无机化学第五版习题答案
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4.解: T pV MpV nR mR
= 318 K 44.9 ℃
5.解:根据道尔顿分压定律
p(N2) = 7.6104 Pa p(O2) = 2.0104 Pa p(Ar) =1103 Pa
pi
ni n
p
6.解:(1) n(CO2 ) 0.114mol; p(CO2 ) 2.87 104 Pa
= 3283.0
kJ·mol1 < 0
该反应在 298.15K 及标准态下可自发向右进行。
2.解: rGm = 113.4 kJ·mol1 > 0 该反应在常温(298.15 K)、标准态下不能自发进行。
(2)
r
H
m
=
146.0
kJ·mol1;
r
S
m
= 110.45 J·mol1·K1; rGm = 68.7 kJ·mol1
p (H2O) = 2.02105 Pa
p (CO2) = 1.01105 Pa,
p (H2) = 0.34105 Pa
CO(g) + H2O(g) CO2(g) + H2(g)
起始分压/105 Pa
1.01 2.02
1.01 0.34
J = 0.168, K p = 1>0.168 = J,故反应正向进行。
rGm (298.15 K) = 243.03 kJ·mol1
lg K (298.15 K) = 40.92, 故 K (298.15 K) = 8.31040
lg K (373.15 K) = 34.02,故 K (373.15 K) = 1.01034
6.解:(1) rGm =2 f Gm (NH3, g) = 32.90 kJ·mol1 <0 该反应在 298.15 K、标准态下能自发进行。 (2) lg K (298.15 K) = 5.76, K (298.15 K) = 5.8105
N2(g) +
3H2(g)
2NH3(g)
新平衡浓度/(mol·L1)
1.2
0.50+(30.2) x
0.5020.20
Kc
= (0.50 2 0.20)2 1.2 (0.50 3 02 x)3
>0
该反应在 700 K、标准态下不能自发进行。
3.解:
r
H
m
=
70.81
kJ·mol1
;
r
S
m
= 43.2 J·mol1·K1; rGm
= 43.9 kJ·mol1
(2)由以上计算可知:
r
H
m
(298.15
K)
=
70.81
kJ·mol1;
r
S
m
(298.15
= 27.2
(2)
PCl5(g) PCl3(g) + Cl2(g)
新平衡浓度/(mol·L1)
0.10 + y
0.25 y 0.25 + 0.10 y 2
Kc =
(0.25 y)(0.30 y) mol·L1 (0.10 y)
=
0.62mol·
L1
(T 不变, K c 不变)
K =
p (H2O) / p 3 p (H2 ) / p 3
p (H2O) 3 p (H2 ) 3
5.解:设
r
H
m
、
r
S
m
基本上不随温度变化。
r Gm
=
r
H
m
T
·
r
S
m
rGm (298.15 K) = 233.60 kJ·mol1
(2) T2 = pV2 = 320 K nR
(3)W = (pV) = 502 J (4) U = Q + W = -758 J (5) H = Qp = -1260 J
11.解:NH3(g) +
5 O2(g) 4
2标98准.15态K NO(g) +
3 H2O(g) 2
12.解: r H m = Qp = 89.5 kJ
2
2
r
H
m
=
86.229 kJ·mol1
CO(g) + 1 Fe2O3(s) → 2 Fe(s) + CO2(g)
3
3
r
H
m
= 8.3 kJ·mol1
各反应
r
H
m
之和
r
H
m
=
315.6
kJ·mol1。
(2)总反应方程式为
3 C(s) + O2(g) + 1 Fe2O3(s) → 3 CO2(g) + 2 Fe(s)
8.解: rGm = f Gm (CO2, g) f Gm (CO, g) f Gm (NO, g) = 343.94 kJ·mol1< 0,所以该反应从理论上讲是可行的。
9.解:
r
H
m
(298.15
K)
=
f
H
m
(NO,
g)
=
90.25
kJ·mol1
r
S
m
第 1 章 化学反应中的质量关系和能量关系 习题参考答案
1.解:1.00 吨氨气可制取 2.47 吨硝酸。 2.解:氯气质量为 2.9×103g。
3.解:一瓶氧气可用天数
