CHEMICAL ENGINEERING

For additional information concerning heat transfer and Often at system pressures close to atmospheric:
fluid mechanics, refer to the HEAT TRANSFER, THER- fiL ≅ Pisat
MODYNAMICS, or FLUID MECHANICS sections.
The fugacity coefficient Φ̂ i for component i in the vapor is
CHEMICAL THERMODYNAMICS calculated from an equation of state (e.g., Virial).
Vapor-Liquid Equilibrium Sometimes it is approximated by a pure component value
For a multi-component mixture at equilibrium from a correlation. Often at pressures close to atmospheric,
f̂ iV = f̂ i L , where Φ̂ i = 1. The fugacity coefficient is a correction for vapor
phase non-ideality.
f̂ i V = fugacity of component i in the vapor phase, and For sparingly soluble gases the liquid phase is sometimes
L represented as
f̂ i = fugacity of component i in the liquid phase.
f̂ i L = xi k i
Fugacities of component i in a mixture are commonly
calculated in the following ways: where ki is a constant set by experiment (Henry’s constant).
Sometimes other concentration units are used besides mole
For a liquid f̂ i L = xi γ i f i L , where fraction with a corresponding change in ki.
xi = mole fraction of component i, Reactive Systems
γi = activity coefficient of component i, and Conversion: moles reacted/moles fed
fiL = fugacity of pure liquid component i. Extent: For each species in a reaction, the mole balance
ˆ P , where may be written:
For a vapor f̂ i V = y i Φ i
molesi,out = molesi,in + viξ where
yi = mole fraction of component i in the vapor, ξ is the extent
Φ̂ i = fugacity coefficient of component i in the vapor, and vi is the stoichiometric coefficient of the ith
species, sign of which is negative for
P = system pressure. reactants and positive for products.
The activity coefficient γi is a correction for liquid phase Limiting reactant: reactant that would be consumed first if
non-ideality. Many models have been proposed for γi such reaction proceeded to completion. Other reactants
as the Van Laar model: are excess reactants.

§ A x ·
−2 Selectivity: moles of desired product formed/moles of
lnγ1 = A12 ¨¨1+ 12 1 ¸¸ undesired product formed.
© A21 x2 ¹ , where Yield: moles of desired product formed/moles that would
−2
§ A21 x2 · have been formed if there were no side reactions
lnγ 2 = A21 ¨¨1+ ¸¸
and limiting reactant had reacted completely.
© A12 x1 ¹
Chemical Reaction Equilibrium
γ1 = activity coefficient of component 1 in a two-
component system, For reaction

γ2 = activity coefficient of component 2 in a two- aA + bB⇋cC + dD

component system, and ∆Go = –RT ln Ka
A12, A21 = constants, typically fitted from experimental data.
Ka =
(aˆ )(aˆ ) = ∏ (aˆ )
c
C
d
D νi
The pure component fugacity is calculated as:
(aˆ )(aˆ )
a
A
b
B i
i , where
L
fi = Φisat Pisat exp{viL (P – Pisat)/(RT)}, where
f̂ i
Φisat = fugacity coefficient of pure saturated i, âi = activity of component i = o
fi
Pisat = saturation pressure of pure i,
viL = specific volume of pure liquid i, and fio = fugacity of pure i in its standard state
R = Ideal Gas Law Constant. νi = stoichiometric coefficient of component i
o
∆G = standard Gibbs energy change of reaction
Ka = chemical equilibrium constant

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 CHEMICAL ENGINEERING (continued)

For mixtures of ideal gases: The Arrhenius equation gives the dependence of k on
fio = unit pressure, often 1 bar temperature

fˆi = yi P = pi k = Ae −E a RT
, where
A = pre-exponential or frequency factor,
where pi = partial pressure of component i.

Then K a = K p =
(p )(p ) = P
c
C
d
D c + d − a −b (y )(y )
c
C
d
D
Ea = activition energy (J/mol, cal/mol),

