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1第一章答案1.147℃2.467g3.(1)0.42mol22222CONOCOO(2)42.9%11.9%45.2%(3)0.45atm0.47atm(4)1.40gxxxpp4.13.7%5.35.7g6.10.2g7.(1)4.9g·dm−3(2)12atm(3)67%(4)10atm8.224224NONO(NO)(NO)(1)0.55atm0.45atm(2)%37.9%%62.1%ppww9.300mL,83.3mL10.A3O4(g)11.222ON(O)(1)0.75atm(2)0.5atm0.25atm(3)%66.7%ppx12.1.137atm13.(Ar)(Ne)%74.76%%25.24%ww14.M=322.6g/mol∴为Fe2Cl615.C2H4Cl216.26(CO)(CH)%60%%40%VV17.(1)0.02226mol(2)0.02226mol(3)0.50dm3(4)2.5×10−3%18.第一种C2H4:50%,C2H2:50%;第二种C2H6:25%,C2H2:75%。19.220.321.29.2%22.0.021atm23.0.982dm3,1.79g24.90%25.(1)444mmHg6678CHCH(2)251mmHg193mmHgpp26.128mmHg27.(1)1.8%(2)10928.分子量为2.70×104聚合度为16729.0.02mol30.83.5kPa31.(1)8.00dm3(2)18.1g32.0.77atm33.0.576atm(110℃)0.982atm(140℃)23.403kJ·mol−1141.1℃34.13835.(1)0.31mmHg(2)196.5mmHg36.22(N)(O)%32.5%%67.5%VV37.1.1×108mmHg38.6.51mL39.C12H1040.50041.341.842.10943.(C7H6O2)244.0.0024℃45.9246.−0.712℃47.−3.03℃48.(1)10.8mol/1kg溶剂(2)18.1dm3(3)105.53℃49.20350.5℃(K)·kg·mol−151.(1)100.414℃(2)2.98×103Pa(3)2.01×103kPa52.(1)0.30mol·dm−3(2)−0.56℃53.(1)69978(2)454.3336355.1223356.8.12atm57.0.462atm58.6126122211NaClCHOCHO59.0.0826l·atm·mol−1·K−160.(1)969J(2)305Kρ(g·dm−3)p(Pa)22071.5×10533077.9×10544083.5×105350Kρ(g·dm−3)p(Pa)22095.2×105330119.3×105440148.8×105(3)从上表中可知,在临近临界温度时,压力增加10bar,密度增大几乎2倍,所以应在临界点更容易调制流体的密度。2(4)(a)C6H5CH2OH+12O2C6H5CHO+H2O(b)副反应C6H5−CHO+12O2C6H5−COOH(Acid)C6H5−COOH+C6H5−CH2OHC6H5−CO(OCH2−C6H5)(ester)(5)(a)CH3OH+CO2CH3OCO(OCH3)+H2OCH3OH+COCl2CH3OCO(OCH3)+2HCl(b)C4H8ONH+CO2+还原剂(Red)C4H8ON−CHO+(Red−O)∴该反应需要还原剂,例如H2、CO等。C4H8ONH+CO2+H2C4H8ON−CHO+H2OC4H8ONH+COC4H8ON−CHO(6)第一个理由:CO2无毒,而CO和COCl2有毒;第二个理由:CO2既可以作反应剂又可以作溶剂,不需要另外加溶剂。还有一个原因是可以减少大气中CO2的排放量,减小温室效应。用CO2作反应物的主要障碍是CO2的反应活性比CO或COCl2小得多,因此必须寻找适合的催化剂。第二章答案1.(1)363.6J,(2)87.0cal2.(1)9atm·dm3,(2)−9atm·dm3,(3)9atm·dm33.(1)146.23kJ,(2)−511.98kJ4.2.94×104kJ5.37.67kJ6.2.5kJ7.−41.16kJ8.−772J9.ΔH=125.4J,ΔU=−481J10.W=Q=5.61kJ,ΔU=ΔH=011.W=Q=811J,ΔU=ΔH=012.ΔHm=−57.9kJ·mol−1,ΔUm=−56.3kJ·mol−113.ΔHm=−322.7kJ·mol−1ΔUm=−325.2kJ·mol−114.ΔH=−92.2kJ·mol−1ΔU=−87.2kJ·mol−115.(1)ΔH=41.8kJ(2)ΔH=83.7kJ(3)ΔH=−20.92kJ16.ΔHmΔSmΔGm(kJ·mol−1)(J·mol−1·K−1)(kJ·mol−1)(1)290.2244.1217.43(2)164.3116.2129.7(3)−77.4971.81−98.93反应(1)的转化温度为1189K,反应(2)的转化温度为1414K,反应(3)ΔG0,但若O2过量,则发生C4H6+11/2O2=4CO2+3H2O(g),此反应T2.35×107K时均有ΔGm0,反应自发进行,难以控制。∴反应(1)适合。17.(1)−137.07kJ·mol−1,(2)−630.59kJ·mol−1(3)44.18kJ·mol−118.1.88kJ·mol−119.−454.8kJ·mol−120.−127kJ·mol−121.−811.3kJ·mol−122.(1)−847.6kJ·mol−1,(2)−1423kJ·mol−1(3)−402.0kJ·mol−1,(4)−86.61kJ·mol−1(5)−137.0kJ·mol−123.