Theoretical Foundations of Chemical Engineering, Vol. 39, No. 4, 2005, pp. 419–424.

Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 39, No. 4, 2005, pp. 444–450.
Original Russian Text Copyright © 2005 by Chesnokov.

Mass Transfer in Liquids

V. M. Chesnokov
Moscow State University of Applied Biotechnology, ul. Talalikhina 33, Moscow, 109316 Russia
e-mail: vmches@comail.ru
Received July 7, 2004

Abstract—The mass-transfer problem is considered for a dispersed phase consisting of Brownian particles of
any nature in an arbitrary liquid medium. The propagation of Brownian particles through the liquid at some dis-
tance from the solid walls of a channel is described with a high accuracy by a first-order partial differential equa-
tion. This equation is an analogue of the Liouville equation for the evolution of the density of points of a micro-
system in the phase space. Example solutions to the equation derived are given.

The mass transfer problem in liquid flows through
channels and hollows of various shapes is encountered
in many processes of the chemical and food industries
where multiphase liquids move. In the food industry,
these processes are exemplified by milk skimming in
cream separators, milk refinement from the finest solid
particles in refiners, separation of livestock blood
obtained during slaughter into erythrocytes and plasma
in separators, and blending of food (milk, ground meat,
soft cheeses, and the like) with various additives that
consist of the finest solid or liquid particles. In the
chemical industry, examples are flows of dissolved
macromolecules, wood pulps (in paper manufacturing),
latex particles suspended in emulsion dyes, reinforcing
particles in polymer melts, and the like.
Here, we consider the mass-transfer problem as
applied to the dispersion, in a given volume, of some
portion of a liquid medium (hereafter, a liquid) that
contains a weight or volume concentration u0 of a
highly dispersed substance (an additive), while the rest
of the liquid does not contain this substance or contains
it in small amounts. The goal of the dispersion is to
equalize the additive concentration over the entire vol-
ume occupied by the liquid.
Analytical investigations of the transfer of a highly
dispersed additive in processes of the food and chemi-
cal industries frequently employ the convective diffu-
sion equation [1, 2]
∂u/∂t + ( v ∇ )u = D∆u.
The velocity field of the liquid is known, and the diffu-
sion coefficient is set to be constant. Equation (1) may
be written in dimensionless form using the relation-
ships between the dimensional and the dimensionless
variables written in the Cartesian coordinates:
x = l 1 x', y = l 2 y', z = l 3 z', t = t t'
v x = V 1 v 'x , v y = V z v 'y , v z = V 3 v 'z .
V1, V2, and V3 are not independent quantities. Rather,
they are related through the incompressibility equation.
Setting that the dimensionless form of the incom-
pressibility equation is the same as its dimensional
form, we have
V 1 /l 1 = V 2 /l 2 = V 3 /l 3 . (3)
In addition, let characteristic dimensions and, accord-
ingly, characteristic velocities along axes x and y be
identical; i.e., V1 = V2 = V and l1 = l2 = l. In this case,
substituting expressions for dimensional quantities (2)
into Eq. (1) and taking into account relationships (3),
we arrive at the following dimensionless form of
Eq. (1):
Sh∂u/∂t' + ( v'∇' )u = D'∆'u. (4)
Here, Sh = l/VT, ∇' = (∂/∂x') i + (∂/∂y') j + (∂/∂z') k ,
∆' = ∂2/∂x'2 + ∂2/∂y'2 + m2∂2/∂z'2, m = l/l3, and D' = D/Vl.
Equation (1) or (4) is a parabolic second-order par-
tial differential equation. The solution of this equation
should obey the initial and boundary conditions that are
imposed by the physical contents of the problem.
The initial conditions are imposed by the initial con-
centration distribution in the volume in question. The
boundary conditions are formulated at the inlet and out-
let of the channel and at the walls of the channel.
An exact solution of Eq. (1) can be found only for
some very simple particular cases and for selected ini-
tial conditions. As applied to dispersion processes,
(1) however, Eq. (1) can be simplified appreciably in view
of an insignificant diffusion of the additive (Brownian
particles); the diffusion coefficient D is low. This fol-
lows from the definition of the diffusion coefficient D
for Brownian particles [3, 4]: D = kTB (k = 1.38 × 10–23
J/K, B = 1/3πµd).
Calculations show that, for Brownian particles with
diameters of about 10–6 m in a liquid with a viscosity µ
(2) of about 10 Pa s, the diffusion coefficient D at room
temperature is about 10–16 m2/s, which is a negligible

