Theoretical Foundations of Chemical Engineering, Vol. 39, No. 4, 2005, pp. 385–392.

Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 39, No. 4, 2005, pp. 407–414.
Original Russian Text Copyright © 2005 by Serafimov, Timoshenko.

Analysis of Distillation Using the Mass-Transfer Equation

in Multicomponent Mixtures
L. A. Serafimov and A. V. Timoshenko
Lomonosov State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 117571 Russia
e-mail: a-timoch@mtu-net.ru
Received April 23, 2004

Abstract—The vector equation of mass transfer in multicomponent systems, the conditions for the existence
of singular points, and the temperature distributions along the height of a two-section distillation column are
analyzed.

Previously [1], in terms of the thermodynamics of responding to the operating tie line (the difference
irreversible processes, we derived the vector equation Y − X).
of mass transfer in multicomponent systems: The equilibrium tie-line vector is related to the par-
tial derivatives of the equilibrium temperature by the
dm 1 equation [2, 3]
---------
dF
 B 11 B 12 B 13 … … B 1n – 1  ∂T
dm 2   --------
---------  B 21 ∂x 1
dF B 22 B 23 … … B 2n – 1 
 
B 33 … … B 3n – 1  ∂T
dm 3
--------- =  B 31 B 32 --------
  ∂x 2
dF  … … … …… … 
…  … … … …… …  –∆S
LV ∂T
  --------
… B n – 13 … … B n – 1n – 1  ∂x 3
 B n – 11 B n – 12
dm n – 1 …
--------------- (1)
dF …
∂T
--------------
B B
( y1 – x1 ) – ( y1 – x1 ) ∂x n – 1
B B
( y2 – x2 ) – ( y2 – x2 )
 g 11 g 12 g 13 … … g 1n – 1 
*
B B
( y3 – x3 ) – ( y3 – x3 ) .  
 g 21 g 22 g 23 … … g 2n – 1 
…………………  
=  g 31 g 32 g 33 … … g 3n – 1 
…………………  
(3)
B B  … … … …… … 
( yn – 1 – xn – 1 ) – ( yn – 1 – xn – 1 )  … … … …… … 
In vector form, this equation is written as  
 g n – 11 g n – 12 g n – 13 … … g n – 1n – 1  êÚ
B B
dm 1 /dF = ( B ij ) ( Y – X ) – ( Y – X ) , (2)
B B
where dm i /dF is the componentwise mass-transfer den- y1 – x1
sity vector, (Bij) is the positive definite symmetric mass- B
y2 – x2
B

B B
transfer coefficient matrix, and ( Y – X ) – ( Y – X ) is B
y3 – x3
B
* ,
the vector of componentwise mass-transfer driving
forces. The vector of componentwise driving forces ………
decomposes into the vector corresponding to the equi- ………
librium liquid–vapor tie line (the difference YB – XB of B B
the concentrations at the interface) and the vector cor- yn – 1 – xn – 1

0040-5795/05/3904-0385 © 2005 MAIK “Nauka /Interperiodica”

386 SERAFIMOV, TIMOSHENKO

where ( ∂T /∂xi) is the vector of the partial derivatives of d x1

the equilibrium temperature with respect to the compo- --------
sition, gij are the second derivatives of the Gibbs poten- dH
 B 11 B 12 B 13 … … B 1n – 1 
tial g, and ∆SLV is the entropy of the differential phase d x2
--------  
transition of an infinitely small amount of the liquid dH  B 21 B 22 B 23 … … B 2n – 1 
phase to the vapor phase. In vector form, Eq. (3) is writ-  
d x 3 = --- A  B 31 B 32 B 33 … … B 3n – 1 
ten as --------
dH L … … … …… … 


