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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)
?1?fH?m/ kJ?mol ? ?
?1?1 S?m/ J?mol?k
?1 = kJ?mol?1 ?rH?m(298k) = [??(? ] kJ?mol
?1?1 = J?mol?1?k?1 ?r S?m(298k) = ? J?mol?k
( 2 ) ∵是等温等压变化
?1 ∴ Qp = ?rH?m(298k) ? N = kJ?mol ? 2mol = kJ
W = ?P??V = ?nRT = ?2 ? J?k?1?mol?1 ? 298k = ? J
= ? kJ (或 ? )
∴ ?U = Qp + W = kJ ? = kJ
17解(1) N2 (g)+ 2O2 (g) == 2 NO2 (g)
?1 0 0 ?fH?m/ kJ?mol
?1?1 S?m/ J?mol?k
?1 ? 2 = kJ?mol?1 ∴ ?rH?m(298k) = kJ?mol
?1?1?1?1?1?1 ?r S?m(298k) = ( J?mol?k ) ? 2 ? J?mol?k ) ? 2 ? J?mol?k
= ? J?mol?1?k?1
(2) 3 Fe(s) + 4H2O (l) == Fe3O4 (s ) + 4 H2 (g)
?1 0 ? ? 0 ?fH?m/ kJ?mol
?1?1S?m/ J?mol?k ?1?1 ∴?rH?m(298k) = [? ? (? ? 4 ) ] kJ?mol = kJ?mol?1?1?r S?m(298k) = [ ? 4 + ) ? ? 3 + ? 4 )] J?mol?k
= ( ? ) J?mol?1?k?1 = J?mol?1?k?1
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18. 解: 2Fe2O3 (s) + 3C (s ,石墨) == 4 Fe (s) + 3 CO2 (g)
?1?fH?m(298k)/ kJ?mol ?
?1?1S?m(298k)/ J?mol?k
?1 ? ?fG?m(298k)/ kJ?mol
?? ∵ ?rG?m = ?rHm ? T ? ?r Sm
∴ kJ?mol?1 = kJ?mol?1 ? 298 k??r S?m
?1?1 ∴?r S?m= J?mol?k
??1?1?1?1?1?1∴ ?r S?m= 3 Sm( CO2(g) 298k) + J?mol?k? 4 ? J?mol?k? 2 ? J?mol?k? 3
?1?1?1?1∴S?m( CO2(g) 298k) = 1/3 + ? ) J?mol?k = J?mol?k
??fH?m(298k, C (s ,石墨))=0 ?fGm(298k, C (s ,石墨))=0
??fH?m(298k, Fe (s))=0 ?fGm(298k, Fe (s))=0
???rH?m=3?fHm(298k, CO2(g) ) ?2?fHm(298k, Fe2O3 (s) )
?1? kJ?mol?1 =3?fH?m(298k, CO2(g) ) ?2 ? (? kJ?mol) ?1?1 ∴ ?fH?m(298k, CO2(g) ) = 1/3 ? kJ?mol = ? kJ?mol
??同理 ?rG?m=3?fGm(298k, CO2(g) ) ?2?fGm(298k, Fe2O3 (s) )
?1? kJ?mol?1 = 3?fG?m(298k, CO2(g) ) ?2 ? (? kJ?mol ) ?1 = ? kJ?mol?1 ∴ ?fG?m(298k, CO2(g) ) = 1/3 ? ) kJ?mol
19.解 6CO2(g) + 6H2O(l) == C6H12O6 (s) + 6O2(g)
?1 ?fG?m(298k)? kJ?mol ? ? 0
?1?1 >0 ∴ ?rG?m(298k) = [ ? (? ? 6 ) ? (? ? 6 ) ] kJ?mol = kJ?mol
所以这个反应不能自发进行。 22
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20.解(1) 4NH3(g) + 5O2(g) == 4NO(g) + 6H2O(l)
?1?f G?m(298k) /kJ?mol ? 0 ?
