MEESE FUNDAMENTALS OF CHEMICAL ENGINEERING

Two-phase systems

States of the matter

SINGLE PHASE SINGLE PHASE

ONE COMPONENT SEVERAL COMPONENTS
LIQUID-SOLID MIXTURES
GAS-VAPOR
TWO PHASES SEVERAL FASES
ONE COMPONENT SEVERAL COMPONENTS
LIQUID-VAPOR
LIQUID-SOLID PURE PHASE COMPONENTS IN ALL
SOLID-VAPOR THE PHASES

LIQUID-VAPOR (LIQ-LIQ SOL-LIQ SOL-VAP)

CHEMICAL
EQUILIBRIUM

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Two-phase systems (VLE)

By WilfriedC at English Wikipedia, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=7437968

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Two-phase systems (VLE)

By WilfriedC at English Wikipedia, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=7438068

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Two-phase systems (VLE)

Equilibrium conditions

Tl Tv : chemical potential
V yi 0
RT ln f f: fugacity
Pl Pv
L xi il vi fil f vi
P,T
General VLE: Regular solution theory (fl x f l ), non-ideal solution ( ), high pressure ( )
i ii i i

: fugacity coefficient
v
: activity coefficient Py i i f l xi i i
Fundamental equation for VLE

l sat sat l sat

At low P ( ~ 1), Pyi Psatx fi i Pi exp v i P Pi
i ii RT

And for an ideal liquid

solution (similar
Pyi Psat
i xi
Raoults law
compounds that do not
Poynting factor
interact)
(often ~1, except
at very high P)

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Two-phase systems (VLE)

Activity coefficient: models

Margules (1895) ln 1 x 22 A12 2 A 21 A12 x1 ln 2 x 21 A 21 2 A12 A 21 x 2

van Laar (1910) ln B12 ln B21

2
1 2 2
1 B12 x1 / B21x2 1 B 21x2 / B12 x1

Wilson (1964) ln ln x x x 12 21 v2 a12

1 1 2 12 2 x x x 12 exp
x
1 2 12 2 1 21 v1 RT
12 21
21
v1 a 21
exp
ln 2 ln x 2 x1 21 x1 x x x v RT
x 1 2 12 2 1 21 2

NRTL (Non Random Two Liquids, 1968)

2 2
2 G G G G
ln 1 x 21 12 12 2 ln 2 x2 12 21 21 2
2 21 x1 x2 G21 x x G 1 12
x x G x x G
2 1 12 2 1 12 1 2 21

G12 exp ; G21 exp b12 b21

12 21 12
; 21
R T R T
UNIFAC (Abrams & Prausnitz, 1975), UNIQUAC (group contribution)

comb res
ln i ln i ln i (See details in Thermodynamics books)

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Two-phase systems (VLE)

VLE at low P: cases1
V yi
Bubble pressure (T i xi known; P i yi unkonwn)
L xi Dew pressure (T i yi known; P i xi unkonwn)
Bubble temperature (P i xi known; T i yi unkonwn)
P,T Dew temperature (P i yi known; calcules T i xi unkonwn)

- Determination of bubble temperature (binary system)

Number of variables = 6
2 degrees of freedom If, for instance, P and x1 Bubble T
Equations = 4

Remember also y1P x P sat

11 1
xi 1; yi 1
y2P 2 x 2P2sat
P x P0 T x P0 T T
1 1 1 2 2 2

(in general, for C components) P x P0 T

i i i
i 1...C
1
Algorithms for each case can be found in J.M. Smith, H.C. van Ness, M.M. Abbott, Introduction to chemical engineering thermodynamics,
7 ed., McGraw-Hill (2005), Ch. 14.

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Two-phase systems (VLE)

ELV through EOS (preferred for nearly ideal systems at high pressure)
fv fil
i
v l v l
yP xP y x
i i i i i i i i
l
yi
Ki x i iv
i
i
EOS for mixtures are needed. For instance:

- Redlich-Kwong-Soave (SRK)
R2T 2 RT
RT aT a aC ; aC 0.42748 C ; b 0.08664 C
P PC PC
2
v b vv b 1 1 Tr ; 0.48508 1.55171 0.15613 2

Mixture rules:

am T x i x j aij T bm T x i bi
i 1...c j 1...c i 1...c
0.5
aij T ai T a j T 1 c ij c m T xi aij
i 1...c

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Two-phase systems (VLE)

ELV through EOS

The expression of the coefficient factor of a compound in a mixture is:

n z dv
ln i 1 ln z
v,T,n j i
v
v ni

For instance, applied to the SRK equation results in

ln i ln v v bi R 2T cbm ln v vb
v bm m m m

am bi 1 1 v bm

ln ln z
R T bm v bm bm v
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Chemical-reaction equilibrium

All the reactions progress until a equilibrium is reached if you do not stop them
or removes some product so the equilibrium can never be reached.

