Chapter 8-Vapor Liquid and Liquid Liquid Equilibria-P

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1. DISSOLUTION OF GAS IN LIQUID

PHYSICAL CHEMISTRY 1
Consider: solution (saturated i) = gas i
Gibbs’s phase rule:

CHAPTER 8: f=c–p+2=2–2+2=2
VAPOR−LIQUID AND LIQUID−LIQUID EQUILIBRIA
→ Solubility: x = f (T, P)
✓ T = const → x = f (P)
✓ P = const → x = f (T)
→ P and T can affect

Dr. Nguyen Van Dung
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology (HCMUT)
the solubility of a gas in solution → Rule??
Email: nvdung@hcmut.edu.vn
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
2 3
1. DISSOLUTION OF GAS IN LIQUID 1. HENRY’S LAW
Effect of P to x (solubility)
At a constant temperature, the solubility of a gas (solute) in a liquid is
proportional to the partial pressure of that gas on the liquid phase.
Pi
xi = kH . Pi
✓ Applied limits:
− Ideal solution or Pi = H . xi
− Infinite dilute solution xi
✓ With real solution:
ai = kH . Pi
− Replace C by a:
− Apply experiment equations (concentration C, solubility S):
S = a + b.Pi + c.P i2
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
4 5
1. HENRY’S LAW 1. HENRY’S LAW
6 7
1. SREDER’S EQUATION 1. SREDER’S EQUATION
Effect of T on solubility of gas – Sreder’s equation Effect of T on solubility of gas – Sreder’s equation
i (gas) = i (solution) + Hdis.   ln xi 
Pi   = i2
Kx =
x i ( solution ) x i
=   ln K x 
  =
H  T  P RT
Pi ( gas ) Pi  T  P RT
2
xi – At P = const, assume i = const:

  ln xi  H dis .
  = x2 T2
i i  1 1 
 T  P RT
2
Hdissolution= condensation + dissociation + Solvation

 d ln xi =
x1
T RT 2 dT ln x2 = ln x1 −  − 
R  T2 T1 
1
Ideal solutions: dissociation + Solvation  0 Hdissolution= condensation = i

i  1 1 
xi T
 d ln x =  RT
i
i
2
dT ln xi = −  − 
R T To 
  ln xi  Since : condensation < 0 → i < 0 xi =1 T0
  = i2
 T  P RT at P = const, T increases xi decreases
To: boiling temperature of component i
8 9
2. VAPOR- LIQUID EQUILIBRIUM 2. IDEAL, MISCIBLE SOLUTIONS
➢ The solubility of a liquid in another liquid is depended on the

➢ Consider: (A-B)solution = (A-B)vapor xBv
nature of the solute, the solvent, and the temperature; pressure
has little effect. General rule: polar substances tend to dissolve in ➢ Gibbs phase rule:
polar solvents, and nonpolar substances dissolve in nonpolar
solvents. (polar - hydrophilic or nonpolar - hydrophobic). f=c–p+2=2–2+2=2
➢ Classify: → 2 out of 4 variables are independent: x Bl

✓ Ideal, miscible solution T, P, xBl, x Bv A+B
✓ Real, miscible solution
✓ Partially miscible liquids ✓ If T = const: f = 2 – 2+ 1 = 1 → P, xBv are a function of xBl
✓ Two immiscible liquids ✓ If P = const: f = 2 – 2+ 1 = 1 → Ts, xBv are a function of x Bl
Ex: Ethanol and water – Miscible solution
Benzene and water – Two immiscible liquids
Phenol and water – Partially miscible liquids
10 11
2. IDEAL, MISCIBLE SOLUTIONS 2. IDEAL, MISCIBLE SOLUTIONS
x Bv Limitation of the Raoult’s law:

