J. F. RICHARDSON
AbstractThe ~ffu~~ties of acetone, carbon tetraehloride and water vapours in air have been
determined experimentally using the method first developed by WINKELMANNand values have
been obtained over a range of operating conditions to an accuracy of within f 2 per cent. The
evaporation of twocomponent liquid mixtures, consisting of a volatile and a nonvolatile material
has also been been studied in the same apparatus. It has been shown that, when the nonvo~t~e
liquid is the denser, the liquid remains completely mixed and the evaporation rate can therefore
be simply calculated for rm ideal mixture. When the nonvolatile component is the less dense,
convective mixing is negligible and the mass transfer in the liquid is a process of unsteady state
molecular diffusion.
tetrachloride). The method of investigation which bath. This air stream entered through the horizon
was adopted was to allow the mixture to evaporate tal section B of the evaporation tube and the air
at constant temperature in a vertical tube across leaving the tube was metered. The walls of the
the top of which was passed an air stream in bath were of glass and the level of the liquid in the
which the vapour was carried away. The rate of tube was measured by means of a cathetometer to
evaporation was measured by observing the rate of within 0.002 cm. At the beginning of an experi
fall of the liquid surface. ment the liquid was introduced into the tube and
A series of pre~nary experiments was carried allowed to reach the temperature of the bath
out using the pure volatile liquid, in order to before the passage of air was commenced. Read
examine the reproducibility of results and the ings of liquid level were then obtained as a function
effect of experimental conditions. As a result of of time.
these experiments, values of the diffusivity of three The effect of the operating variables was studied
vapours in airacetone, carbon tetrachloride and using acetone as the liquid. At a given tempera
waterhave been obtained. ture, the two important variables were the rate of
passage of air and the diameter of the tube. The
APPARATUS AND EXPERIXENTAL air rate was varied between 05 and 2.1 cms/sec
METHOD and three tube diameters were used (4, 6 and
The method adopted was based on that origin 8 mm). The lower permissible limit of air rate is
ally used by STEFAN [l] and W~N~EL~ANN [z], set by the necessity of main~ning an approxima
and subsequently modified by a number of workers tely zero concentration of vapour at the mouth of
including LEE and WILKE [3]. The liquid to be the tube, and the upper limit by the production of
evaporated was contained in the vertical limb of excessive turbulence in the upper parts of the
the tube shown in Fig. 1, the upper section A, diffusing vapour. In tubes of too small diameter,
serving merely for the introduction of the liquid. the overall rate of diffusion will be affected by the
velocity profile over the crosssection, and in
excessively large tubes, turbulence is induced too
readily.
N=
c P
!!!=D _..!c%‘In_!i!?
‘dt “h pB~
where h is the distance between the air stream and
Tube diameters the liquid surface at time t, PBS, PB1 are the partial
4,60nd8mm
pressures of air in the air stream and at the surface,
p is the molar density of the liquid, 0, is the
I'm.1. tivaporationtube. diffusivity of the vapour in air, and CDTis the total
molar concentration of gas and vapour in the
diffusion region ; this will be constant and equal
The tube was immersed in a the~ostatieally to the number of moles of gas plus vapour per
controlled bath. Air from a cylinder of compressed unit volume in the tube. In a given experiment,
gas passed through a copper coil immersed in the h and t are the only variables and therefore on
bath and its temperature was raised to that of the integration :
235
J. F. RICHARDSON
h2  ho2
__ = (2) Thus, if r& is plotted against h  h,, a straight
t
where h, is the initial value of h. line should be’obtained. The diffusivity D, can
Now the effective distance, h, over which then be calculated from the slope s ;
molecular diffusion is occurring cannot be estim
ated accurately because of endeffects ; the position i.e. (4)
Dv = 2s C,, ln’P,/P,,
of the liquid surface cannot be defined precisely
because of the curvature of the meniscus, and at and the effective initial distance over which
the upper end of the tube turbulence is induced in diffusion is occuring can be calculated from the
the diffusing vapour. On the other hand, values of intercept on the ordinate axis, A typical curve is
h  h, can be measured very accurately and it is shown in Fig. 2,
therefore convenient to rearrange equation (2) as :
@  ho)(h  ho+
 2ho)_ 2Wm ln pB2 Results
t P pB~ The effect of tube diameter and air flow rate
t was studied using acetone at 30°C. In each case,
@  ho)
Isee h = 20, G, 1,” PB&‘BI the results were corrected to standard atmos
P ho pheric pressure by multiplying by the factor
(3) P/760.