?1?1∴?rG?m(298k) =[ (? ?6 + ? 4 ? (? ?4 ] kJ?mol = ? kJ?mol<0
∴ 此反应能自发进行。
(2) 2SO3(g) == 2SO2(g) + O2(g)
?1 ?f G?m(298k) / kJ?mol ? ? 0
?1?1 ∴?rG?m(298k) = [(? ?2 ? (? ? 2] kJ?mol= kJ?mol > 0
∴ 此反应不能自发进行。
21.解 (1) MgCO3(s) == MgO(s) + CO2(g)
?1 ? ? ? ?fH?m(298k)/ kJ?mol
?1?1 S?m(298k)/ J?mol?k
?1 ?f G?m(298k) / kJ?mol ? ? ?
?1 ∴ ?rH?m(298k) = [ ? + (? ? (?] = kJ?mol
?1?1 ?rS?m(298k) = [ + ? ] = J?mol?k
?1 ?rG?m(298K) = [ (? +(??(?] = kJ?mol
???1?1?1 (2) ?rG?m(1123K) = ?rHm(298k)?T? ?rSm(298k) = kJ?mol ? 1123k ? J?mol?k
= kJ?mol?1 ? kJ?mol?1 = ? kJ?mol?1
又 ∵ RTlnK?(1123k)= ? ?rG?m(1123k)
∴ J?mol?1?k?1?1123 k?ln K?(1123k) = ?(? kJ?mol?1
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∴ K?(1123k) = ? 103
?? (3) ∵ 刚刚分解时 ?rG?m(T) =?rHm(298k)?T? ?rSm(298k) =0
116.77kJ?mol?1 ∴ 分解温度T可求: T???666.5k ??1?1?rSm(298k)175.2J?mol?k?rHm(298k)? ∴ 分解最低温度为 k
22.解法一: K? (298k)= ? 1016
16??1?1?1 ∴?rG?m(298k) = ?RTlnK(298k)= ? J?mol?k?298k?ln ? 10) = ? kJ?mol
?? ∵?rG?m(298k) = ?rHm(298k)?298k? ?rSm(298k)
∴? kJ?mol?1 = ? kJ?mol?1?298k??rS?m(298k)
?1?1 ∴?rS?m(298k) = J?mol?k
?? ∴?rG?m(500k) = ?rHm(298k)?500k? ?rSm(298k)
= ? kJ?mol?1?500k? J?mol?1?k?1= ? kJ?mol?1
??1?1? 而 ?rG?m(500k) = ?RTlnK(500k)= ? J?mol?k? 500k?ln K(500k)
??rGm(500k)97.26?103J?mol?1 = = ?1?1RT8.315J?mol?k?(500k) ∴ ln K?(500k)= ?
∴ K?(500k) = ? 1010 解法二:
???rHm(298k)1K?(500k)1?( ∵ ln? = ?)
R500298K(298k)?(?92.31?103J?mol?1)?202?()k= ? =
8.315J?mol?1?k?1500?298K?(500k)∴ ? = ? 10-7
K(298k) ∴ K?(500k) = ? 10-7 ? K?(298k) = ? 10-7 ? ( ? 1016 ) = ? 1010
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23.解: N2(g) + 3H2(g) == 2NH3(g)
?1 ?fH?m(298k)/ kJ?mol 0 0 ?
?1?1 S?m(298k)/ J?mol?k
?1?1∴ ?rH?m(298k) = 2?(? kJ?mol = ? kJ?mol
?1?1?1?1S?m(298k) = (2? ? ?3? ) J?mol?k= ? J?mol?k
?? ?rG?m(T) = ?rHm(298k) ?T? ?rSm(298k) =0
= ? kJ?mol?1 ?T? (? J?mol?1?k?1 ) =0
?91.8?103J?mol?1 ∴ T = = k
?198.04J?mol?1?k?1 ∴ T> 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K? (T)为: K? (T) = K1? (T) ? K2?(T) ∴ 该反应各温度下的平衡常数为: T/(k) K? (T)
973 1073 1173 1273 ???根据 ?rG?m(T) = ?RT ln K (T) = ?rHm(T) ?T? ?rSm(T)
???rHm?rSm?) lnK(T)??(RTR??m?m
???rHmK1(T)11假设 ?rH(T), ?rS(T)不变, 则ln???(?)
RT1T2K2(T)∵K1? (T)〈 K2?(T) T1〈 T2 即 T ↑ 则 K? (T) ↑ ,?rHm? > 0 ∴该正反应为吸热反应。
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