n1 ( p p1)V1 (13.2103 -1.01103 )kPa 32L 9.6d
n2
p2V2
101.325kPa 400L d-1
p (NH3 )
K =
1
3
p (N2 ) / p 2 p (H2 ) / p 2
p (NH3 ) / p
(3) K c = c (CO2 )
K p = p (CO2 )
K = p (CO2 ) / p
(4) K c
=
c (H2O) 3 c (H2 ) 3
Kp =
y =0.01 mol·L1, (PCl5) = 68%
(3) 平衡浓度/(mol·L1)
PCl5(g) PCl3(g) + Cl2(g)
0.35 z
z
0.050 + z
Kc =
(0.050 z)z = 0.62 mol·L1 0.35 z
z = 0.24 mol·L1, (PCl5) = 68%
0.50 0.50
2.0
2.0
Kc
=
c(PCl3 )c(Cl 2 ) c(PCl5 )
= 0.62mol· L1,
(PCl5) = 71%
PCl5(g) PCl3(g) + Cl2(g)
平衡分压
0.20 RT V
0.5 RT 0.5 RT
V
V
K =
p (PCl3 ) / p p (Cl2 ) / p p (PCl5 ) / p
(2) p(N2 ) p p(O2 ) p(CO2 ) 3.79104 Pa
(3) n(O2 ) p(CO2 ) 2.67 104 Pa 0.286
n
p
9.33104 Pa
7.解:(1)p(H2) =95.43 kPa
(2)m(H2) = pVM = 0.194 g
7. 解:(1) rGm (l) = 2 f Gm (NO, g) = 173.1 kJ·mol1
lg K1 =
f Gm (1) 2.303 RT
= 30.32, 故
K1 = 4.81031
(2) rGm (2) = 2 f Gm (N2O, g) =208.4 kJ·mol1
17.解:
r
H
m
=2
f
H
m
(AgCl,
s)+
f
H
m
(H2O,
l)
f
H
m
(Ag2O,
s)2
f
H
m
(HCl,
g)
f
H
m
(AgCl,
s)
=
127.3
kJ·mol1
18.解:CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
r
H
m
=
f
H
m
RT
8.解:(1) = 5.0 mol (2) = 2.5 mol
结论: 反应进度()的值与选用反应式中的哪个物质的量的变化来进行计算无关,但与反应式的 写法有关。
9.解: U = Qp p V = 0.771 kJ 10.解: (1)V1 = 38.3 10-3 m3= 38.3L
10. 解: 平衡分压/kPa
H2(g) + I2(g)
2HI(g)
2905.74 χ 2905.74 χ
2χ
(2x)2
= 55.3
(2905.74 x)2
χ = 2290.12 p (HI) = 2χ kPa = 4580.24 kPa
n = pV = 3.15 mol RT
11.解:p (CO) = 1.01105 Pa,
(CO2,
g)
+
2
f
H
m
(H2O,
l)
f
H
m
(CH4,
g)
= 890.36 kJ·mo 1
Qp = 3.69104kJ
第 2 章 化学反应的方向、速率和限度 习题参考答案
1.解:
r
H
m
=
3347.6
kJ·mol1;
r
S
m
= 216.64 J·mol1·K1; rGm
rU m = r H m nRT = 96.9 kJ
r
H
m
=
226.2
kJ·mol1
13.解:(1)C (s) + O2 (g) → CO2 (g)
r
H
m
=
f
H
m
(CO2,
g)
=
393.509
kJ·mol1
1 CO2(g) + 1 C(s) → CO(g)
p (CH4 ) p (H 2O)
K =
p (CO) / p p (H2 ) / p 3 p (CH4 ) / p p (H2O) / p
(2) K c
=
1
3
c (N2 )2 c (H2 ) 2
c (NH3 )
Kp
=
1
3
p (N2 )2 p (H2 ) 2
比较(2)、(3)结果,说明最终浓度及转化率只与始、终态有关,与加入过程无关。
14.解: 平衡浓度/(mol·L1)
N2(g) + 3H2(g) 2NH3(g)
1.0 0.50
0.50
Kc =
c(NH3 )2 c(N2 )c(H 2 )3
= 2.0(mol ·L1 ) 2
