KUC: ​Modified

Raoult’s Law
Review
• What is bubble point?
• What is dew point?
• We have previously go through
the 2 ​simplest models for solving
VLE ​problems
–Raoult’s Law ​–Henry’s Law
VLE
Modified
Raoult’s Law Henry’s Law ​
K-Values
Raoult’s Law ​

Modified Raoult’s Law

Telah diketahui asumsi-asumsi dalam Hk.
Raoult: 1). V phase is an ideal gas 2). L
phase is an ideal solution (kurang realistik)
Bila asumsi 2) dr Hk. Raoult di atas
dikoreksi dan digantikan dengan suatu
koefisien yang menyatakan deviasi dari
keadaan ideal fase cair, maka Hk. Raoult
menjadi:
iPxPy ​ =​ γ
i​ γ​ iii ​

(
sat ​
​ ,...,2,1= )
​ ​ N​
Koeffisien

aktivitas adalah fungsi komposisi fase cair (x) dan T.

Untuk sistem 2 komponen: Koef. aktivitas diberikan
oleh pdktn salah satunya dgn pers Margules 1
parameter dgn A=f(T)

γ
ln ​γ
i ​= ​Ax ​i 2​
​ '
adalah koefisien aktivitas (activity
coefficient), =1=larutan ideal
 y
1= ​Karena ​∑​i ​
i​&
maka

P Px ​ γ
∑ ​​i iii ​

sat

​
P=
 Py ​ 1
∑​ iii ​

γ​sat i
For bubble point
calculations
For dew point
calculations

x
1= ​∑​i i​ ​
EXAMPLE 10.3: For the system
methanol(1)/methyl acetate(2), the
following equations provide a
reasonable correlation for the activity
coefficients:

​ ​ = ​Ax ​
ln γ
ln ​γ ​1 =
​ ​Ax ​2 2​
​ 2​ 1

2​Where

A=2.771-0.00523 T.
Antoine equation:
P ​=

Px ​ γ
∑​ iii ​

sat
i
=

∑ ​424.53
i

ln
P1​
sat

​
kPa =
59158.16)( ​
-​ P ​1
T Kelvin ​31.3643 - 424.33 ​
Py ​
γ​
iii ​ sat

ln
P
2​sat

kPa ​= ​ -​
​ 4.2665 - ​Find:
25326.14 ​ T Kelvin 5
a) P and y1, for x1=0.25 and T=318.15K (kasus
BULB P) b) P and x1, for y1=0.60 and T=318.15K
(kasus DEW P) c) T and y1, for x1=0.85 and
P=101.33kPa (kasus BULB T) ​d) T and x1, for
y1=0.40 and P=101.33kPa (kasus DEW T) PR
a) ​P and y​1 ?
​ for x​1​=0.25 and
T=318.15K ​This is a BUBL P
calculation. ​For T=318.15K, the

Antoine equations yield: ​

P​ 1 sat
​ ​ =

51.44 ​PkPa ​ 2 sat

​ ​ =

64.65 ​kPa ​ Activity coefficients

are calculated from the given

equations;
ln ​γ ​ = ​Ax ​ 2​γ ​
ln ​γ ​1 =
​ ​Ax ​2 2​
​ 2​ 1​ 1
=​ Ax ​
exp( ​ 2​
2​
75.0107.1exp)
​ ​ =​
=γ Ax ​
2​ exp( ​ 1

2​
25.0107.1exp) ​
=​
[ ​( ​[ ​( ​ P

Px ​ γ
∑​ iii ​

sat
i

Where ​A=2.771-0.00523 T. ​ )( ) 2​ ​]
=​
864.1 ​)( )​ 2​
]​ =​
072.1
 =
∑​
P Px ​ γ
i​ iii ​

sat
P= ​
)64.65)(072.1)(75.0()51.44)(864.1
)(25.0( + ​P =​
50.73 ​kPa y​
= ​Px ​111 ​
1​
​ y​ ​2 =
γP ​ =
​ 1 - ​y 1 ​ 718.0

Atau:
=​ ​ ​
​ x 222
=P
sat ​ 282.0 ​y 2​ ​ γ
=​
Ps​ at ​ 718.0
ALGORITMA PERHITUNGAN BUBL
P
BUBL P CALCULATION
​
Find sat
P
i​

Find ​i​γ

Find P from equation 10.6 ​sat sat PxPxP

​
​222 111 γ
​ γ

+=
Find ​i​y ​from equation 10.5 ​PPxy ​sat
γ ​=
iii i ​

b) ​P and x​1 ?,
​ for y​1​=0. 60 and
T=318.15K ​This is a DEW P
calculation.
Utk T=318.15K, nilai P​sat ​dari pers
Antoine dan A tidak berubah. Tetapi
nilai koef aktivitas tidak ​dapat
diketahui karena nilai x​i ​(komposisi
cairan) tidak diketahui
​
P=