Raoult’s law: Partial vapor pressure of a
– Ideal solutions
component is directly proportional to its mole – Solvent of infinitely dilute
fraction in the solution solutions
l
𝑃𝒔𝒐𝒍𝒗𝒆𝒏𝒕 = 𝑃𝒔𝒐𝒍𝒗𝒆𝒏𝒕 . 𝑥𝒔𝒐𝒍𝒗𝒆𝒏𝒕
Pi = k R .xil A+B
Henry’s law is applicable for
At xil = 1: kR = Pio, vapor pressure of pure component = f (T) solute of infinitely dilute solutions:
1
𝑃𝒔𝒐𝒍𝒖𝒕𝒆 = 𝑥
𝑘 𝒔𝒐𝒍𝒖𝒕𝒆
𝑃 = 𝑃𝒐 . 𝑥
12 13
(P-x) diagram: P
– Apply Raoult’s law: PBo
PAo
0 xBl 1
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Konovalop’s Iaw xAv , xBv 𝑃 𝑃 .𝑥 𝛼. 𝑥

𝑥 = = =
– Danton’s law: 𝑃 +𝑃 𝑃 + (𝑃 − 𝑃 ). 𝑥 1 + (𝛼 − 1). 𝑥
– Raoult’s law: = PB0/PA0

l
Bv
PA = P .x
0
A
l
A ; PB = P .x B
0 l
B
A+B Consequences:
xil increases → xiv increases
𝑥𝒗 𝑃 𝑥 𝑥
𝒗 = . = 𝛼. (Konovalop I) TBb < TAb → PBo > PAo → xBv > xBl xBv
𝑥 𝑃 𝑥 𝑥 x Bl
“B” is boiled easier than “A”

= PB0/PA0: separation coefficient/distillation coefficient
A Bl
xBl →
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2. IDEAL, MISCIBLE SOLUTIONS 2. LIQUID – VAPOR EQUILIBRIUM
P = const
Point F T T
Boiling temperature (Tb) of a liquid mixture (xBl)? Vapor
L 2 ToA *V
l1 ; l2 ; l3 1
Raoult’s law: Pt = PAo + (PBo- PAo).xBl
Q 1
*Q
Clasius – Clapeyron’s equation/Antoine’s equation: v1 ; v2 ; v 3 1
PAo = f (T) ; PBo = g (T) V 2 *L ToB
Liquid
The liquid mixture starts to boil when: Pt = Poutside
0 1
𝒙𝒐𝑩
Tb = f (xBl)
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2. LIQUID – VAPOR EQUILIBRIUM 2. LIQUID – VAPOR EQUILIBRIUM
1/ Initial composition 𝒙𝒐𝑩 at liquid T T

Vapor
state:
ToA T T
Vapor
+ T1: begin to boil
𝒗 v3 ToA
+ 𝒙𝑩𝟏 : composition of first bubble T3 l3 Q v2 v3
T2 l2 * T3 l3
2/ Initial composition 𝒙𝒐𝑩
at vapor v1 Q v2
T1 l1 T2 *
state: To B
l2 v1 𝑔 𝑄𝑣
T1 l1 =
+ T3: begin to condense To 𝑔𝒗 𝑄𝑙
𝒍
Liquid B
+ 𝒙𝑩𝟑 : composition of first liquid
0 𝒍 𝒍 𝒙𝒐𝑩 𝒙𝑩𝟐 𝒙𝒗𝑩𝟏 1
𝒗 Liquid
drop 𝒙𝑩𝟑 𝒙𝑩𝟐
0 𝒍 𝒍 𝒙𝒐𝑩 𝒙𝑩𝟐 𝒙𝒗𝑩𝟏 1
𝒗
3/ Initial composition 𝒙𝒐𝑩 at T2 (liquid-vapor equilibrium): 𝒙𝑩𝟑 𝒙𝑩𝟐
𝒍
+ 𝒙𝑩𝟐 : composition of B in liquid phase
𝒗
+ 𝒙𝑩𝟐 : composition of B in vapor phase
20 21
Give T-x diagram (x = molar fraction) for methanol & water at 1 atm Real, miscible solutions
At 𝒙𝒐𝑴 = 0.34, determine:
100 Real
+ T begin to boil
95
+ Composition of 2 phases
at 80 oC 90
Ideal
+ Molar ratio of 2 phases T ( oC) 85
at 80 oC 80
75
70
65
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Water xM Methanol
Negative deviation
22 23
Real, miscible solutions Real, miscible solutions
“Konovalop II” law:

