15.55 a The equilibrium would shift to the right.. b Equilibrium would shift to the left.. An increase in pressure shifts the equilibrium to the left, restoring the color by producing N0
Trang 114.81 Since the methanol contains no oxygen-I 8, the oxygen atom must
o
II CH-O+P- O-H
O- H
14.83 Most transition metals have several stable oxidation states This
in a broad range of reactions 14.85 (a) Rate = k[CH3COCH3l[H+l
~-(Fe3+ undergoes a redox cycle: Fe3+ • Fe2+ • Fe3+) The
uncatalyzed reaction is slow because both 1- and S 2 0 ~ - are negatively
14.89 (a) rate = k[Alo = k,
[A]
[Al = -kt + [Alo,
Time
[Al o
-(b) 1 2 2k (c) t = 2t l/2 ' 14.91 There are three gases present and we
can measure only the total pressure of the gases To measure the partial
pressure of azomethane at a particular time, we must withdraw a sample
of the mixture, analyze and determine the mole fractions Then,
Pa zo m e th a n e = X azo m e thane X P total
14.93
2XG
G l + X l
2EG
14.95 (a) A catalyst works by changing the reaction mechanism, thus
lowering the activation energy (b) A catalyst changes the reaction
mechanism (c) A catalyst does not change the enthalpy of reaction (d) A
catalyst increases the forward rate of reaction (e) A catalyst increases the
reverse rate of reaction 14.97 At very high [Hll, k l [H 2l > > 1 and
,
•
,
ANSWERS TO ODD-NUMBERED PROBLEMS
k [NOF[H?l k
k 2 [ H l l k 2
[H2l, k l [H 2l < < I and
kl[NOF[H z l
rate = - ' - -
-=-14.99
:2 2 5 0 , - - - -:;. -,
~
8 2.00
o
-o
o
- 1 50
x
"
~
'" 1.00
e:::
-.,& 0 50 JL- - - - r - - - , - - - - , - - 1
- 0.50 1.00 1.50 2 00 2.50
[Dinitrogen Pentoxide] (M)
AP- 11
rate = k[N 10 5 ], k = 1.0 X 10- 5 S - I 14.101 The red bromine vapor
methyl radical then reacts with Br l , giving the observed product and
regenerating a bromine atom to start the process over again: ·CH3 +
Br2 • CH3Br + Bf" , Bf" + CH4 • HBr + ·CH3 and so on
14.103 Lowering the temperature would slow all chemical reactions,
brain 14.105 (a) Rate = k[X][yf (b) k = 0.019 M - lS - I 14.107 Second
reactions, the rate of reaction increases with temperature 14.111 (a) Ea
5.7 X 105 yr 14.115 (a) Catalyst: Mn2+ ; intermediate: Mn3+ First step
has the same phase (aqueous) as the reactants 14.1170.45 atm 14.119
(a) 6.[Bl / M = k l [Al - k 2 [Bl (b) [Bl = (k llk 2 )[Al 14.121 (a) k =
intermediates (c) The third step is rate determining (d) The reaction
(b) 2.5 X 10- 5 M i s (c) 8.3 X 10- 6 M
1
14.129 11 = 0 , ti l? = C I = C[Al o;
- [Al o
1
t = C :- = C·
11 = 1
1
11 = 2, t ill
=C [Al a
14.131 (a) 1.13 X 10-3 Mlmin (b) 6.83 X 10- 4 Mlmin; 8.8 X 10- 3 M
14.133 Second order, 0.42 IM·min 14.135 kl is 60% larger than k l •
Chapter 15
•
15.11 1.08 X 10 7 15.21 (1 ) Diagram (a), (2) Diagram (d) Volume
15.27 (a) 8.2 X 10-2 (b) 0.29.15.29 Kp = 0.105, K c = 2.05 X 10- 3
15.317.09 X 10- 3 15.33 Kp = 9.6 X 10- 3, K c = 3.9 X 10 - 4 15.35
4.0 X 10- 6 15.375.6 X 1013 15.39 The equilibrium pressure is less
1.80 X 10-4 M [HBrl = 0.267 M 15.45 P eoCl , = 0.408 atm, Peo =
Trang 2AP-12 ANSWERS TO ODD-NUMBERED PROBLEMS
PC! , = 0.352 atm 15.47 Pco = 1.96 atm, Pco , = 2.54 atm 15.49 The
-forward reaction will not occur 15.55 (a) The equilibrium would shift to
the right (b) The equilibrium would be unaffected (c) The equilibrium
would be unaffected 15.57 (a) No effect (b) No effect (c) Shift to the
left (d) No effect (e) Shift to the left 15.59 (a) Shift to the right (b)
Shift to the left (c) Shift to the right (d)Shift to the left (e) A catalyst
has no effect on equilibrium position 15.61 No change 15.63 (a) Shift
to right (b) No effect (c) No effect (d) Shift to left (e) Shift to the right
[because NaOH(aq) reacts with CO (g) to produce NaHC0 3 ( aq ) ] (f) Shift
to the left [because HCl(aq ) reacts ;.'lith CaC03(s) to produce CO z( g )
and other products] (g) Shift to the right (the decomposition of CaC03
is endothermic) 15.65 (a) 20 3 (g) • • 30 2 (g), !:ili0 = -284.4 kJ
(b) Equilibrium would shift to the left 15.67 (a) P 0 = 0.24 atm;
PC! , = 0.12 atm (b) 0.017.15.69 (a) No effect (b) More CO2 and H20
15.71 (a) 8 X 10- 44 (b) A mixture of H z and O z can be kept at room
temperature because of a very large activation energy 15.73 K p = 1.7,
P A = 0.69 atm, P B = 0.81 atm 15.75 1.5 X 105 15.77 PH , = 0.28 atm,
PC! , = 0.051 atm, PH CI = 1.67 atm 15.795.0 X 101 atm i5.81 0.0384
15.83 328 atm 15.85 6.3 X 10- 4 15.87 P N , = 0.860 atm PH , = 0.366 atm
P N H = 4.40 X 10- 3 atm 15.89 (a) 1.16 (b) 53.7%.15.91 ( it ) 0.49 atm
3
(b) 0.23 (23%) (c) 0.037 (3.7 %) (d) Greater than 0.037 mol 15.93 [H2]
= 0.070 M [12] = 0.1 82 M [HI] = 0.825 M 15.95 (c) N20 i colorless)
- _ 2N02(brown) is consistent with the observations The reaction is
endothermic so heating darkens the color Above 150°C, the O2 breaks
up into colorless NO and O2 : 2N0 2 (g) • 2NO ( g ) + 0 2( g ) An
increase in pressure shifts the equilibrium to the left, restoring the color
by producing N02 15.97 (a) 4.2 X 10- 4 (b) 0.83 (c) 1.1 (d) 2.3 X 103
and 2.1 X lO-z 15.99 (a) Color deepens (b) Increases (c) Decreases
(d) Increases (e) Unchanged 15.101 Potassium is more volatile than
sodium Therefore, its removal shifts the equilibrium from left to right
15.1033.6 X 10- 2 15.105 (a) Shifts to the right (b) Shifts to the right
(c) No change (d) No change (e) No change (f) Shifts to the left 15.107
(a) 1.85 X 10- 16 (b) 1.02 X 10- 14, 1.01 X 10-7 M 15.109 P , 0, = 0.09
atm, P N O , = 0.100 atm 15.111 (a) 1.03 atm (b) 0.39 atm (c) 1.67 atm
(d) 0.620- (62.0%).15.113 (a) K p = 2.6 X 10- 6, K c = 1.1 X 10- 7 (b)
2.2 g, 22 mg/m3, yes 15.115 There is a temporary dynamic equilibrium
between the melting ice cubes and the freezing of water between the ice
cubes 15.117 [NH3] = 0.042 M , [N2] = 0.086 M, [H z ] = 0.26 M
-15.119 (a) Kp = ? P (b) If P increases, the fraction z (and
therefore, x ) must decrease Equilibrium shifts to the left to produce less
NO z and more N20 4, as predicted 15.121 P s o p , = 3.58 atm, P so, = P C! ,
= 2.71 atm 15.1234.0
Chapter 16
