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Student Study Guide and Solutions M anual

fo r A t k in s a n d Jo n e s ' s

C H E M I C A L P R I N C I P L E S
The Quest f o r Insight

Fifth Ed itio n

Jo h n K r e n o s
R u tg er s . T h e S tate U n ive r s ity o f N e w Jers ey

Jo s e p h P o te n z a
R u tg ers , T h e S ta te U n iv e r s ity o f N e w Jers ey

C a r l H o e ge r
U n iv e r s ity o f C a lifo r n ia , San D ie g o

L a u r e n ce L a ve lle
U n iv e r s ity o f C a lifo r n ia , Los A n g e le s

Y in fa M a
M is s o u r i U n iv e r s ity o f S cien ce a n d T e c h n o lo g y

IS
W .H . F r e e m a n a n d C o m p a n y
N ew York

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IS B N - 13: 9 7 8 - 1 - 4 2 9 2 - 3 1 3 5 - 0
IS B N - 10: 1 - 4 2 9 2 - 3 1 3 5 - 1

© 2 005, 2 0 0 8 , a n d 2 0 1 0 b y W .H . F r eem a n a n d C o m p a n y

A l l rig h ts r es er ved .

P r in te d in th e U n ite d S tates o f A m e r ic a

First P r in tin g

W .H . F r eem a n a n d C o m p a n y
41 M a d is o n A v e n u e
N e w Y o r k . N Y 10010
H o u n d s m ills , B a s in g s to k e R G 2 1 6XS E n gla n d

w w w .w h fr e e m a n .c o m

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C O N T E N T S
P r eface v
A ck n o w led gm en t s v //

S T U D Y G U ID E SG _
1 A to m s : T h e Q u a n tu m W o r ld 1
2 C h e m ic a l B on d s 15
3 M o le c u la r S h a pe a n d S tru ctu re 25
4 T h e P r o p er ties o f G a s es 35
5 L iqu id s a n d S olid s 45
6 In o r g a n ic M a ter ia ls 57
7 T h er m o d yn a m ic s : T h e First L a w 71
8 T h e r m o d yn a m ic s : T h e S econ d a n d T h ir d La w s 85
9 P h ys ica l E q u ilib ria 99
10 C h e m ic a l E q u ilib ria
11 A c id s a n d Bases 129
12 A q u eo u s E q u ilib ria I 45
13 E l e c t r o c h e m i st r y I55
14 C h e m ic a l K in etics I 59
15 Th e E lements: Th e M a in G rou p E lements 18 7
16 T h e E lem en ts: T h e d B lo ck 217
17 N u c le a r C h e m is tr y 233
18 O r g a n ic C h e m is tr y 1: T h e H yd r o ca r b o n s 245
19 O r g a n ic C h e m is tr y II: P o lym er s a n d B io lo g ica l
C om p ou n d s 257

S O L U TIO N S M A N U A L SM _
F u n d a m en ta ls 3
1 A t o m s: T h e Q u a n t u m W o rld 53
2 C h e m ic a l B on ds 75
3 M o le c u la r S hape a n d S tru ctu re 97
4 T h e P ro p er ties o f G a ses 119
5 L iqu id s a n d S olid s I 47
6 In or g a n ic M a te r ia ls 171
7 T h er m o d yn a m ic s : T h e First L a w 183
8 T h er m o d yn a m ic s : T h e S econ d a n d T h ir d La w s 211
9 P h ys ica l E q u ilib ria 239
10 C h e m ic a l E q u ilib ria 273
11 A c id s a n d B ases 313
12 A q u eo u s E q u ilib ria 355
13 E le ctro ch em is tr y 395
14 C h e m ic a l K in etics 435
15 Th e Elements: Th e M a in G rou p E lements 4 59
16 T h e E l e m e n t s: T h e d B l o c k 4 79
17 N u c le a r C h e m is tr y 499
18 O r g a n ic C h em is tr y 1: T h e F iyd r oca rb o n s 521
19 O r g a n ic C h em is tr y II: P o ly m e r s a n d B io lo g ica l
C om p ou n d s 543

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SO L U T I O N S M A N U A L

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FUNDA M ENT A LS

A .l (a ) ch em ica l; (b ) physica l; (c ) physical

A .3 Th e temperatu re o f the inju red camper, the eva pora tion and condensation

o f w a ter are physica l properties. Th e ignition o f propane is a chemica l

change.