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420 CHESNOKOV

value. For larger particle sizes, the diffusion coefficient Here,

is still smaller. The diffusion coefficient is very small t t
even for water solutions; it amounts to about 10–7 m2/s.
From this, the dimensionless diffusion coefficient D' = I 1 ( x, z, t ) = ∫ v dt,
x I 2 ( x, z, t ) = ∫ v dt.
z (9)
D/Vl is also quite small provided that the product Vl is 0 0
at least two orders of magnitude higher than the diffu- Thus, the solution of Eq. (5) is an arbitrary function of
sion coefficient D. This constraint actually always the arguments on the left-hand sides of Eq. (8); i.e.,
holds if we consider the liquid flow at distances from
the channel walls longer than the Brownian particle u = Φ [ x – I 1 ( x, z, t ), z – I 2 ( x, z, t ) ]. (10)
sizes.
The form of the function on the right-hand side of
Near the walls, D' is not necessarily small; in this Eq. (10) is imposed by the initial concentration distri-
case, the characteristic size must be a value on the order bution u0(x, z). In this case, taking into account relation-
of the Brownian particle size and the characteristic ships (9), we obtain
velocity must be the particle velocity in the near-wall
layer, which can be quite low. It is noteworthy that, for Φ ( x, z, 0 ) = u 0 ( x, z ). (11)
particle sizes far larger than Brownian particle sizes, The first example will be the mass transfer of an
Eq. (1) does not hold; for such particles, their intrinsic additive with the initial concentration u0 distributed at
weight and the liquid drag should be taken into account.
the initial moment of time in the steady Bingham flow
From the above, we can take that the transfer of an along a channel formed by two parallel walls with a
additive by the liquid flow is the major mass-transfer constant pressure difference. The velocity field for such
mechanism with the wall effect ignored. Dispersion a flow was determined in [6].
mainly occur by convective mass transfer. By virtue of For the case at hand, Eq. (6) reads
this, the diffusion coefficient D in Eq. (1) or the dimen-
sionless diffusion coefficient D' in Eq. (4) may be set ∂u/∂t + v ( z )∂u/∂x = 0. (12)
equal to zero (D ≈ 0, D' ≈ 0). Here,
Therefore, we will consider the solution of an equa-
1 dp 2 2
tion that resembles the Liouville equation for the evolu- v ( z ) = ------ ------ [ z – h – 2z 1 ( z – h ) ]
tion of the density of points of a microsystem in the 2µ dx
(13)
phase space [5]. In this way, from Eq. (1) for D ≈ 0, we 1 dp 2 2
have = ------ ------ [ ( z – z 1 ) – z 0 ]
2µ dx
∂u/∂t + ( v ∇ )u = 0. (5) for the shear flow region and
This is a first-order partial differential equation, 1 dp 2
v = – ------ ------ z 0 (14)
which always has a unique analytical solution for a con- 2µ dx
tinuous and single-valued function v (x, y, z, t) and for for the plastic flow region, dp/dx = –∆p/l is the pressure
a chosen initial concentration distribution u0(x, y, z). gradient, ∆p is the pressure difference over a channel
Evidently, the solution of Eq. (5) does not satisfy the portion of length l, and z1 = τ0l/∆p.
boundary conditions for near-wall concentrations.
However, the wall effect is indirectly taken into account Let the concentration propagation be symmetric rel-
through the features of the liquid flow formed by the ative to the median plane z = 0; this should be reflected
walls (this does not refer to the case where the wall in the initial condition. Under the specified conditions,
itself is the source of particles, e.g., where the diffusion the solution of Eq. (12) is the function
dissolution of the wall occurs). u = Φ [ x – v ( z )t ]. (15)
Consider a plane problem of concentration propaga- Here, v(z) is determined from Eq. (13) for the shear
tion. For this problem, Eq. (1) and the relevant charac- flow or is substituted by v from (14) for the plastic flow.
teristic equation are The coordinate x is the Lagrangian coordinate of a point
in the concentration distribution region.
∂u ∂u ∂u
------ + v x ------ + v z ------ = 0, (6) Let the initial concentration distribution u0 be a col-
∂t ∂x ∂z umn function in segment [0, x0] (Fig. 1). The function
Φ[x – v(z)t] (15) should satisfy the initial condition
dt = dx/v x = dz/v z . (7)
t = 0, u ( x, z, 0 ) = u 0 ( x, z )
Integrating Eqs. (7) yields two independent first inte-
grals  u 0 = const, x ∈ [ 0, x 0 ]
= 
x – I 1 ( x, z, t ) = C 1 , z – I 2 ( x, z, t ) = C 2 . (8)  u 0 = 0, x > x 0 .

