DESUBLIMATION OF TWO-COMPONENT VAPORS ON THE SURFACE OF AN ANNULAR-TUBE COLD TRAP

Hiroaki UEDA and Yoichi TAKASHIMA

The Research Laboratory for Nuclear Reactors,

Tokyo Institute of Technology, Tokyo 152
Numerical analyses were carried out on the desublimation rate of two componentvapors from a gaseous mixture including a noncondensablegas in an annular cold trap, assuming that two vapors formed a compact solid phase and were insoluble in the solid state. It was predicted that there were two different patterns on the distribution of the mass fraction in the solid phase, where one showeda continuous changeand another had a maximum a minimum. or The experimental studies were madeusing benzene and p-xylene as vapors. As the /i-xylene mass fraction in the solid phase increased, the solid phase varied from a compact form to a frosty form, and consequently its apparent density decreased. The experimental results were in very good agreement with the calculated results on the thickness, and also fairly good on the distribution of mass fraction in the solid phase.

Intr o du cti on In our previous paper3\ the desublimation rate and the freezing state on the surface in a cold trap were
observed and theoretically components gas mixture. studied by using a two It was shown there that

would cause interesting

position

phenomena for the desubliresults

mated solid phase. Hence, the state of the growing solid phase was observed and its thickness and comwere measured. The experimental

were compared with the calculated results. 1. Theoretical Consideration 1. 1 A model for numerical analyses Let us consider an annular-tube cold trap in which the temperature of the inner tube is uniform and the outer wall is thermally insulated from the atmosphere. In the annulus, the flow is assumed to be laminar,

ing one component of condensable vapor but also fractionating binary vapors on the cold surface.
mation from a ternary gaseous mixture including one component noncondensable and on the desubli-

the growth rate of the solid phase could be estimated by the numerical analyses and the aspect of the desublimation solid would be significantly dependent on the operating condition such as the temperature of the cold surface, the fraction of noncondensable gas and the feed rate. The cold trap could be applied not only for separat-

and the total pressure keeps constant along the tube.

However, there is very little information on desubli-

The desublimation rates of binary vapors are predominantly controlled by their diffusion in the gas phase.

mated solid phase consisting of binary components.

In the present paper, the numerical analyses were carried out on the desublimation rate through an annular-tube cold trap by applying Toor's method to the diffusion equations. It was assumed that

Twocondensable componentsare assumedto form a compact solid phase with a smooth surface and to be completely insoluble in each other in solid state, because the state of the desublimated solid phase is

strongly dependent on the temperature of the cooling

surface and the composition, and it is very difficult

the solid phase was compact and had a smooth surface and the binary desublimated components were mutu-

ally insoluble. On the other hand, the experimental studies were madeusing two condensable components of benzene and /?-xylene. The vapors are representative organics, and it was expected that the appreciable difference between these saturation vapor pressures
Received May18, 1976. Correspondence concerning this article should be addressed to Y. Takashima. H. Ueda is now with Tokyo Shibaura Electric Co., Ltd., Kawasaki 210.

all cases. Under these assumptions, the numerical analyses for the desublimation rates were performed in two steps;

to make the model which can be generally applied for

(I) The local mass and heat transfer coefficients are evaluated by obtaining distributions of mass fraction and temperature.
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

(II) The thickness and the composition of the growing solid phase are calculated assuming that the local

transfer

coefficients are maintained

constant

inde-

pendent of the time. 1. 2 Basic equations in step (I)

by

If the radial mass flux of a noncondensable gas is assumed to be zero1*, the axial velocity, V, is derived
as
V={\ -o)el-coe2)VJ(l -o)1-w2)
(10)
dojj

Each mass flux of vapors (denoted by 1 and 2) diffusing through a noncondensable gas (by 3) is given

Accordingly, the radial velocity, U, becomes

1-o)1-a)2 ty PeMij dR If the radial velocity on the cold surface, Ue, is known, U can be also obtained by the following equation;
u=
yy
(ll)

^-pgiDijPwj+pgWiV 0=1, 2) (1) 3 where the diffusivity in a multicomponent mixture,