−16.72kJ·mol−124.131.3kJ·mol−125.8.03kJ·mol−1,62.05kJ·mol−126.ΔH=−1266kJ·mol−10,放热反应27.Δf4,CH(g)mH=−75.3kJ·mol−128.(1)ΔcHm=−1781.35kJ·mol−1(2)61.43kJ·mol−129.(1)增加;(2)减少;(3)增加;(4)减少;(5)增加;(6)增加30.−30.49J·mol−1·K−131.(1)前者大。前者可逆变化所需热量大于后者可逆变化所需热量。(2)前者大。前者是自发过程ΔS总0,后者是可逆过程ΔS总=0。(3)后者大。升高到同温度时,不可逆过程的熵变比可逆过程大,现在不可逆地升高到80℃,所以后者的熵变更大。32.−44.4J·mol−1·K−133.84.37J·mol−1·K−134.(1)−1.72×104J·K−1(2)2.02×104J·K−1(3)3.0×103J·K−135.(1)1.22J·K−1(2)6.04J·K−136.(1)2.09J·K−1(2)−2.09J·K−14(3)037.(1)不对,对于孤立体系,自发过程是熵增加的过程。(2)不对,在等温、等压,作膨胀功时,自发过程是自由能减少的过程。(3)不对,ΔH不是判断反应自发与否的判据。38.此反应向右进行。39.(1)反应向右进行,(2)反应向左进行。40.(1)Δn(g)=1,∴ΔS0。(2)ΔG0,此反应不能自发。(3)T986K时,此反应能自发。41.−355.0kJ·mol−142.−118.5kJ·mol−143.−817.6kJ·mol−144.−26.7kJ·mol−145.ΔG=−54.8kJ·mol−1,ΔH=−51.59kJ·mol−1,ΔS=10.52J·mol−1·K−1。46.−2880kJ·mol−147.ΔG=99.56kJ·mol−1,ΔH=149.64kJ·mol−1,ΔS=168.1J·mol−1·K−1。48.−95.2kJ·mol−149.T(1)907.8K,T(2)697K∴(2)在较低温度下进行。50.897.8K51.1896K52.Ag2O:468KCuO:1679K53.第一个反应:ΔH=2172kJ·mol−1ΔS=635.1J·mol−1·K−1ΔG,298=1981kJ·mol−1T≥3419K,很难达到。第二个反应:ΔH=827.03kJ·mol−1ΔS=53.86J·mol−1·K−1ΔG,298=810.37kJ·mol−1T≥15355K,无法达到。554.c112222c1122223c1322223c132222c111222222[NO](1)[N][O][HCl](2)[H][Cl][NH](3)[N][H][ClF](4)[Cl][F][NOCl](5)[N][O][Cl]KKKKK55.c22c2c32-3c232c22(1)[CO][HO](2)[CO](3)[(CH)CO](4)[Cl][CO](5)[N]KKKKK56.1.69×10657.p(1)p(2)41.51,0.1552KK58.40%59.70%60.33.3%61.57.3%62.37.8%63.18.5%64.NO2:5.14×10−3mol·cm−3N2O4:1.00×10−3mol·cm−365.5.39atm66.87.8%67.(1)nX=1.8mol,nY=2.4mol(2)Kc=0.0772Kp=2.52×10−368.5.79×10−369.34FeOCO=0.07mol,=1.07molnn,2FeOCO=3.29mol,=1.23molnn70.0.024371.0.34mol72.(1)1.64×10−4,(2)13.3atm,(3)15%73.正反应放热的,∵低温时Kc值大,意味着6逆反应是吸热的,∴正反应是放热的。74.Kc=1.1475.0.03976.24.89atm77.(1)80%,(2)Kc=147.7,Kp=678.(1)Kp=4.00×10−4322NH2CO(2)4.48102.2410pp79.49.680.x=0.08时,α=0.45x=0.20时,α=0.42x=0.40时,α=0.35681.1.8282.308dm383.0.22484.0.75atm85.(1)77.8g·mol−1(2)18.3%224NONO(3)0.309atm0.691atmpp(4)0.13886.32NHHS0.17atm,0.62atmpp87.3.4888.3.46×10−3mol·dm−389.(1)0.94(2)Kc=2.1×102mol−1·dm3,Kp=5.1atm−190.(1)离解度增加。(2)离解度不变。(3)离解度增加。(4)离解度降低。(5)离解度降低。91.(1)会,净分解,∵Qp=20Kp(2)净分解,∵分解反应吸热,温度升高,平衡左移。(3)无影响92.Kp=7.919×10893.22COCO(1)0.983atm,1.6910atmpp(2)57.2atm,(3)−40.4kJ·mol−194.ΔGkJ·mol−1K(1)−229.31.563×1040(2)−29.251.346×105(3)−207.82.656×10367(4)−346.836.264×106095.(1)−11.097kJ·mol−1,(2)ΔG721=−23.45kJ·mol−1ΔG623=−21.77kJ·mol−196.10.1097.17.149kJ·mol−198.(1)图略,(2)58.99kJ·mol−1(3)−(4):T(℃)ΔGkJ·mol−1ΔS(J·mol−1·K−1)254.853181.66353.016181.76451.230181.6399.(1)−155kJ·mol−1(2)−116kJ·mol−1(3)不能,因为缺少Ba
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