Introductory Chemical Engineering

Thermodynamics

Chapter 9 - Introduction to Multicomponent Systems

By J.R. Elliott and C.T. Lira

INTRODUCTION TO MULTICOMPONENT SYSTEMS
The primary difference between pure and multicomponent systems is that we must now
consider the impacts of changing the composition on the Gibbs energy. Beyond that, the
Gibbs energy must still be minimized, the calculus of classical thermodynamics must be
applied, the fugacities of the components in the phases must be equal, and, in general, the
problem is pedagogically the same as the phase equilibrium problem for pure
components. The computational methodology gets more complicated because there is
more to keep track of. And the best choice of "equation of state" can change quite a bit
depending on the nature of the solution. In this context, "equation of state" refers to any
model equation for the thermodynamic properties of mixtures. But computations and
equation of state development should not seem unfamiliar at this stage in the course.

eg. dU(T,P,n) = (∂U/∂P)T,ndP + (∂U/∂T)P,n dT + Σ (∂U/∂ni)P,T,nj≠i dni

eg. dG(T,P,n) = (∂G/∂P)T,ndP + (∂G/∂T)P,n dT + Σ (∂G/∂ni )P,T,nj≠i dni
At constant moles of material, the mixture must follow the same constraints as any other fluid.
That is, we only have two state variables left if we keep the composition constant.
⇒ (∂G/∂P)T,n = V and (∂G/∂T)p,n = -S ; Fundamental properties
therefore dG = VdP - SdT + Σ (∂G/∂ni)T,P,nj≠i dni
µi ≡ (∂G/∂ni )T,P,nj≠i ≡ "chemical potential"

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 1

Equilibrium Constraint: equality of chemical potentials
dG = 0 = Σ µi dni equilibrium, constant T and P
Define system of two components (eg. EtOH+H2O) between two phases (eg. vapor and
liquid).
µ 1L dn1L + µ 2L dn2L + µ V1 dn1V + µ V2 dnV2 = 0
but if component 1 leaves the liquid phase then it must enter the vapor phase (and
similarly for component 2).
⇒ dn1 = − dn1 and dn2 = − dn2
L V L V

( V V V
)
⇒ µ1 − µ1 dn1 + µ 2 − µ 2 dn 2 = 0
V
(
L V
)
Therefore,
µ V1 = µ 1L and µ V2 = µ 2L .
Chemical potential of a pure fluid
µj ≡ (∂ G / ∂ni ) T ,P ,n = (∂ (nG ) / ∂ni ) = G (∂n / ∂ni ) + n(∂G / ∂ni ) n →n
ni → n j ≠i
ni →n ni → n i

but n(∂ G / ∂ni ) n →n = n(∂G / ∂n) and G = G (T , P) ≠ f (n) ⇒ n(∂G / ∂n) = 0.

i

Therefore, µ j ni →n = G
Note: This means GL = GV for pure fluid, as before.
Thus, µi is a "generalized G" for components in mixtures.

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 2

Equilibrium Constraint: equality of fugacities
Fugacity - "escaping tendency"
For a pure fluid:
ln(f/P) ≡ (G-Gig)/RT

For mixtures, generalize:

ln(f/P) ≡ (G-Gig)/RT to RTln( f$ i/P) ≡ (µi - µiig)
where f$ i fugacity of component i in a mixture.

Equality of fugacities as a criterion of phase equilibrium

( ) (
µ Vi T eq , P eq = µ iL T eq , P eq )
By definition, µ i
V
(T eq
, P ) − µ (T , P ) = RT ln[ f$ (T
eq L
i
eq eq
i
V eq
) (
, P eq / f$i L T eq , P eq )]
(
but, µ i T , P − µ i
V eq eq L
) (T , P ) = 0 ⇒ ln( f$ / f$ ) = 0
eq eq
i
V
i
L

f$i V = f$i L at equilibrium.

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 3

Activity, Activity Coefficient, and Fugacity Coefficient
"Activity" ai = f$i /fi° Ionic solutions, reactions

"Activity coefficient" = γi = f$i /(xi fi°) Low pressure phase equilibria

"Fugacity coefficient" = φi = f$i /(xi P) High pressure phase equilibria

where fi° is the value of the fugacity at standard state. The most common standard state
is the pure component at the same temperature and pressure as the system of interest. In
that case fi° = fi. Note that the defining equation for activity coefficient can be rearranged
to become an equation for calculating the fugacity of a component in a mixture. This is
the general procedure used for liquids.
f$i L = γ i xi f i o = γ i xi f i o ≡ γ i xi φi P

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 4

IDEAL SOLUTIONS
The simplest solution model is to assume that interaction energiess in the mixture are like
interaction energies in the pure fluid. e.g. 35Cl2 mixed with 37Cl2
then, ∆H mix = 0 and H Tot = Σ ni Hi
is is

As for the entropy change of mixing, the loss of order due to mixing is unavoidable
∆ S mix
is
/ R = − Σ xi ln ( x i )
∆Gmix
is
∆Hmix
is
∆Smix
is

Combining ⇒ RT = RT − R = +∑ xi ln( xi )
The definition of fugacity in terms of a change in free energies gives:
∆Gmix ni (µ i − Gi ) =  f$i 
= ∑n ∑ xi ln f 
RT RT  i
∆Gmix (µ i − Gi ) =  f$i 
Thus, for an ideal solution, RT = ∑ xi ∑ xi ln f 
RT  i
⇒ f$i is / f i = xi ⇒ f$i is = xi f i