Dij9 is assumed to be constant, although the actual

value of Dij should be dependent on the mass fraction (Appendix 1). The equation of continuity for vapor / is given by, in a dimensionless form
do), . da)i_ 1 /d2Q)j 1 dojj\ V'dZ~+U~dR -1f^ewVd^^+'RdR ) (2)

-* {*>"-&

J2i

VRdR )

(12)
system,

Whenthe distribution of (pi is calculated by solving Eq. (5), the dimensionless mass flux on the cold surface
between Z and Z+AZ in the converted N%ci, are obtained by

where the term of the axial diffusion is neglected, and

the dimensionless velocities, U and V, and the Peclet number, PeMij, are defined by
V=vjvzme, U=vr/vzme, PeMij=2vzme{r2-r^)IDij Z=z/2(r2-r0 R^rlKr.-n), (3)

tfA,

=-TTl^-T^=-5^[5*
{p.Dtl2(rt-rd} UAZ)l)R?

ti

VBdRJ
(13)

where Df corresponds to Pe%i9 that is, Pe%i=2vzme

in

The boundary conditions are

V= V.(R), y=0 V=0, U=0, a)i=<oei o)i=coci da)JdR=0 at at at Z=0 R=Ri R=R2

The dimemensionless mass flux on the cold surface

the original system, n%ei(=nreil2pgD1(r2-r^),

is

(4)

related to Ntci as the following equation;

N&^ Z aitPeyPeiJni.,
When n\ci is obtained, the radial velocity

(14)

The velocity distribution at the entrance to a cooling tube, Ve(R), can be obtained from the solution of the
Navier-Stokes equation in a fully-developed and

on the
(15)

isothermal flow (Appendix 2).

cold surface is given by Ue = ZntdlPe*Mt

-N&^ShMrt-^-PetrfrtU.
where

By using Toor's method for solving

equations

of

multicomponent diffusion2^ Eq. (2) can be converted

8Z~ru3R Pel5\8R2"*"R 3R) K)

to the following equation which is equivalent to a binary diffusion equation ; VW' 4-Tj W* =-L-(^L+ Wl \ (5)

The local Sherwood number, Shi, in the converted system is obtained by

(16)

cP^A^^

VRdRJ^

VRdR

(17)

where the variable, <bu introduced here is given by

(6)
i

By using Shi9 the n\Gi can be calculated by the following equation ;

-ntci where
Aii

and the Peclet number in a converted system, Pe%j9 is derived as 2IPe* M1,2={\IPeM11)+{\IPeM22)

= J] Aij(a)mj3

o)cj)-Pe%io)ei

Uc
-a12a21)

(18)

={Shi

-(Peli/Pe^j)aijajiShj}/(l

Aii= {Shi-(PeyPeiJ)Shd}adi/(l
where Pei1>Pei2 if PeM11>PeM22. (7) The constant
(hj=l,2: i*j)

-- a1ia1d

(19)

and
SR2 lrB2 \ VRdR (20) WiVRdR

<Xij are obtained from the following relations;

ati= {(llPeid-(llPeMii)}PeMtj
au=l (i,j=1,

2:

ij)

(8)

The reverse transform from (pj to on is given by a><=( 2 aiW)/o-) (9) where a^ is a co factor of a^.
VOL 10 NO. 1 1977

by

The energy flux in a ternary mixture is expressed

^ -k^T+

tn^iT-

TJ

(21)

Hence, the energy equation in a dimensionless form

becomes dS.rTd9 dZ+

time. The dimensionless heat flux is rewritten as

dR 1 /d*S 1 PeT\dRi+RdR ( ' da>i\d& dS ni,
-qif=Nu(9mef) (33)

+ ( Z n-w)-w (22) where the thermal conduction in the axial direction and is neglected and the dimensionless groups, 0, PeT
Ttare 6 = (TTc)/(Te - Tc) (23) (24)

is

Using Eq. (30), the local growth rate of solid phase

d5+ _ dt+ r^2i-n+
(34)

where
t += t/{4p.1(rirjtlp9Dt}

(35)

