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Formula Rio
Formula Rio
I. General thermodynamics
nsp
different entity in reaction (product or reactant) at physical state ps (gas, liquid, solid)]
Standard heat of reaction: H R ,298
0
v H i
0
f ,i
d ln K eq H 0
T c d
T T1 T 2 T12
K eq (T )
R ln b ln
K eq (T1 ) T1 2 6
c d 3 1 1
H R0 ,T1 bT1 T12 T1
2 3 T T1
where b v b ,i i c vici , d vi di
fi T , P, yi
a
fi T ,1bar ,standard condition
activity: i 0
Ideal gases: ai Pi P yi P P
0 0
P ve
Chemically pure liquids: ai 1 , high pressure: i
a exp RT
dP
1
1
Ideal liquid solutions: ai xi
Liquid solutions: ai i xi
Solids: (analogous expressions to the ones for liquids)
vi vi
Ideal gas mixtures: K eq i i
y vi
vi i gas
P
i
K
i
K
y P i gas
,
vi
i gas
where K y y
i
vi
i K ivi
i
General Notation
γi = activity coefficient of species i (liquids)
ΔGT = Gibbs free energy difference
ΔHf0 = standard enthalpy (heat) of formation (T = 298K, P = 1bar)
μi = chemical potential of species i
vi = stoichiometric coefficient of species i
Φi =fugacity coefficient of species i
ai = activity of species i
CP = heat capacity under constant pressure
fi = fugacity of species i
Keq = equilibrium constant
P = pressure (P0: standard pressure)
Pi = partial pressure of species i
R = universal (ideal) gas constant (8.314 5 J/K-mol = 82.057 cm3 atm/K-mol)
T = temperature
ve = molar volume of liquid
yi = molar fraction of species i
--------------------------------------------------------------------------------------------------------
P 1 c 1 P
Brunauer-Emmett-Teller (B.E.T.): V P P V c
0 m cVm P0 ,
c exp q1 q2 RT
2
| q1 = heat of adsorption of first layer,
| q2 = heat of liquefaction,
| V = volume (quantity) of adsorbed gas at pressure P,
| P0 = saturation pressure at the temperature of adsorption
| Vm = volume (quantity) of adsorbed gas for the formation of monolayer
| R = universal (ideal) gas constant (8.314 5 J/K-mol = 82.057 cm3 atm/K-mol)
| T = temperature
Henry isotherm: K P
2
M
3
Vm Nav
S a a 1.09
N av
B.E.T-calculated total surface area: g V ,
B.E.T-calculated area (Nitrogen specific): Sg cm /g 4.35 10 Vm cm /g
2 4
3
| Nav = Avogadro number (6.0231023 molecules/mol)
| M = molecular weight of adsorbed gas
| Vm = volume (quantity) of adsorbed gas for monolayer
| V = gram-molecular volume (STP) = 22400 cm3 /g-mol
| ρ = density of adsorbed gas
| a = projected area of molecule on the surface (2-D, close packing)
General Notation
Θ = surface coverage
ka = kinetic coefficient of adsorption
kd = kinetic coefficient of desorption
P = pressure
--------------------------------------------------------------------------------------------------------
III-IV. Chemisorption
Empirical thermodynamic criteria for chemisorption:
4) | S | 10 (cal/mol-K)
5) | S | 12.2 0.0014 H (cal/mol-K)
--------------------------------------------------------------------------------------------------------
3
V. External heat and mass transfer
n 1
kn asCA,b
Damköhler number (nth-order reaction):
Da
kg am
d pU f
Reynolds number (Re): f
f
Schmidt number (Sc): D
f AB
kg d p
Sherwood number (Sh): D
AB
cp f
Prandtl number (Pr): kf
h dp
Nusselt number (Nu): k
f
Pr
Lewis number (Le): Sc
kg d p
2.0 0.6Re 2 Sc 3
1 1
kf
kg f 2/3
