第九章 统计热力学初步
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第九章 统计热力学初步. § 9.1 粒子各运动形式的能级及能级的简并度 § 9.2 能级分布的微态数及系统的总微态数 § 9.3 最概然分布与平衡分布 § 9.4 玻耳兹曼分布 § 9.5 粒子配分函数的计算 § 9.6 系统的热力学能与配分函数的关系 § 9.7 系统的摩尔定容热容与配分函数的关系. 目 录. § 9.8 系统的熵与配分函数的关系 § 9.9 其它热力学函数与配分函数的关系 § 9.10 理想气体反应的标准平衡常数 § 9.11 系综理论简介. 导论:. - PowerPoint PPT PresentationTRANSCRIPT
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U N V p
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9.1 n te-rv
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t rven n 3n3 23n 5 ;3 3n 3 3 = 3n 6
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kR/ L=1.38110-23 J K-1
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ge,0 gn,0
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9.2
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N NUV (9/2)hAB C
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n0 n1 n2 n3 ni ni i I0 3 0 0 3 9h/2 II2 0 0 1 3 9h/2 III1 1 1 0 3 9h/2
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N = 3U = 9h /2ABC
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DWD
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WD
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N i n1 n2
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m PA 1/6
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2. 1024 NU V
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NU V P P = 1 / PD = WD /
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3. N, U, V 9.2.21, 3, 6, P1 = 1/10 P2 = 3/10 P3 = 6/10 3
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N ABAM BN M
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M M = N/ 2 WB
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N = 10 N = 20 WD PD 9.3.1 9.3.2
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9.3.1 N=10 AB =1024
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9.3.2 N=20 AB = 1048 576 N 1020 N =10 PB = 0. 246 N =20PB=0. 1762
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N N=10M = 4560. 656 N=20M = 89 10 11 12 0.737 PD /PB =19. 3. 1 PD / PB N NM/N=0. 5
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1
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N,U,V
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N
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NUV WD 9.2 ni WD
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*2.
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n x ( n 2 ) 1 2 F Z
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V
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WD ni
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ni ln WD
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gi gi = gt,i gr,i gv,i ge,i gn,i (9.5.2)
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2.q
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0 i i i i 0 i 0 = i 0 ( 9. 5. 5 )
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t,0 0 r,0 = 0 q t0 qt qr0 qr qv0 qv 10
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ni
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pV = nRT n = N /L pV = NRT/L = NkT ( k = R/L) V = NkT/p m =M /L
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9.5.2 T =300 K V =10 6 m3 qt ft
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v v >> r v= 5982 K vCO= 3084 K v >> T qv qv
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q0 q
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Um = Ut + Ue + Un
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*3.
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2.CV,t CV,r CV,v
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9.7.1 CO r= 2.77 K v= 3070 K 101.325 kPa 400 K CV,m CV,m,=( 18.223 + 7.683110 -3 T/K1.172 10 -6 T 2/K2 ) J mol-1 K-1
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* 9.7.2 -PbAl Cp,m 3R CV,m= CV,v R CV,m= CV,v = 3R Cp,m CV,m Cp,m 3R Cp,m = CV,m = CV,v = 3R -
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2. N PB = WB / ln WB / ln 1 ln WB ln
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N 1024 ln WB ln ,
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N WB S = k ln WB (9.8.2)
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0 K COCOCOCO OCCOOCOC = 2N R ln 2
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S = S t + S r + S V + S e + S n 9.8.6
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A B
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St m N T V
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9.8.2 298. 15 K 146.6 J mol-1 K-1
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298.15 K 146.6 J mol-1 K-1 0.2%
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6.
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CO T 0 K = 1
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S0=0 S > 0
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12A G
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9.9.1 HI r =9.0 K v =3200 K 500 K HI
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4.
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9.10
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9.11 N
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N N ON
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1 NVT 2N V U 3 VT N1 N2 1 2
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NV T (N ) N t = N NV t = N V Et N T
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A(N,V,T)