PeT =2pgCpvzme(r2 -r1)/kg } i r 2

ri =| S(Cpi- Cp8)i>iif/
0=1 at Z=0, 0-0 at

2C1,i;fm-(ra-r1)
R=RU d&/dR=0 at R=R2 (25)

The axial variations of the average mass fraction for each, wmi9 and of the dimensionless average tem-

The boundary conditions are

perature, m, become respectively

da)mi
(l -(Dmi-G)m3)

dZ
d8m
(1 -<wmi-(om2)

=-K
-Q)el-Q)e2)

(1

(36)
dZ

From the temperature distribution obtained by solving Eq. (22), the dimensionless energy flux on the cold surface between Z and Z+AZ, q%c, are calculated by
qto=
qrc

=-K
(1 -Q)el-0)e2)

PeT

VPel.

x (em-8f)
where K=2(R1+ d+)/{Rl-(R1+ d+Y}

(37)

{kt{T.pem

T.)l2{rt-rd}
rr^2 ~iz+az

(38)

The local Nusselt number are obtained by

-q%c=Nu6w

mated solid
(27)

The mass fraction at the interface of the desubliis expressed by the following relation,

using Eq. (29). 3

(39)
(40)

where
SB2 6VRdR \ VRdR ICB2 (28)

1. 2 Basic equations in step (II) In order to obtain the time variations of the thickness and composition, the physical properties of the

where

i>;f=c1 exp {i/(j;+i;'/)} B't= TJbt, B't'=(T.-TJIbt

desublimated solid phase have to be given. If the solid phase is composedof heterogeneous mixture of two components, the vapor pressure of component /, pfi9 equals to the vapor pressure in the case of only one component ;
Pfi =P?i (29) For the density and thermal conductivity of such heterogeneous solid, we assume the following relations with those for the solid consisting of a pure substance ;
ps= i/ii()si/pSi) i

and constants, at and bu are inherent in each substance. The sensible and latent heat transfers from the gas
phase balance the thermal conduction through the solid phase. Therefore, the energy balance at the

interface becomes
qh+Z^nhi^u~
where
B=Bi+8+

=Qt
(41)

^=PgD*Ltlk9{TeT0) 2 <pk=ks/kg= %7}ia)u r]i=ksi/kg

(42)

When the interface temperature rises with the increase of the thermal resistance due to accumulation of the desublimated solid phase, the dimensionless

and the ks is obtained by Eq. (31). The temperature distribution in the solid phase is Inserting Eq. (43) into Eq. (41), an equation for the interface temperature can be obtained.
If Fi(6f) can be approximately expressed

mass flux becomes, by using Eqs. (15) and (18),

X o)fi{^
A;

as a

2Aik(a)nk-o)fk)}]l(l

-(ofi

-Q)fj)

(32)

linear equation, li&f+nii (lt, ryii=constant), easily obtained by (Appendix 3)

6f=(~S2V522-451,S3)/251
JOURNAL OF CHEMICAL ENGINEERING

0f can be
(44)
OF JAPAN

where A^ is assumed to be constant regardless of the

With the increase of the interface temperature, nB/j9 often exceeds zero in its calculation procedure. However, the sublimation never take place there. Therefore, n%fj is regarded as being zero whenever ^J/i>0. In such a case, n%fi and <ofj become, respectively, (Appendix 4)
( 2 \ I

-nRfi=

\ Y^Aik{(Dmk-(ofk)

V {l --G)fi)

(45) (46)
analyses is

cofj=(-E2+

V E\-^EXE^\2E2

1. 3 Calculation procedure and results

shown in Fig. 1. Equations

The flow diagram for the numerical

to be satisfied simultaneously. Therefore, trial and error for making these satisfactory are required, where ex is 10"4. The interface temperature is obwhere 4 is 10~4. Equations (36) and (37) are solved

(5), (10) and (12) have

tained by solving Eq. (41) using the Newton's method,

numerically by the Runge-Kutta method.
Weshall define here a reference distance for the

desublimation of ternary gaseous mixture to evaluate a necessary cooling length, as it was made for a binary

gaseous mixture in the previous report3). It is the distance, Zd(=zJ2(ra-rj))9 up to which 90% of the total desublimated volume on the cold surface is

occupied, and Zd can be expressed by the following

equation ; Jo X [0)el(l l -o)cl-O)e2 -O)e2)