16.3 (a) both (b) base (c) acid (d) base (e) acid (f) base (g) neither (h)
base (i) acid CD acid 16.5 (a) N02 (b) HS04 (c) HS - (d) CN- (e)
HCOO- 16.7 (a) CH2CICOO- (b) 104, (c) H2P04 (d) HPO ~ - (e) PO ~ -
(f) HSO 4' (g) SO ~ - (h) 103 , (i) SO ~ - (j) NH3 (k) HS- (1) S2- (m)
ClO- 16.17 7 1 X 10- 12 M 16.19 (a) 3.00 (b) 13.89 16.21 (a) 3.8 X
10 - 3 M (b) 6.2 X 10- 12 M (c) 1.1 X 10- 7 M (d) 1.0 X 10- 15 M 16.23
pH < 7: [H+] > 1.0 X 10- 7 M , acidic; pH > 7: [H+] < 1.0 X 10- 7 M,
basic; pH = 7: [H+] = 1.0 X 10- 7 M , neutral 16.252.5 X 10- 5 M 16.27
0.0022 g 16.33 (a) - 0.0086 (b) 1.46 (c) 5.82.16.35 (a) 6.17 X 10- 5 M
(b) 2.82 X 10-4 M (c) 0.105 M 16.37 (a) pOH = -0.093, pH = 14.09
(b) pOH = 0.36, pH = 13.64 (c) pOH = 1.07, pH = 12.93.16.39 (a)
1.1 X 10- 3 M (b) 5.5 X 10- 4 M 16.47 (a) Strong (b) Weak (c) Weak
(d) Weak (e) Strong 16.492.59.16.515.17.16.534.80 X 10 - 9.16.55
1.8 X 10- 3 M 16.576.80 16.61 6.97 X 10- 7 16.63 11.98.16.65 (a) A
-has the smallest Kb value (b) B- is the strongest base 16.692.0 X 10- 5;
1.4 X 10- 11 ; 5.6 X 10- 10; 2.4 X 10-8 16.71 (1) c (2) band d 16.73
1.40 (0.040 M HCI), 1.31 (0.040 M H2S04), 16.75 1.0 X 10-4 M , 1.0
X 10- 4 M, 4.8 X 10- 11 M 16.77 1.00 16.81 (a) H2S04 > H2Se04' (b)
and CH30 - from methanol The C6H50 - is stabilized by resonance:
The CH30 - ion has no such resonance stabilization A more stable
conjugate base means an increase in the strength of the acid 16.89 (a)
Neutral (b) Basic (c) Acidic (d) Acidic 16.91 HZ < HY < HX 16.93
Cr03 < Cr Z 0 3 < CrO 16.103 Al(OH)3(s) + OW(aq) • Al(OH)4
( aq ), Lewis acid-base reaction 16.107 AICl3 (AI3+) is a Lewis acid, Cl
-is a Lewis base 16.109 CO2, S02, and BCI3 (other answers are possible) 16.111 (a) Acid = AlBr3, base = Br- (b) Acid = Cr, base = CO (c) Acid
= Cu2+, base = CN- 16.113 (b) represents a strong acid (c) represents a
weak acid (d) represents a very weak acid 16.115 In theory, the products
will be CH 3 COO - ( aq) and HCI ( aq) but this reaction will not occur to any measurable extent 16.117 pH = 1.70, % ionization = 2.26% 16.119 (c) 16.121 (a) For the forward reaction NH ~ and NH3 are the conjugate acid and base pair, respectively For the reverse reaction NH3 and NH2 are the
conjugate acid and base pair, respectively (b) H+ corresponds to NH!;
OH- corresponds to NH2 · For the neutral solution, [NH:] = [NH z ]
16.123 K = , [HA] "" 0.1 M, and [A ] "" 0.1 M Therefore,
16.127 (a) H- (basel) + H20 (acid2) • OH- (basez) + H z (acid I ) ' (b) H- is the reducing agent and H20 is the oxidizing agent 16.129 2.8 X
10-2 16.131 PH3 is a weaker base than NH3 16.133 (a) HN02 (b) HF
(c) BF3 (d) NH3 (e) H2S03 (f) HC03 and COj- The reactions for
(f) are: HC0 3 (aq) + H + (aq) • CO z (g) + H 2 0(l), CO ~ -(aq)
+ 2H +( aq ) • CO z (g) + H z O(I) 16.135 (a) trigonal pyramidal
(b) H40 2+ does not exist because the positively charged H30+ has no affinity to accept the positive H+ ion If H40 2+ existed, it would have
a tetrahedral geometry 16.137 The equations are: Cl z (g) + H20(l)
• • HCI(aq) + HCIO(aq), HCl(aq) + AgN03(aq) • AgCl(s) +
HN0 3 ( aq) In the presence of OH- ions, the first equation is shifted to the right: H+ (from HCl) + OH- • H20 Therefore, the concentration
of HCIO increases (The 'bleaching action' is due to CIO- ions.)
16.13911.80.16.141 (a) 0.181 (18.1 %) (b) 4.63 X 10 - 3.16.1434.26
16.1457.2 X 10 - 3 g 16.147 1.000 16.149 (a) The pH of the solution ofHA
would be lower (b) The electrical conductance of the HA solution would
be greater (c) The rate of hydrogen evolution from the HA solution
would be greater 16.151 1.4 X 10 - 4 16.153 2.7 X 10- 3 g 16.155 (a)
- _ NH 3 ( aq ) + 30 H - ( aq ) (b) N3- 16.157 In inhaling the smelling
salt, some of the powder dissolves in the basic solution The ammonium ions react with the base as follows: NH; (aq) + OH -(aq) • NH 3 (aq)
+ H20 It is the pungent odor of ammonia that prevents a person from fainting 16.159 (c) 16.16121 mL 16.163 Mg 16.165 Both NaF and SnF2 provide F - ions in solution The F - ions replace OH- ions during the remineralization process 5Ca2+ + 3Pol - + F - • CaS(P04)3F
(fluorapatite) Because F - is a weaker base than OH- , fluorapatite is
more resistant to attacks by acids compared to hydroxyapatite
Chapter 17
17.5 (a) 2.57 (b) 4.44.17.9 (c) and (d) 17.11 8.89 17.130.024.17.15 0.58.17.179.25 and 9.18.17.19 Na2A1NaHA 17.21 (1) a, b, and d; (2) a
(highest concentration) 17.27202 g!mol 17.290.25 M 17.31 (a) 1.10 X
102 g/mol (b) 1.6 X 10- 6.17.335.82.17.35 (a) 2.87 (b) 4.56 (c) 5.34
(d) 8.78 (e) 12.10 17.37 (a) Cresol red or/phenolphthalein (b) Most
of the indicators in Table 17.3 are suitable for a strong acid-strong base
titration Exceptions are thymol blue and to a lesser extent, bromophenol blue and methyl orange (c) Bromophenol blue, methyl orange, methyl
Trang 3red, or chlorophenol blue 17.39 Red 17.41 (1) Diagram (c), (2) Diagram
(b), (3) Diagram (d), (4) Diagram (a) 17.49 (a) 9.1 X 10 - 9 M (b) 7.4 X
10 -8 M 17.511.8 X lO - /l 17.533.3 X lO-93 17.559.52.17.57 Yes
17.63 (a) 1.3 X lO- z M (b) 2.2 X lO- 4 M (c) 3.3 X lO-3 M 17.65
(a) 1.0 X lO- s M (b) 1.1 X 10- 10 M 17.67 (b), (c), (d), and (e) 17.69
(a) l.6 X lO- z M (b) 1.6 X lO- 6 M 17.71 Fe(OH)z will precipitate
17.73 [Cd2+] = 1.1 X lO- 18 M , [Cd(CN)~ - ] = 4.2 X lO-3 M, [CW]
= 0.48 M 17.75 3.5 X lO- s M 17.77 (a) The equations are as follows:
Culz(s), • Cuz + (aq) + 2I - (aq), Cu 2+ (aq) + 4NH 3 (aq) • •
the first step to form the complex ion [Cu(NH3)4f+, effectively removing
the Cuz+ ions, causing the first equilibrium to shift to the right (resulting
+ Br - (aq), Ag + (aq) + 2CN - (aq) • • [Ag(CNhnaq) (c) Similar
to parts (a) and (b): HgClz(s) • Hg z + (aq) + 2CI - (aq), Hg 2+ (aq) +
8.11, Fe(OH)3 will precipitate but Zn(OH)z will not 17.830.011 M
17.85 Chloride ion will precipitate Ag + but not Cu2+ So, dissolve some
solid in H20 and add HCI If a precipitate forms, the salt was AgN03'
A flame test will also work: Cu2+ gives a green flame test 17.872.51
to 4.41 17.89 1.3 M 17.91 [Na+] = 0.0835 M, [HCOO-] = 0.0500 M ,
