1.887 and the Ag-I distance (309 pm).51 × 10-3 Lattice Energy. 2. (b) Using the equation L.00 × 10-3 2. since we know that hydrogen peroxide does react to form water in the lung. kJ∙mol-1 759 700 645 632 601 A high correlation (R2 = 0. the oxygen in water has an oxidation number of -2. and that this conversion is borne by the change in oxidation states. however. = 218331(1 − d*/d)/d) + 54.2.19 × 10-3 3. pm 274 294 329 345 361 (1 − d*/d)/d 3.E.
The negative charge is most likely to be concentrated at the oxygen atoms. The resulting compound is named hydroquinone. 2. (c) The protons will bond to the oxygen atoms. which are -1.the Ag+ ion is more polarizable than the alkali metal cations of similar size and therefore the bonding in AgI is more covalent.97 (a) O H H O (b) All the atoms have formal charge 0 except the two oxygen atoms. O H H H O H H H H H 2_ . Oxygen atoms are the most negative sites in the molecule and act as Lewis bases due to their lone pairs of electrons.
2.99 Number of Z 26 52 16 39 30 Configuration [Ar]3d6 [Kr] 4d105s25p56s1 [Ne]3s23p6 [Kr]4d1 [Ar] 3d84s2 unpaired e 4 2 0 1 2 Element Fe Te S Y Zn Charge 2+ 222+ 2+ Energy state ground excited ground ground excited 2.101 (a) H O N C O H O +1 -1 N C O H O +1 N C -1 O (b) H C H S O H C H S +1 O -1 (c) H C H N +1 N -1 (d) O +1 -1 N C N O N C N .
.. O ... -1 O . ... O .. . O . ... Cl O . . .. ... .. [Xe] 4f145d106s2. ... Cl O .. O . ..-1 .. -1 O ... Cl O . . Cl O . . .... . +2 Cl O . Cl O .... Cl O .... O ... O . . ... ..2. +1 Cl O . . . -1 Cl O ... O .. Cl O . .... O -1 . -1 . ............. Cl O . -1 O ..103 R H C H C H C H C R' C H H R C H C H C H C R' C H R H C H C H C H C R' C H 2. O .. -1 Cl O ... . -1 . Cl O . .... . . .. O O -1 . (c) [Xe]4f145d10.. . .107 (a) . -1 .. .. -1 . Cl O . . . .. . . . +1 .. ... 1+. O .-1 . it is probably more covalent which is consistent with the fact that the 3+ ion is more polarizing.. O .. .. 2. . O Cl O ..... +1 .. O .. O ... . O . O -1 O O .... O . . O . .. . -1 .-1 . ..... .... II: Tl2O. O ... . O ... O .. ... ... . O .... ... . +2 ..... O -1 .. .-1 O . -1 -1 O .105 (a) I: Tl2O3... ... O . +1 . -1 Cl O . +1 . . -1 .. O O . .. . O . -1 .. . .. . -1 . +1 . -1 O . O .. .. . -1 .. . -1 ... O . . O ....... -1 . (b) 3+. O +2 .. (d) Because compound II has a lower melting point... +3 . .. O . O ... O .. . O . ... -1 ... O ..... .... -1 . .. . O . -1 .. -1 .... -1 . .. O . . ....... +2 . .. . ... .
This result is reasonable because oxidation numbers are assigned by assuming ionic bonding. the four structures with three double bonds also fit because.111 Look at the Lewis structures for the molecules: -1 +1 -1 +1 (a) C O (b) O O (c) O O O -1 +1 -1 +1 (d) O S O (e) N N O (f) Ar Of these. and e can all function as greenhouse gases 2. 5 p m .109 The alkyne group has the stiffer C—H bond because a large force constant. However.113 Since the halogen all have an odd number of valence electrons (7). we can estimate the average bond length to be 1 4 3 ( 1 7 0 p m ) + ( 1 4 0 p m ) = 1 4 7 .5 pm longer than observed. results in a higher-frequency absorption. d. The structure with all single bonds fits this criterion best.The four structures with three double bonds (third row) and the one with four double bonds are the most plausible Lewis structures according to formal charge arguments because these five structures minimize the formal charges. 2. interhalogen compounds of the type XX’n will be radicals and therefore . (b) The structure with four double bonds fits these observations best since its bond lengths would all be 140 pm. or only 4 pm shorter than the observed length. k. c. 2. or just 3. (d) Approaches (a) and (b) are consistent but approach (c) is not. a. if the double bonds are delocalized by resonance. 4 (c) 7+.
this suggests that the S-S bond (which is 9 pm shorter than a Cl-Cl single bond) has some double bond character.extremely reactive unless the total number of halogens is an even number.5. on average. ICl3 as examples: Cl I Cl Cl I Cl Cl 2. Look at ICl2 vs.117 (a) The Lewis structures of NO and NO2 are: N -1 O +1 (best possible structure) +1 -1 O N O O N O (equivalent resonance structures) .5 it can be determined that. From Table 2. This can only be achieved if n is odd. 2. the Cl-Cl bond length is 199 pm. From Table 2. here the S-S bond length in S2F2 is reported to be 190 pm. (b) and (c) The Lewis structures for the two possible S2F2 are: +1 -1 F S favored S F F S S F isomer 1 F F +1 -1 F S F favored S S S isomer 2 If resonance is occurring then one would expect that the S-S bond length is indeed between a single and a double bond in length. an X-Y bond is approximately 20 pm longer that a X=Y bond.115 (a) Compare the length of a S-S bond to that of a Cl-Cl bond.
05 g N 2 O5 × 1 mol N 2 O5 108. based on oxidation number. Nitric acid is produced (f) 4. From Table 2. (c) 0 0 0 N N +1 O O -1 0 (d) O N O -1 +1 0 +1 O O N O -1 O 0 (e) N2O5(g) + H2O(l) 2 HNO3(aq). . (b) An N-O single bond should have a bond length of 149 pm while an NO double bond should have a bond length of 120 pm (values are obtained by summing the respective covalent radii values from Figure 2.From Table 2. NO2: +4. The bond dissociation energy of each NO bond in NO2 is 469 kJ mol-1.02 g N 2 O5 × × 2 mol HNO3 = 7.5 the length of a N-O triple bond can be estimated to be between 105 and 110 pm.50 1. suggesting that the resonance picture of NO2 is a reasonable one.00 L 10-2 mol ⋅ L-1 HNO3 (g) The oxidation number of nitrogen for the various nitrogen oxides are as follows: NO: +2. and N2O5: +5. N2O5 should be the most potent oxidizing agent of the nitrogen oxides. which is right in line with the Lewis structure of NO. N2O3: +3. which is about half-way between a N-O double and an N-O single bond.50 1 mol N 2O5 × × 10-2 mol HNO3 Molarity = 7. the average bond dissociation energy of a N=O bond is 630 kJ mol-1. Since NO itself has a bond length of 115 pm.21).50 10-2 mol HNO3 = 7. as it possesses the most positive oxidation number for N of the group. An oxidizing agent is a species that wants to gain electrons.4. this suggests that its actual bond order is somewhere between that of a double and a triple bond.