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普通化学(新教材)习题参考答案
第一章 化学反应的基本规律 (习题P50-52)
16解(1) H2O( l ) == H2O(g)
DfH/ kJmol-1 -285.83 -241.82
S/ Jmol-1k-1 69.91 188.83
DrH(298k) = [-241.82-(-285.83) ] kJmol-1 = 44.01 kJmol-1
Dr S(298k) = (188.83-69.91) Jmol-1k-1 = 118.92 Jmol-1k-1
( 2 ) ∵是等温等压变化
∴ Qp = DrH(298k) N = 44.01 kJmol-1 2mol = 88.02 kJ
W = -PDV = -nRT = -2 8.315 Jk-1mol-1 298k = -4955.7 J
= -4.956 kJ (或 -4.96kJ )
∴ DU = Qp + W = 88.02 kJ - 4.96kJ = 83.06 kJ
17解(1) N2 (g)+ 2O2 (g) == 2 NO2 (g)
DfH/ kJmol-1 0 0 33.2
S/ Jmol-1k-1 191.6 205.14 240.1
∴ DrH(298k) = 33.2 kJmol-1 2 = 66.4 kJmol-1
Dr S(298k) = ( 240.1 Jmol-1k-1 ) 2 -(205.14 Jmol-1k-1 ) 2 - 191.6 Jmol-1k-1
= - 121.68 Jmol-1k-1
(2) 3 Fe(s) + 4H2O (l) == Fe3O4 (s ) + 4 H2 (g)
DfH/ kJmol-1 0 -285.83 -1118.4 0
S/ Jmol-1k-1 27.3 69.91 146.4 130.68
∴DrH(298k) = [-1118.4 - (-285.83 4 ) ] kJmol-1 = 24.92 kJmol-1
Dr S(298k) = [(130.68 4 + 146.4 ) - (27.3 3 + 69.91 4 )] Jmol-1k-1
= ( 669.12 - 361.54 ) Jmol-1k-1 = 307.58 Jmol-1k-1
18. 解: 2Fe2O3 (s) + 3C (s ,石墨) == 4 Fe (s) + 3 CO2 (g)
DfH(298k)/ kJmol-1 - 824.2
S(298k)/ Jmol-1k-1 87.4 5.74 27.3
DfG(298k)/ kJmol-1 -742.2
∵ DrG = DrH - T • Dr S
∴ 301.32 kJmol-1 = 467.87 kJmol-1 - 298 k•Dr S
∴Dr S= 558.89 Jmol-1k-1
∴ Dr S= 3 S( CO2(g) 298k) + 27.3 Jmol-1k-1 4 -87.4 Jmol-1k-1 2 - 5.74 Jmol-1k-1 3
∴S( CO2(g) 298k) = 1/3 (558.89 +192.02 - 109.2 ) Jmol-1k-1 = 213.90 Jmol-1k-1
DfH(298k, C (s ,石墨))=0 DfG(298k, C (s ,石墨))=0
DfH(298k, Fe (s))=0 DfG(298k, Fe (s))=0
DrH=3DfH(298k, CO2(g) ) -2DfH(298k, Fe2O3 (s) )
467.87 kJmol-1 =3DfH(298k, CO2(g) ) -2 (- 824.2 kJmol-1)
∴ DfH(298k, CO2(g) ) = 1/3 (467.87-1648.4) kJmol-1 = -393.51 kJmol-1
同理 DrG=3DfG(298k, CO2(g) ) -2DfG(298k, Fe2O3 (s) )
301.32 kJmol-1 = 3DfG(298k, CO2(g) ) -2 (-742.2 kJmol-1 )
∴ DfG(298k, CO2(g) ) = 1/3 (301.32 - 1484.4 ) kJmol-1 = -394.36 kJmol-1
19.解 6CO2(g) + 6H2O(l) == C6H12O6 (s) + 6O2(g)
DfG(298k)/ kJmol-1 -394.36 -237.18 902.9 0
∴ DrG(298k) = [ 902.9 - (-237.18 6 ) - (-394.36 6 ) ] kJmol-1 = 4692.14 kJmol-1 >0
所以这个反应不能自发进行。
20.解(1) 4NH3(g) + 5O2(g) == 4NO(g) + 6H2O(l)
Df G(298k) /kJmol-1 -16.4 0 86.57 -237.18
∴DrG(298k) =[ (-237.18) 6 + 86.57 4 - (-16.4) 4 ] kJmol-1 = -1011.2 kJmol-1<0