+ Q GT ln PBJPBI
Table 1. l$ cct sf tube diuwzeter and air .flkm rates on apparent &ff&vitl/
It will be seen that the results do not vary by In a number of the experiments in the 6 mm
more than f 2 per cent from the mean value of tube, the intercept on the t/(h  h,) axis was
0*112 cm2/sec, and it is therefore concluded that measured, and the effective position of the top of
neither tube diameter nor air rate has a critical the region of molecular diffusion was determined.
effect for the ranges investigated. The succeeding
experiments were all carried out in the 6 mm tube, TWOCOMPONENT MIXTURESVOLATILE LIQUID
with an air flow of about 1 cm3/sec. The variation LESS DENSE
of diffusivity Dr with temperature B is seen in
The evaporation of a mixture of equal volumes
Fig. 3, and the diffusivities of acetone and carbon
of acetone and dibutyl phthalate in the 6 mm tube
0.14, 1 I was studied at 42°C. Measurements were taken in
the same way as for single component liquids.
Dibutyl phthalate can be considered as entirely
nonvolatile (vapour pressure at 42°C is
2 x 1O4 mm Hg), and on the assumption that the
mixture is ideal, the relation between the partial
pressure at the interface and the concentration of
acetone in the liquid at the interface is given by
Raoult’s Law. As the residue is considerably
denser than the evaporating liquid, it will be
assumed that it mixes completely with the bulk of
the liquid which will therefore be of uniform
I I I I I I I I composition throughout at any given time, so that
Q’s10 20 30 40 50 60 70
the partial pressure of acetone vapour at the inter
Temperature, “C
face, and hence the evaporation rate, can be cal
FIG. 3. Diffusivities of acetone and carbon tetrachloride in
air as function of temperature. culated in terms of the amount of evaporation
which has taken place up to that time. These
tetrachloride vapours in air are given to within various assumptions will be justified if the meas
approximately 2 per cent by the relations : ured and calculated amounts of evaporation
Acetone D, = 0.087 + O00086 8 (5) correspond during the whole course of the experi
Carbon ment. The calculated amount of evaporation is
tetrachloride D, = 0.076 + 0.00032 B (6) obtained as follows.
After time t, the number of moles of the more
GUSH [5] obtained a value of O111 cm2/sec for volatile component which have evaporated
the diffusivity of acetone for temperatures
= (h  h,) pv A. Thus, if n, and n, are the num
between 30 and 50°C. bers of moles of the volatile and nonvolatile
No values for the diffusivities are quoted in the components initially, the mole fraction of the
literature, but approximate values have been
fir  (h  h,) POA
calculated from Gilliland’s equation and compared volatile liquid at time t =
n, + n2  (h  h,) p,A’
below with those calculated from equations (5) The molar concentration of vapour at the surface
and (6) at 42°C the temperature at which the of the liquid is therefore
experiments with 2component mixtures were
carried out. n,  (h  ho)~1, A
Acetone
Carbon
tetrachlwide
C” = cfxl
(n,+n,(hh,)p,A (7)
From equations (5) and (6) O1 23. 0490 cm2/sec where C,, is the corresponding value for the pure
From Gilliland’s equation 0.113 0.081 cm2/sec
volatile liquid at the same temperature.
An isolated measurement for water at 46°C gave Now the rate of diffusion through the gas phase
a value of 0.258 cm2/sec. is strictly given by equation (1). However, the
237
J. F. RICHARDSON
ratio P/P,, was equal to 1.18 at the commence between t and h (in hours and centimetres respect
ment of the experiment, and fell rapidly during the ively) becomes :
initial stages to a value of approximately unity. t = Oq641h2 adoh + 35.6 
Since an algebraic relation between h and t can be
 413 log,, (756  h) (10)
obtained only when the ratio is unity, this sim
plification was introduced, because it was con
sidered that the resulting errors would be less
than those introduced by a graphical solution of
the problem.
Thus, from Fick’s Law,
lit _&Lh&I)
=
dh D,C, IJo0
+
On integration :
f, hr
t = $jE; (he  ho%) ~
Do;:o A (h  h,)  PIG. 4. Experimentaland calculated resultsfor evapor
ation of equivolume mixtures of acetone and dibutyl
phthalate at 42°C.