LV B
– ∆S gradT = ( g ij ) ( Y – X ).
B
…  … … … …… … 
 
…  B n – 11 B n – 12 B n – 13 … … B n – 1n – 1 
The operating tie-line vector y – x is the difference d xn – 1
-------------- (7)
of the compositions in the cores of the flows of the
dH
vapor and liquid phases, which can be expressed as [4]
B B
y – x = ( 1 – m ) ( x P – x ). (4) ( y1 – x1 ) – ( y1 – x1 )
B B
( y2 – x2 ) – ( y2 – x2 )
Here, x P is the composition vector of the distillate or B B
the bottoms product, x is the current composition of * ( y3 – x3 ) – ( y3 – x3 ) .
the liquid phase at a certain height of the column, and …………………
m = L/V is the ratio of the amounts of the liquid (L) and
…………………
vapor (V) phases. In the rectifying section of the col-
B B
umn, m < 1, and in the stripping section, m > 1. ( yn – 1 – xn – 1 ) – ( yn – 1 – xn – 1 )
Earlier [4, 5], Eq. (1) was analyzed in detail in the (Bij) is a positive definite symmetric matrix; therefore,
case in which the matrix (Bij) is diagonal. However, for for the set of differential equations that is represented
qualitative analysis of the distillation paths of multi- by vector equation (7), the following theorem is valid
component mixtures, the matrix (Bij) need not be [6]: “Let A: Rn Rn be a linear operator all eigenval-
assumed to be diagonal and the general case can be ues of which have positive real parts; then, the set
considered. n
Ẋ = ( A ) X*, X* ∈ R (8)
First of all, let us derive, from Eq. (1), an equation is topologically equivalent to the standard set
of distillation paths for a column with a differential n
change in the compositions of the phases. Among such Ẋ = EX*, X* ∈ R .” (9)
columns are film columns and packed columns. Since
dF is the area of an infinitely small geometric surface of Here, Ẋ is a derivative and X* is a vector.
mass transfer between the phases, we can write the rela- In our case, the role of the linear operator in this the-
tion between the column height differential and the dif- orem is played by the positive definite symmetric
ferential of the area of the geometric surface of mass matrix (Bij), all characteristic values of which are posi-
transfer: tive real numbers. The role of the vector X is played by
B B
dF = AdH, (5) the vector ( Y – X ) – ( Y – X ) . Consequently, the set
dx A B B
where A > 0 is a certain coefficient. For a film column, ------ = --- ( B ij ) ( Y – X ) – ( Y – X ) (10)
dl L
neglecting the thickness of the liquid film flowing down
the wall, we obtain is topologically equivalent to the set
B B
A = πD, d x/dl = E ( Y – X ) – ( Y – X ) , (11)
where E is the unit matrix. The topological equivalence
where D is the column diameter. means that sets (9) and (10) have the same singular
Equation (1) is based on the assumption of equimo- points of the same types. Therefore, a qualitative anal-
lar transfer. Then, L = const and the change in the con- ysis of the types of singular points can be performed
centration of the ith component, e.g., in the liquid using the set of Eqs. (11). Obviously, the general con-
phase, due to mass transfer can be represented as dition that a certain point is singular is
B B
dm i = d ( Lx i ) = Ld x i . (6) ( y – x ) – ( y – x ) = 0. (12)
The following cases are possible:
Taking into account expressions (5) and (6), Eq. (1) is B B
written in the form y – x = 0, x p – x = 0, and d x/dH = 0 (13)

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 ANALYSIS OF DISTILLATION USING THE MASS-TRANSFER EQUATION 387

(singular points of this type characterize the ends of a Since, at a singular point, xB = x, we obtain
continuous distillation column with a full condenser)
B P
and d x/dH = x ( K i – m ) + mx . (16)
ã ã
y –x = y–x (14) The product mxP is a certain constant quantity.
(along with general cases, condition (12) is also met in Let us transfer the origin of coordinates to the singu-
the particular case of the minimal reflux ratio and, lar point by taking
hence, the minimal m).
0
Singular points that meet conditions (13) can char- x = xi + ξi , i = 1, 2, 3, …, n – 1; (17)
acterize equilibrium open evaporation systems, for
which singular points can be of the generalized node or expand the quantity (Ki – m) in a Taylor series; and
generalized saddle type [4]. retain only the linear terms. Then, by imposing singu-
Let us consider singular points that meet condi- lar-point conditions (14), we obtain that, for the ith
tions (14). For this purpose, using Eq. (4), we rewrite component,
set (11) in the form n–1
0 ∂K i
B
d x/dH = ( K i – 1 ) X – ( m – 1 ) ( x – x ) , (15)
P ( K i – m )ξ i + ∑ x --------
∂x i dξ ,
j
j (18)
1
where Ki is the equilibrium distribution coefficient of
the ith component, i = 1, 2, …, n – 1; Ki is a scalar quan- where i = 1, 2, …, n – 1, and j = 1, 2, …, n – 1.
tity; and (Ki – 1) is a diagonal matrix. Taking i and j = 1, 2, …, n – 1, we obtain