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

 MASS TRANSFER IN LIQUIDS 421

t=0 Thus, the initial rectangular concentration distribu-

z t = t1 tion x ∈ [0, x0], z ∈ [0, h] will evolve with time to
h t = t2 acquire the patterns shown in Fig. 1. The evolution of
the Lagrangian coordinate x of a point in the concentra-
tion distribution region for z1 ≤ z ≤ h may be demon-
z1
strated by a spatial plot x = x(z, t) (Fig. 2). Figure 2
displays two surfaces: x = x0 + v(z)t (the upper surface)
and x = v(z)t (the lower surface). The space between
these surfaces is the concentration distribution space
0 x u(x, z, t) = u0. Here v(z) is determined from Eq. (13).
x0 x0 x0 For the plastic flow region, the spatial concentration
distribution diagram is the region confined between
Fig. 1. Evolution of the initial rectangular shape of the addi- planes x = vt and x = vt + x0 (here v is determined from
tive distribution region for the Bingham fluid flow between Eq. (14); these planes are normal to coordinate plane
plane-parallel surfaces. x, t) and bound by coordinate plane x, t and plane z = z1.
From Figs. 1 and 2, the concentration region u0
propagates in accordance with the laws governing the
From this, change in the Lagrangian coordinates of points of this
region. From these figures (especially, from Fig. 1), one
can also see that the portion of the concentration distri-
 u 0 = const, x ∈ [ 0, x 0 ]
Φ( x ) =  bution region (the additive region) that falls in the plas-
 u 0 = 0, x > x 0 , tic flow region is fully removed from the channel; the
(16) portion that falls in the shear flow region is extended,
 u 0 = const, x – v ( z )t ∈ [ 0, x 0 ] thins out, and holds to the walls.
Φ [ x – v ( z )t ] =  For the same case, we will find the distribution law
 u 0 = 0, x – v ( z )t > x 0 . for the additive concentration u(x, z, t) in the shear flow

2
z
1
0.08 0.04

0.2

0.4

0.6

0.8

Fig. 2. Change in the Lagrangian coordinates x of points in the concentration distribution region for z1 ≤ z ≤ h.

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

422 CHESNOKOV

(a) (b) (c)

u u
0.8 0.8 u
0.8
0.6 0.6
z 0.6
0.4 0.4 0.08
z z 0.4
0.08 0.2 0.08 0.2 0.04 0.2
0.04 0.04
0 0 0
0.4 0.4 0.4
0.8 x 0.8
x x 0.8

Fig. 3. Variation of the additive concentration u(x, z, t), initially distributed over the entire flow region according to law (17) at t =
(a) 0, (b) 0.5, and (c) 1 s.

region given that at the initial moment it was distributed this case, function (10) in view of Eq. (9) and vz = 0
over the bulk of the liquid according to transforms to

