CHE3165 Supplementary Formula Sheet

Formulae and General Data

• Atomic weights: H = 1, C = 12, N = 14, O = 16, S = 32, Cl = 35.5

• Gas constant: R = 8.312 J/mol.K
• Pressure: 101, 324 Pa ⌘ 1 atm ⌘ 760 mm Hg
• Acceleration due to gravity: g = 9.81 m/s2
• Properties of water (unless otherwise stated): ⇢ = 1000 kg/m3 , µ = 1.00 mPa.s

Stagewise contacting of totally immiscible phases

V1 Vn VN +1
yA1 yAn yAN +1
1 .... n .... N
L0 Ln LN
xA0 xAn xAN
The subscript (A) is often omitted on the composition variables when no confusion is possible.
Equilibrium General: yAn = f (xAn )
Gas-liquid (Henry’s Law): pA = HxA yA = H 0 x A
Liquid - liquid (Nernst): yA = mxA
Composition/flow variables - definitions:
XA = xA /xB L0 = LxB V 0 = V yB B ⌘ inert componenet
For binary mixtures - xA + xB = 1
Operating line:
✓ ◆ ✓ ◆
Ln V1 yA1 L0 xA0
yAn+1 = xAn +
Vn+1 Vn+1
✓ ◆ ✓ 0 ◆✓ ◆ ✓ ◆ ✓ 0 ◆✓ ◆
yAn+1 L xAn yA1 L xA0
= +
1 yAn+1 V0 1 xAn 1 yA1 V0 1 xA0
✓ 0◆ ✓ 0◆
L L
YAn+1 = 0
XAn + YA1 XA0
V V0

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Absorption Factor: A = LAVE /mVAVE

( LAVE and VAVE are geometric mean values)

Transfer from V to L (Absorption):

yAN +1 yA1 AN +1 A
= N +1
yAN +1 mx0 A 1
⇣ ⌘
yAN +1 mxA0
ln yA1 mxA0 1 A1 + 1
A
N=
ln A
When A = 1
yAN +1 yA1
N=
yA1 mxA0

Transfer from L to V (Stripping, Liquid–liquid extraction):

xA0 xAN (1/A)N +1 (1/A)

=
xA0 yAN +1 /m (1/A)N +1 1
h⇣ ⌘ i
xA0 yAN +1 /m
ln xAN yAN +1 /m (1 A) + A
N=
ln(1/A)
When A = 1
xA0 xAN
N=
xAN yAN +1 /m

Liquid-liquid extraction (partially miscible)

(x, y, z are solute mass/mol fractions)

⇢
L0 + VN +1 = M = LN + V1
L0 x0 + VN +1 yN +1 = M zM = LN xN + V1 y1
⇢
L0 V1 = = LN VN + 1 = Ln Vn+1
L0 x0 V1 y1 = z = LN xN VN +1 yN +1 = Ln xn Vn+1 yn+1

Binary distillation (McCabe Thiele)

(A = M.V.C.) (x, y are M.V.C fractions)

Raoult: pA = xA pA p B = xB pB

Volatility: kA = y/x kB = (1 y)/(1 x)

Relative volatility: ↵ = kA /kB

Equilibrium curve (constant ↵):

↵x
y=
1 + (↵ 1)x

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Adiabatic flash:

V
y
F
zF
L
x

F zF = V y + Lx (x, y in equilibrium)

Total
condenser

V1
D
(1) L0 xD
(n)

Vn+1 Ln
F
zF
Lm 1 Vm

(m)

(N )
VN +1

Reboiler
LN
(N + 1)

W
xW

Operating lines:

◆
✓ ✓ ◆
Ln DxD
yn+1 = xn +
Vn+1 Vn+1
✓ ◆ ✓ ◆
Lm 1 W xW
ym = xm 1
Vm Vm

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Constant molar overflow assumption:

Vn+1 = V
Ln = L

Vm = V
Lm 1 = L

Feed stream:
q = moles liquid in stripping section arising from one mole of feed

q-line: ✓ ◆ ✓ ◆
q zF
y= x+
1 q 1 q

Reflux ratio:
RD = L0 /D

Murphree Efficiency: ✓ ◆
yn yn+1
EM =
yn⇤ yn+1

Molecular Di↵usion

Fick’s Law (Equimolar counter di↵usion) - binary:

