Homework (Ch 10)

Practice

1. 根據筆記上例題給的數據，用 EXCEL 畫出 P-x-y 和 x-y 圖

2. 閱讀課文，並試圖理解 Figure 10.3-2 中 Critical Locus 的物理意義

Illustration
10.1-2
10.1-3
10.2-1

Problem
10.2-7
10.2-16
 10.2

10.2-7 a) x1P1vap + x 2 P2vap = P = bubble point pressure

Equimolar mixture ⇒ x1 = x2 = 0.5
P=
2
(
1 vap
P1 + P2vap )
P1vap P2vap
b) x1P1vap + y1P = 0.5 P1vap ; y1 = ; y =
P1vap + P2vap P1vap + P2vap
2

∂ ⎛ AN1 N 2
⎞
c) G ex = Ax1 x 2 G1ex = ⎜ ⎟ = Ax 2 − Ax1 x 2 = Ax 2
2

∂N1 ⎝ N1 + N 2
⎠
⎛ Ax 2 ⎞
2
⎛ Ax12 ⎞
G1ex = RT ln γ1 ⇒ γ1 = exp ⎜ ⎟ and γ 2 = exp ⎜ ⎟
⎝ RT ⎠ ⎝ RT ⎠
For an equimolar liquid mixture
⎛ A ⎞ ⎛ A ⎞
γ1 = exp ⎜ ⎟ γ 2 = exp ⎜ ⎟
⎝ 4RT ⎠ ⎝ 4RT ⎠
⎛ A ⎞ vap ⎛ A ⎞ vap
x1 γ1P1vap + x 2 γ 2 P2vap = P = 0.5 × exp ⎜ ⎟ P1 + 0.5 × exp ⎜ ⎟ P2
⎝ 4RT ⎠ ⎝ 4RT ⎠
⎛ A ⎞ vap
P = 0.5 exp ⎜
⎝ 4RT ⎠
(
⎟ P1 + P2
vap
)
d) x1γ1P1VAP = y, P
⎛ A ⎞ vap
0.5 exp ⎜ ⎟ P1
xγP vap
⎝ 4RT ⎠
y1 = 1 1 1
=
⎛ A ⎞
P
( )
P1vap + P2vap 0.5 exp ⎜ ⎟
⎝ 4RT ⎠
P1vap P2vap
⇒ y1 = and y2 =
P + P2vap
1
vap
P + P2vap
1
vap

So while the bubble point pressure changes in going from the ideal to this
nonideal mixture, the bubble point vapor compositions are unchanged.
 10.2

10.2-16 a) G ex = Ax1x 2
which immediately gives RT ln γ1 = Ax 22 and RT ln γ 2 = Ax12
so
( 3750 − 8T ) x 22 ( 3750 − 8T ) x12
ln γ1 = and ln γ 2 =
RT RT
b) Since

∂ ⎛G⎞ ∂ ⎛ G ex ⎞ 2 ∂ ⎛ 3750 − 8T ⎞ 3750

H = −T 2 ⎜ ⎟ ⇒ H ex = −T 2 ⎜ ⎟ = −T ⎜ ⎟ x1 x 2 = + T 2 2 x1 x 2
∂T P ⎝ T ⎠ ∂T P ⎝ T ⎠ ∂T ⎝ T ⎠ T
H = 3750 x1 x 2
ex

H ex − G ex
also G ex = H ex − TS ex Sex =
T

Sex =
[3750 − 3750 + 8T ] x x = 8x1 x 2
1 2
T

1 2 J
∆H = 3 moles × 3750 × × = 2500 J
3 3 mol
1 2 ⎧ 1 2⎫
∆S = Sex − R ∑ N i ln x i = 8 × × − 8.314 ⎨1 ln + 2 ln ⎬ = 0.7777 − 8.314 ( −1.9096 ) = 15.10 J / mol ⋅ K
3 3 ⎩ 3 3⎭
⎡ ( 3750 − 8 × 320 ) 2 2 ⎤ ⎛ 4⎞
c) γ B = exp ⎢ × × ⎥ = exp ⎜ 0.44729 × ⎟ = e0.19879 = 1.220
⎢⎣ 8.314 × 320 3 3 ⎥⎦ ⎝ 9⎠
⎡ 3750 − 8 × 320 1 1 ⎤ ⎛ 0.44729 ⎞
γ C = exp ⎢ × × ⎥ = exp ⎜ ⎟ = 1.1183
⎣ 8.314 × 320 3 3⎦ ⎝ 9 ⎠
1 2
PBubble = ∑ x i γ i Pivap = × 1.220 × 0.3203 + × 1.1183 × 0.3218 = 0.3702 bar
3 3
應該要乘以3 mole

5.333 21.21