[OW] = 0.0335 M, [H+] = 3.0 X lO-13 M, [HCOOH] = 8.8 X 10- 11 M
17.93 Most likely the increase in solubility is due to complex ion
formation: Cd(OH)z(s) + 20H - (aq)' • Cd(OH )~- (aq) This is a
Lewis acid-base reaction 17.95 (d) 17.97 [Ag+] = 2.0 X lO-9 M , [Cn =
0.080 M, [Znz+] = 0.070 M, [N03 ] = 0.060 M 17.990.035 gIL 17.101
2.4 X lO- l3 17.103 1.0 X lO- s M Ba(N03) is too soluble to be used
for this purpose 17.105 (a) AgBr precipitates first (b) [Ag+] = 1.8 X
lO- 7 M (c) 0.0018%.17.1073.0 X lO-8 17.109 (a) H+ + OH- •
HzO: K = l.0 X 1014 (b) H+ + NH3 • NH~ :
K 5.6 X 10-10
•
Broken into two equations:
CH3COOH • CH3COO- + H+: Ka
Broken into two equations:
CH3COOH • CH3COO- + H+: K
NH3 + H + .+ NH~: 11 K ~
K= K a _ 1.8x10-s =3.2 x I04
K' 5.6 X 10- 10
•
17.111 (a) 500 mL of 0.40 M CH3COOH mixed with 500 mL of 0.40 M
CH3COONa (b) 500 mL of 0.80 M CH3COOH mixed with 500 mL of
0.40 M NaOH (c) 500 mL of 0.80 M CH3COONa mixed with 500 mL of
0.40 M HCl 17.113 (a) Increase (b) No change (c) No change (d) pK
very large 17.115 (a) Add sulfate Na2S04 is soluble, BaS04 is not (b)
Add sulfide K2S is soluble, PbS is not (c) Add iodide ZnI2 is soluble,
HgI2 is not 17.117 The amphoteric oxides cannot be used to prepare
polyphenols have a dark color In the presence of citric acid from lemon
17.123 (c) 17.125 Precipitation would be minimized by decreasing pH
17.127 At pH = 1.0, the predominant species is +NH3-CH2-COOH
At pH = 7.0, the predominant species is +NH3-CHz-COO- At pH
= 12.0, the predominant species is NH2- CHz-COO- 17.129 (a) pH
= 4.74 The pH of a buffer does not change upon dilution (b) Before
dilution, pH = 2.52; after dilution, pH = 3.02.17.1314.75.17.133 (a)
The strongest acid group (with the lowest pK.) ionizes first, followed by
the successively weaker acids They are, in order: COOH: pK = 1.82,
NH +: pK = 6.00, NHj : pKa = 9.17 (b) The dipolar ion is the product
of the second i onization (c) pi = 7.59 ( d) The pair shown in th e secon d
ionization, since the pKa for that pair is closest to the required pH of 7.4
Chapter 18
18.9 The probability that all the molecules will end up in the same flask
(either the flask on the left or the flask on the right) is (a) 0.125 (b) 1.95
X 10-3 (c) 1.24 X lO-6o The probability that all the molecules will end
up in one particular flask is (a) 0.063 (b) 9.8 X 10- 4 (c) 6.2 X lO-61
18.11 (a) Negative (b) Positive (c) Positive (d) Negative 18.15 (c) < (d)
< (e) < (a) < (b) 18.17 (a) 47.5 J I K mol (b) - 12.51 JI K mol (c)
-242 8 J I K· mol 18.23 (a) -1139 kJ I K mol (b) - 140.0 kJI K mo!
(c) - 2935.0 kJ/K mol 18.25 (a) Spontaneous at all temperatures
(b) Spontaneous below 111 K 18.27 Fusion: 1.00 X 102 J I K mol,
vaporization: 93.6 J I K mol 18.29 -226.6 kJ/mol 18.31 75 9 kJ of Gibbs free energy released 18.350.35 18.3779 kJ/mo! 18.39
(a) 39 kJ/mol, 1 X lO-7 (b) 48 kJ/mol 18.41 (a) 1.6 X lO-23 atm
(b) 0.535 atm 18.4323.6 rrunHg 18.4793 18.49 When Humpty broke into pieces, he became more disordered (spontaneously) Humpty couldn't be put together again because all the King's horses and all the King's men
could not reverse the spontaneous process (Too great a negative entropy
change would have been required.) 18.51 E and H 18.53 42°C 18.55
(a) t:.H is positive, t:.S is positive, t:.G is negative (b) t:.H is positive, t:.S
is positive, t:.G is zero (c) t:.H is positive, t:.S is positive, t:.G is positive
18.57 t:.S is positive 18.59 (a) Trouton's rule is a statement about t:.S ~.P (See Equation 18.9) In most substances, the molecules are in constant and random motion in both the liquid and gas phases, so t:.S ~ ap =
90 J / mol·K (b) But in ethanol and water, there is less randomness of the molecules due to the network of H -bonds, so t:.S ~a p is greater 18.61
(a) 2CO(g) + 2NO(g) • 2CO z(g) + N z (g) (b) CO is the reducing agent NO is the oxidizing agent (c) 3 X lO 120 (d) 1.2 X lO14, reaction proceeds to the right (e) No 18.632.6 X 10- 9 18.65 703°C 18.6738 kJ
18.69174 kJ / mol 18.71 (a) Positive (b) Negative (c) Positive
(d) Positive 18.73625 K We assume that t:.H o and t:.S o do not depend
on temperature 18.75 No A negative t:.G o tells us that a reaction has the potential to happen, but gives no indication of the rate 18.77 (a)
- lO6.4 kJ/mol, 4 X 1018 (b) - 53.2 kJ/mol, 2 X lO9 18.79 Talking involves various biological processes (to provide the necessary energy)
that lead to an increase in the entropy of the universe Since the overall process (talking) is spontaneous, the entropy of the universe
must increase 18.81 (a) 86.7 kJ / mol (b) 4 X 10- 31 (c) 3 X lO-7 (d) Lightning supplies the energy necessary to drive this reaction, converting the two most abundant gases in the atmosphere into NO(g) The NO gas
dissolves in the rain, which carries it into the soil where it is converted into
nitrate and nitrite by bacterial action This "fixed" nitrogen is a necessary nutrient for plants 18.83 673.2 K.18.85 (a) 7.6 X lO I4 (b) K = 4.1 X 10- 12
18.87 (a) Disproportionation redox (b) 8.2 X lOIS (c) Less effective
18.89 1.8 X 1070 18.91 t:.Ssys = 91.1 J/K , t:.Ssurr = -91.1 J/K, t:.Suniv = O
Conclusion: the system is at equilibrium 18.93 t:.G = 8.5 kJ / mol 18.95
(a) CH3COOH, t:.Go = 27 kJ/mol , CH2CICOOH, t:.G o = 16 kJ/mo!
(b) Entropy dominates (c) Breaking and making of specific 0 - H bonds
Other contributions include solvent separation and ion solvation
(d) The CH3COO- ion, which is smaller than the CHzClCOO- ion, can participate in hydration to a greate ~ extent, leading to more ordered
solutions 18.97 Xeo , = 0.55 X eo = 0.45 18.99249 J / K 18.101 3 X
-10 s 18.103 t:.Ssys = - 327 J I K mol, t:.Ssurr = 1918 J I K mol, t:.SlIniv
= 1591 J I K mol 18.105 q and ware not state functions 18.107 t:.G, t:.S , and t:.H are all negative 18.109 (a) S = 5.76 J / K ( mol (b) The fact that the actual residual entropy is 4.2 J/K(mol means that the orientation
is not totally random 18.111 t:,.H 0 = 33.89 kJ/mol, t:.s o = 96.4 J / mol'K , t:.G o = 5.2 kJ / mo!