u 0 ( x ) = c 0 exp ( – ax ).
2 2U 0 –nz ωt
(17)
In this case, function (15) should conform to the initial
condition Φ(x) = c0 exp(–ax2). From this,
u ( x, z, t ) = Φ [ x – v ( z )t ]
2
(18)
= c 0 exp [ – a ( x – v ( z )t ) ] .
Figure 3 displays spatial plots of this function for
various moments of time and for c0 = 0.9, a = 10 m–2,
µ = 10 Pa s, h = 0.1 m, and dp/dx = –∆p/l = –104 Pa/m.
One can see from Fig. 3 that the additive concentration
rapidly decreases with time along the entire length of
the channel except for a narrow region near the walls.
Near the walls, the concentration abruptly increases
(the thickness of the near-wall additive region
decreases and the concentration in this region abruptly
increases along the entire length of the channel).
The next example will be the mass transfer in an
unbounded volume of a viscous liquid caused by har-
monic in-plane oscillations of an infinite plane surface.
The determination of the velocity field for this viscous
flow (the problem of the propagation of transverse
oscillations in a viscous liquid) is considered, e.g., in
[7]. This field is defined by the function
v ( z, t ) = U 0 e
– nz
cos ( ωt – nz ). (19)
Here
n = ( 2ω/ν )
1/2
. (20)
The oscillating plane coincides with coordinate
plane Oxy. The oscillations occur along the x axis. In
ωt
u ( x, z, t ) = Φ x – ---------e sin ------ cos  ------ – nz . (21)
ω 2 2 
Let the concentration distribution at the initial
moment correspond to function (17). Then, arbitrary
function on the right-hand side of Eq. (21) should be
equal to function (17) at the initial moment. On this
basis, the concentration propagation during the oscilla-
tions of an unbounded plane is described by the func-
tion
u ( x, z, t ) = c 0 exp
2U 0 –nz ωt ωt 2 (22)
– a x – ---------e sin ------ cos  ------ – nz .
ω 2 2 
Let us draw spatial plots of this function (Fig. 4) for
several moments of time and for c0 = 0.9, a = 10 m–2,
U0 = 10 m/s, ω = 2π s–1, and v = 0.01 m2/s. From the
plots in Fig. 4, the concentration significantly varies
only within a rather narrow region contiguous to the
oscillating surface. From Eq. (22), at t = T' = 1 s, the
concentration distribution pattern will correspond to
the initial distribution at t = 0.
The last example will concern the features of the
evolution of the additive concentration distribution
region in a ring-shaped gap between coaxial cylinders
(Fig. 5). Let the outer cylinder be immobile and the
inner one rotate at a constant angular speed. The gap
between the cylinders is filled with a Bingham fluid.
The velocity field for this case was determined in [6].
Two regions were shown to exist in the ring-shaped
gap: a shear flow region approaches the inner cylinder
r ∈ [R1, R0] and an immobile plastic flow region
approaches the outer cylinder r ∈ [R0, R2] (Fig. 5).

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

 MASS TRANSFER IN LIQUIDS 423

(a) (b) u
u 0.8
0.8

0.4
0.4

–1 –1 0
0 0
1 0
0.05
x
0.05 1
x 0
z
0.10
z

(c) (d)
u u
0.8 0.6
0.4 0.2
–1 0
0 0 0.05
1
0.10 z
x
0.05
0.5
0.10 1
z x

Fig. 4. Variation of the additive concentration u(x, z, t) initially distributed according to law (17) during harmonic oscillations of an
unbounded plane at t = (a) 0, (b) 0.2, (c) 0.4, and (d) 0.6 s.

The mass-transfer equation written in cylindrical y

coordinates (with the z axis coinciding with the rotation
axis of the inner cylinder) is
∂u v ϕ ∂u
------ + ------ ------ = 0. (23)
∂t r ∂ϕ
Assume that, at the initial moment, there was a region ϕ0
R1
with a constant concentration u0 bounded by a portion
of a circular sector with a central angle ϕ0 (Fig. 5). O x
Then, the solution of Eq. (23) satisfying this starting
condition is the function
R2 R0
u ( r, ϕ, t )
 u 0 = const, ϕ – ( v ϕ t/r ) ∈ [ 0, ϕ 0 ] (24)
= 
 u 0 = 0, ϕ – ( v ϕ t/r ) > ϕ 0 .
From function (24), the portion of the sector that falls Fig. 5. Evolution of the initial additive concentration distri-
in the plastic flow region (vϕ = 0) will hold its place and bution region in a ring-shaped gap between two coaxial cyl-
retain its shape, while the portion of the sector in the inders during the rotation of the inner cylinder.