∴ 此反应能自发进行。
(2) 2SO3(g) == 2SO2(g) + O2(g)
Df G(298k) / kJmol-1 -371.1 -300.19 0
∴DrG(298k) = [(-300.19) 2 - (-371.1) 2] kJmol-1= 141.82 kJmol-1 > 0
∴ 此反应不能自发进行。
21.解 (1) MgCO3(s) == MgO(s) + CO2(g)
DfH(298k)/ kJmol-1 -1111.88 -601.6 -393.51
S(298k)/ Jmol-1k-1 65.6 27.0 213.8
Df G(298k) / kJmol-1 -1028.28 -569.3 -394.36
∴ DrH(298k) = [ -601.6 + (-393.51) - (-1111.88)] = 116.77 kJmol-1
DrS(298k) = [ 213.8+ 27.0 - 65.6] = 175.2 Jmol-1k-1
DrG(298K) = [ (-394.36) +(-569.3)-(-1028.28)] = 64.62 kJmol-1
(2) DrG(1123K) = DrH(298k)-T DrS(298k) = 116.77 kJmol-1 - 1123k 175.2 Jmol-1k-1
= 116.77 kJmol-1 -196.75 kJmol-1 = -79.98 kJmol-1
又 ∵ RTlnKq(1123k)= - DrG(1123k)
∴ 8.315 Jmol-1k-11123 kln Kq(1123k) = -(-79.98) kJmol-1
∴ Kq(1123k) = 5.25 103
(3) ∵ 刚刚分解时 DrG(T) =DrH(298k)-T DrS(298k) =0
∴ 分解温度T可求:
∴ 分解最低温度为666.5 k
22.解法一: Kq (298k)=5.0 1016
∴DrG(298k) = -RTlnKq(298k)= -8.315 Jmol-1k-1298kln(5.0 1016) = -95.26 kJmol-1
∵DrG(298k) = DrH(298k)-298k DrS(298k)
∴-95.26 kJmol-1 = -92.31 kJmol-1-298kDrS(298k)
∴DrS(298k) =9.90 Jmol-1k-1
∴DrG(500k) = DrH(298k)-500k DrS(298k)
= -92.31 kJmol-1-500k9.90 Jmol-1k-1= -97.26 kJmol-1
而 DrG(500k) = -RTlnKq(500k)= -8.315 Jmol-1k-1 500kln Kq(500k)
∴ ln Kq(500k)= - = = 23.40
∴ Kq(500k) = 1.45 1010
解法二:
∵ ln =
== -15.05
∴ = 2.9 10-7
∴ Kq(500k) =2.9 10-7 Kq(298k) = 2.9 10-7 ( 5.0 1016 ) = 1.45 1010
23.解: N2(g) + 3H2(g) == 2NH3(g)
DfH(298k)/ kJmol-1 0 0 -45.9
S(298k)/ Jmol-1k-1 191.6 130.68 192.8
∴ DrH(298k) = 2(-45.9) kJmol-1 = -91.8 kJmol-1
S(298k) = (2192.8 -191.6 -3130.68 ) Jmol-1k-1= -198.04 Jmol-1k-1
DrG(T) = DrH(298k) -T DrS(298k) =0
= -91.8 kJmol-1 -T (-198.04 Jmol-1k-1 ) =0
∴ T = = 463.5 k
∴ T>463.5 k 时 反应能自发进行。
24.解:(1)-(2)得: CO2(g) +H2(g)⇌ CO(g) + H2O(g)
根据化学平衡得多重规则,
此反应的Kq (T)为: Kq (T) = K1q (T) K2q(T)
∴ 该反应各温度下的平衡常数为:
T/(k)
973
1073
1173
1273
Kq (T)
0.618
0.905
1.29
1.66
根据 DrG(T) = -RT ln Kq (T) = DrH(T) -T DrS(T)
假设 DrH(T), DrS(T)不变, 则
∵K1q (T)〈 K2q(T) T1〈 T2 即 T ↑ 则 Kq (T) ↑ ,DrHm > 0
∴该正反应为吸热反应。
25.解: 平衡反应 2SO2(g) + O2(g) ⇌ 2SO3(g)
初始时各物质的量/mol 1 1 0
平衡时各物质的量/mol 1-(1-0.615)2 (1-0.615)2
=0.23 0.615 =0.77
平衡时物质总量 = (0.23 +0.615 + 0.77 )mol = 1.615 mol
∴ = 29.43
26解: (1) (2)
(3)
27.解法一: 根据阿仑尼乌斯公式: (T1=301k)
(T2=278k)