dξ  0 ∂K 0 ∂K 0 ∂K 0 ∂K 1

--------1  K 1 – m + x 1 ---------1 x 1 ---------1 x 1 ---------1 …… x 1 -------------
- 
dH  ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
  ξ1
dξ 2  0 ∂K 0 ∂K 0 ∂K 0 ∂K 2 
-------- x 2 ---------2 K 2 – m + x 2 ---------2 x 2 ---------2 …… x 2 -------------
-
dH  ∂x 1 ∂x 2 ∂x 3 ∂x n – 1  ξ2
 
dξ 3 =  0 ∂K 0 ∂K 0 ∂K 0 ∂K 3  ξ 3 . (19)
--------  x 3 ---------3 x 3 ---------3 K 3 – m + x 3 ---------3 …… x 3 -------------
-  *
dH  ∂x 1 ∂x 2 ∂x 3 ∂x n – 1  …
…  … … … …… …  …
 
…  … … … …… …  ξn – 1
dξ n – 1  ∂K ∂K ∂K n – 1 ∂K 
--------------  0 n–1
x n – 1 --------------
-
0 n–1
x n – 1 --------------
-
0
x n – 1 --------------
- ……
0 n–1 
K n – 1 – m + x n – 1 --------------
-
dH  ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
Let us transform Eq. (19) using the relation [4]

0 ∂K ∂y i
K i + x i --------i = -------, (20)
∂x j ∂x j

which is derived by differentiating the quantity Ki = yi/xi with respect to the concentrations of the component.
Using relation (20), we can rewrite the matrix of coefficients of Eq. (19) in the form
 ∂y ∂y ∂y ∂y 1 
 --------1 – m --------2 --------3 …… -------------
- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 ∂y ∂y ∂y ∂y 2 
 --------2 --------2 – m --------2 …… -------------- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 
 ∂y ∂y ∂y ∂y 3 
 --------3 --------3 --------3 – m … … --------------  . (21)
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 … … … …… … 
 
 … … … …… … 
 ∂y n – 1 ∂y n – 1 ∂y n – 1 ∂y n – 1 
 ------------- ------------- ------------- … … -–m
-------------
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 

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388 SERAFIMOV, TIMOSHENKO

On the basis of matrix (21), we write the characteristic equation

 ∂y 1 ∂y ∂y ∂y 1 
 -------- – m – λ --------2 --------3 …… -------------- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 ∂y ∂y 2 ∂y 2 ∂y 2 
 --------2 -------- – m – λ -------- …… -------------- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 
 ∂y 3 ∂y 3 ∂y 3 ∂y 3  = 0.
 -------- -------- -------- – m – λ … … -------------- 
(22)
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 … … … …… … 
 
 … … … …… … 
 ∂y ∂y ∂y ∂y 
 n–1
------------- n–1
------------- n–1
------------- n–1
-–m–λ
… … -------------
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
Let us subtract and add unity to each diagonal term of the characteristic equation and then introduce the fol-
lowing notation [5]:
m + 1 – λ = λ*. (23)
Then, Eq. (22) takes the form
 ∂y 1 ∂y ∂y ∂y 1 
 -------- – 1 – λ* --------2 --------3 …… -------------
- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 ∂y ∂y ∂y ∂y 2 
 --------2 --------2 – 1 – λ* --------2 …… -------------- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 
 ∂y ∂y ∂y ∂y 3  = 0.
 --------3 --------3 --------3 – 1 – λ* …… -------------- 
(24)
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 … … … …… … 
 
 … … … …… … 
 ∂y n – 1 ∂y n – 1 ∂y n – 1 ∂y n – 1 
 ------------- ------------- ------------- …… -------------- – 1 – λ* 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 

The matrix corresponding to determinant (24) is not
symmetric. Therefore, the fact that the roots of the char-
acteristic equation are real has to be proven.
Note that Eq. (24) is identical to the characteristic
equation that is obtained to prove which type of singu-
lar points can characterize equilibrium open evapora-
tion systems. This allows one to differentiate Eq. (3)
with respect to the composition and, after imposing the
conditions for a singular point in an equilibrium open
evaporation system, to obtain the matrix equation