Fig. 1 Block diagram of numerical calculation

-G)c2)-O)cl(l

+C{(oe2(l -o>ei)-a)M ->ci)}] (47) The effect of mass fraction at the entrance on the reference distance and the effect of parameter ^ is shown in Fig. 2. The mass fraction at a given point in the solid phase is invariant with time. However, the mass fraction averaged in the radial direction, co8lt&Y9 varies
with the growth of solid phase, and the co8li&Y is
(48)

expressed by

^1,av=2f1+a+o)sl^^/{(^1+^+)2-^}

Fig. 2 Time dependency of Z&

The axial distribution of o)sl^Y is shown in Figs. 3 and 4, where the dotted line represents the mass fraction of component 1 averaged in the whole solid phase on
the cold surface, (o8lt&y, and it is calculated from
= a>,i(l-(Pa)-a>fli(l-Q>e2) Sl'aV O)el-O)cl+O)e2-(Dc2 ,49x

fraction on the cold surface and that at the entrance. The effect of the difference of the saturation relation on &>si,av is shown in Fig. 4. The values ofcosi,&Y in

The effect of the mass fraction at the entrance on

a>8i,av is shown in Fig. 3. Inthe case of(a), the o)sli&y increases near the entrance, and decreases beyond a given distance. Whereas, in the case of (b), the ft>si,av increases continuously. The difference is due

both cases of(a) and (b) are same at t=0, and the part which is relatively rich in component 1 extends faster in the case of(a), where the mass fraction of component 1 increases more significantly with the temperature at
the interface. 2. Experimental

to the capacity of desublimation of each component which is controlled by the relation between the mass
VOL. 10 NO. 1 1977

The flow diagram is shown in Fig. 5. We used a horizontal annular-tube cold trap where the inner

Fig. 3 Distribution

ofa>slta

Fig. 6 Desublimating state

Fig. 7 Desublimating state

sure was measured by D.O.P. manometers and varied 1

Fig. 4 Time variation ofcosl>&Y

The vapors used here were benzene (denoted by 1) and/7-xylene (by 2). Nitrogen gas (by 3) was used as a noncondensable gas. The thickness of the desublimated solid phase was measured from time to time with an accuracy of 0.05 mmby a travelling microscope. After the feed of the
gaseous mixture was stopped, the outer tube was immediately removed, and several fragment of solid phase were scraped in an area of 1 cm2 by a knife. The chips of the solid were melted, and its composition was analyzed by a gas chromatography.

to 10 Torr.

Fig. 5 Flow diagram of experimental apparatus

tube is 1.9cm in diameter and 90cm in length. The glass-made outer tube is 8.0 cm in diameter and is
thermally insulated from the atmosphere. The de-

3. Desublimating State and Apparent Density Photographs of the solid phase, which is formed with a single component, are shown in Fig. 6. The

aspects of the desublimated solid phase tend to change from a compactstate to a frosty one as the temperature
of a cooling surface becomes lower. For /?-xylene,

tails are described in the previous paper3). The inner cooling tube is kept at low temperature with a circulating brine (trichlene) cooled by a refrigerator.
fO

The temperature

on the cold

surface

was

the solid surface at rc=228K is frosty in (a), while the solid surface at rc=244K is compact and smooth
as shown in (b). On the other hand, for benzene,

mostly kept from 221K to 231K. The total pres-

the solid phase at rc=228K is compact and semiJOURNAL OF CHEMICAL ENGINEERING OF JAPAN

transparent.

Photographs of solid phase composed of two components are shown in Fig. 7, at a>i^=0.90 and ^si,av==0.59. When the ratio of^-xylene to benzene

in the solid phase is low, the solid phase is compact and opaque. However, as the ratio of p-xylene increases, the surface of solid phase becomes frosty. The variation of apparent density of the solid phase, pa9 with o)sl)SuY at t=30 min is shown in Fig. 8.

