Thermodynamics

• Multicomponent mixtures: non-ideal liquid

solutions
Non-ideal Ideal
𝑝𝑖∗
= 𝑦𝑖∗ = 𝑚𝑥𝑖 𝑝𝑖∗ = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
𝑝𝑡
𝑝𝑖∗ 𝑃𝑖
𝑠𝑎𝑡
1 2 = 𝑦𝑖∗ = 𝑥𝑖
Partial pressure of

𝑝𝑡 𝑝𝑡
solute in gas

Mole fraction of
solute in liquid
 Thermodynamics
• Multicomponent mixtures: non-ideal liquid
solutions
• Henry’s law
Deviation from Henry’s law:
𝑝𝑖∗ • Chemical reaction with solvent
= 𝑦𝑖∗ = 𝑚𝑥𝑖 • Electrolytic dissociation (ammonia-water)
𝑝𝑡
• Non-ideal gas
1 2
Partial pressure of
solute in gas

Mole fraction of
solute in liquid
Choice of solvent for absorption
• High gas solubility
• Chemically similar: miscible liquids
• For ideal liquid solutions, solubility is independent of
solvent liquid
• For absorption with chemical reaction, reaction should
be reversible for recovery of solute (example: hydrogen
sulfide + ethanolamine)
• Low volatility
• Non-corrosive
• Inexpensive
Choice of solvent for absorption
• Low viscosity – higher heat transfer and mass
transfer
• Non-toxic, non-flammable, chemically stable, low
freezing point
 Material balance: countercurrent
Gas out
Total gas flux (mol/area.time) = G
• Insoluble gas flux = GS
Liquid in • Solute A flux = yG = YGS

As y decreases, G also decreases

GS remains constant

𝑝𝐴
𝑦=
(𝑝𝐴 + 𝑝𝐺𝑠 )

1−𝑦
Liquid out 𝑝𝐺𝑠 = 𝑝𝐴
𝑦
𝑝𝐺𝑠 𝑣 𝑝𝐴 𝑣 1 − 𝑦
Gas in =
𝑅𝑇 𝑅𝑇 𝑦
 Material balance: countercurrent
Gas out
Total gas flux (mol/area.time) = G
• Insoluble gas flux = GS
Liquid in • Solute A flux = yG = YGS

𝑝𝐺𝑠 𝑣 𝑝𝐴 𝑣 1 − 𝑦
=
𝑅𝑇 𝑅𝑇 𝑦

1−𝑦
𝐺𝑆 = 𝑦𝐺
𝑦
𝑦
Liquid out 𝐺𝑆 = 𝑌𝐺𝑆 = 𝑦𝐺
1−𝑦

𝑦
Gas in 𝑌=
1−𝑦
 Material balance: countercurrent
Gas out
Total gas flux (mol/area.time) = G
• Insoluble gas flux = GS
Liquid in • Solute A flux = yG = YGS

𝑦 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴
𝑌= =
1−𝑦 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐺𝑆

Y = Mole ratio

𝑌
Liquid out 𝑦=
(1 + Y)

Gas in 𝑌𝐺 𝐺
𝑌𝐺𝑆 = 𝑦𝐺 = 𝐺𝑆 =
(1 + Y) (1 + Y)
 Material balance: countercurrent
Gas out
Total liquid flux (mol/area.time) = L
• Nonvolatile solvent flux = LS
Liquid in • Solute A flux = xL = XLS

𝑥 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴
𝑋= =
1−𝑥 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐿𝑆

X = Mole ratio

𝑋
Liquid out 𝑥=
(1 + X)

Gas in 𝑋𝐿 𝐿
𝑋𝐿𝑆 = 𝑥𝐿 = 𝐿𝑆 =
(1 + X) (1 + X)
 Material balance: countercurrent
Gas out
G2, GS, Y2, y2
Mass balance on solute A
Liquid in
L2, LS, X2, x2 𝑋𝐿𝑆 + 𝑌1 𝐺𝑆 = 𝑋1 𝐿𝑆 + 𝑌𝐺𝑆

𝐺𝑆 (𝑌1 − 𝑌) = 𝐿𝑆 (𝑋1 − 𝑋)

Liquid: L, LS, X, x
Gas: G, GS, Y, y Straight line between (X1, Y1) and (X2, Y2)

Liquid out
L1, LS, X1, x1

Gas in
G1, GS, Y1, y1
 Material balance: countercurrent
Gas out Mass balance on solute A
G2, GS, Y2, y2
𝐺𝑆 (𝑌1 − 𝑌) = 𝐿𝑆 (𝑋1 − 𝑋)
Liquid in
L2, LS, X2, x2 Straight line between (X1, Y1) and (X2, Y2)