~A(~~+h,)111jl~~(hh,))(9)
The experiments were carried out at 42°C with In Fig. 4 is shown the ex~~mentaliy deter
mixtures consisting initially of equal volumes of mined relationship between h and t together with
dibutyl phthalate and acetone. Under these that calculated from equation (10). The agree
conditions, the values of the quantities in equation ment is seen to be within 4 per cent over the whole
(9) were as follows : range, with the theoretical curve slightly below
the experimental one. This small difference could
0,764 be attributed to small inaccuracies in experiment
PO= x = 0.0132 g moles/cm3
or to the assumption that P/P,, is equal to unity.
D, = 0,123 cmz/sec = 443 cm2/hr (from equa
tion 5) TWOCOMPONENTMIXTURESVOLATILE LIQUID
n, = 2 x 0.764 = 0.0263 g moles. DENSER
58 When the volatile liquid is denser than the
nonvolatile component, the residue after evapor
n2 = 2 x y7G = 0.00753 g moles. ation is of relatively low density and therefore
shows little tendency to mix with the bulk of the
A = 0.312 cm2
liquid. Under these circumstances, therefore,
h, = 1.15 cm diffusion must take place through the bulk of the
c ~ E y, EC!y, l liquid phase before further evaporation can occur..
00
760 315 22,400 Since the capacity of the vapour phase is very
= 2.32 x 1O5 g moles/cm3. much less than that of the liquid phase, it will be
assumed that in the gas phase the rate of transfer
On substitution and simplification, the relation is proportional to the overall concentration
238
The evaporation of twocomponent liquid mixtures
gradient and that in the liquid phase the transfer is intervals. This procedure was necessary because
an unsteady state diffusional process. The liquid it was not found possible to express C, as a simple
depth was assumed to be effectively infinite. algebraic function of t.
Measurements of the rate of evaporation of a The solution of equation (14) is given in Appen
mixture of equal volumes of carbon tetrachloride dix 2 as:
and dibutyl phthalate in the 6 mm tube at 42”C,
should then enable the liquid phase diffusivity, D,
to be calculated. If the calculated value of D
over the whole duration of the experiment remains
constant the above assumptions concerning the
mechanism of the process would appear to be
justified. (for t > t,) (15)
The rate of diffusion in the gas phase is given
At time t, the molar rate of evaporation per unit
by :
area is given by
dh
P”z=
o,c, (11)
h
dh
= P”Z (16)
where C, is the molar concentration of vapour at
the liquid surface at time t. If the mixture is ideal, Then from equations (13), (15) and (16), at time t,
Raoult’s Law will be applicable and the molar
concentration of the volatile component in the (h WWn,  (h WW,,,
liquid at the surface C, will be proportional to l/q 1
the concentration in the vapour.
(hW’Wo  (hWW, = p fj
i.e. C, = kc,, (12)
+
6 1 ’ dt
(17)
1
t=t, c=c, (h dh/dt),_,  (h dh/dt),+,
t=t, C=C, etc. l/t  t,
239
J.F. RICHARDSON
:&AH
K
ii
0 200 400 600 800 1000 120014001600 1800 2OOO22002400
r,b
FIG. 5. Experimental figures for the evaporation of equivolume
mixture of carbon tetmchloride and dibutyl at 42%
.
tration was starting to change rapidly at the
c!$! 2 (say)
= 2.2
i 1 (1% bottom of the tube and it was no longer justifiable
to consider the liquid depth as infinite. A rough
Ex~rimen~l measurements of a mixture of
calculation has shown that the concentration at
equal volumes of carbon tetrachloride and dibutyl
the bottom of the tube would have changed by
phthalate were made over a period of 4400 hr and
about 20 per cent after 1000 hr. The mean value
values of a were calculated at various times from
of (dh/dt)/a over the period was O113 hr*/cm.
the experimental results. The results are given in
Hence the mean value for the diffusivity for the
Fig. 5 and Table 2,
carbon tetrachloride  dibutyl phthalate system
was given by equation (19) as 0.028 cm2/hr.
Table 2. Calculation of liquid phase diffusivity for
carbon tetrachloride in dibutyl phthalate CONCLUSIONS

The WI~K~L~ANN method has been used with
Time, t dh/dt (I
dh/dt
varying experimental conditions to determine the
W (cm/hr) (cmZ/hr1,5) CT
diffusivity of a vapour in air. It has been con
10 0*0095 0.138 0.069
cluded that the results obtained are substantially
20 o@l70 0.0943 O074 independent of both air rate and tube diameter,
50 0%)060 0.0585 0.103 over the range investigated. Values of diffusivities
100 0.0052 o041 0.127 have been obtained for acetone, carbon tetra
500 0.0022 0.0204 0.108
chloride and water vapours to within an estimated
1000 O0016 o0133 0.120
2606 0.0011 o+m94 0.117 accuracy of & 2 per cent.