Chapter 19
19.1 (a) 2H+ + HzOz + 2Fe2+ • 2Fe3+ + 2H20 (b ) 6H+ + 2HN03 +
3Cu • 3Cu2+ + 2NO + 4H20 (c) H20 + 2Mn04 + 3CN- •
Trang 4AP-14 ANSWERS TO ODD-NUMBERED PROBLEMS
2Mn02 + 3CNO- + 20H- (d) 60H- + 3Br2 • Br03 + 3H20 +
5Br- (e) 2SzO~- + 12 • S4 0~- + 21- 19.11 3Ag+(l.0 M) + Al(s)
- _ 3Ag(s) + AlH (l.O M), E~ell = 2.46 V 19.13 CI2(g) and Mn0 4 ( aq)
19.15 (a) Spontaneous (b) Not spontaneous (c) Not spontaneous (d)
Spontaneous 19.17 (a) Li (b) H2 (c) Fe2+ (d) Br- 19.213 X 1054
19.23 (a) 2 X 1018 (b) 3 X 108 (c) 3 X 1062 19.25 - 81 kJ, 2 X 1014
19.29 1.09 V 19.31 E~ell = 0.76 V; E eel! = 0.78 V 19.33 6.9 X 10- 38
19.39 l.09 V 19.43 12.2 g Mg 19.45 It is less expensive to prepare 1 ton
of sodium by electrolysis 19.470.012 F 19.495.33 g Cu, 13.4 g Br2'
19.517.70 X 103 C 19.53 l.84 kg/h 19.5563.3 g / mol 19.5727.0 g / mol
19.63 (a) (i) H2(g) • 2H + (aq) + 2e - ; Ni 2+(aq) + 2e- • Ni(s);
(ii) Hz(g) + N i 2+ (aq) • 2H + (a q ) + Ni(s); (iii) Reaction will proceed
to the left (b) (i) 2Cqaq ) • Clz(g) + 2e-; 5 e- + 8H +(a q) +
Mn04 (aq) • Mn 2+(aq) + 4H 2 0(l); (ii) l6H +(a q) + 2Mn04 (a q ) +
lOC qaq) • 2Mn2+(aq) + 8H 2 0 (l) + 5CI2(g); (iii) Reaction will
proceed to the right (c) (i) Cr(s) • Cr H( aq) + 3e - ; Zn 2+ (a q ) +
2e - • Zn(s); (ii) 2Cr(s) + 3Zn 2+(a q ) • 2Cr 3+( aq) + 3Zn(s),
(iii) 2Cr H (aq) + 3Zn(s) • 2Cr(s) + 3Zn 2+( aq ) Reaction will
proceed to the left 19.650.00944 g S02' 19.67 (a) 2Mn04 + 6H+ +
5H20 2 • 2Mn2+ + 8H20 + 502, (b) 0.0602 M 19.690.232 mg
Ca/mL blood 19.715 X 10- 13 19.73 (a) 3.14 V (b) 3.13 V 19.75 E eeu =
0.035 V 19.77 Mercury(I) is Hg;+ 19.79 [Mg2+] = 0.0500 M, and Mg(s)
-= l.44 g [Ag ] = 7 X 10-» M 19.81 (a) Hydrogen gas, 0.206 L
(b) 6.09 X 1023 e - / mol e - 19.83 (a) -1356.8 kJ / m ol (b) 1.17 V 19.85
+3 19.876.8 kJ /mo l , 0.064.19.891.4 A 19.91 +4.19.93 l.60 X
10- 1 9 C le - 19.95 Cells of higher voltage require very reactive oxidizing
and reducing agents, which are difficult to handle Batteries made up of
several cells in series are easier to use 19.972 X 1020 19.99 (a) E~ed for
X is negative (- 0.25 V), E ~ed for Y is positive (+0.34 V) (b) E ~ll =
0.59 V 19.101 (a) Gold does not tarnish in air because the reduction
potential for oxygen is not sufficiently positive to result in the oxidation
of gold (b) Yes, E ~ell = 0.19 V (c) 2Au(s) + 3F2(g) • 2A uF 3( aq)
19.103 [Fe2+] = 0.0920 M, [FeH ] = 0.0680 M 19.105 The two half
reactions are: H 2 0 2 ( aq) + 2H + (a q ) + 2e - • 2H20(l), 1.77 V;
H 20 2( aq) • Oz(g) + 2H + (aq) + 2e - , -0.68 V Overall:
2H 2 0z(aq) • 2H 2 0 (l) + 0 2(g ), E O = 1.09 V (spontaneous) 19.107
(a) Unchanged (b) Unchanged (c) Squared (d) Doubled (e) Doubled
19.109 As [H+] increases, F2(g) does become a stronger oxidizing agent
19.111 4.4 X 102 atm 19.113 (a) Half-reactions: 1 120 2 (g) + 2e - •
0 2 - (aq) , Zn(s) • Zn 2+( aq) + 2e - Overall: Zn(s) + 1I20z(g) •
ZnO (s), E~ell = 1.65 V (b) 1.63 V (c) 4.87 X 103 kJ/kg Zn (d) 64 L of
air 19.115 -3.05 V 19.117 1 X 10- 14 19.119 (a) 3600 C (b) 105 A·h
(c) E ~ell = 2.01 V, t1G o = -388 kJ / mol 19.121 $217.19.123 -0.037 V
19.125 2 X 1037
Chapter 20
20.5 (a) ~~ Na (b) : H (c) 6 n (d) ~~ Fe (e) _ _ ~f3 20.13 2.72 X 1014 glcm 3
20.15 (a) Nl (b) Se (c) Cd 20.174.85 X 10 L kg 20.19 (a) 6.30 X 10-12 J,
9.00 X 10- 13 J / nucleon (b) 4.78 X 10- 11 J, 1.37 X 10- 12 J / nucleon
20.23 (a) 2~~Th " ) 2~~ Ra ~) 2~~ Ac ~) 2~g Th
(b) 2~~U " ) 231Th
90 ~ ) 231 Pa
91 " ) 2~~ Ac
(c) 237 Np " ) 233Pa ~) 233U " ) 229Th
20.254.89 X 1019 atoms 20.273.09 X 103 yr 20.29 A = 0 mol, B =
0.25 mol, C = 0, D = 0.75 mol 20.31 5.5 dpm 20.33 Mass ratio UlPb =
43.3:1 20.37 (a) 14N(ex,p)170 (b) 9Be(ex,n)12c (c) 238U(d,2n)238Np
20.39 (a) 4oCa(d,p)4ICa (b) 32S(n,pi2p' (c) 239Pu(ex,n)242Cm
20.41 1§~ Hg + 6n ) 1§6 Hg ) I j~ Au + :p 20.53 Thefact that
the radioisotope appears only in the 12 shows that the 103 is formed only
from the 10 4' 20.55 Add iron-59 to the person's diet, and allow a few days
for the iron-59 isotope to be incorporated into the person's body Isolate
red blood cells from a blood sample and monitor radioactivity from the
hemoglobin molecules present in the red blood cells 20.61 3.96 X 1015
20.63 65.3 yr 20.65 70.5 dpm
2067 • (a) 23592 U + 0 5 6 0In -7 14° Ba + 3 In + 9363Kr '
(b) 235U + In -7 144CS + 90 Rb + 2 In
(c) 235 U + In -7 87Br + 146La + 3 In
(d) 23592 U + 0 In -7 16062 Sm + 30 72 Zn + 4 0 In 20.69 (a) ~ H -7 _ ~ f3 + ~ He
(b) 2~~ Pu -7 i ex + 2~~U
(c) 1353 1 1-7 -01(.) 1-' + I~I )4 Xe
(d) 251 98 Cf -7 4 2 ex + 247 96 Cm 20.71 Because both Ca and Sr belong to Group 2A, radioactive strontium
that has been ingested into the human body becomes concentrated in
bones (replacing Ca) and can damage blood cell production 20.73
Normally the human body concentrates iodine in the thyroid gland The purpose of the large doses of KI is to displace radioactive iodine from the
thyroid and allow its excretion from the body
20.75 (a) 2~~ Bi + i ex ) 2~~ At + 2 6n
(b) 2098 3 ' Bi(ex 2n) 28511 At '
20.77 2.77 X 103 yr 20.790.069%.20.81 (a) 5.59 X 10- 15 J and 2.84 X
10-13 J (b) 0.024 mol (c) 4.26 X 106 kJ 20.83 2.8 X 1014.20.856.1 X
1023 atoms/mol 20.87 (a) 1.73 X 10- 12 J (b) The a particle will move
away faster because it is smaller 20.89 U-238, t 1/2 = 4.5 X 109 yr and Th-232, t ll2 = 1.4 X 1010 yr They are still present because of their long half lives 20.91 8.3 X 10- 4 nm 20.93 3H 20.95 A small scale chain
reaction (fission of 235U) 20.97 2.1 X 102 g/mol 20.99 (a) r = r o A 11 3
( r o is a proportionality constant) (b) 1.7 X 10- 42 m3 20.101 0.49 rem
Chapter 21
21.5 X = 3.30 X 10- 4, ppm = 330.21.7 In the stratosphere, the air temperature rises with altitude This warming effect is the result of
exothermic reactions triggered by UV radiation from the sun 21.11
260 nm 21.21 3.2 X 1012 kg 0 3, 4.0 X 1037 molecules 0 3, 21.23 CC4 +
HF • HCl + CFCl3 (Freon-II), CFCl3 + HF • HCl + CF2Cl2
(Freon-12) 21.25479 kJ/mol , this is sufficient to break the C-Cl bond, but not enough to break the C- F bond
:Cl-O-N-O: II
21.27 : 0 : , .<;:) - Q' 21.39 2.6 X 10 ton S02' 21.41 4.8 X
1016 kg ice 21.49 5.2 X 108 L S02' 21.57 (a) rate = k[NOf[02]' (b)
rate = k[NO] 2 (c) tl l2 = 1.3 X 103 min 21.594.1 X 10 - 7 atm, 1 X