A .5. (a ) Ph ys ica l; (b ) C h em ica l; (c ) C h em ica l

A .7 (a ) in ten sive; (b ) intensive; (c ) exten s ive; (d ) exten sive

( \
1 A'/log rah?
A .9 (a ) 1000. grain x = 1 kilogra in
1,000 grain

100 centibatman \
(b ) 0.01 batman x = 1 centib atman
V 1 batman )

1 megamutchkin ] . ,, -
(c ) l x l 0b mu tchkin x - - - - - ^- - - - - - - - - - - - = 1 megamu tchkin 1
0
106 mutchkin J

1 pint 1 quart 0.946 L 1000 m L

A .ll 1.00 cu p x ( ^ ---- ) x ( - 1, ) x ( - - - - - - - - ) x ( — — ---- ) = 236 m L
2 cups 2 pints 1 quart 1L

. m
A . 13 a - —
V
f 112.32 e mL 1

29.27 m L - 23.45 m L cm

- 19.3 g • c m '-'

SM -3
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3.13 Th e L ew is structures are

F- O O ,

(a ) Th e shape o f C F,C l is tetrahedral; all h a logen — C — ha logen a n gles shou ld be

a p p roxim a tely 109.5°. A X 4;

(b ) T e C l 4 m olecu les w ill be see saw shaped w ith C l— Te— C l b ond angles o f

a p p roxim a tely 90° and 120°. A X (E;

(c ) C O F 2 m olecu les w ill be trigonal planar w ith F — C F and O — C — F angles

o f 120°. A X , ;

(d ) CH~ ions w ill be trigonal pyra m ida l w ith H — C — H a ngles o f s ligh tly less

than 109.5°. A X , E

3.15 (a ) Th e angles represented b y a and b are expected to b e ab ou t 120°, w h ile c is

exp ected to b e ab ou t 109.5° in 2, 4- pentanedione. A ll o f the a n gles are expected

to b e ab ou t 120° in the a cetyla cetona te ion.

(b ) Th e m a jor d ifferen ce arises at the C o f the origin a l sp 2- h yb rid ized C H 2

grou p, w h ich u pon deprotona tion and resonance goes to sp2 h yb rid iza tion with

on ly three grou ps attached (th e dou b le- headed a rrow is read as “ in resonance

w ith ” ):

H H

3.17 (a ) s ligh tly less than 120; : (b ) 180°; (c ) 180°; (d ) s ligh tly less then

109.5°

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7.95 A p p en d ix 2 A p rovides us w ith the heat o f form a tion o f

h ( g ) at 298K (+ 6 2 .4 4 kJ • m ol-1) and the heat ca pa cities o f

I, ( g ) (36.90 J - K ' 1 • m o r 1) and I 2( s ) (54.44 J ' K " 1 • m ol-1). W e can

calcu late theA/ / sub° at 298K:

1, ( s ) ---- > 1, ( g ) A//sub0 = + 62.44 kJ • m o l"1

W e can calcu late the enthalpy o f fu s ion from the rela tion sh ip

= AH

but these va lu es need to b e at the same temperatu re. T o correct the va lu e

for the fa ct that vve w a n t all the nu mb ers for 298K, w e need to alter the

heat o f va p oriza tion , u sing the heat capacities for liqu id and gaseou s

iodine.

1,(1) at )8 4 .3 ° C - - - - - ■+ 1, ( g ) at 184.3°C A t f v>p0 = + 41,96 k.l • m ol 1

From S ection 6.22, w e fin d the fo llo w in g rela tion sh ip

& H ,, U + & C PJ ( T 2 - T t)

= A + 3M7, 5, ° + ( C PJ ( I2,g ) - C P,„°(12>I)) ( T2 - T t)

= + 41.96 kJ- m or'

+ (36.90 J • K~ ' • m ol-1 - 8 0 .7 J - K ' 1 • m o r ') ( 2 9 8 K - 4 7 5 . 5 K )

= + 4 9 .7 3 k J - m o l'1
S o, at 298K:

+ 62.44 kJ ■m o l'1 - A H (J + 49.73 kJ • m ol-1

A H tJ = + 1 2 .7 1 k J - m o !''

7.97 First, w e ’ ll w7ork ou t h ow much heat w a s requ ired to raise the temperatu re

o f the w a ter sample: 9 = g C A T = (1 5 0 g ) ( 4 . 1 8 J . ° C V ) ( 5 . 0 0 * C ) = 31353

S in ce b oth the w a ter and ice samples w ere at 0.00° C and the w a ter sample

took 0.5 h to get to 5.00° C , w e can estimate that the ice took 10.0 h to

melt. I f 3135 J o f heat w ere transferred in 0.5 h, then the amou nt o f heat

transferred in 10.0 h is,

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There is a correlation between the bond dissociation energy and the free
energy o f formation o f the atomic species, but the relationship is clearly
not linear.