P P At turning point (minimum/maximum)
PB0 PB0
P T = const PB0
PA0 PA0 𝒗
PA0
0 xB 1 0 xB 1
𝒗
dP = 0
Maximum point Minimum point
0 xB 1
24 25
Real, miscible solutions
Azeotrope
T = const
P T
Liquid P = const
Vapor
L=V
Azeotrope
L=V
Vapor
Azeotropic
Liquid
A xB B solution A xB B
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2. DISTILLATION 2. DISTILLATION
➢ Distillation, is the process of separating the components or ✓ Distillation of a liquid mixture without azeotropic solution
substances from a liquid mixture by using selective boiling and
condensation. T T
Vapor
ToA V
l3
l2
v1
l1 * Q v2
v3
To B
Liquid L
0 xB 1
28 29
✓ Distillation of a liquid mixture with azeotropic solution: only For azeotropic mixtures T
separate one component and azeotropic solution. • Change the pressure
T T
• Add a third component P1
ToA V1 Vapor P2
l3 Effect of total pressure P3
T3 l2
Q1 A xB → B
T2 l1 * v1 ➢ Examples:
T1 v2 Boiling temp. at 1 atm (oC) B (wt%) in
v3 ToB (A/B) azeotropic
Azeo.
L1 A B mixture
mix.
Liquid H2O/C2H5OH 100.00 78.30 78.15 95.57
C2H5OH 0.61 CCl4 H2O/n-C3H7OH 100.00 97.19 87.72 71.69
xCCl4→ H2O/HCl 100.00 85.00 108.5 20.24
30 31
Distillation of wine
32 33
3. PARTIALLY MISCIBLE LIQUIDS 3. LIQUID – LIQUID EQUILIBRIUM
Ex: phenol – water; butanol – water; trimethylamine – water - In heterogeneous region: 2 solutions
K - K point (critical point):
Consider: butanol – water
p= 2
Q3 c=2
p = 2; c = 2
P = const Saturated B in W P = const
f=c–p+1=1 xB(1)
dT = 0 → T = const
xB(2) f=c–p+0=0
Saturated W in B
Heterogeneous → 1 solution
(T, x): Only 01
independent If T = const , xB(i) = const
variable
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3. LIQUID – LIQUID EQUILIBRIUM 3. LIQUID – LIQUID EQUILIBRIUM
Phase “w” disappears
K - At Q3: xB(w) = n3 K
xB(B) = b 3
Q3 Q3
Increase temp. T2 T3
Increase temp. T2 T3
- At Q2: xB(w) = n2
xB(B) = b 2
Heterogeneous Increase temp. T1 T2

Heterogeneous Increase temp. T1 T2
- At Q1: xB(w) = n1
xB(B) = b 1
36 37
3. LIQUID – LIQUID EQUILIBRIUM 3. LIQUID – LIQUID EQUILIBRIUM
Experimental method for construction the (T-x) phase

diagrams
a. Chemical method:
Mixing two component at a temperature → two phases
are formed at equilibrium → Separating the phase
→ Analysing the chemical composition of the two phases.
b. Physico-chemical method:
The (T-x) curve: the system changes from transparent to
opaque (or reverse).
→ with each value of xi determine the coresponding Ti at
which the system changes from transparent to opaque (or
reverse).
38 39
3. LIQUID – LIQUID EQUILIBRIUM 4. TWO IMMISCIBLE LIQUIDS
Give T-x diagram (x = weight percent) of phenol & water at 1 atm
Ex: water – benzene; chloroform – methanol
+ Determine critical point
At 50 oC, determine: p= 3
+ Maximum solubility of phenol in water c=2
f=c–p+2=1
+ Maximum solubility of water in phenol
+ Mix 100 g water with 100 g phenol,

calculate the masses of the obtained (T, P, x): Only 01
independent variable
phases
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4. TWO IMMISCIBLE LIQUIDS 4. TWO IMMISCIBLE LIQUIDS
PA 0 TAo
Pi = Pi = f (T )
0 T
P = PA + PB = PA0 + PB0 = f (T ) PB
PB = f(T)
Pexternal
PA = f(T)
PA
T
𝑥 𝑃 𝑃 PB 0 T o(boiling) TBo
= = = 𝑔(𝑇)
𝑥 𝑃 𝑃
→ Calculate the ratio of T 0(mix) < T0A T 0(mix) < T0B