2 2 2 2
∂ T ∂ T ∂ T ∂ T
--------2- ----------------- ----------------- … … ----------------------
∂x 1 ∂x 1 ∂x 2 ∂x 1 ∂x 3 ∂x 1 ∂x n – 1
2 2 2 2
∂ T ∂ T ∂ T ∂ T
----------------- --------2- ----------------- … … ----------------------
∂x 2 ∂x 1 ∂x 2 ∂x 2 ∂x 3 ∂x 2 ∂x n – 1
2 2 2 2
– ∆S
LV ∂ T ∂ T ∂ T ∂ T (25)
----------------- ----------------- --------2- … … ----------------------
∂x 3 ∂x 1 ∂x 3 ∂x 2 ∂x 3 ∂x 3 ∂x n – 1
… … … …… …
… … … …… …
2 2 2 2
∂ T ∂ T ∂ T ∂ T
---------------------- ---------------------- ---------------------- … … -------------
-
∂x n – 1 ∂x 1 ∂x n – 1 ∂x 2 ∂x n – 1 ∂x 3 2
∂x n – 1

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 ANALYSIS OF DISTILLATION USING THE MASS-TRANSFER EQUATION 389

 ∂y ∂y ∂y ∂y 1 
 --------1 – 1 --------2 --------3 …… -------------
- 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 g 11 g 12 g 13 … … g 1n – 1   ∂y ∂y ∂y ∂y 2 
   --------2 --------2 – 1 --------2 …… -------------- 
 g 21 g 22 g 23 … … g 2n – 1   ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
   
=  g 31 g 32 g 33 … … g 3n – 1   ∂y ∂y ∂y ∂y 3 
  * --------3 --------3 --------3 – 1 … … --------------  .
 … … … …… …   ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 
 … … … …… …   … … … …… … 
   
 g n – 11 g n – 12 g n – 13 … … g n – 1n – 1   … … … …… … 
 ∂y n – 1 ∂y n – 1 ∂y n – 1 ∂y n – 1 
 ------------- ------------- ------------- … … -------------- – 1 
 ∂x 1 ∂x 2 ∂x 3 ∂x n – 1 

Thus, the matrix on the basis of which characteristic n–1n–1

LV dT *
equation (24) is written can be regarded as a function of
the matrices (gij) and (∂2T/∂xi∂xj). The matrix
– ∆S ---------- =
dt ∑∑g ki ( y i – x i ) ( y k – x k ). (28)
i = 1k = 1
(∂2T/∂xi∂xj) is symmetric, and the matrix (gij) is sym-
In Eq. (28), on the left-hand side is the derivative of
metric and positive definite. Consequently, according to temperature with respect to the parameter t, which char-
a known theorem [7], the sought matrix (∂yi/∂xj) has acterizes the temperature change in distillation, and on
real characteristic roots; i.e., the set of Eqs. (11) has sin- the right-hand side is the quadratic form corresponding
gular points only of the generalized node or generalized to the equilibrium liquid–vapor tie line. According to
saddle type. Then, the set of primary equations (10) the conditions [8] for the thermodynamic stability of
also has singular points only of the generalized node or the liquid phase to continuous changes, the coefficient
generalized saddle type. In this case, if all λi > 0, then matrix gki and all its principal minors are positive defi-
there is an unstable node; if all λi < 0, then there is a sta- nite; i.e.,
ble node; and if some λi are positive and the others are
negative, then there is a generalized saddle.  g 11 g 13 … … g 1n – 1 
g 12
We used expression (23) formally for proving that  
the characteristic roots of the equation of degree n – 1  g 21 g 22 g 23 … … g 2n – 1 
 
are real. Since the singular points that meet conditions  g 31 g 32 g 33 … … g 3n – 1  > 0,
(13) and (14) are of different nature, expression (23)  
cannot be used to draw any far-reaching conclusions at  … … … …… … 
this step.  … … … …… …  (29)
 