120
e
100

9
&
9
O E 60

o
c
o
4) 20
4*

0
0 10 20 30 40 50 60

atomic number

For the heavier three halogens, there is a trend to decreasing free energy o f
formation o f the atoms as the element becomes heavier, but fluorine is
anomalous. The F— F bond energy is lower than expected, owing to
repulsions o f the lone pairs o f electrons on the adjacent F atoms because
the F— F bond distance is so short.

10.109 (a) Using the thermodynamic data in Appendix 2A:

Br,(g) —» 2 Br(g)
A G ° = 2(82.40 kJ •mol-1) - 3.11 kJ - mol*' =161.69 kJ • m ol ’ 1

= 4 .5 x 1 0 '*

For equilibrium constant calculations, this is reasonably good agreement

with the value obtained from part (a), especially if one considers that A/ / 0
w ill not be perfectly constant over so large a temperature range.
(b) We will use data from Appendix 2A to calculate the vapor pressure o f
bromine:

SM -305
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(b) £°(Cc4*/Ce^) = + 1.61 V (anode)

£°(M n04 “/Mn2*) = +1.51 V (cathode)

Because £°(Cc‘u /Ce3+) > f°(M n 04 */Mn24), the reaction does not favor

products.
(c) £°(Pb4+/Pb2+) = +1.67 V (anode)

E°( Pb2’ /Pb) = -0.13 V (cathode)

Because £°(Pb4+/Pb2+) > E°(Pb24 /Pb), the reaction docs not favor

products.

(d) £°(NOj “/N O ,/H +) = +0.80 V (cathode)

£°(Zn2* /Zn) = -0.76 V (anode)

Because £ 0(N 0 3“/NO, /H +) > E°(Zn2* /Zn), the reaction favors

products.
£ °cc|, = +0.80 V - (-0.76 V) = +1.56 V

NOj “ is the oxidizing agent.

13.33 (a) We want E° for T]3+ <ac0 + 3 e“ -+ Tl(s), n - 3.

This reaction is the reverse o f the formation reaction:
Tl(s) -» Tl3+(aq) + 3 e"

Therefore, for the T1" /T1 couple, A^ = “ 2 15 kJ' mo> ’

A G ° r = - ij / r£ ° = - 2 1 5 k J - m o l* 1

£ 0 _ aG °. - -2 -1 5 xlQ? J-moP1 _ |07>|3V

- n F -3 x 9.65 x 104 C-moP1
(b) Using the potential from part (a) and the potential from Appendix 2B

for the reduction o f Tl* t we can decide whether or not Tl* will
disproportionate in solution. The equation of interest is
3 Tl+(aq) -» 2 Tl(s) + Tl^aq).
The half-reactions to combine arc:

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Because we are not given v , it is easiest to make a relative comparison by

taking the ratio o f v for the C— D molecule versus v for the C— H

molecule:

1 k j n c mu (12.011) (1.0078)
2* m - p mt + mu 12.011 + 1.0078
" c mo (12.011) (2.0140)
_L (Z * Z m --D
mc + mn 12.011 + 2.0140
2* V lV - H

( 12.105 N
,1 3 .0 1 9 ,
0.73422
v 24.1 90v
,1 4 .0 2 5 ,

We would thus expect the vibrational frequency for the C— D bond to be

approximately 0.73 times the value for the C— H bond (lower in energy).

17.57 To determine the effective half-life we need to determine the effective rate
constant, k E. This constant is equal to the sum o f the biological rate

constant (/:B) and the radioactive decay rate constant (£R), both o f which

can be obtained from the respective half-lives:

+ /tR + - ^ - = 1.56x 10 2 d '1

90.0 d 87.4 d
In 2
(effective) = -i
= 44.4 d
1.56x10 2 d

17.59 Remember to convert g to kg.

(a) E = m cz = (1 .0 x 10~J k g)(3 .0 0 x 10s m s '1)2

= 9 .0 x l 0 13 k g •m 2 • s~2 = 9 . 0 x l 0 ,J J

(b) £ = m e1 = (9 .1 0 9 x 1 0 -” kg)(3.00 x 10s m - s 1)2

= 8.20 x 1O '’4 kg • m 2 • s '2 = 8.20 x 10 ' u J

(c) E = m e1

£ = (1 .0 x 1 O '’5 kg) (3.00 x 10s m •s ' 1) 2 = 90. kg ■m 2 • s '2 = 90. J

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