2009.2.08
1 0 * 9 1 * 18 2 4 9 0 12 2 6 0 10 0 16 2 5 12 2 6 0 99 9 * 6thp204-243 ) 108 1
0-1 0-2 0-3 1-1 1-2 du = δ Q + δ W () δ W = PdV e U=f(T) 1-3 H=U+PV H=Q P δq=dh H=Q P 1-4 2 Q P C P =( H/ T) P Q P = H = nc P dt -- Q P = H=n V H m ξ=(n (ξ) -n (0) )/ν r H m = r H/ξ=Q P /ξ=(q V + n (gas) RT)/ξ r H m r H m = ν H,m = ν f H,m T d( r H m )/dt = C P 1-5 - 1-6Joule-Thomson - U H ( H ) Joule-Thomson T p T ( ) H = p ( H T) U H 1-7 > δq/t >0 2-1 ds = δq/t S=0 < δq/t <0 S S S 2-2 S 2-3 Gibbs Helmholtz 2-4 G Gibbs S=Q R /T;() S= p 1 2 nc 1 S=/T ; r S m = ν S,m r S m >δw G G=H-TS -dg T P =δw <δw <0 G -dg T P <0 G G G >0 G/ ξ T P =0 G = H - (TS), G= H-T S G=0; P,m /T dt r G m = ν G,m = ν f H,m = r H m -T r S m rgm 2
2-5 dg= SdT+VdP [ ( G/T)/ T]= H/T 2 Maxwell S p S V = = V p T T T V T p H G V = ( ) S = ( ) T p A p G S = ( ) V = ( ) T T p 2-6 ds = dse + ds ( ds i i δq ds e = + S, mdn + k piln pi T i 2-7 Z = ( Z/ n ) T P nj Z = n Z ; ndz = 0 µ µ = ( G/ n ) T P nj µ dg = SdT+VdP+ ν µ 3-1 3-2 oltzmann 3-3 µ =µ T+RTlnP /P Ω Ω A N q = ktln N! 4-1 =C-Φ+ 2-b C=S-R-R 4-2 4-3 5-1 Vant Hoff Ehrenfest dp C p = dp/dt = Hm/T Vm, dt TV α, T-x(y) T-x(y) T-x(y) - <0 ( G/ ξ) T P = ν µ = 0 >0 ( G/ ξ) T P r G m r G m r G m ξ 3
K =exp(- r G m /RT) 5-2 --K K K p K f K pk a K c/c r G m = ν f H,m = r H m - T r S m K K : 5-3 6-1 Gγ dln K /dt= r H m /RT 2 PA Gibbs dg = SdT + VdP + ν µ + γda γ = ( G/ A) T P n =( G/ A) T P n G=γA γ A 6-2 Laplace P=2 γ / R Kelvin RTlnp g / p 0 =2 γ M/R ρ θ=bp/(1+bp) θ=γ/ Γ (Γ=V/W Γ =V/W) 6-3 Langmuir 1/V=1/V +1/bV p A= V N 0 S/V m W -Young 6-4 Gibbs Γ = -C/RT(dγ /dc) 7-1 r = dc A /ν dt 7-2 7-3 (k=aexp(-e a /RT)) aa+dd dc A /adt=kc α A C β D ; nk aa, dc A /adt=kc A, lnc A.0 /C A =akt aa, dc A /adt=kc 2 A, 1/C A -1/C A.0 =akt dln k/dt= E a /RT 2,lnk 2 /k 1 =E a (T 2 -T 1 )/RT 1 T 2 lnk = -E a /RT+constant E a. E * -E E a, -E a, = r H m - ν RT 7-4 7-5 7-6 E a E a - 4
7-7 8-1 8-2 8-3 9-1 9-2 9-3 k=rt/n 0 h(p /RT) (1-n) e rsm /R e n e - Ea/RT k=rt/n 0 h(c ) (1-n) e rs m/r e e - Ea/RT 10-6 ~10-7 m q= ν e /ν W /M F G=1/R, κ=1/ρ (κ=g l/a), Λ m =κ/c Λ m C C Λ m Λ m GκΛ m Λ m C -- C Λ m Λ m K sp Debye Huckel Onsager i 0 - E E Nernst E=E -RT/ZF ln a ν ( p ) E r G m = -ZFE r H m = -ZFE+ZFT( E/ T) P E r S m = ZF( E/ T) P γ ± ph(k K sp K) - ϕ <ϕϕ >ϕ i 0, ϕ ϕ- η=ϕ-ϕ η=ϕ -ϕ V V=ϕ -ϕ =E-η-η V V=ϕ -ϕ =E+η+η ϕ ϕ U U I 1/λ 4 ζζ=6πη U U. Cm, Z, U U. CCm, Z, 5
0-1 J. H. van t Hoff (1711-1765) W. Ostwald (18521911) (18531932) 6
0-2 200 7
CH4+S CS2+H2.. 8
2008-2015 0-3.. 9
... 100% 5th546 150 396 458 6831010 184342830313130 10514 121214182015 21234392237302426 Noyes Sherril Chemical Principle. 498 2000.3 10
5th546 150 396; 70% 30% Fe(OH) 3 11