Previously [8], the temperature change in equilib-  g n – 11 g n – 12 g n – 13 … … g n – 1n – 1 
rium open evaporation was studied in detail. In this
case, the temperature is thermodynamically equilib-  g 11 g 12 
rium. It is of interest to investigate the temperature dis-   > 0, g 11 > 0.
tribution along the height of a distillation column. For  g 21 g 22 
this purpose, the van der Waals–Storonkin equation is
commonly used [8]. At constant pressure, this equation Consequently, according to the Sylvester criterion
has the form [7], the quadratic form is also positive definite. Since
n–1n–1
the amount of the liquid in distillation decreases (dt <
0), we obtain
∑∑g
LV
– ∆S dT * = ki ( y i – x i )d x k . (26)
i = 1k = 1
dT */dt > 0; (30)
Equilibrium open evaporation is described by the set i.e., in equilibrium open evaporation, the temperature
of equations continuously increases. At the singular point, dT/dt = 0;
i.e., T = const as dt –∞.
d x k /dt = y k – x k , k = 1, 2, 3, …, n – 1, Obviously, according to previous data [9], in real
(27)
dt = d ln l, distillation, the temperature also increases in the course
of the process. Note that the above result was obtained
where l is the residual amount of the liquid phase. for thermodynamically equilibrium temperature. The
Taking the derivative in the direction of distillation mass-transfer equation is used for thermodynamically
and substituting expression (27), we obtain the equation nonequilibrium temperature T. However, if T is

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390 SERAFIMOV, TIMOSHENKO

regarded as a certain smooth function of the tempera- Multiplication of the matrices (gij) and (Bij) with the
ture at the interface between the equilibrium phases, subsequent multiplication of the product by the scalar
then the direction of the temperature change in distilla- quantity A/L yields
tion can be determined. The method proposed is based
on the assumption that the temperatures of the cores of  g 11 g 12 g 13 … … g 1n – 1 
the flows and the interface temperature are interrelated.  
 g 21 g 22 g 23 … … g 2n – 1 
In other words, the interface temperature is a function  
of the flow core temperatures. --- 
A g 31 g 32 g 33 … … g 3n – 1 
In the case under consideration, the van der Waals– L … … … …… … 

Storonkin equation has the form 
 … … … …… … 
B n–1n–1  
dT dx  g n – 11 g n – 12 g n – 13 … … g n – 1n – 1 
– ∆S --------- =
dH ∑∑g ij ( y i – x i ) -------.
dH
(31)
i=1j=1  B 11 B 12 B 13 … … B 1n – 1 
 
The derivatives dT B/dH
and d x /dH are taken in the  B 21 B 22 B 23 … … B 2n – 1 
direction of the distillation path, i.e., are directional  
derivatives. Since the matrix (gij) is symmetric, Eq. (31) ×  B 31 B 32 B 33 … … B 3n – 1  (34)
 
can be represented in the form [10]  … … … …… … 
LV dT
 … … … …… … 
B B
∆S ------- = ( y – x )  
dH  B n – 11 B n – 12 B n – 13 … … B n – 1n – 1 

g 11 g 12 g 13 … … g 1n – 1  C 11 C 12 C 13 … … C 1n – 1 
 
g 21 g 22 g 23 … … g 2n – 1  C 21 C 22 C 23 … … C 2n – 1 
(32)  
× g 31 g 32 g 33 … … g 3n – 1 dx
-------. =  C 31 C 32 C 33 … … C 3n – 1  .
dH  
… … … …… …  … … … …… … 
… … … …… …  … … … …… … 
 
g n – 11 g n – 12 g n – 13 … … g n – 1n – 1  C n – 11 C n – 12 C n – 13 … … C n – 1n – 1 
Since the matrices (gij) and (Bij) are positive definite
In this case, ( y – x ) is a row vector and d x /dH is a and symmetric and A/L > 0, the matrix (Cij) is positive
column vector. Replacing the column vector by its definite. Then, Eq. (28) can be represented in the form
value from Eq. (7), we obtain [10]
dT A B B
∆S ------- = --- ( y – x )
B
dT B B B B B B
dH L – ∆S --------- = y 1 – x 1 , y 2 – x 2 , …, y n – 1 – x n – 1
dH
g 11 g 12 g 13 … … g 1n – 1  C 11 C 12 C 13 … … C 1n – 1 
g 21 g 22 g 23 … … g 2n – 1  
 C 21 C 22 C 23 … … C 2n – 1 
g 31 g 32 g 33 … … g 3n – 1  
× C 33 … … C 3n – 1 
… … … …… … × C 31 C 32
 
 … … … …… … 
… … … …… …  … … … …… … 
g n – 11 g n – 12 g n – 13 … … g n – 1n – 1  
 C n – 11 C n – 12 C n – 13 … … C n – 1n – 1 