General:
dcA
JA⇤ = DAB
dz
Ideal gas:
⇣p ⌘ dy
Tot A
JA⇤ = DAB
RT dz

Stationary component (gas):

NA = JA⇤ + yA (NA + NB )
⇣p ⌘ ✓ y ◆ ✓ 1
◆
Tot A
= DAB
RT z yB LogMean

Di↵usion in solids
dcA
NA ⇡ JA⇤ = DAB
dz
Gases through solid films:
DAB SAB dpA
NA ⇡ ·
0.0224 dz
PAB dpA
= ·
0.0224 dz

SAB = Solubility of A in B (m3 A at STP)/(m3 solid)

PAB = “Permeability” of A in B

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Gases in granular beds:
dcA
NA0 = De↵ ·
dz

NA0 = Flux based on superficial conditions

✏
De↵ = DAB
⌧

E↵ect of temperature and pressure on DAB :

Gases
T 1.75
DAB /
pTot

Liquids (dilute):
T
DAB /
µ

Knudsen di↵usion (SI Units):

Kn =
d r
3.2µ RT
=
pTot 2⇡MA

Flux:
DKA dpA
NA = ·
RT r dz
T
DKA = 47.5d
MA

Film Mass Transfer Coefficients

Gas film (bulk ! interface) - equimolar counter transfer:

0
N A = kC (cA cAi ) = ky0 (yA 0
yAi ) = kG (pA pAi )

Stationary component:
0
k C = kC /yB LogMean

Liquid film (interface ! bulk) - equimolar counter transfer:

0
N A = kC (cAi cA ) = kx0 (xAi xA )

Stationary component
0
kC ⇡ kC /xB Logmean

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Dimensionless groups:

0 l
Sherwood : Sh = kC
D
lv⇢
Reynolds : Re =
µ
µ
Schmidt : Sc =
⇢D
Sh
Stanton : St =
ReSc
Sh
jD (⌘ jM ) =
ReSc 1/3
l = characteristic linear dimension

Transfer between immiscible phases

(Gas ! liquid)

NA = KC0 (cA c⇤A ) = Ky0 (yA ⇤

yA 0
) = KG (pA p⇤A ) (Gas)
= KC0 (c⇤A cA ) = Kx0 (x⇤A xA ) (Liquid)

where

y⇤A =H 0xA ; p⇤A =H xA ( Gas)

yA = H0x⇤A = H00c⇤A (Liquid)

Interface:

yAi = H0 xAi = H00 cAi

pAi = HxAi

Overall coefficients:
1 1 H0
= +
Ky0 ky0 kx0
1 1 1
= + 0
Kx0 0
H ky 0 kx
0 , K0 , K0
Analogous equations for KG L C

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Gas Absorption (Stripping) - Continuous Contact Process

V V2 L2 L
Y 2 y2 x 2 X2

(2) a = interfacial area per

z2 unit volume of
packed tower
Z = packed
bed height S = tower cross-
sectional area
z1 (1)

V V1 L1 L
Y 1 y1 x 1 X1
General:

Z y2 Z x2
V ( dy) L ( dx)
Z= · = ·
y1 N aS (1 y) x1 N aS (1 x)

Manipulation of the above:

Z y2 Z y2
V ( dy) V (1 y)⇤LM ( dy)
Z= · = ·
y1 Ky aS (1 y)(y y ⇤ ) y1
0
Ky aS (1 y) (y y ⇤ )

Dilute solutions:

(1 y)⇤LM
⇡ 1.0
(1 y)
✓ ◆Z y2
Vave ( dy)
Z⇡
Ky0 aS y1 (y y ⇤ )

Additionally - Henry’s Law holds

✓ ◆ ✓ ◆
Vave (y2 y1 )
Z = ( 1)
Ky0 aS (y y⇤) Log Mean 1!2
⌘ Hoy Noy

Analogous equations for gas film basis, and for liquid-phase balances.

Z = Hy Ny = HG NG = Hoy Noy = HoG NoG

= Hx Nx = HL NL = Hox Nox = HoL NoL

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