The density of the solid phase composed of benzene only should be 1.02 g/cm3, and the value is maintained
for <wsi,av>0.8. However, pa begins to decrease owing to the growth of frost when a>8i,av becomes

less than 0.8, that is, pa tends to decrease if the feed rate of a benzene at the entrance decreases relatively to that ofp-xylene. The apparent density varies with time as shownin Fig. 9. In an example of(D, the solid phaseiscompact

Fig. 8 Effect of ft>sl>av on apparent density

before t=\0 min, and then frost gradually increases

with time. In each example, pa increases

due to the
with Cal-

vapor diffusion among the frost.

4. Comparison of Experimental Results

culated Results
The comparison of the experimental rasults with the calculated ones can be shown in the thickness and the
composition in the solid phase, if it consists of the
Fig. 9 Time dependence of apparent density

compact solid with a smooth surface. The density,

p8i9 and thermal conductivity,

k8i9 of the pure solid

are needed in its calculation. For benzene at Tc= 230K, the properties are obtained by the method
psl=1.02g/cm3 and &sl=0.00050 cal/cm"sec"K. The solid phase of/>-xylene at about Tc=230K is frosty, and the properties cannot be evaluated. Accordingly, the values of the density and the thermal conductivity at TC=244Kfor the compact solid phase were used as being ^2=0.98 g/cm3 and &s2=0.00045 cal/cm-secK. The calculated results were in very good agreement with the experimental results in the thickness, and also fairly good in the distribution of mass fraction as shown in Fig. 10. The experimental results for a frosty solid phase are shown in Fig. ll, where the thickness and the composition cannot be estimated by numerical analyses owing to the porous structure. The <w,i,av at =60 min near the entrance is significantly lower in comparison with the 6>8l>av at -0, because of the higher resistance of heat transfer.

presented in the previous paper3), and are evaluated as

Fig. 10 Comparison of experimental results with calculated results on d+ and <osl}&Y

Conclusion
It was shownin a previous paper that the desublimation rate of a vapor from binary gaseous mixture
could be estimated by the numerical analyses and

Figure 12 shows the experimental results on <w8i,av in the case of relatively higher total pressure and larger
flow rate of the inert gas. There is no significant change on the characteristics of desublimation between those data and the others.
VOL 10 NO. 1 1977
ll

that the freezing state was significantly

dependent on

the operating condition. Hence, in the present paper

smooth surface and was insolube in each other in the

we considered the desublimation for two component vapors which formed a compact solid phase with a

1 [j /J U~~ (1/M)LPVMt

1\^ ll Mj)+MjJ^,

coj

\Mj
0)i

M3)p

_f

/J

1\

1\

an

/J

l_\(i

2. Velocity distribution

at the entrance, Ve
(A-3) -/.)}]

Fe=^{l -(A2R)2+A3 In (^2U)} =r1/r2, ^=2/[l +a:2-{(1 -A;2)/ln(l A2=2(1 -k), ^3=(l -A:2)/ln(l/A:)

3. Constants in Eq. (44)

Fig. ll Thickness and a>slf&r for frosty solid phase

ft=s

y2i-iv{i i
i

+l;(ji-/Wi)}-(i i
i

-i;iWi)/& i

SBl+d+r Yu ^iiltyu
Y2i =ti{(mi Yu = %i{(l
2

-iPeiilPei^jyu}
- V)yu -mjylj -mi)y2i
2

-liy2i

+{Pe%ilPe%3)ljy2j)

+(PeiJPelJ)mjy2j}

yii

= TikAi1c,

y2i ^ Ti(o)mk-mk)Aik

4. Constants in Eq. (46)

Fig. 12 Experimental results on distribution of <a>si,av
E^ iPeyPeMMuKl E2 = -(PeljlPeii){Aii(a)mi afi) -a)fi) -Ajj(omj +AijQ)mi}l(l -o)fi) +Au

solid state. From those theoretical consideration and experimental studies, the following conclusion