结合上述两式,得:
改写此式,得 …….(1)
因为,反应速率与变酸时间成反比,因此, ……(2)
将(2)代入(1),
= 7.52104 Jmol-1 = 75.2kJmol-1
27.解法二: ∵ k= A
∴ = = Exp
又∵反应速率与变酸时间成反比
∴ = = Exp = 12
∴ = 75.2 kJmol-1
28.解: I2 ⇌ 2 I (快)
H2 + 2H ⇌ 2HI (慢)
快反应,很快达到平衡,故有: Kq(T)= =
∴ [I]2 = Kq(T) [I2]
对于分步反应,总的反应速率由较慢的步骤决定,即由第二步反应决定,
即:v = k[H2][I]2 其中[I]2 项可用 [I]2 = Kq(T) [I2] 这一式子代入。
∴ v = k[H2][I]2 = k[H2](Kq(T) [I2])=(kKq(T))[H2][I2] = k’[H2][I2]
29.解:v = k[CO][NO2] = 0.50 dm3 mol-1s-1 0.025 moldm-3 0.040 moldm-3
= 5.010-4 mol dm-3s-1
30.解:(1)-(2)=(3)
∴ = = = 2.0 10-10
第二章 水基分散系 习题 (P68-69)
11.解: (1) 盐酸溶液的量浓度C ==12.23 moldm-3
(2) 溶液的质量摩尔浓度m为:
= = = 16.44 molkg-1
(3) 按照(2)计算结果,该盐酸溶液中,每kg H2O中含16.44 molHCl,
而1kg H2O相当于 = 55.56 mol H2O
∴ 该溶液中溶剂H2O与溶质HCl的摩尔总数为:
=(55.56 + 16.44 ) mol =72 mol
∴ = = 0.23 = = 0.77
或 = 12.23 mol
= 41.32 mol
∴ = = 0.23 = = 0.77
12. 解: (1) = 37.5%
(2) = = 10.43 moldm-3
(3)乙醇的摩尔分数为:
= 0.67
(4) = 13.04 mol kg-1
13.解:设应加入尿素的量为m,
∵ (为溶液中尿素的摩尔分数)
∴ 0.200 kPa = 3.17 kPa
∴ = = 0.0631
∴ = 0.0631
=
可得: m = 224.5g
14.解:∵
设该溶质的摩尔质量为M
则 29.30 kPa - 27.62 kPa = 29.30 kPa
=
∴ M = 86.93 gmol-1
15. 解:(1) 相同质量(10g)的情况下:
= 58.5 =80 =132
∴ 物质的质量摩尔浓度m分别为 0.171molkg-1 0.125 molkg-1 0.076 molkg-1
考虑电离结合实际粒子浓度 m’ 0.342molkg-1 0.250 molkg-1 0.228 molkg-1
DTf 最多 次之 最小
(2)相同物质量(0.01mol)时的冰点下降顺序:
(NH4)2SO4 > NH4NO3 > NaCl
(3C) (2C) (2C)
16.解: ∵ 两溶液的凝固点下降相同: = m1 = m2 =
∴ m1 = m2 即: = (M为所求未知物的摩尔质量)
∴ M = 171.04 gmol-1
17.解: = Kbm
= 80.960C - 80.150C = 0.810C = 0.81k
∴ 0.81k = 2.53 kkgmol-1
得出溶液中溶解的单质硫的摩尔质量为M = = 253 gmol-1
∴ 该单质硫分子中含硫原子数为X = = 8
18.解: = m
8 k = 1.86 kkgmol-1
∴ m = 774.2 g
19.解: = m
按题意可得:16k = 6.85 kkgmol-1
(M为该有机物的摩尔质量)
∴ M = = 29.97 gmol-1
20.解: = Kbm ∴ 0.4550C = 0.455 k = Kb
∴ Kb = = 3.85 kkgmol-1
21.解:P = = cRT
∴ P = 0.20 moldm-3 8.315 Pam3k-1mol-1 298k = 4.956105 Pa
而 rgh = P 式中r=1000kgm-3 为水柱密度,g=9.8 ms-2 为重力加速度。
∴ 树汁可被提升的高度:h = =
= = 50.57 m
22.解:(1)P = cRT
= 8.315Jmol-1k-1 298k
= [(0.00444 + 0.00292)moldm-3] 8.315 Jmol-1k-1 298k
= 0.00736 moldm-38.315 Pam3k-1mol-1 298k = 18.24 kPa
(2) 18.24 kPa = 8.315Jmol-1k-1 298k
∴ 化合物的摩尔质量为 M =
= 271.69 gmol-1
(3) ∴溶液的凝固点下降:= m = 1.86 kkgmol-1
= 0.01358 k 0.014k
∴ 溶液的实际冰点为Tf = 273 k - 0.014 k = 272.99 k
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