第一章习题答案
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《物理化学简明教程》第1章习题解答
1.1 解:等压p1= p2=pex
W = -pex(V2-V1)=p1V1-p2V2=nR(T1-T2)= 1 8.314 (-1) = -8.314 J
1.2 解:(1)据理想气体状态方程nRTpV,得
333m 1094224101000300314810..pnRTV
外压始终维持恒定,系统对环境做功
331001024.942102494.2exWpVJ
(2)
2122212213433()()11()11108.31430010010()2.2510J10010100010exexexexWpVpVVnRTnRTpppnRTppp
(3)等温可逆膨胀:
212112334--ln-ln100010-103.314300ln10010-5.7410vvWpdVVnRTVpnRTp
1.3 解:(1) W = -pex(Vs-Vl) = pexm(1/l-1/s) = 105 1 18 10 -3 ( 1/1103-1/0.92103 ) = -0.157 J
(2) W = - pex (Vg-Vl) = pm/l - pVg = pnM/l –nRT = 10511810 -3 /11103 -1 8.314 373.15 =
-3101 J
1.4 解: 最少功即为可逆压缩功
(1)对理想气体 10 mol,300 K
1000 kPa,V1 10 mol,300 K
100 kPa,V2 1513221118.314423.15100.035181 m35.181 Lln101.08.314423.15ln35.1814425.45 JnRTVpVWpdVnRTV
(2)对范德华气体
2002362306310()()422.51037.0710NHanpVnbnRTVaPammolbmmol
求V1
32211101100()0pVnRTnbpVnab
忽略300nab项,则有
2211101102210110110116556525255321()0()()42(18.314423.15137.071010)210(18.314423.15137.071010)4101422.5102100.035097(m)35.097(L)pVnRTnbpVnanRTnbpnRTnbppnaVpWpdV220210222000102136326()ln()1010137.0710422.510118.314423.15ln()0.0351137.07100.0351(4426.6737.963)4338.71 JannRTdVVnbVVnbananWnRTVnbVV
1.5 解: (1) ,221(HO,g)()135(673.15373.15)10.50KJpmQnCTT
(2)2121dd2mTTTT,pTcTbTanTCnQ
31322122123121TTcTTbTTan
1336223molJ37367310002231373673104914211004001629mol1...
= 10.85kJ 1.6 解:
1122522151112,21,21,11536.0102901450K1.210()()(1)1.210201014502.5(1)24000.0J290vvmvmvmpVnRTpVnRTpTTppVpVTQUnCTTCTTCRTRTRR
1.7 解 经过计算,列出下列方框图
过程(1)=a+b
过程a为恒压过程
321()101325(11.222.4)101134.84JaWpVV
,21213()1()2318.314(136.5273)1702.29J22837.13JavmaaaaUnCTTRTTQHUW
过程b为恒容过程
0bW
,21,213()18.314(546136.5)5106.874J25()18.314(546136.5)8511.458J2bbvmbpmUQnCTTHnCTT
11111134.84J2269.74J3404.584J5674.33JababababWWWQQQUUUHHH
过程(2)= c+d
过程c为恒温过程 a b
恒温可逆 1mol理气
273K
22.4 L
p 1mol理气
136.5K,11.2L,p
1mol理气
273K,5.6L,4p 1mol理气
546K
11.2 L
4p c d 恒压 恒容
恒压 21005.6ln18.314273ln3146.503J22.4ccccUHVQWnRTV
过程d为恒压过程
321,212222224()4101325(11.25.6)102269.68J5()18.314(546273)5674.305J23404.62J876.82J 2527.80J 3404.62J 5674.305JdddpmdddcdcdcdWpVVQHnCTTUQWWWWQQQUQWHHH
比较两过程数据,有12121212,,,QQWWUUHH,说明Q和W是途径函数,而U,H是状态函数。
1.8 解:
22333001013250821554Pa370exTpppT
1221222112212121231213()()()(1)(1)1013250300.1518.314300.151101325370.1517740JexWpVpVVpVpVnRTnRTpppTnRTpTpTnRTpT
212,31,31017740J120.92701464J129.10702037J14641774016276JVmpmWWWWUnCttHnCttQUW t1=27oC
p1=101.325 KPa
V1 恒温,恒外压 t2=27oC
p2= pex
V2 t3=97oC
p3=1013.25 KPa
V3= V2 恒容 1.9 解:3111(100/28)8.314273.150.0803m101000nRTVp
(1)等容加热22111.5101000273.15409.7K101000pTTp
0W
,1002.5(409.7273.15)10136.4J28vmQUnCTR
,1003.5(409.7273.15)14191.0J28pmHnCTR
(2)等压膨胀2211273.152476.3KVTTV
1010000.08038110.3JexWpV
,1003.5(476.3273.15)28387.1J28pmQHnCTR
,1002.5(476.3273.15)20276.5J28vmUnCTR
(3)恒温可逆膨胀 0,0UH
12100ln8.314273.15ln25621.8J28pWQnRTp
(4)绝热,恒外压0,QWU
21,2121221()()100100282.5(273.15)227.7K228exVmpVVnCTTRTVRTTV
,1002.5(227.7273.15)3373J28vmWUnCTR
,1003.5(227.7273.15)4723J28pmHnCTR
1.10 解:5351010102.2mol8.314273.15pVnRT
(1)绝热可逆过程 Q = 0 111111222125135553510273.1510143.49K
=ppTpTTTp
,212.21.58.314(143.49273.15)3557J VmWUnCTT
,212.22.58.314(143.49273.15)5929J pmHnCTT
(2)反抗恒外压绝热膨胀 Q = 0,WU
21,21212212212112121211.5()()11.5()()51717273.15185.7K2525VmexnRTnRTnCTTpVVppppnRTTnRTTpTTTTTT
,212.21.58.314(185.74273.15)2398.2J VmWUnCTT
,212.22.58.314(185.74273.15)3997J pmHnCTT
1.11 解:(1)水在同温同压的条件下蒸发
3133311022592.259KJ
1.010 8.314373.15172.4J18102.2610172.42086.6JglgHQWpVVpVnRTUQW
(2)
,UH为状态函数,所以值同(1)中的值 373.15 K,H2O(l)
100 kPa 373.15 K,H2O(g)
50 kPa 373.15 K,H2O(g)
100 kPa I II