1​ Py ​
∑​ γ​
i ​ ii sat

ln ​γ

= ​Ax ​
1​ 2​
2​
ln ​γ ​2 =
​ ​Ax ​1 2
​

Mk perhit. DEW P dpt dilakukan dgn

iterasi sbb: ​1) mula2 asumsikan
γ​1​=γ​2​=1.0 (Ideal solution) ​2) Hitung
DEW P:
​
P=
 1​
​ ​ γ​ ​
∑ Py i ii sat

3) Hitung x​1​=y​1​P/γ​1​P​1​sat ​dan x​2=1-x​

i​ ​ 1

4) menggunakan x​1 ​& x​2 ​ini, hitung γ​1

dan γ​2 5)
​ ​untuk ​kembali ​hitung ​ke
step ​DEW ​2 ​P, ​gunakan ​ulangi terus
nilai γ​menerus
1 dan
​ γ​2 ini
​
sampai (konvergen)
nilai γ​1 dan
​ γ​2 tidak
​ lg berubah
Hasil iterasi:
catt: iterasi ini dapat diimplementasikan dalam
excel/kalkulator
menggunakan algoritma subtitusi berurut (ingat
kuliah metode numeris). Dapat pula trial dgn solver
P = 62.89 kPa x​1 = ​ 0.8169 ​γ​1 =
​ 1.0378 ​γ​2 =
​ 2.0935

2​2 1 ​ln ​Ax ​= ​γ

ALGORITMA HITUNG DEW P
DEW P CALCULATION
P
Find ​
sat
i​

Find ​γ ​1& ​ ​γ ​2.​ Initial guess is=1

Find P using equation 10.7
P
=
Py 1​ ​sat ​11 ​y ​2 22 ​P sat
​ ​
PPyx ​ =
γ ​1 + γ​ ​Find xi using equation 10.5 ​ i​

γ​
i​ ii sat

Evaluate from the given equation

NO
Converge? YES
It is the P dew. Find liquid phase mole fraction

1​ = ​γ 11
​
​ 1​
Py P
& ​x 2​ =
sat ​ ​
1 - ​x ​1

c). T and yi?, for x1=0.85 and

P=101.33kPa (BUBL T calculation)
P=​

Px ​ γ
∑​ iii ​

sat

i​ Analisa: yg belum diketahui γ dan

Pi-sat ​Rumus-rumus:

ln
P1​
sat

kPa ​=
59158.16)( ​
-​
T Kelvin ​31.3643 - 424.33

ln
P
2​sat

​
kPa =

-​
.14 25326 ​ T Kelvin ​54.2665 - 424.53
 ln ​γ ​ = ​Ax ​
ln ​γ ​1 =
​ ​Ax ​2 2​
​ 2​ 1

2​
A=2.771-0.00523 T.
Solusi trial T. Coba rancang solver
nya!
d) T and xi? ​(TUGAS DI
RUMAH, tak ​dikumpul)
for y1=0.40 and P=101.33kPa
(DEW T calculation!)
COBA RANCANG DENGAN
SOLVER! ​RUMUS-RUMUS:
​
P=

1​ Py ​
∑​ γ​
i ​ ii sat

i
ln
P1​
sat

kPa ​=
59158.16)( ​
-​
​ 1.3643 - 424.33
T Kelvin 3

ln
P
2​sat

kPa ​=

-​
.14 25326 ​ T Kelvin ​54.2665 - 424.53
ln ​γ ​ = ​Ax ​
ln ​γ ​1 =
​ ​Ax ​2 2​
​ 2​ 1
2​A=2.771-0.00523 T. ​
trial T & X
simultan, or trial T & Ɣ simultan???...
PR1: For the system
methanol(1)/methyl acetate(2), the
following equations provide a
reasonable correlation for the activity
coefficients:
ln ​γ ​ = ​Ax ​
ln ​γ ​1 =
​ ​Ax ​2 2​
​ 2​ 1

2​Where

A=2.771-0.00523 T ​Antoine equation:

ln
31.3643 ​ =-​
1​
59158.16)( ​ 424.33​2​ - 424.53
=

∑​ i

P​
sat

kPa ​= - ​
T Kelvin -​ ​ln
P

kPa ​
sat ​
25326.14 54.2665
​ ​T Kelvin F​ ind: a).
P and yi, for x1=0.4 and T=330K (BULB P)
b). P and xi, for y1=0.5 and T=330K (DEW P) ​c). T
and yi, for x1=0.6 and P=90kPa (BUBLB T) ​d). T
and xi, for y1=0.45 and P=90kPa (DEW T)

P​ Px ​ γ ​
Rumus-rumus: BULB ​ P/T: ​ iii ​ sat

DEW P/T:
P ​=
 1​
∑ y​ ​ ​γ​ P​ ​
i ii sat

PR2
Data-fata untuk sistem ethyl ethanoate (1)
dan n- heptane (2) pada 70 C adalah sbb:

Tentukan DEW P pada 70 C dan y1=0.1

menggunakan ​iterasi berurut dan solver