1016 moleculeslL 21.65 378 g CO 21.67 Of green house gas, toxic to humans, attacks rubber; S02: toxic to humans, forms acid rain; N02:
forms acid rain, destroys ozone; CO: toxic to humans; PAN: a powerful
lachrymator, causes breathing difficulties; Rn: causes lung cancer 21.69
(a) K e = [0 2 ][HbCO] / [CO][Hb0 2 ] (b) 4.7 X 10- 2.21.71 (a) 2N20 + O2
-+ 4NO and NO + 0 3 • N02 + O2 (b) N20 is a more effective
greenhouse gas than CO2 because it has a permanent dipole (c) 3.0 X
1010 mol 21.731.8 X 1019,6.4 X 1016.21.75 (a) High reactivity of the
OH radical (b) OH has an unpaired electron; free radicals are always
OH + S02 • HS03 and HS03 + O2 + H20 • H2S04 + H02
21.77 The blackened bucket has a large deposit of elemental carbon
C + CO2 • 2CO A smaller amount of CO is also formed as follows: 2C + O2 • 2CO 21.79 The use of the aerosol can liberate CFCs
that destroy the ozone layer 21.81 C-Cl = 340 kJ / mol, so the photons
well Light of wavelength 409 nm (visible) or shorter will break the
C-Br bond 21.83 (a) 6.2 X 108 (b) The CO2 liberated from limestone
contributes to global warming 21.85 Most water molecules contain
oxygen-16, but a small percentage of water molecules contain
oxygen-18 The ratio of the two isotopes in the ocean is essentially constant, but
the ratio in the water vapor evaporated from the oceans is
temperature-dependent, with the vapor becoming slightly enriched with oxygen-18
as temperature increases The water locked up in ice cores provides a
Trang 5historical record of this oxygen-l8 enrichment, and thus ice cores contain
information about past global temperatures
Chapter 22
22.11 (a) +3 (b) 6 (c) Oxalate ion 22.13 (a) Na = + 1, Mo = +6
(0 = -2) (b) Mg = +2, W = +6 (0 = -2) (c) Fe = 0 (CO is a
ne utral ligand) 22.15 (a) Cis-dichlorobis(ethylenediamine)cobalt(III)
(b) Pentamminechloroplatinum(IV) chloride (c) Pentamminechlorocobalt
(III) chloride 22.17 (a) [Cr(enhClzt (b) Fe(CO)s (c) Kz[Cu(CNM (d)
[Co(NH3MHzO)C I]Clz·
22.23 (a) 2, (b) 2,
22.25 (a) 2 geometric isomers (trans- and cis-):
(b)Twoopli'']i'o~,,, ~ ~
22.31 When a substance appears to be yellow, it is absorbing light
from the blue-violet, high energy end of the visib le spectrum Often
this absorption is ju st the tail of a strong absorption in the ultraviolet
Substances that appear gree n or blue to the eye are absorbing light from
the lower energy red or orange part of the spectrum Cyanide ion is a
v ery strong field ligand It causes a larger crystal field sp litting than
water, resulting in the absorp tion of higher energy (shorter wave l ength)
radiation w h en a d electron is excited to a higher energy d orbita!
22.33 (a) Orange (b) 255 kJ/mo! 22.35 2.0 mol, [Co(NH3 )4C l z]CI 22.37
!:J wo uld be greater for the higher oxidation state 22.41 Use a radioactive
label such as 14CN- (in NaCN) Add NaCN to a sol ution of K3Fe(CNk
Isolate some of the K3Fe(CN)6 and check it s radioactivity If the complex
shows radioactivity, then it must mean that the CN- ion has participated
in the exchange reaction 22.43 CU(CN)2 is the whi te precipitate It is
s o luble in KCN(aq), due to formation of [CU(CN)4]2- , so [Cu2+ ] is
too s mall for Cu2+ ions to precipitate with su lfide 22.451.4 X lO z
22.47 The purple color is caused by the build-up of deoxyhemoglobin
Whe n either oxy hemo g lobin or deoxyhemoglobin take s up CO, the
c arbony lhem og lobin takes on a red co lor , the same as oxyhemoglobin
22.49 Mn3+ 22.51 Ti3+ lFe3+ 22.53 1.6 X 104 g/mo! There are
four iron atoms per hemoglobin molecule 22.55 (a) [Cr(HzO)6]CI3
num ber of ions: 4 (b) [Cr(HzO)5CI]CI2' H zO , number of ions: 3 (c)
[Cr(HzO)4ClzlC I'2H zO, number of ions: 2 Compare the compo und s
with equal molar amounts of NaCI, MgClz, and FeC l 3 in an electrical
cond uctanc e experiment 22.57 -1.8 X 102 kJ/mol, 6 X 1030 22.59 Iron
i s much more abundant that cobalt 22.61 Oxyhemoglobin absorbs higher
energy li ght than deoxyhemoglobin Oxyhemoglobin is diamagnetic
(low spin), while deoxyhemoglobin is paramagnetic (high spin) These
differe nce s occur be cause oxygen (O z ) is a strong-field ligand 22.63
Znz + Cu + , Pbz+ are iO ions ; V5+, Ca z+, Sc 3+ are dO ions 22.65 Dipole
moment measurement Only the cis isomer h as a dipole moment 22.67
EDTA sequesters metal ions (like Ca2+ and Mg2+) which are essential for
growth and f unction , thereby depriving the bacteria to grow and multip l y
a" /b b" /a a" /c 22.69 Three isomers: Pt P \ / P \
d/ "c d/ c d b 22.712.2 X lO- zo M 22.73 (a) 2 7 X 10 6
(b) A so lubl e copper(I)
s alt could not be isol ated from an aqueous so lution becau se it would
dispro portionate before it could be crys talli zed
Chapter 23
23.13 4.5 X 105.23.15 Ag, Pt, and Au will not be oxidized, but the other
meta ls will 23.17 (a) 8 9 10IZ cm3 (b) 4.0 108 kg S02' 23.19 AI, Na ,
ANSWERS TO ODD-NUMBERED PROBLEMS AP-15
and Ca would require electrolysi s 23.33 (a) 2Na(s) + 2H 2 0(l) -2NaOH(aq) + H2(g) (b) 2NaOH(aq) + COz(g) - Na 2 C03(aq) +
HzO(l) (c) Na Z C0 3 (s) + 2HCI(aq) - 2NaCI(aq) + CO 2 (g) +
H 20(l) (d) NaHC0 3 (aq) + HCI(aq) - NaCI(aq) + COz(g) +
H z O(l) (e) 2NaHC03( s ) - Na Z C0 3 (s) + CO z (g) + HzO(g)
(f) Na2C03 (S) - no reaction Unlike CaC0 3 (s), Na2C03(S) is not decomposed by moderate heating 23.35 5.59 L 23.39 First magnesium is treated with concentrated nitric acid (redox reaction) to obtain magnesium nitrate: 3Mg(s) + 8HN0 3 (aq) - 3Mg(N0 3 )z(aq) + 4H z O(l) +
2NO(g) The magnesium nitrate is recovered from solution by evaporation, dried, and heated in air to obtain magnesium ox id e: 2Mg(N03)z(s) -2MgO(s) + 4NOz(g) + 0 2 (g) 23.41 The e l ectron configuration of magnesium is [Ne]3s 2 The 3s electrons are outside the neon core (shielded), so they ha ve relatively low ionization energies Removing the third electron means separating an electron from the neon (closed shell) core, which requires a great deal more energy 23.43 Even though helium and the Group 2A metals have ns 2 outer electron configurations, helium has a closed shell noble gas configuration and the Group 2A metals do not The electrons in He are much closer to and more strongly attracted
by the nucleus Hence, the electrons in He are not easily removed Helium
is inert 23.45 (a) CaO (b) Ca(OH)z 23.49 60.7 h 23.51 (a) 1.03 V (b) 3.32 X 104 kllmo! 23.53 4AI(N03Ms) - 2AI20 3 (s) + 12NOz(g) +