Ez = -Aji(o)mi

-(ofi)

were derived ;
desublimation

1) The numerical analyses were carried out on the

rate of binary vapors in an annular-

Nomencl ature Cpi = heat capacity at constant pressure of a gas

[cal/g -

K]

tube type of cold trap. It was predicted that there

were two different patterns on the distributions of mass fraction in the solid phase depending on the mass fraction at the entrance and the cooling surface. One of them was verified by the experiment using benzene and /7-xylene as vapors. 2) It was observed that the solid phase varied from a compact form to a frosty form with increase ofpxylene mass fraction in the solid. Accordingly, the

Cp = average heat capacity at constant pressure of a gaseous mixture [cal/g "K] Dij = diffusivity in a multicomponent mixture
[cm2/sec]

Df = diffusivity
&ij G Li
Mt Nt

= diffusivity in a binary mixture = flow rate = latent heat

in converted system

[cm2/sec] [mol/hr] [cal/g]

[cm2/sec]

= molecular weight = mass flux in converted system

[g/mol] [g/cm2 - sec]

apparent density of the solid phase decreased as the feed rate of 77-xylene increased relatively. 3) The calculated results were in very good agreement with the experimental results on the thickness, and also fairly good on the distribution of mass fraction. Therefore, the analyses could be applied generally for the insoluble and compact solid phase.
Appendix 1. Relation between Dij and i^y
Du^ -EjjKEnEjj-EtjEji) D^EijKEuEjj-EijEjt) nj=\^\ \ *** / (A~V (A-2)

Nf = dimensionless mass flux in converted system [-] Nu = local Nusselt number [-] rti, rii = mass flux in original system [g/cm2 "sec] rii = dimensionless mass flux in original system [-]

P pi pf

= total pressure [mmHg] = partial pressure of a vapor [mmHg] = saturation vapor pressure of a pure solid [mmHg]

Peitij = Peclet number for mass transfer [-] Pe\ = Peclet number for mass transfer in converted sys tem [-] PeT = Peclet number for heat transfer [-]
q, q = heat flux [cal/cm2 " sec]

q+
R

= dimensionless

= dimensionless radial distance

heat flux

[-]

[-]

12

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OF JAPAN

Shi T t t+ U V v,v Z

= dimensionless inner radius = dimensionless outer radius = distance radial = inner radius = outer radius
= temperature = time = dimensionless time

[-] [-]

<f> <?>

i *

[cm] o) i [cm] ft>si, av [cm]

sl,a

= converted mass fraction [-] = dimensionless parameter defined in Eq. (42) [-]
mass fraction mass fraction of component 1 averaged for radial direction in solid phase average mass fraction of component1 for whole desublimated solid
cold surface entrance to cooling section

= local Sherwood number in converted system [-]

= dimensionless velocity in radial direction = dimensionless velocity in axial direction
= velocity

[K] [sec] [-]

<Subscripts>
f e c

[cm/sec]
[cm]

[-] [-]

zd z
zd

= dimensionless axial distance = dimensionless reference distance

= distance axial

[-] [-]

interface between gas and solid phase gas phase component /, /

solid phase
axial direction vapor 1 or inner radius vapor 2 or outer radius noncondensable gas

Rtr s

average in cross section of an annulus radial direction

= reference distance

[-]

an
Ti c Vi K

= constant for variable conversion [-] = dimensionless parameter defined in Eq. (24) [-] = dimensionless parameter defined in Eq. (35) [-] = dimensionless parameter defined in Eq. (42) [-]
= dimensionless = rjr2 temperature [-] [-]

Z,z 1 2 3

Literature Cited
1) Bassel, W. D. and J. C. Smith: AIChE /., 9, 826 (1963). 2) Toor, H. L.: ibid., 10, 448 (1964). 3) Ueda, H. and Y. Takashima: /. Chem. Eng. Japan, 9, 121
(1976).

= dimensionless number obtained from Eq. (19) [-] = dimensionless parameter defined in Eq. (42) [-]
P Pa d d+

= density

[g/cm3]

= apparent density ofdesublimated solid [g/cm3] = thickness of desublimated solid [cm] = dimensionless thickness of desublimated
solid

(Presented at the 41st Annual Meeting of The Soc. of Chem. Engrs., Japan, at Sendai, April 1976.)

[-]

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10

NO.

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