Chapter 10 - VLE From An Equation of State
Chapter 10 - VLE From An Equation of State
Chapter 10 - VLE From An Equation of State
and noting,
∂ A
∑
dA = -PdV - SdT + ∂n
i
i T ,V ,n
dni
j ≠i
we may substitute
dA = dG - PdV - VdP = VdP - SdT + ∑ ∂ G ∂n
i
i T , P ,n
dni - PdV - VdP
j ≠i
( ∑ n j B jj ) (∑ n ) ∂(∑ n B )
2
∂ ( A − A ) / RT 1∂ 2 B jj
ig
j j jj
= =
∂ n k T ,V ,nk ≠i V ∂n k V ∂n k
∂ ( ∑n )=
(∑n )
B jj
Bkk ⇒ ln( ϕ k ) =
2
( ∑ y B ) − ln Z
j
B kk B jj − ln Z = 2 ρ
∂n k V j j jk
bρ =
n (∑ y j bj ) = (∑n j bj ) ⇒ ∂bρ = b k
V V ∂n k V
∑ ∑n n a ( ∑n )( ∑ n ) ( ∑n )
2
Note: For aij= a ii a jj , i j ij = i aii j a jj = j a jj
( ∑n )
2
∂ ( ΣΣni n j a ij ) ∂
( ∑n )
j a jj
= = 2 a kk a jj
∂n k ∂n k j
n bk 2 Σn j a kj bk ρ 2 ρΣ x j a kj
ln( ϕ k ) = − ln( 1 − bρ ) + − − ln Z = − ln( 1 − bρ ) + − − ln Z
1 − bρ V VRT 1 − bρ RT
B a A a jk A jk bk Bk
bρ ≡ ; ≡ ; ≡ ; ≡
Z bRT B a A b B
2Σx j Akj
ln( ϕ k ) = − ln( Z − B ) +
Bk
−
Z−B Z
{[ ]}
A − A ig
RT
= − n ln(1 − bρ) −
an 2
nbRT 8
] [
ln 1 + ( 1 + 2 )bρ − ln 1 + ( 1 − 2 )bρ
bρ =
n (∑ x j bj ) = (∑ n j bj ) ⇒ ∂bρ = b k
V V ∂n k V
∑ ∑n n a = ( ∑n )( ∑n ) ( ∑n )
2
Note: For aij= a ii a jj , i j ij i aii j a jj = j a jj
∂ ( ∑n a )
2
∂ (an ) ∂ ( ΣΣni n j a ij )
( ∑n )
2
j jj
= = = 2 a kk a jj
∂n k ∂n k ∂n k j