若使 N2 的平衡浓度增加到 1.2mol· L1,设需从容器中取走 x 摩尔的 H2。
lg
K
2
=
f Gm (2) 2.303 RT
= 36.50, 故
K
2
=
3.21037
(3) rGm (3) = 2 f Gm (NH3, g) = 32.90 kJ·mol1
lg
K
3
=
5.76,
故
K
3
=
5.8105
由以上计算看出:选择合成氨固氮反应最好。
2
3
2
3
r
H
m
=
315.5
kJ·mol1
由上看出:(1)与(2)计算结果基本相等。所以可得出如下结论:反应的热效应只与反应的
始、终态有关,而与反应的途径无关。
14.解:
r
H
m
(3)=
r
H
m
(2)×3-
r
H
m
(1)×2=1266.47
kJ·mol1
15.解:(1)Qp
=
(298.15
K)
=
12.39
J·mol1·K1
r
Gm
(1573.15K)≈
r
H
m
(298.15
K)
1573.15
r
S
m
(298.15
K)
= 70759 J ·mol1
lg K (1573.15 K) = 2.349, K (1573.15 K) = 4.48103
12.解:(1) NH4HS(s) NH3(g) + H2S(g)
平衡分压/kPa
x
x
K = p (NH3 ) / p p (H2S) / p = 0.070
则 x = 0.26100 kPa = 26 kPa
平衡时该气体混合物的总压为 52 kPa
(2)T 不变, K 不变。
NH4HS(s) NH3(g) + H2S(g)
平衡分压/kPa
25.3+ y y
K =(25.3 y) / p y / p = 0.070
13.解:(1)
y = 17 kPa PCl5(g) PCl3(g) + Cl2(g)
平衡浓度/(mol·L1)
0.70 0.50 2.0
K)
=
43.2
J·mol1·K1
r Gm
=
r
H
m
T
·
r
S
m
≤0
T
≥
r
H
m
(29
8
.15K)
= 1639 K
r
S
m
(298.15K)
4.解:(1) K c
=
c (CO) c (H2 ) 3
c (CH4 ) c (H 2O)
Kp
=
p (CO) p (H2 ) 3
r
H
m
==
4
f
H
m
(Al2O3,
s)
-3
f
H
m
(Fe3O4,
s)
=3347.6
kJ·mol1
4.解: T pV MpV nR mR
= 318 K 44.9 ℃
5.解:根据道尔顿分压定律
p(N2) = 7.6104 Pa p(O2) = 2.0104 Pa p(Ar) =1103 Pa
pi
ni n
p
6.解:(1) n(CO2 ) 0.114mol; p(CO2 ) 2.87 104 Pa
= 3283.0
kJ·mol1 < 0
该反应在 298.15K 及标准态下可自发向右进行。
2.解: rGm = 113.4 kJ·mol1 > 0 该反应在常温(298.15 K)、标准态下不能自发进行。
(2)
r
H
m
=
146.0
kJ·mol1;
r
S
m
= 110.45 J·mol1·K1; rGm = 68.7 kJ·mol1
p (H2O) = 2.02105 Pa
p (CO2) = 1.01105 Pa,
p (H2) = 0.34105 Pa
CO(g) + H2O(g) CO2(g) + H2(g)
起始分压/105 Pa
1.01 2.02
1.01 0.34
J = 0.168, K p = 1>0.168 = J,故反应正向进行。
rGm (298.15 K) = 243.03 kJ·mol1
lg K (298.15 K) = 40.92, 故 K (298.15 K) = 8.31040
lg K (373.15 K) = 34.02,故 K (373.15 K) = 1.01034
6.解:(1) rGm =2 f Gm (NH3, g) = 32.90 kJ·mol1 <0 该反应在 298.15 K、标准态下能自发进行。 (2) lg K (298.15 K) = 5.76, K (298.15 K) = 5.8105
N2(g) +
3H2(g)
2NH3(g)
新平衡浓度/(mol·L1)
1.2
0.50+(30.2) x
0.5020.20
Kc
= (0.50 2 0.20)2 1.2 (0.50 3 02 x)3
>0
该反应在 700 K、标准态下不能自发进行。
3.解:
r
H
m
=
70.81
kJ·mol1
;
r
S
m
= 43.2 J·mol1·K1; rGm