Bottom

Y1
Liquid: L, LS, X, x
Gas: G, GS, Y, y

Y
Liquid out
L1, LS, X1, x1 Top

Y2
Gas in
G1, GS, Y1, y1
X2 X1 X
Why is operating line above equilibrium curve?
 Material balance: countercurrent
Gas out Mass balance on solute A
G2, GS, Y2, y2
𝐺𝑆 (𝑌1 − 𝑌) = 𝐿𝑆 (𝑋1 − 𝑋)
Liquid in
L2, LS, X2, x2 Straight line between (X1, Y1) and (X2, Y2)

Top

Y2
Liquid: L, LS, X, x
Gas: G, GS, Y, y

Y
Liquid out
L1, LS, X1, x1
Y1 Bottom
Gas in
G1, GS, Y1, y1 X X1 X2

Stripper
 Material balance: countercurrent
Gas out Mass balance on solute A
G2, GS, Y2, y2 𝑦 𝑥
𝐺𝑆 𝑌1 − = 𝐿𝑆 𝑋1 −
1−𝑦 1−𝑥
Liquid in
L2, LS, X2, x2 Curve between (x1, y1) and (x2, y2)

Bottom

y1
Liquid: L, LS, X, x
Gas: G, GS, Y, y

y
Liquid out
L1, LS, X1, x1 Top

y2
Gas in
G1, GS, Y1, y1
x2 x1 x
 Material balance: countercurrent
Gas out Minimum liquid/gas ratio
G2, GS, Y2, y2 𝐿𝑆
(𝑌1 − 𝑌) = (𝑋 − 𝑋)
𝐺𝑆 1
Liquid in
L2, LS, X2, x2 Y1, Y2, X2, GS are fixed. Choose LS

Bottom

Y1
Liquid: L, LS, X, x
Gas: G, GS, Y, y

Y
Liquid out
L1, LS, X1, x1 Top

Y2
Gas in
G1, GS, Y1, y1
X2 X1 X
Material balance: countercurrent
Minimum liquid/gas ratio
Bottom
𝐿𝑆
Y1

(𝑌1 − 𝑌) = (𝑋 − 𝑋)
𝐺𝑆 1
Y

Y1, Y2, X2, GS are fixed. Choose LS

Top
Less LS:
Y2

• Less cost
• Closer to equilibrium curve
• Less driving force for mass transfer
X2 X1 X • Slower kinetics
• More residence time
• Bigger equipment
 Material balance: cocurrent

Gas out Mass balance on solute A

G1, GS, Y1, y1
Liquid in 𝑋𝐿𝑆 + 𝑌𝐺𝑆 = 𝑋1 𝐿𝑆 + 𝑌1 𝐺𝑆
L2 , L S , X 2 , x 2
𝐺𝑆 𝑌 − 𝑌1 = −𝐿𝑆 (𝑋 − 𝑋1 )

Liquid out
L1, LS, X1, x1
Gas in Liquid: L, LS, X, x
G2, GS, Y2, y2 Gas: G, GS, Y, y
Straight line between (X1, Y1) and (X2, Y2)
with negative slope
 Material balance: cocurrent
Mass balance on solute A

Gas out 𝐺𝑆 𝑌 − 𝑌1 = −𝐿𝑆 (𝑋 − 𝑋1 )

G1, GS, Y1, y1
Liquid in
L2 , L S , X 2 , x 2 Inlet

Y2
Y1
Liquid out Exit
L1, LS, X1, x1
Gas in Liquid: L, LS, X, x Y
G2, GS, Y2, y2 Gas: G, GS, Y, y
X2 X1 X
Material balance: cocurrent
Mass balance on solute A
Inlet
Y2

𝐺𝑆 𝑌 − 𝑌1 = −𝐿𝑆 (𝑋 − 𝑋1 )

• Very tall tower built in two parts –

Y1

second column run in cocurrent mode

Exit
to save pipeline costs for gas (large
Y

diameter)

Liquid
X2 X1 X

Gas
Material balance: cocurrent
• Pure gas absorption into liquid
• No difference between countercurrent and cocurrent
• Rapid irreversible chemical reaction inside liquid
• Only 1 theoretical stage needed
 Countercurrent multistage
Gas out
G1, GS, Y1, y1
Liquid in Y1
L0 , L S , X 0 , x 0 X1
Y2
X2
Y3
X3
Y4
X4
YN-2
XN-2
YN-1
XN-1
YN
Gas in XN
GN+1, GS, YN+1, yN+1 Liquid out
LN, LS, XN, xN