2NO 2 g N 2O4 g

M.J. Shultz Why Equilibrium? Understanding the Role of Entropy of Mixing Journal of Chemical Education 76, 1391-1393 (1999)

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Chemical-reaction equilibrium

The general chemical reaction can be written as

1 A1 2 A2 ... 3 A3 4 A4 ...

- Definition of the reaction coordinate or reaction progress ()*

dn1 dn2 dn3 dn4

... d
1 2 3 4

dni id

ni0 ni
ni ni0 i
i
See that reaction progress () and conversion (X) have similar definition, but are not identical. has
units (moles), X has not. They only shows the same value when i is 1 and we start from 1 mol of
reactant (basis of calculation).
* Be careful with the sign of i! (positive for products, negative for reactants)

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Chemical-reaction equilibrium

The equilibrium condition for a chemical reaction is Equilibrium

constant

Go
i i
ai i exp i KT
i RT

Standard G
of reaction
RT lnK Go Go
i i
i

where Activity
fi
ai
fio

and Go iis a standard state conveniently selected.

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Chemical-reaction equilibrium

An important issue is how K(T) depends on the T,

Standard H
of reaction

d Go / RT Ho

(This is a
dT RT2
well-known
dependence)
RT lnK Go

dlnK Ho
dT RT2

KT Ho 1 1 vant Hoff law

ln (not rigorous but good
K T0 R T T0 enough in many cases)

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Chemical-reaction equilibrium

How concentrations are related in equilibrium: gaseous phase reaction

Standard state: ideal gas ideal at a standard pressure of 1 bar fo Po 1 bar

i

i
f i Does K(T) have units?
KT ai i
i i Po

yP i

KT i i But are important the

units used for P?
i Po
Approximation (?):
KT Good at low P or if K 1
i
yiP
i K i i

i
What is KP? Kp Pi i
KT K1
i
Escola Tcnica
Again, if P is low or K 1 Kp K T Superior (often
dEnginyeria K 1)
Qumica
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Chemical-reaction equilibrium

How concentrations are related in equilibrium: liquid phase reaction

Standard state: pure liquid at a standard pressure of 1 bar f io

f xf
i i ii

i x i fi fi sat vi sat

ai fo i xi fi fi exp P P
o
i fi RT

P Psat

KT xi i exp
i iv i
i
RT i

KT xi i Kx K
Approximation (often acceptable): i
i
Law of mass action
i
Approximation (often inacceptable): KT xi i
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Chemical-reaction equilibrium

Example
Production of methanol.

CO g 2H2 g CH3OH g

The reaction takes place at 500C. Determine the pressure in the reactor, if a H2/CO
ratio 3 to 1 is fed, in order the conversion (with respect to CO) to be higher than 10%.
Assume ideal gas behaviour for the gaseous phase.

Standard enthalpies and free energies of formation at 298 K.

Hf, 298 (kJ/mol) Gf, 298 (kJ/mol)

CO (g) -110.250 -137.169
CH3OH (g) -200.660 -161.960

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Chemical-reaction equilibrium

Example
CO g 2H2 g CH3OH g

PCH3OH 1 yCH3OH
K Assuming ideal gas
2 behaviour: i = 1
PCO PH22 P2 yCO yH2

CO H2 CH3OH Total
Initial 1 3 0 4
Change - -2 -2
Final 1- 3-2 4-2

yCO 1 ; yH 3 2 OH
; yCH
2 3
4 2 4 2 4 2
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Chemical-reaction equilibrium

Example
CO g 2H2 g CH3OH g

1 4 2
P
K773 1 3 2

yCO 0.2368 ; yH2 0.7369 ; yCH3OH 0.0263

0.1
Which is the value of the constant at 773 K?
G oT
ln K T
R T
kJ
G 0298 161.960 137.169 24.791
mol
24.791 103

ln K298 K298 22163

8.314 298.15
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Chemical-reaction equilibrium

Example
CO g 2H2 g CH3OH g

KT2 H0 1 1
ln K R T T
T1 2 1

kJ
H 0298 200.660 110.250 90.410
mol

K 90.410 10 3 1 1 10 6
ln K 773 8.314 K 773 22163 1.826 10 4.05 10
298 773 298

Here, the higher is T, the lower is K, but is it always in this direction or does it depend on something?

Replacing in the above expression, P 225 bar

This is (why?), P 225 bar

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Hands-out 07

During combustion, formation of nitrogen oxides can occur -which generate acid rain- following
the stoichiometric equation.
N2 (g) + O2 (g) NO2 (g)
Which could the highest temperature be in an incineration plant if the upper NO 2 level allowed
is 10 ppm in the chimney flue? Assume that the feed is atmospheric air (21% of O 2) and the
combustion takes place at 1.5 bar (because of pressure drop in the chimney).

Standard enthalpies and free energies of formation at 298 K.1

N2 (g) O2 (g) NO2 (g)

Gf,298 K (J/mol) --- --- 51310
Hf, 298 K (J/mol) --- --- 33180

1 J.M. Smith, H.C. Van Ness, M.M. Abbot Introduccin a la Termodinmica en Ingeniera Qumica 5 ed., McGraw Hill, 1997

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