B 11 B 12 B 13 … … B 1n – 1
B B
B 21 B 22 B 23 … … B 2n – 1 y1 – x1
B B
× B 31 B 32 B 33 … … B 3n – 1 (33) y2 – x2
… … … …… … ×
B
y3 – x3
B
(35)
… … … …… … …………
B n – 11 B n – 12 B n – 13 … … B n – 1n – 1 …………
B B
B B
× (y – x ) – (y – x) . yn – 1 – xn – 1

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 39 No. 4 2005

 ANALYSIS OF DISTILLATION USING THE MASS-TRANSFER EQUATION 391

the column height are similar to the temperature distri-

B B B B B B
– y 1 – x 1 , y 2 – x 2 , …, y n – 1 – x n – 1 butions along the equilibrium open evaporation path.
B B
Let us now assume that ( y – x ) – ( y – x ) = 0; in this
 C 11 C 12 C 13 … … C 1n – 1  B B
  case, ( y – x ) = ( y – x ) . Then, according to Eq. (30),
 C 21 C 22 C 23 … … C 2n – 1  dTB/dH = 0.
 
× C 31 C 32 C 33 … … C 3n – 1  Thus, at singular points, the temperature is constant.
  In ordinary distillation, in any of the column sections,
 … … … …… … 
 … … … …… …  B B
we have ( y – x ) > ( y – x ) . Hence, taking into
  account that the coefficient matrices of the quadratic
 C n – 11 C n – 12 C n – 13 … … C n – 1n – 1  and bilinear forms are identical and that, in the above
B B
case, ( y – x ) > 0 and ( y – x ) > 0, we have dT B/dH < 0.
y1 – x1 Thus, in ordinary distillation, in each of the sections,
the temperature decreases from the bottoms product to
y2 – x2 the feed tray and from the feed tray to the distillate. In
y3 – x3 reversible distillation, at each point of the column,
× .
………… B B
dT/dH = 0 and ( y – x ) – ( y – x ) = 0; i.e., the distilla-
………… tion path consists of singular points. In this case, the
driving force of the process at each point of the path is
yn – 1 – xn – 1 zero; consequently, unlike the cases considered earlier,
the process does not run—we perform it imaginarily.
Thus, the interface temperature is a function of the dif- Therefore, along the reversible distillation path, the
ference of the quadratic form corresponding to the temperature changes since each singular point has its
equilibrium liquid–vapor tie line and the linear form own temperature. Of interest is reverse distillation at
corresponding to the equilibrium and operating tie
B B
lines. Let the reflux ratio be infinite; then, the operating dT/dH > 0, when ( y – x ) < ( y – x ) [11]. Note that
tie-line vector is zero and Eq. (28) takes the form elements of reverse distillation take place in extractive
B distillation.
dT B B B B B B
– ∆S --------- = y 1 – x 1 , y 2 – x 2 , …, y n – 1 – x n – 1
dH
NOTATION
 C 11 C 12 C 13 … … C 1n – 1  A—linear operator;
  Bij—coefficients of the mass-transfer equation;
 C 21 C 22 C 23 … … C 2n – 1 
  C—transforming matrix;
× C 31 C 32 C 33 … … C 3n – 1  (36) D—diameter of a column;
 
 … … … …… …  E—unit matrix;
 … … … …… …  F—interfacial area;
 
 C n – 11 C n – 12 C n – 13 … … C n – 1n – 1  g—molar Gibbs potential;
H—column height;
B B K—distribution coefficient;
y1 – x1 L—amount of liquid in a column;
B B
y2 – x2 l—length;
B B m—distillation parameter;
× y3 – x3 . mi—amount of the ith component;
………… n—number of components;
………… S—entropy;
B B
yn – 1 – xn – 1 T—temperature, K;
t—time;
The quadratic form is positive definite; therefore,
with an increase in the column height H (dH > 0), both V—amount of vapor in a column;
the interface temperature TB and the temperatures of the X—composition vector of the liquid phase;
contacting phases decrease. Consequently, if the reflux xi—concentration of the ith component in the liquid
ratio is infinite, then the temperature distributions along phase;

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 39 No. 4 2005

392 SERAFIMOV, TIMOSHENKO
Y—composition vector of the vapor phase;
yi—concentration of the ith component in the vapor
phase;
λ—roots of the characteristic equation;
ξ—increment.
SUPERSCRIPTS
B—interface (boundary);
L—liquid phase;
P—product;
V—vapor phase;
0—initial value.
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Vol. 39 No. 4 2005