(p )(p )
a
A
b
B (y )(y )
a
A
b
B
T = temperature (K), and
R = gas law constant = 8.314 J/(mol⋅K).
For solids âi = 1
In the conversion of A, the fractional conversion XA, is
For liquids âi = xi γi defined as the moles of A reacted per mole of A fed.
The effect of temperature on the equilibrium constant is XA = (CAo – CA)/CAo if V is constant
d lnK ∆H o Reaction Order
=
dT RT 2 If – rA = kCAxCBy
where ∆Ho = standard enthalpy change of reaction. the reaction is x order with respect to reactant A and y order
with respect to reactant B. The overall order is
HEATS OF REACTION
n=x+y
For a chemical reaction the associated energy can be defined
in terms of heats of formation of the individual species ∆Ĥ of ( ) BATCH REACTOR, CONSTANT T AND V
at the standard state Zero-Order Reaction
(∆Ĥ ) =
o
r
o
(
¦ i ∆Ĥ f i − ) ( o
¦ i ∆Ĥ f )
i
– rA = kCAo = k (1)
products reactants – dCA /dt= k or
-kt
The standard state is 25°C and 1 bar. CA = CAo e
The heat of formation is defined as the enthalpy change dXA /dt = k/CAo or
associated with the formation of a compound from its CAo XA = kt
atomic species as they normally occur in nature (i.e., O2(g),
H2(g), C(solid), etc.) First-Order Reaction
The heat of reaction for a combustion process using oxygen – rA = kCA
is also known as the heat of combustion. The principal – dCA/dt = kCA or
products are CO2(g) and H2O(e). ln (CA/CAo)= – kt
CHEMICAL REACTION ENGINEERING dXA/dt = k (1 – XA) or
A chemical reaction may be expressed by the general ln (1 – XA)= – kt
equation Second-Order Reaction
aA + bB ↔ cC + dD. – rA = kCA2
The rate of reaction of any component is defined as the – dCA/dt = kCA2 or
moles of that component formed per unit time per unit
volume. 1/CA – 1/CAo = kt
dXA/dt = kCAo (1 – XA)2 or
1 dN A
− rA = − [negative because A disappears] XA/[CAo (1 – XA)] = kt
V dt
− dC A Batch Reactor, General
− rA = if V is constant
dt For a well-mixed, constant-volume, batch reactor
The rate of reaction is frequently expressed by – rA = dCA/dt
–rA = kfr (CA, CB,....), where t = −C Ao ³oX A dX A (− rA )
k = reaction rate constant and
CI = concentration of component I.

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 CHEMICAL ENGINEERING (continued)

If the volume of the reacting mass varies with the For binary system following Raoult's Law
conversion according to α = (y/x)a /(y/x)b = pa /pb, where
V = VX A=0 (1 + ε A X A ) pi = partial pressure of component i.
V X A =1 − V X A =0 Continuous Distillation (binary system)
εA = Constant molal overflow is assumed (trays counted
V X A =0
downward)
then
Overall Material Balances
t = −C Ao ³ oX A dX A [(1 + ε A X A )(− rA )] Total Material:
F = D+B
FLOW REACTORS, STEADY STATE
Space-time τ is defined as the reactor volume divided by the Component A:
inlet volumetric feed rate. Space-velocity SV is the FzF = DxD + BxB
reciprocal of space-time, SV = 1/τ. Operating Lines
Plug-Flow Reactor (PFR) Rectifying Section
C Ao VPFR dX A Total Material:
τ= = C Ao ³oX A , where
FAo (− rA ) Vn+1 = Ln + D
FAo = moles of A fed per unit time. Component A:
Vn+1yn+1 = Lnxn + DxD
Continuous Stirred Tank Reactor (CSTR)
For a constant volume, well-mixed, CSTR yn+1 = [Ln /(Ln + D)] xn + DxD /(Ln + D)
Stripping Section
τ V X
= CSTR = A , where Total Material:
CAo FAo − rA
Lm = Vm+1 + B
– rA is evaluated at exit stream conditions.
Component A:
Continuous Stirred Tank Reactors in Series
Lmxm = Vm+1ym+1 + BxB
With a first-order reaction A → R, no change in volume.
ym+1 = [Lm /(Lm – B)] xm – BxB /(Lm – B)
τN-reactors = Nτindividual
Reflux Ratio
N ª§ C ·
1N º
Ǭ Ao Ratio of reflux to overhead product
= ¸¸ − 1» , where
k «¨© C AN ¹ » RD = L/D = (V – D)/D
¬ ¼
N = number of CSTRs (equal volume) in series, and Minimum reflux ratio is defined as that value which results
in an infinite number of contact stages. For a binary system
CAN = concentration of A leaving the Nth CSTR. the equation of the operating line is
DISTILLATION Rmin xD
y= x+
Flash (or equilibrium) Distillation Rmin + 1 Rmin + 1
Component material balance: Feed Condition Line
FzF = yV + xL slope = q/(q – 1), where
Overall material balance: heat to convert one mol of feed to saturated vapor
q=
F=V+L molar heat of vaporization
Differential (Simple or Rayleigh) Distillation
§W · dx
ln¨¨ ¸ = ³ xx
W ¸ o
y −x
© o¹
When the relative volatility α is constant,
y = αx/[1 + (α – 1) x]
can be substituted to give
§W · 1 ª x(1 − xo ) º ª 1 − xo º
ln¨¨ ¸= ln « » + ln « »
© Wo ¹ (α − 1) ¬ xo (1 − x ) ¼
¸
¬ 1− x ¼

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 CHEMICAL ENGINEERING (continued)

