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Actiivity Model-1
Actiivity Model-1
Thermodynamics
Therefore ∑ n ( ∂ ln γ
i i )
/ ∂n j = 0 Gibbs-Duhem for activity coefficients
∂( ∆ G / RT )
E
For a binary mixture, subtracting the ideal solution result to get the excess energy gives,
a 11 a 22 x12 a 11 + 2 x 1 x 2 a 12 + x 22 a 22
U = x1
E
+ x2 −
V1 V2 x 1V1 + x 2V2
where kij is an adjustable parameter also called the binary interaction coefficient
The activity coefficient expressions become
RT ln γ 1 = V1Φ 22 ( δ 1 − δ 2 + 2 k 12 δ 1 δ 2 ) ; RT ln γ 2 = V2 Φ 12 (δ 1 − δ 2 + 2 k 12 δ 1δ 2 )
2 2
RT RT A 21 V2
NOTE: Do NOT estimate A12 and A21 from δ1 and δ2. This how we rename this
particular grouping of parameters to obtain two adjustable parameters, A12 and A21.
∆G E U E A12 A21 x1x2
= =
RT RT RT ( x1 A12 + x2 A21 )
Giving expressions for the activity coefficients,
A12 A21
ln γ 1 = ln γ =
A12 x1 ; A21 x 2
2 2 2
(11.28)
+ +
A21 x 2
1 1
A12 x1
The point of van Laar theory is to use experimental data for mixtures to estimate the
values of A12 and A21. These equations can be rearranged to obtain A12 and A21 from γ1
and γ2 given any one VLE point.
x 2 ln γ 2 x1 ln γ 1
2 2
A12 = ln γ 1 1 + A21 = ln γ 2 1 +
x1 ln γ 1 x 2 ln γ 2 (11.29)
A12 = ln γ 1 1 + A21 = ln γ 2 1 +
x1 ln γ 1 x 2 ln γ 2
= 1.3424 ; = 1.8814
γ1 = 1.580; γ2=1.386
= − = x1 ln 1 + x 2 ln 2 + Φ1Φ2 ( x1v1 + x 2 v 2 )
NkT NkT Nk x1 x2 RT
Φ2 ( δ 1 − δ 2 )
v1 2 2
ln γ 1 = ln(Φ1 / x1 ) + (1 − Φ1 / x1 ) +
RT
Φ1 ( δ 1 − δ 2 )
v2 2 2
ln γ 2 = ln(Φ2 / x2 ) + (1 − Φ2 / x 2 ) +
RT
Excess Entropy/Nk
2.5
0.35 0.43 1.19 1.99
0.4 0.47 1.34 2.25 V 2/V1= 100
2
0.45 0.52 1.48 2.51
0.5 0.55 1.62 2.76 1.5
0.55 0.58 1.75 3
0.6 0.61 1.86 3.23 1
0.65 0.62 1.96 3.44 V2/V1=10
0.7 0.62 2.04 3.63 0.5
0.75 0.6 2.1 3.8
0.8 0.57 2.11 3.92 0
0.85 0.51 2.07 3.98 0 0.2 0.4 0.6 0.8 1
0.9 0.41 1.93 3.92 -0.5
0.95 0.26 1.55 3.59
0.975 0.15 1.13 3.08 x1
1 0 0 0
xj xi Ωij
1 = x jj / x j ∑ xi Ωij ⇒ = ∑ xi Ωij ⇒ xij =
⇒
i x jj i ∑ xk Ωkj
k
O O X O
X O X X
X X X O X O
O X O X
O X
O X O X
X O O X
O X X X O
O# 1 2 3 4 5 6 7 8 9
#X’S 3 3 3 2 1 1 0 2 2 = 17
#O’S 2 0 0 0 1 0 3 1 1 = 8
U − U ig 1 ni N A σ ij3 N A ε ij
= ∑∑x j ∫ g ij 4πrij2 drij
RT 2 V RT
Substituting Ncj, Λij, and xij into the energy equation for mixtures
( U − U ig ) = 21 ∑ x j Nc j ∑ xij εij ~(11.77)
j i
If we assume that Ncj = Nci ≡ z where z is assumed to be the same coordination number
for all the components,
xi Ω ij
= ∑x Nc j ∑ xij ( ij - ); UE = ∑ x j Nc j ∑
1
E 1 ( ij - ij )
∑x Ω
U 2 j jj 2 (11.80)
j i j i i ij
k
∑ x j ln(Φ j /x j ) -5∑ q j x j ln(Φ j /θ j )
GE
RT
=− ∑ q j x j ln
∑ xi Ω ij +
j i j j
ln γ k = ln γ COMB
k + ln γ RES
k
ln γ kCOMB = ln (Φ k / xk ) - (1 − Φ k / xk ) - 5qk [ln(Φ k / θ k ) − (1 − Φ k / θ k )]
x j Ω kj
ln γ kRES = qk 1 − ln ∑ xi Ω ik − ∑ xi Ω ij
i j ∑
i
∫ π
NA
− 2ε ij
N Au ij g ij 4 r 2
dr aij ε jj σ ij3
Ω ij ≡ = ~
a jj ε ij
∫ N Au jj g jj 4πr dr σ 3jj
NA
⇒ − 2ε jj
2