components in vapor phase
✓ Tb of the mixture depends on external pressure, does not depend on
the composition.
✓ Tb of the mixture is lower than that of the pure substances.
42 43
4. STEAM DISTILLATION 4. TWO IMMISCIBLE LIQUIDS
Minimum amount of water (kg) required to distill 1 kg of A: 𝑷𝒐𝑯𝟐𝑶 𝟏𝟖 Determine the temperature for steam distillation:
𝒈𝑯𝟐𝑶 = .
𝑷𝒐𝑨 𝑴𝑨
44 45
5. THREE PARTIALLY-MISCIBLE LIQUIDS 5. THREE PARTIALLY-MISCIBLE LIQUIDS
• (x-x-x) phase diagram ✓ Miscibility of the components in the system depend temperature.
✓ At P or T = const:
f=c–p+1=4–p 0, p 4
Maximum No. of phases is 4.
✓ At P and T = const:
f=k–p=3–p 0, p 3
Maximum No. of phases is 3.
Ex: Ternary diagram of Acetone
(A) – Ethyl acetate (B) – Water
(C) at 30 oC & 1 atm
(A, B and A, C: miscible liquids;
Equilateral triangle B, C: partially-miscible liquids)
46 47
5. TERNARY SYSTEMS AND TRIANGULAR DIAGRAMS 5. TERNARY SYSTEMS AND TRIANGULAR DIAGRAMS
Adding component C into Q: Ex: A mixture of acetic acid, butanol and water with its initial composition at
➢ Q → Q1 → a2 B. Determine the composition of mixture B and formed phases (A, C)?
➢ Inside aKb: heterogeneous,
➢ Phase “a”: a → a1 → a2
consist of two conjugate
solutions ➢ Phase “b”: b → b1 → b2
➢ Out of aKb: homogeneous ➢ No. of phases: f = 2
➢ K: plait point → c= k – f = 3 – 2 = 1
 compositions of a conjugate solution can be
calculated from compositions of the other.
T = const
P = const
Tarachenco’s empirical rule:
Conjugate lines meet each others at a point (S).
Lever rule:
g a1 Q1b1
=
g b1 a1Q1
48 49
5. LIQUID–LIQUID EXTRACTION 5. LIQUID–LIQUID EXTRACTION
Liquid–liquid extraction (solvent extraction), is a method to separate

compounds or metal complexes, based on their relative solubilities in two
different immiscible liquids, usually water (polar) and an organic solvent
(non-polar). There is a net transfer of one or more species from one liquid
into another liquid phase, generally from aqueous to organic. The solvent
that is enriched in solute(s) is called extract. The feed solution that is
depleted in solute(s) is called the raffinate.
50 51
5. LIQUID–LIQUID EXTRACTION 5. LIQUID–LIQUID EXTRACTION
- A & B: Miscible Nernst’s distribution law

- C & B: immiscible If a solute Y distributes itself between two non miscible solvents
- C & A: Miscible A & B at constant temperature & X is in the same molecular
condition in both the solvents, then:
When add C into A-B:
➢ System point: M0 → M CY / A K: distribution coefficient
➢ Two phases separated: =K (partition coefficient/
• b: high conc. of B
• a: A–C (+ small amount of B)
CY / B partition ratio)

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1

1. DISSOLUTION OF GAS IN LIQUID

Gibbs’s phase rule:

→ P and T can affect

xi – At P = const, assume i = const:

Hdissolution= condensation + dissociation + Solvation

Ideal solutions: dissociation + Solvation  0 Hdissolution= condensation = i

➢ The solubility of a liquid in another liquid is depended on the

➢ Classify: → 2 out of 4 variables are independent: x Bl

x Bv Limitation of the Raoult’s law:

Konovalop’s Iaw xAv , xBv 𝑃 𝑃 .𝑥 𝛼. 𝑥

– Raoult’s law: = PB0/PA0

“B” is boiled easier than “A”

1/ Initial composition 𝒙𝒐𝑩 at liquid T T

“Konovalop II” law:

Phase “w” disappears

Heterogeneous Increase temp. T1 T2

Experimental method for construction the (T-x) phase

+ Mix 100 g water with 100 g phenol,

→ Calculate the ratio of T 0(mix) < T0A T 0(mix) < T0B

Liquid–liquid extraction (solvent extraction), is a method to separate

- A & B: Miscible Nernst’s distribution law

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