30 z (g) 23.55 The "bridge" bond s in Al z CI 6 break at high temperature:
AlzCI 6 (g) ~ 2AICI3( g ) This increases the number of molecules in the gas phase and causes the pressure to be higher than expected for pure
A1 z CI 6 23.57 A12CI6: each aluminum atom is Sp 3 hybridized; A1CI3: the aluminum atom is Sp 2 hybridized 23.59 65.4 glmol (Zn) 23.61 Water should not be affected by the copper purification process under standard conditions 23.63 (a) 1482 kJ (b) 3152.8 kJ 23.65 Mg(s) reacts with
N z (g) to produce Mg 3 N z( S) at high temperatures 23.67 (a) In water the aluminum(III ) ion causes an increas e in the concentration of hydrogen ion (lower pH) This results from the effect of the sma ll diameter and high charge (3 + ) of the aluminum ion on surrounding water molecules The aluminum ion draws electrons in the 0- H bonds to it self, thus allowing easy formation of H + ions (b) A1(OH) 3 is an amphoteric hydroxide
It wi ll dissolve in strong base with the formation of a complex ion AI(OHMs) + OW(aq) - A1(OH)4(aq) 23.69 CaO(s) + 2HCI(aq)
- CaCl z (aq) + H z O(l) 23.71 Metals have closely spaced energy levels and a very small energy gap between filled and empty levels 23.73 NaF: cavity prevention (F - ) LiC03: antidepressant (Li + ) Mg(OHh: lax ative (Milk of Magnesia ® ) CaC03: calcium supplement; antacid BaS04: radiocontrast agent 23.75 Both Li and Mg form oxides (Li zO and MgO) Other Group 1A metals (Na, K, etc.) a l so form peroxides and superoxides In Group lA, only Li forms nitride (Li 3 N) , like Mg (Mg3N2) Li res emble s Mg in that its carbonate, fluoride, and phosphate have low s olubilities 23.77 Zn 23.79 87.66 % Na20 and 12.34% Na202' 23.81 727 atm
Chapter 24
24.11 Element number 17 is the halogen, chlorine Since it is a nonm eta l , chlorine will form the molecular compo und HCI Element 20 is the alkaline earth metal calcium which will form an ionic hydride, CaHz A water solution of HCI is called hydrochloric acid Calcium hydride will react according to the equation CaH z (s) , + 2HzO(I) - Ca(OH)z(aq)
+ 2H2(g) 24.13 NaR: ionic compound, reacts with water as follows:
NaR(s) + H z O ( l) - NaOH ( aq) + H z (g) ; CaR2: ionic compound , reacts with water as follows: CaR2(s) + 2H20(l) - Ca(OH)z(s) + 2H z (g);
CH4: covalent compound , umeactive, bums in air or oxygen: CHig) +
20 z (g) - CO z (g) + 2H z O(l) ; NH 3 : covalent compound, weak base in water: NH 3 (aq) + H z O(I) ~ NH ; (aq) + OH - aq);
H z O: covalent compound , forms strong intermolecular hydrogen bonds, good solvent for both ionic compounds and substances capable of forming hydrogen bonds; HCI: covalent compound (polar ), acts as a strong acid in water: HCI(g) + H z O(l) - H 3 + (aq) + CC(aq)
24.15 CaH z ( s ) + HzO(l) - Ca(OHMaq) + 2Hig) , 22 7 g CaHz 24.17 CuO(s ) + Hz(g) - Cu( s) + H z O( g ) 24.25 ~C =Cp -
Trang 6AP -16 ANSWERS TO ODD-NUMBERED PROBLEMS
24.27 (a) 2NaHC03(s) • Na2C03(S) + H 2 0( g) + CO 2 (g) (b)
Ca(OHMaq) + CO 2 (g) • CaC03(s) + H 2 0(l ) The visual proof
is the formation of a white precipitate of CaC03 24.29 Heat causes
bicarbonates to decompose according to the reaction: 2HCO~ o +
COj- + H20 + CO2, Generation of carbonate ion causes precipitation of
the insoluble MgC03 24.31 The wet sodium hydroxide is first converted
H 20( I), and then to sodium hydrogen carbonate: Na 2 C0 3 (aq) + H 2 0(l)
carbonate precipitates (the water solvr nt evaporates since NaHC03 is
not hygroscopic) Thus, most of the white solid is NaHC03 plus some
> (NH2hCO(s) + H 2 0 (I) The reaction should be run at high
pressure 24.43 The oxidation state of N in nitric acid is + 5, the highest
oxidation state for N N can be easily reduced to oxidation state + 3
24.45 (a) NH4N0 3(s) •
N 2 0(g) + 2H 2 0(I ) (b) 2KN03(s) • 2KN02(s) + 02(g) (c)
Pb(N03M s) • PbO(s) + 2N02(g) + O zCg) 24.47 KN03(s) +
86.7 kJ / mol (b) K = K p = K c = 4 X 10- 31 24.51 125 g / mol, P4 24.53
4HN03 + P40 lO • 2N 20 S + 4HP03, 60.4 g 24.55 Sp 3 24.63
- 198.3 kJ/mol , K = Kp = K c = 6 X 1034 24.65 (a) To exclude light (b)
0.371 L 24.67 F = - 1, 0= 0.24.69 (a) HCOOH(l) • CO (g) +
H 2 0(I) (b) 4H 3 PO il) • P40 IO(S) + 6H 2 0 (l ) (c) 2HN0 3 (l) + =='
form OF6 there would have to be six bonds (twelve electrons) around the
oxygen atom This would violate the octet rule 24.73 35 g C12 24.75
9H2SOiaq) + 8Nal(aq) • 412(s) + H 2 S (g) + 8Na HS0 4 (aq) +
4H 2 0(l) 24.79 (a) H- f.: H- f.: (b) W H- :f.f 24.81 (a) Linear
(b) Tetrahedral (c) Trigonal bipyramidal (d) See-saw 24.83 25.3 L C12
24.852.81 L 24.87 1 2 0 5 (s) + 5CO (g) • 5C0 2 (g ) + 1 2(s), iodine is
reduced and carbon is oxidized 24.89 (a) 2H 3 P0 3 (aq) • H 3 PO iaq) +
PH 3 (g) + 0 2(g) (b) Li4C(s) + 4HCI(aq) • 4LiCl(aq) + CH 4 (g)
(c) 2HI(g) + 2HN0 2 (aq) , 1 2 (s) + 2NO (g) + 2H 2 0 ( I ) (d) H 2S(g)
CO2, 24.93 O 24.95 PC!; , tetrahedral, Sp 3 hybrids; PC16 , octahedra!,
s p 3d 2 hybrids 24.97 K 298 = 9.61 X 10- 22, K m = 1.2 X 10-15 24.99 The
glass is etched (dissolved) uniformly by the reaction 6 HF (aq) + Si02(s)
+ H 2 SiF 6 (aq) + 2H 2 0 (l) 24.101 1.18.24.1030.833 gIL The molar
mass derived from the observed density is 74.41, which suggests that the
molecules are associated to some extent in the gas phase This makes
sense due to strong hydrogen bonding in HF
Chapter 25
25.3 The monomer must have a triple bond 25.5 There are two possible polymers, but if they are long enough, the difference would be negligible:
° I I
I
-SH
° II
HN-CH-C-O
CH-OH
I
CH3
II
II
°
N-CH-C-OH
I
CH-OH
I
CH3
°
I
I
SH
25.9 (1) Sc (s) + 2C2HsOH(l) • Sc(OC2Hs)(alc) + 2H+(alc)
("alc" indicates a solution in alcohol); (2) Sc(OC2Hs)(alc) + 2H 2 0(I)
• Sc(OHMs) + 2C2HsOH(alc); (3) Sc(OHM s) • ScO(s) +
2H 2 0(g ) 25.11 Bakelite is best described as a thermosetting composite
polymer 25.15 No These polymers are too flexible, and liquid crystals require long, relatively rigid molecules 25.19 Alternating condensation
age; composite fillings tend to shrink 25.25 sp2 25.27 Dispersion forces
25.31 (a) 4+ 5: n-type (b) 4+ 3: p-type 25.35 Bi2Sr2Cu06' 25.37 Two are +2 ([Ar]3£), one is + 3 ( [Ar]3d 8 ) The +3 oxidation state is unusual
for copper 25.39 H2N-fCH2)8 NH2 HO-C-fCH:m C-OH 25.41 In a plastic (organic) polymer: covalent, disulfide (covalent),