Mass transfer in fixed-bed reactors: Dj Sc f Re
G
h
Heat transfer in fixed-bed reactors:
jH Pr 2/3 f Re
cpG
f(Re) can be calculated from the following empirical equations:
Condition Expression
Re < 200 jD 1.66Re0.51
Re > 200 jD 0.98Re0.41
Dwivedi & Upadhay Re > 10 B jD 0.458Re0.407
4
Petrovic & Thodos 3 < Re < 2000 (gases) B jD 0.357Re0.359
Wilson & Geankoplis 55< Re < 1500 (liquids) B jD 0.250Re0.31
Wilson & Geankoplis 0.0016< Re < 55 (liquids) B jD 1.09Re2/3
1 Ca 1 n Da
H CA,b
where f cpTb
d pG
30 5000 , j or j :
Fluidized bed reactors in the range f 1 B H D
0.44
d pG
jH 1.77
f 1 B (same for jD)
k2 as
1
k C
Sp 1 A
kg am B
1
k 2 CB b k a C 1
1 s
A kg am k1as
g m B B b g m A
ka C ka A
| subscript b in concentration ratio denotes bulk stream
General Notation
dp = diameter of catalytic particle
ρf = density of fluid
μf = (dynamic) viscosity of fluid
U∞ = fully developed velocity of fluid
DAB = diffusivity of A in the reaction mixture
kg = mass transport coefficient
h = heat transport coefficient
kf = thermal conductivity of fluid
cp = specific heat of fluid
G = mass velocity of fluid
5
εB = porosity of bed
E = activation energy of reaction
kn = intrinsic kinetic coefficient per unit of catalyst surface area
CA,b = concentration of A in the bulk stream
CA,s = concentration of A on the catalyst surface
as = surface area of the catalyst per unit volume of catalyst particle
am = external surface area of the catalyst per unit volume of catalyst particle
n = external effectiveness factor
R = universal (ideal) gas constant (8.314 5 J/K-mol = 82.057 cm3 atm/K-mol)
Tb = temperature in the bulk stream
Ts = temperature on the catalyst surface
Sp = observed selectivity
--------------------------------------------------------------------------------------------------------
1 8RT
D u u
MA
Normal diffusion (kinetic theory of gases): AB A , A
3
| u A = mean velocity of molecules A
| R = universal (ideal) gas constant
| T = temperature (K)
| MA = molecular weight of A (g/mol)
| λ = mean free path
6
| σAB = collision diameter of the Lennard-Jones potential between a pair of molecules of
kinds A and B (Å)
| εAB = well depth of the Lennard-Jones potential between a pair of molecules of kinds A
and B (J/mol)
| ΩAB = collision integral (dimensionless)
| kB = Boltzmann constant (1.98710-3 kcal/mol-K = 1.38010-23 J/K)
| Tb = normal boiling temperature (K)
| Tc = critical temperature (K)
| Vb = volume per mole at normal boiling point (cm3/mol)
| Vc = critical volume (cm3/mol)
8 T M B
D 7.4 10
Normal diffusion in liquids (Wilke-Chang equation): B VA0.6
AB
1 k 1 D jk aj
1 n
1 ak ak
k j
n
ak
1 j y j k 1 D jk
y k y j
| a j | , j | a |
k 1
1 yj
D j ,m
k j j
k 1 a j
a S g
Knudsen diffusion: K ,A
MA MA
| DK,A = (Knudsen) diffusivity of A (cm2/s)
| a = pore diameter (cm)
| MA = molecular weight of A (g/mol)
| ε = porosity of solid
| Sg = total surface area of solid (cm2)
| ρa = apparent density of solid (g/cm3)
| T = temperature (K)
7
Diffusion in porous medium, total diffusivity (simplified):
1
D
1 1
DAB DK ,A
Diffusion in porous medium, total diffusivity (explicit):
1
D JB
1 w yA 1 , w 1
JA
DAB DK ,A
| JA = molar flux of A, treated as vector.
| JB = molar flux of all entities except A, treated as vectors.