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

424 CHESNOKOV
shear flow region will move through the ring-shaped
gap and acquire the form of a helix wound around the
rotating cylinder.
Figure 5 demonstrates approximate shapes of the
concentration region acquired in a half-rotation (the
darker field) and in a full rotation (the lighter field) of
the inner cylinder.
With each rotation of the inner cylinder, the helical
concentration region u0 will thin out but the winding
density in the shear space r ∈ [R1, R0] will progressively
increase. Thus, the additive concentration in this region
will equalize; i.e., dispersion of the additive in the
Bingham medium will occur.
The approach we exploited in investigating the mass
transfer in liquids can provide a basis for the develop-
ment of dispersion control methods in liquids. In the
above settings, mass transfer is independent of the
properties of the transferred medium (the only require-
ment for the additive is its high dispersity). In this case,
investigation must focus on hydrodynamic processes
generated by dispersion of Newtonian and non-Newto-
nian liquids in various blenders.
NOTATION
B—mobility of Brownian particles, m/(N s);
C1, C2—integration constants;
c0—initial concentration of the dispersed phase
(additive) in the liquid in the chosen section of the
channel (dimensionless);
D—diffusion coefficient of the dispersed phase
(additive) in the liquid, m2/s;
D'—dimensionless diffusion coefficient;
d—diameter of Brownian particles, m;
h—half-width of the channel between two plane-
parallel walls, m;
k—Boltzmann constant, J/K;
l—length of the channel formed by plane-parallel
walls, m;
l1, l2, l3—characteristic dimensions of the liquid flow
in the directions of axes x, y, and z, m;
p—pressure at a point in the liquid, Pa;
R0—radius of the cylindrical boundary between the
shear and the plastic flow regions of the Bingham fluid, m;
R1—radius of the inner (rotating) cylinder, m;
R2—radius of the outer (immobile) cylinder, m;
r—radial cylindrical coordinate, m;
T—absolute temperature, K;
T'—oscillation period of a plane, s;
t—time, s;
t —characteristic time, s;
t'—dimensionless time;
U0—oscillation velocity amplitude of the plane, m/s;
u—concentration of the dispersed phase in the liq-
uid (dimensionless);
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
u0—initial concentration of the dispersed phase
(additive) in the liquid (dimensionless);
V1, V2, V3—characteristic flow velocities in the
directions of axes x, y, and z, m/s;
v —velocity of a point of the liquid, | v |, m/s;
vx, vy, vz—projections of the velocity of a point of
the liquid onto the Cartesian axes, m/s;
x, y, z—Cartesian coordinates of a point of the liquid, m;
x', y', z'—dimensionless Cartesian coordinates of a
point of the liquid;
x0—longitudinal width of the initial additive distri-
bution region in a channel with plane-parallel walls, m;
z0—width of the shear flow region in a channel with
plane-parallel walls, m;
z1—transverse coordinate of boundary points that
demarcate the shear and plastic flow regions in a chan-
nel with plane-parallel walls, m;
∆—Laplace operator in the Cartesian coordinates;
∆'—Laplace operator in the dimensionless Carte-
sian coordinates;
µ—dynamic (plastic) viscosity of the liquid, Pa/s;
ν—kinematic viscosity of the liquid, m2/s;
τ0—critical shear stress of a viscoelastic (Bingham)
liquid, Pa;
ϕ—angular cylindrical coordinate (dimensionless);
ϕ0—central angle of the sector to which the additive
is confined at the initial moment (dimensionless);
ω—cyclic oscillation frequency of the plane, s–1;
∇—nabla operator in the Cartesian coordinates;
∇'—nabla operator in the dimensionless Cartesian
coordinates;
Sh—Strouhal number.
REFERENCES
1. Shul’man, Z.P., Konvektivnyi teplomassoperenos reo-
logicheski slozhnykh zhidkostei (Convective Heat and
Mass Transfer of Rheologically Complex Liquids), Mos-
cow: Energiya, 1975.
2. Semenov, E.V., Karamzin, V.A., and Novikova, G.D.,
Metody raschetov gidromekhanicheskikh protsessov v
pishchevoi promyshlennosti (Methods for Calculating
Hydromechanical Processes in Food Industry), Moscow:
Mosk. Gos. Univ. Pishchev. Proizv., 2002.
3. Zel’dovich, Ya.B. and Myshkis, A.D., Elementy mate-
maticheskoi fiziki (Elements of Mathematical Physics),
Moscow: Nauka, 1973.
4. Klimontovich, Yu.L., Statisticheskaya fizika (Statistical
Physics), Moscow: Nauka, 1982.
5. Goldstein, H., Classical Mechanics, Cambridge, Mass.:
Addison-Wesley, 1950. Translated under the title Klas-
sicheskaya mekhanika, Moscow: Gostekhizdat, 1957.
6. Gnoevoi, A.V., Klimov, D.M., and Chesnokov, V.M.,
Theory of the Flow of Bingham Media, Preprint of Inst.
of Appl. Math., Russ. Acad. Sci., Moscow, 1998, no. 626.
7. Hunt, J.N., Incompressible Fluid Dynamics, New York:
Wiley, 1964. Translated under the title Dinamika neszhi-
maemoi zhidkosti, Moscow: Mir, 1967.
Vol. 39 No. 4 2005