H-bonds and dispersion forces; in ceramics, mostly ionic and network
covalent 25.43 Fluoroapatite is less soluble than hydroxyapatite, particularly in acidic solutions Dental fillings must also be insoluble
25.45 The molecule is long, flat, and rigid, so it should form a liquid
crystal
Trang 7Answers
To PRE-PROFESSIONAL PRACTICE EXAM PROBLEMS
Chapter 1 Chapter 8 Chapter 15 Chapter 22
Chapter 2 Chapter 9 Chapter 16 Chapter 23
Chapter 3 Chapter 10 Chapter 17 Chapter 24
Chapter 4 Chapter 11 Chapter 18 Chapter 25
Chapter 5 Chapter 12 Chapter 19
Chapter 6 Chapter 13 Chapter 20
Chapter 7 Chapter 14 Chapter 21
AP-17
Trang 8A
absolute entropies, 735 , 736
absolute temperature scale, 424
absolute zero, 10, 424
absorbed, 531
acceptor impurities, 890
accuracy, 18-19
acid-base indicators, 698-700
acid-base reactions , 121-122 , 125-126
acid-base neutralization, 124
Br¢nsted acids and bases, 122-124
strong acids and bases, 122
acid-base titrations, 144-146, 690-691
acid-base indicators, 698-700
strong acid-strong base titrations, 691-692
strong acid-weak base titrations, 696-698
weak acid - strong base titrations , 693-696
acid ionization constant, 648
acid rain , 838 , 843-845
acids
in molecular compounds, 50, 51
oxoacids, 59
strong, 112, 113, 122
acids and bases, 634-635
acid-base properties of oxides and
hydroxides, 667 - 668
acid-base properties of salt solutions , 662-667
acid-base properties of water, 637-639
Br¢nsted , 636-637
conjugate acid - base pairs, 654-657
diprotic and polyprotic acids , 657-659
Lewis acids and bases, 668-670
molecular structure and acid strength, 660-662
pH scale, 639 - 644
strong, 644-647
weak acids and acid ionization constants,
647-652
weak bases and base ionization constant s ,
652-654
actinide series , 225
action potential , 776
activated complex, 564
activation energy, 563
active metals, 130, 258
active site, 575
active transport, 643
activity series, 130, 131
actual yield, 96
addition polymerization , 936
addition polymers, 395-396, 397, 936-941
addition reactions , 386-388 adenosine diphosphate (ADP), 389 adenosine triphosph a te (ATP), 389 adhesion , 468
adsorbed , 531 aerosol, 845 Agriculture , U.S Departm e nt of , 159
airbag,433 alcohols, 367, 370 , 372 aldehydes , 367, 370, 373 aliphatic compound s, 365 alkali metals , 45, 891 - 893 alkaline batteries, 777 alkaline earth metals , 45, 893-895 alkanes, 51, 52, 365 , 368
alkyl group , 366 , 367 , 368 alkynes, 943
allotropes , 48 , 910 alloys, 883 alpha (a) particle s, 38 alpha (a) rays , 38 altitude sicknes s, 448 aluminum , 895-897 alums, 897
amalgam
defined , 883
dental, 759, 950 amide group , 367 , 370 amide ion s , 912 amide linkages , 464 amides, 367, 370, 373 amines, 367 , 370 , 373 amino acid re s idue, 464 amino acids, 370 , 397-399
amino group, 367 , 370 ammonia, 912
amorphous solids , 8 4
amount-volume relation s hip , 425-426 amphoteric , 266 , 637
amplitude, 194
analogues , 363 angular momentum qu a ntum number, 213 , 214 anions , 55
anisotropic, 947 Annan, Kofi, 829
anode, 36 , 763, 766 antacids, 642 - 643 antibonding molecular orbital , 343 aqueous solutions , 506
acid-base reaction s , 121-126
Index
aqueous defined, 77 aqueous reactions and chemical anal ysis, 142-147
concentration of solutions, 136-142
general properties of , 112-116
oxidation-reduction reactions, 126 - 13 6 precipitation reactions, 117-121
Ari s totle , 34 Arm s trong, Lance, 73 aromatic compounds , 365 Arrheniu s acid , 123 Arrhenius ba s e , 123
Arrhenius equation, 564-565
Arrhenius , Svante , 122
arsenic, 905 artificial joints , 951 - 952
a s corbic acid , 33 , 635, 671
A s ton , F w., 43
a t a ctic , 941 atmo s phere Earth 's , 830-833 phenomena in the outer layers, 83 3 - 834 atmosphere s (atm), 418
atmospheric pressure, 417
atomic bomb, 812 atomic ion s , 55-56
atomic line s pectra, 201-202
a tomic ma ss, 46 atomi c ma ss unit (amu), 46
atomic number (Z) , 40, 239 atomic orbital s, 212 , 216 , 219
d orbitals and other higher-ener gy o r bi tals
217-218 energie s of orbitals, 218, 219-22 0 forbitals,218
hybridization of, 327-334, 351
P orbitals, 217
s orbital s , 216-217
a tomic radiu s, 246-247 , 255
a tomic theory, 34-36 atomic weight , 46
atom s , 4 atomic mass scale and average a t omic mass
46-47 atomic number, mass number , an d isOl ope5_
40-43
atomic theory, 34-36
defined , 36
h drogen atom, 200 - 208, 212 structure of, 36-40
attracti on , 160
Trang 91-2 INDEX
attractive forces, 245, 457
Aufbau principle, 221
aurora australis, 833
aurora borealis, 833
autoionization of water, 638
Avogadro, Amedeo, 425
axial, 316
B
•
balanced equations, 77-78
ball-and-stick models (molecular art), 5
band theory, 888
band theory of conductivity, 888
conductors, 888-889
barometer, 418, 419
base
Br0nsted acids and bases, 122-124
defined, 112
basic oxygen process, 885-886
batteries
defined, 777
fuel cells, 778-779
lead storage, 777-778
lithium-ion, 778
Becquerel, Antoine, 38
belt of stability, 800
bends, the, 438
beta-particle emission, 800-801
beta (f3) particles, 39
beta (f3) rays, 39
bimolecular, 569
binary hydrides, 907-908
binary molecular compounds, 49, 51
biological catalysts, 575-577
biological concentration cells, 776
biomedical materials, 949-952
bioterrorism agents, 3, 23
bipolar disorder, 267
birth defects, 363
blackbody radiation, 197
blast furnace, 884, 885
blood, maintaining pH of, 689-690
blood alcohol concentration (BAC), 111
blood doping, 591
blood plasma, 689, 690
body-centered cubic cell, 474
208,212 atomic line spectra, 201-202
line spectrum of hydrogen, 202-207
boiling point, 485
boiling-point elevation, 519-520
Boltzmann constant, 729
bomb calorimetry, 175 bond angle, 316, 319
bond enthalpy, 286, 300-303, 324
bond order, 343-344 bonding molecular orbital, 342
boron neutron capture therapy (BNCT), 797 Boyle, Robert, 421
Breathalyzer test, Ill, 148
bromine, 927
Br0nsted base, 123 Br0nsted, Johannes, 123 Buck, Linda, 313
buckyballs, 953 buffer, 683
with a specific pH, 688-689
calculating the pH of a buffer, 684-688
burst lung, 415
c
Cade, Mary, 115
caffeine, 653 calcium, 894-895 calcium ascorbate, 671
calories
caloric content of food, 159
Calorie (Cal) defined, 163