2660 0~00085 0.00324 0.103 The evaporation of a mixture of acetone and
3Oocl omo72 0.00768 0.094 dibutyl phthalate has been studied in the same
4mO 0*06652 O30688 0,076 apparatus and it has been shown that the heavy
 residue sinks and completely mixes with the
remaining liquid. The levels of the liquid surface
Over the period from 50 to 2600 hr, the value of calculated on this assumption were found to agree
(dh/dt)/a remained substantially constant. For closely with the experimental values throughout
lower values of time, the gradient dh/dt was the course of the experiment.
changing very rapidly so that accurate measure When a mixture of carbon tetrachloride and
ments were difficult to obtain. After more dihutyl phthalate evaporates, the evaporation rate
prolonged periods than about 2600 hr, the concen falls off very rapidly with time because the residual
240
The evaporation of twocomponent liquid mixtures
and
investi
s
Taking Laplace Transforms of both sides of equation (20),
co
3C

3t
eN dt = D
s
m
2
3”
3Y2
ePt dt
0 0
chemical industries, both under conditions of
natural evaporation and during the combustion :. (_ )=+p=De
Ct 0
C
JY2
of the liquid in bulk.
i.e.
Acknozoledg<mentsThe author is indebted to Professor
D. M. NEVITT for providing facilities for the experimental F = B, e~d~/D + B2 e~d/b/D
work. :. (21)
241
J. F. RICEABDSON
NOTATION
= : aI + $ ePI1 (as  a,) + . . . .
A = crosssectional area of evaporating surface
a, = mean value of c over internal ta_l to t,
B,, B, = integration constants
6 = k&D,
= $ (co j cl) + $ eP*1 (ca  co) +. . . C = molar concentration of volatile liquid at time t,
depth y below surface
Co = uniform constant value of C at t = 0
f 2.
2P
eP’n(c,+,  CrI) I . . . .
CL = molar concentration of volatile liquid at surface
C, = value of C at t = 1,
Sub~itution
e%
:
C,1)
1 C, = molar concentration of vapour at liquid surface
Cvo = molar concentration of vapour at surbce of pure
liquid
C oT = total molar concentration of gas and vapour
e=Cco
D = liquid phase diffusivity
 D,, = vapour phase diffusi~ty
 C& ey’p’D (25) h = distance over which vapour is diffusing at tima t
I ho = initial value of h

_ (C,  Co) ,PdP/D 
k = Henry’s constant CL/CV
and !!? = _ ’
2l/~D N = molar rate of transfer per unit area
a?4
fil = number of moles of volatile component initially
Y~P/D
eWPta(Cn+l  C& e (24) n2 = number of moles of nonvolatile component
I initially
Taking the inverse transform [4] of equiltion (24), P = total pressure
P, = partial pressure of air
dC 1
= B (C1  CO) eY*/*~~  P Bm = logarithmic mean ptlrtial pressure of air
3Y 22/&t P,, = vapour pressure
1
72=7$ 1 P = parameter in Laplace transformation
(fort
5tm)
r: (%+1 C*+) eY’/4D(tU s = slope of curve in single component experiments
n1 22/wD (t  t,J T = absolute temperature
(25) t=time
When t = t,, the corresponding term is zero for all value y = distance below surface
of 8. p = moIar density of single component liquid
Thus, when y = 0, pu = molar density of more volatile component in
liquid form
o = function of h, t, dh/dt as defined by equations
(18) and (19)
(fort > tn) (26) 0 = temperature in degrees centigrade
REFERENCES
STEFAN J. Wien Ber. II 1873 68 385.
WINKELMANN A. Ann. Phys. 1884 22 1, 154 ; 36 1889 93.
LIXE C. Y. and WILKE C. R. Indwtr. Engng. Chm. 1954 46 2881.
MICKLEY H. S., SHERWOODT. K. and &ED C. E. Applied Mathematics in Chedcal h’ngineering p. 284. McGraw
Hill, New York 1957.
GUSH L. L. Trans. Inst. Ckem. Engrs. 1958 26 142.
242