= 43.9 kJ·mol1
(2)由以上计算可知:
r
H
m
(298.15
K)
=
70.81
kJ·mol1;
r
S
m
(298.15
= 27.2
(2)
PCl5(g) PCl3(g) + Cl2(g)
新平衡浓度/(mol·L1)
0.10 + y
0.25 y 0.25 + 0.10 y 2
Kc =
(0.25 y)(0.30 y) mol·L1 (0.10 y)
=
0.62mol·
L1
(T 不变, K c 不变)
K =
p (H2O) / p 3 p (H2 ) / p 3
p (H2O) 3 p (H2 ) 3
5.解:设
r
H
m
、
r
S
m
基本上不随温度变化。
r Gm
=
r
H
m
T
·
r
S
m
rGm (298.15 K) = 233.60 kJ·mol1
(2) T2 = pV2 = 320 K nR
(3)W = (pV) = 502 J (4) U = Q + W = -758 J (5) H = Qp = -1260 J
11.解:NH3(g) +
5 O2(g) 4
2标98准.15态K NO(g) +
3 H2O(g) 2
12.解: r H m = Qp = 89.5 kJ
2
2
r
H
m
=
86.229 kJ·mol1
CO(g) + 1 Fe2O3(s) → 2 Fe(s) + CO2(g)
3
3
r
H
m
= 8.3 kJ·mol1
各反应
r
H
m
之和
r
H
m
=
315.6
kJ·mol1。
(2)总反应方程式为
3 C(s) + O2(g) + 1 Fe2O3(s) → 3 CO2(g) + 2 Fe(s)
8.解: rGm = f Gm (CO2, g) f Gm (CO, g) f Gm (NO, g) = 343.94 kJ·mol1< 0,所以该反应从理论上讲是可行的。
9.解:
r
H
m
(298.15
K)
=
f
H
m
(NO,
g)
=
90.25
kJ·mol1
r
S
m
第 1 章 化学反应中的质量关系和能量关系 习题参考答案
1.解:1.00 吨氨气可制取 2.47 吨硝酸。 2.解:氯气质量为 2.9×103g。
3.解:一瓶氧气可用天数
n1 ( p p1)V1 (13.2103 -1.01103 )kPa 32L 9.6d
n2
p2V2
101.325kPa 400L d-1
p (NH3 )
K =
1
3
p (N2 ) / p 2 p (H2 ) / p 2
p (NH3 ) / p
(3) K c = c (CO2 )
K p = p (CO2 )
K = p (CO2 ) / p
(4) K c
=
c (H2O) 3 c (H2 ) 3
Kp =
y =0.01 mol·L1, (PCl5) = 68%
(3) 平衡浓度/(mol·L1)
PCl5(g) PCl3(g) + Cl2(g)
0.35 z
z
0.050 + z
Kc =
(0.050 z)z = 0.62 mol·L1 0.35 z
z = 0.24 mol·L1, (PCl5) = 68%
0.50 0.50
2.0
2.0
Kc
=
c(PCl3 )c(Cl 2 ) c(PCl5 )
= 0.62mol· L1,
(PCl5) = 71%
PCl5(g) PCl3(g) + Cl2(g)
平衡分压
0.20 RT V
0.5 RT 0.5 RT
V
V
K =
p (PCl3 ) / p p (Cl2 ) / p p (PCl5 ) / p
(2) p(N2 ) p p(O2 ) p(CO2 ) 3.79104 Pa
(3) n(O2 ) p(CO2 ) 2.67 104 Pa 0.286
n
p
9.33104 Pa
7.解:(1)p(H2) =95.43 kPa
(2)m(H2) = pVM = 0.194 g
7. 解:(1) rGm (l) = 2 f Gm (NO, g) = 173.1 kJ·mol1
lg K1 =
f Gm (1) 2.303 RT
= 30.32, 故
K1 = 4.81031
(2) rGm (2) = 2 f Gm (N2O, g) =208.4 kJ·mol1
17.解:
r
H
m
=2
f
H
m
(AgCl,
s)+
f
H
m
(H2O,
l)
f
H
m
(Ag2O,
s)2
f
H
m
(HCl,
g)
f
H
m
(AgCl,
s)
=
127.3
kJ·mol1
18.解:CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
r
H