calorimeter, l7 5 calorimetry
constant-pressure, l72-l74 defined, 171
specific heat and heat capacity, 171- 172 cancer
drugs, 73 nuclear chemistry in treating, 797
smoking and, 819-820
carbides, 910
carbocation, 387
carbon-14, 563, 806 carbon dating, 806
carbon dioxide, 838-842, 848, 911 carbon disulfide, 921
carbon nanotubes, 953 carbonyl group, 367, 370
carboxy group, 367, 370
carboxylic acids, 367, 370, 372, 662 Carothers, Wallace, 397
catalysis, 573-577, 616-617 catalyst, 573
catenation, 365,910 cathode, 36, 763, 766
cathodic protection, 785
cementite, 886
(CDC), 3, 23
ceramics, 945-946
chain reactions, 396
Chauvin, Yves, 935 chelating agents, 861
chemical analysis, 873
bond enthalpy, 300-303 Born-Haber cycle, 282-284 comparison of ionic and covalent
compounds, 286
drawing Lewis structures, 291-292
ionic bonding, 279-284 lattice energy, 280-281
Lewis structures, 284-285 Lewis structures and formal charge,
292-295
resonance, 295-296 chemical bonds, 47
balancing, 77-81
interpreting and writing, 76-77
chemical equilibrium, 113, 590-591
concept of equilibrium, 592-594
equilibrium expressions, 599-605
606-611 factors that affect, 611-6l7
catalysis, 573-577 dependence of reactant concentration on
time, 555-562
Trang 10dependence of reaction rate on reactant
concentration, 551-555
dependence of reaction rate on temperature,
562- 568 reaction mechanisms, 568-573
reaction rates, 544-550
chemical properties, 15
chemical reactions, 4, 7
comparison of nuclear reactions and, 798
energy changes in, 160-161
chemical reduction, 884
chemistry
defined, 4
study of, 4-6
chemotherapy, 73, 873
chiral, 383
chiral switching, 385
chloralkali process, 923
chlorine, 926-927
chlorofluorocarbons (CFCs), 829, 835, 837-838,
841 , 842 cholesteric, 947
cidofovir, 23
cis isomers, 337, 382, 865-866
cisplatin, 73
Clausius-Clapeyron equation, 470
closed system, 163, 164
closest packing, 475, 478-479
coal, 910
cohesion, 468
coinage metals, 265
colligative properties, 517
collision theory, 562-564
colloids, 530- 532
color, 868-869
combination reactions, 98, 133, 134
combustion analysis of compounds, 87-88
determination of empirical formula, 87
determination of molecular formula, 88
combustion reactions, 98, 134
common ion effect, 682-683, 705-7l0
complex ion, 710
complex ion formation, 710-712
composite materials, 946
compounds, 6-7 See also inorganic
compounds; organic compounds insoluble, 118
ionic, 55, 57-61 , 116, 117-119
molecular, 47, 49- 51 , 116,417
percent composition of, 75-76
soluble, 118
compressibility, gas, 440
concentration cells, 775-776
concentration of solutions
concentration defined, 136
dilution, 137, 140
molarity, 136-137, 138-139
preparing a solution from a solid, 138-139
solution stoichiometry, 141-142
condensation, 470
condensation polymers, 396-397, 941-944
condensation reactions, 396
condensed structural formulas, 376
condensed structures, 376
conducting polymers, 943-944
conduction band, 954
conductivity, 113-114 conductors, 888-889 conjugate acid, 636 conjugate acid-base pairs, 654-657 conjugate base, 636
conjugate pair, 636 constant-pressure calorimetry, 172- 174
constant-volume (bomb) calorimetry, 175-177 constant-volume calorimetry, 175-177
constituent elements, 7 constitutional isomerism, 382 constructive interference, 195, 196 conversion factors, 20
coordinate covalent bonds, 297, 858 coordination chemistry, 856-857
applications of coordination compounds,
873-874
coordination compounds, 858-864 coordination compounds, defined, 858 crystal field theory, 867-872
naming coordination compounds, 862-864 reactions of coordination compounds,
872-873
structure of coordination compounds,
864-867 coordination numbers, 473, 861 copolymers, 396, 939
copper, 898 core electrons, 244 con'osion, 784-785 coulomb (C), 289 Coulomb's law, 245, 386, 800 covalent bond, 284
types of covalent bonds, 285-286 covalent bonding, 284
covalent compounds, 286, 925 covalent crystals, 482, 483
covalent hydrides, 908 covalent radius, 246 cowpox, 3
crenation, 524-525
critical mass, 812 critical pressure, 486, 487 critical temperature, 486, 487 cross-links, 937
Crutzen, Paul, 829 crystal field splitting, 867, 868 crystal field theory, 867
color, 868-869 crystal field splitting in octahedral
complexes, 867-868
magnetic properties, 869-871 tetrahedral and square-planar complexes, 871 crystal structure, 472
closest packing, 475, 478-479 packing spheres, 473-475
structures of crystals, 476-477 types of crystals, 480-484
unit cells, 472-473 crystalline solid, 472, 507
cubic cells, 474-475 cubic close-packed (ccp) structure, 478 Cunningham, Orville, 438
curie (Ci), 818, 847 Curie, Marie, 38
cyanides, 911
INDEX
D
d-block elements, ions of, 253-254
d orbitals, 330- 334 Dalton, John, 34-36 Dalton's law of partial pressures, 434-435,
440,442
dative bond, 297 Davisson, Clinton Joseph, 210
de Broglie hypothesis, 208- 210
de Broglie wavelength, 209
Debye (D), 289
decomposition reactions, 98, 133- 134
decompression sickness (DCS), 438
definite proportions, law of, 35
degenerate, 221
delocalized bonding, 351-353 delocalized bonds, 352
delocalized electrons, 944 demineralization, 681
Democritus, 34, 35 density, 12- 13, 15
dental implants, 950
dental pain, electrochemistry of, 759
deoxyribonucleic acid (DNA), 400, 401 deposition, 488
derived units, 12-13 destructive interference, 195, 196,208
detergents, 874 dextrorotatory isomer, 384, 866 dialysis, 505
diamagnetic, 342 diatomic molecules, 48
diffraction, electron, 210
diffusion, 444 dilution, 137, 140 dimensional analysis, 20 diodes, 955
dipole-dipole interactions, 462-463 dipole moment, 289-290
dipoles, bond, 321, 322 diprotic acids, 123,657-659 directionality, chemical bonds and, 325 dispersion forces, 465-467
displacement reactions, 130
disproportionation reaction, 134, 917 dissociation, 112, 523, 529
distillation, 887 distribution, 729 diving, 415, 438, 448 donor atoms, 860
donor impurities, 890 doping, 889, 955
double bonds, 285, 336, 338
double-sli experiment, nature of light and,
195-196
Douglas, Dwayne, 114-115
drugs
chiral switching in, 385-386 organic chemistry and, 363
single-isomer versions, 385- 386 drunk driving, III
dry cells, 777 dynamic chemical equilibrium, 113
dynamic equilibrium, 470
1-3