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 5

Raoult's Law
Substituting the ideal solution result ⇒ yi f i = xi f i
V L V L
f$ i
= f$ ⇒
i

(f )
/ P = ϕ (Tri , Pri ,ω i ) for the vapor
i
V

We correct the fugacity of the saturated liquid for the effect of pressure on the liquid.
(
fi sat = Pi satϕ Tri , Prisat , ωi )
(
dG = RTd ln ( f ) ⇒ RT ln fi L / fi sat = GiL − Gisat )
(∂G / ∂P )T = (∂H / ∂P )T − T (∂S / ∂P )T = V − T (∂V / ∂T ) p + T (∂V / ∂T ) p = V
( ) (
⇒ GiL − Gisat = ∫ V L dP ≈ V L P − Pi sat = RT ln f i L / f i sat ) ( )
⇒ fi L / fi sat = exp[V L (P − Pi sat )/ RT ] “Poynting Correction”
Substituting, yi P (Tri , Pri ) xi Pi ϕ (Tri ,Pri ) exp V (P − Pi ) / RT
sat sat L sat
[ ]
K = x i ( i,P
sat
) [V ( − Pi )/ ]
ϕ (Tri , r )
i
P  
Note: at reasonably low pressures,
Pi sat
[ (
ϕ ≈ 1 and exp V L P − Pi sat / RT ≈ 1 ) ] ⇒ Ki =
P “Raoult’s Law”

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 6

 Classes of VLE calculations

Type Information_required Information_computed Convergence

BP T,x P,y Easiest
DP T,y P,x Not bad
BT P,x T,y difficult
DT P,y T,x difficult
FL P,T x,y,L/F Most difficult

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 7

Short-cut Estimation of VLE K-ratios and Initial Guesses for VLE
10 [7 / 3 (1 + ω i )(1 − 1 / Tr i )]
Ki =
Pr i
7
 3 (1+ i )(1−1 /Tri )
 
Bubble Point Pressure: P = = =
sat
iP i Pi i Pc i 10
yi
∑
yi yi P 1
⇒ =
Dew point pressure,: Σ x i = 1 = Σ Ki
=Σ 7 
 3 ( 1+ ωi )( 1−1/ Tri )  P 7 
 3 ( 1+ wi )( 1−1/ Tri ) 
Pci 10 Pci 10
For bubble or dew point temperatures, it is not so straightforward. One guess would be:
T = Σx i Ti sat
T = Σy i Tc i Ti sat / Σy i Tc i
But these are somewhat cruder guesses than for the pressures.

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 8

Example 9.1 Bubble temperature, dew temperature, and flash
A distillation column is to produce overhead and bottoms products having the following
compositions:
z(Overhead)
Propane 0.23
Isobutane 0.67
n-Butane 0.10
Total 1.00
a) Calculate the temperature at which the condenser must operate in order to condense
the overhead product completely at 8 bars.
b) Assuming the overhead product vapors are in equilibrium with the liquid on the top
plate of the column, calculate the temperature of the overhead vapors and the
composition of the liquid on the top plate when operating at the pressure of part (a).
c) Suppose only a partial condensation at 320 K. What fraction of liquid would be
condensed?

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 9

Example 9.1 Bubble temperature…

Solution: Use the short-cut estimates of the K-ratios

a) The maximum temperature is the bubble point temperature.
Guess T=310K Guess T=320K
Ki yi Ki yi
C3 1.61 0.370 2.03 0.466
iC4 0.616 0.413 0.80 0.536
nC4 0.438 0.044 0.58 0.058
0.827 1.061
 1.000 - 0.827 
⇒ T = 310 +  ( 320 − 310) = 317
 1.061 − 0.827 

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 10

Example 9.1 Dew temperature…
b) The saturated vapor is at its dew point temperature.
Guess T=315K Guess T=320K
yi Ki xi Ki xi
C3 0.23 1.81 0.127 2.03 0.113
iC4 0.67 0.70 0.957 0.80 0.838
nC4 0.10 0.50 0.200 0.58 0.172
1.284 1.123

 1.00 − 1123
. 
⇒ T = 320 +  ( 320 − 315) = 324
 1.281 − 1123
. 

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 11

Example 9.1 …Flash
c) This is an isothermal flash problem.
M-Bal:
zC3 = xC3 (L/F) + yC3 (V/F)
zIC4 = xiC4 (L/F) + yiC4 (V/F)
zNC4 = xnC4 (L/F) + ynC4 (V/F)

Where z is the feed compostion and L/F is the liquid to feed ratio. Overall, V/F = 1-L/F,
[ ]
zi = xi ( L / F ) + Ki (1 − L / F )
zi
xi =
Ki + ( L / F ) ( 1 − Ki )
zi Ki
yi =
Ki + ( L / F )(1 − K i )

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 12

Solve (Σxi -Σyi )=0. That is
z i ( 1 − Ki )
Σx − Σy = Σ ≡ Σ Di = 0
Ki + ( L / F ) ( 1 − K i )

Guess L/F=0.5 L/F=0.6 L/F=0.77

zi Ki Di Ki Di Ki Di
C3 0.23 2.03 -0.1564 2.03 -0.1678 2.03 -0.1915
iC4 0.67 0.80 0.1489 0.80 0.1457 0.80 0.1405
nC4 0.10 0.58 0.0532 0.58 0.0505 0.58 0.0465
0.0457 0.0284 -0.0045

 0 + 0.0045 
⇒ L / F = 0.77 +  (0.6 − 0.77 ) = 0.7467
 0.0284 + 0.0045 

Elliott and Lira: Chapter 9 - Introduction to Multicomponent Systems Slide 13