m
=
f
H
m
RT
8.解:(1) = 5.0 mol (2) = 2.5 mol
结论: 反应进度()的值与选用反应式中的哪个物质的量的变化来进行计算无关,但与反应式的 写法有关。
9.解: U = Qp p V = 0.771 kJ 10.解: (1)V1 = 38.3 10-3 m3= 38.3L
10. 解: 平衡分压/kPa
H2(g) + I2(g)
2HI(g)
2905.74 χ 2905.74 χ
2χ
(2x)2
= 55.3
(2905.74 x)2
χ = 2290.12 p (HI) = 2χ kPa = 4580.24 kPa
n = pV = 3.15 mol RT
11.解:p (CO) = 1.01105 Pa,
(CO2,
g)
+
2
f
H
m
(H2O,
l)
f
H
m
(CH4,
g)
= 890.36 kJ·mo 1
Qp = 3.69104kJ
第 2 章 化学反应的方向、速率和限度 习题参考答案
1.解:
r
H
m
=
3347.6
kJ·mol1;
r
S
m
= 216.64 J·mol1·K1; rGm
rU m = r H m nRT = 96.9 kJ
r
H
m
=
226.2
kJ·mol1
13.解:(1)C (s) + O2 (g) → CO2 (g)
r
H
m
=
f
H
m
(CO2,
g)
=
393.509
kJ·mol1
1 CO2(g) + 1 C(s) → CO(g)
p (CH4 ) p (H 2O)
K =
p (CO) / p p (H2 ) / p 3 p (CH4 ) / p p (H2O) / p
(2) K c
=
1
3
c (N2 )2 c (H2 ) 2
c (NH3 )
Kp
=
1
3
p (N2 )2 p (H2 ) 2
比较(2)、(3)结果,说明最终浓度及转化率只与始、终态有关,与加入过程无关。
14.解: 平衡浓度/(mol·L1)
N2(g) + 3H2(g) 2NH3(g)
1.0 0.50
0.50
Kc =
c(NH3 )2 c(N2 )c(H 2 )3
= 2.0(mol ·L1 ) 2
若使 N2 的平衡浓度增加到 1.2mol· L1,设需从容器中取走 x 摩尔的 H2。
lg
K
2
=
f Gm (2) 2.303 RT
= 36.50, 故
K
2
=
3.21037
(3) rGm (3) = 2 f Gm (NH3, g) = 32.90 kJ·mol1
lg
K
3
=
5.76,
故
K
3
=
5.8105
由以上计算看出:选择合成氨固氮反应最好。
2
3
2
3
r
H
m
=
315.5
kJ·mol1
由上看出:(1)与(2)计算结果基本相等。所以可得出如下结论:反应的热效应只与反应的
始、终态有关,而与反应的途径无关。
14.解:
r
H
m
(3)=
r
H
m
(2)×3-
r
H
m
(1)×2=1266.47
kJ·mol1
15.解:(1)Qp
=
(298.15
K)
=
12.39
J·mol1·K1
r
Gm
(1573.15K)≈
r
H
m
(298.15
K)
1573.15
r
S
m
(298.15
K)
= 70759 J ·mol1
lg K (1573.15 K) = 2.349, K (1573.15 K) = 4.48103
12.解:(1) NH4HS(s) NH3(g) + H2S(g)
平衡分压/kPa
x
x
K = p (NH3 ) / p p (H2S) / p = 0.070
则 x = 0.26100 kPa = 26 kPa
平衡时该气体混合物的总压为 52 kPa
(2)T 不变, K 不变。
NH4HS(s) NH3(g) + H2S(g)
平衡分压/kPa
25.3+ y y
K =(25.3 y) / p y / p = 0.070
13.解:(1)
y = 17 kPa PCl5(g) PCl3(g) + Cl2(g)
平衡浓度/(mol·L1)
0.70 0.50 2.0
K)
=
43.2
J·mol1·K1
r Gm
=
r
H
m
T
·
r
S
m
≤0
T
≥
r
H
m
(29
8
.15K)
= 1639 K
r
S
m
(298.15K)
4.解:(1) K c
=
c (CO) c (H2 ) 3
c (CH4 ) c (H 2O)
Kp
=
p (CO) p (H2 ) 3
r
H
m
==
4
f
H
m
(Al2O3,
s)
-3
f
H
m
(Fe3O4,
s)
=3347.6
kJ·mol1