Murphree Plate Efficiency

EME = (yn – yn+1)/( y*n – yn+1), where
y = concentration of vapor above plate n,
yn+1 = concentration of vapor entering from plate below n,
and
y*n = concentration of vapor in equilibrium with liquid
leaving plate n.
A similar expression can be written for the stripping section
by replacing n with m.
Definitions:
α = relative volatility,
B = molar bottoms-product rate,
D = molar overhead-product rate,
MASS TRANSFER
F = molar feed rate,
L = molar liquid downflow rate, Diffusion
RD = ratio of reflux to overhead product, Molecular Diffusion
V = molar vapor upflow rate, N A p A § N A N B · Dm ∂p A
Gas: = ¨ + ¸−
W = weight in still pot, A P © A A ¹ RT ∂z
x = mole fraction of the more volatile component in the
NA §N N · ∂x
liquid phase, and Liquid: = x A ¨ A + B ¸ − CDm A
y = mole fraction of the more volatile component in the A © A A ¹ ∂z
vapor phase. in which (pB)lm is the log mean of pB2 and pB1,
Subscripts Unidirectional Diffusion of a Gas A Through a Second
B = bottoms product, Stagnant Gas B (Nb = 0)
D = overhead product, NA
=
Dm P ( p − p A1 )
× A2
F = feed, A R T ( p B )lm z 2 − z1
m = any plate in stripping section of column,
in which (pB)lm is the log mean of pB2 and pB1,
m+1 = plate below plate m,
n = any plate in rectifying section of column, NI = diffusive flow of component I through area A, in z
direction, and
n+1 = plate below plate n, and
o = original charge in still pot. Dm = mass diffusivity.
EQUIMOLAR COUNTER-DIFFUSION (GASES)
(NB = – NA)
N A A = Dm (R T ) × [( p A1 − p A2 ) (z 2 − z1 )]
Unsteady State Diffusion in a Gas
∂pA /∂t = Dm (∂2pA /∂z2)
CONVECTION
Two-Film Theory (for Equimolar Counter-Diffusion)
NA /A = k'G (pAG – pAi)
= k'L (CAi – CAL)
= K'G (pAG – pA*)
= K'L (CA* – CAL)
where pA*is partial pressure in equilibrium with CAL, and
CA* = concentration in equilibrium with pAG.

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 CHEMICAL ENGINEERING (continued)

Overall Coefficients Concentrations of Vaporized Liquids

1/K'G = 1/k'G + H/k'L Vaporization Rate (Qm, mass/time) from a Liquid Surface
1/K'L = 1/Hk'G + 1/k'L
Qm = [MKASPsat/(RgTL)]
Dimensionless Group Equation (Sherwood)
M = molecular weight of volatile substance
For the turbulent flow inside a tube the Sherwood number
K = mass transfer coefficient
0.8 13
§ km D · § km D · § Dρ · § µ · AS = area of liquid surface
¨ ¸ ¨ ¸ ¨ ¸
¨ D ¸ is given by: ¨ D ¸ = 0.023¨¨ µ ¸¸ ¨ ρD ¸ Psat = saturation vapor pressure of the pure liquid at TL
© m ¹ © m ¹ © ¹ © m¹ Rg = ideal gas constant
where, TL = absolute temperature of the liquid
D = inside diameter,
Dm = diffusion coefficient, Mass Flow Rate of Liquid from a Hole in the Wall of a
V = average velocity in the tube, Process Unit
ρ = fluid density, and Qm = AHCo(2ρgcPg)½
µ = fluid viscosity.
AH = area of hole
CHEMICAL PROCESS SAFETY Co = discharge coefficient
Threshold Limit Value (TLV) ρ = density of the liquid
TLV is the lowest dose (ppm by volume in the atmosphere) gc = gravitational constant
the body is able to detoxify without any detectable effects. Pg = gauge pressure within the process unit
Examples are:
Compound TLV Concentration (Cppm) of Vaporized Liquid in
Ventilated Space
Ammonia 25
Chlorine 0.5 Cppm = [QmRgT
106/(kQVPM)]
Ethyl Chloride 1,000 T = absolute ambient temperature
Ethyl Ether 400 k = nonideal mixing factor
Flammability QV = ventilation rate
LFL = lower flammability limit (volume % in air) P = absolute ambient pressure

UFL = upper flammability limit (volume % in air)

Concentration in the Atmosphere
A vapor-air mixture will only ignite and burn over the range
See “Atmospheric Dispersion Modeling” under
of compositions between LFL and UFL. Examples are:
AIR POLLUTION in the ENVIRONMENTAL
Compound LFL UFL ENGINEERING section.
Ethyl alcohol 3.3 19
Ethyl ether 1.9 36.0
Ethylene 2.7 36.0
Sweep-Through Concentration Change in a Vessel
Methane 5 15 QVt = Vln[(C1  Co)/(C2  Co)]
Propane 2.1 9.5 QV = volumetric flow rate
t = time
V = vessel volume
Co = inlet concentration
C1 = initial concentration
C2 = final concentration

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