MA
For counter-diffusing, binary (A+B) mixture (no reaction):
w 1
MB
D
D
Parallel pore model, effective diffusivity:
e
| ε = porosity of medium
| δ = tortuosity of medium
μ2 1 3 M
D D 2
Dμ
Random pore model, effective diffusivity: e 1 M
M M
1 1
DM , Dμ
1 1 1 1
where
DAB DKA M DAB DKA μ
| subscript M corresponds to macropores
| subscript μ corresponds micropores
Total effective diffusivity (including surface contribution): De,t De KDs
| Ds = surface diffusivity
| ρ = density of the catalyst
| K = equilibrium constant (linear adsorption isotherm)
1
kg
k e ks
Effective thermal conductivity of porous solids:
ks
| ks = thermal conductivity of solid phase
| kg = thermal conductivity of gas phase
| ε = porosity of solid catalyst
8
k1
st
Thiele modulus (plate geometry, 1 -order reaction):
L L
De
| L = half thickness of plate catalyst
| k1 = intrinsic reaction rate constant
CA cosh L z ' z
z'
cosh L
st
Concentration profile (plate geometry, 1 -order reaction): C , L
A,s
tanh L
Internal effectiveness factor (plate geometry, 1st-order reaction): n L
rs k1
Thiele modulus (spherical geometry, 1st-order reaction):
s
3 De
| rs = radius of spherical catalyst
n 1
knCA,s Vp
Thiele modulus (general geometry, nth-order reaction):
L , L
De Sx
| n = integer (order of reaction)
| Vp = volume of particle
| Sx = external surface area of particle
| CA,s = concentration of A on surface
Total effectiveness factor (combined effect of internal and external resistances to mass
transfer) (spherical geometry, 1st order reaction):
1 1 3 2
n * n Bi m
kg rs
Biot number for mass transfer (Bim)
Bi m
De
9
Non-isothermal conditions (spherical geometry, 1st order reaction):
H De
T Ts
ke
CA CA,s
T CA
A , Ts ,
*
In dimensionless form: 1 C *
1 C A
CA,s
De CA,s
Prater number (β): H
ke Ts
10
| k1 = intrinsic rate constant (first order reaction)
| Φs = Thiele modulus
| n = internal effectiveness factor
| δ = fraction of poisoned (deactivated) sites
| rc = radius of active central core
| rs = total radius of the catalyst
--------------------------------------------------------------------------------------------------------
VIII. Catalytic reactors
Fixed bed reactor, generalized mass and heat balance equations:
CA 2CA 2CA 1 CA uCA
De z De r rp B
t z 2 r
2
r r z
T 2T 2T 1 T cpuT
cp ke z 2 ke r 2 rp BH
t z r r r z
| CA = concentration of A
| t = time
| T = temperature
| u = superficial velocity
| ρ = density of fluid
| ρB = density of bed
| rp = global rate of consumption of A per unit mass of catalyst
| (De)z, (De)r = effective diffusivities in axial and radial directions
| (ke)z, (ke)r = effective thermal conductivities in axial and radial directions
dp u dp u
Pe , Pe
Axial and radial Peclet numbers (Pe) for mass: z
De z r
De r
dp u dp u
Pe z , Pe r
Axial and radial Peclet numbers (Pe) for heat: ke z ke r
| dp = diameter of catalytic particles
d reactor i m e e
0.9
hi d reactor dp G dp
0.813 exp 6
Leva formula (heating): kg d reactor
11
0.7
hi d reactor dp G dp
3.50 exp 4.6
Leva formula (cooling): kg d reactor
One-dimensional, plug-flow model, momentum balance:
dP f r u 2 P f r u 2
0 →
dz d p L d p
1 B 1
1.75 150 B
Re d p u
fr Re d p 6
volume of particle
B 3 , ,
external surface area of particle
FA,0
One-dimensional, adiabatic reactor, temperature vs. conversion:
dT H d XA
mc t p
k j
X A0,i j 1
i
X A,i 1 i 2,...., N
Fractional feed stream, conversion:
k
j 1
j
12
i 1
k j
T0, i T0 j 1
i Ti 1 T0 i 2,...., N
Fractional feed stream, temperature:
k
j 1
j
HYPERBOLIC FUNCTIONS:
e x e x
sinh x
2
e x e x
cosh x
2
e x e x
tanh x x
e e x
e x e x
coth x x
e e x
13