Applied Energy 29 (1988) 57-71

Effects of Molecular Diffusion of Salt in Salt-Gradient Solar Ponds

L. B. Mullett and P. T. Tsilingiris*

Department of Engineering, University of Reading, PO Box 225, Whiteknights, Berks RG6 2AY (Great Britain)

SUMMARY The effect of molecular diffusion of salt is not only significant for the smoothing process during the pond's establishment, but also for its operation. An analysis is presented to calculate the rate of salt transport within an isothermal liquid column, according to the molecular diffusion process. Salttransport measurements in laboratory pond models provide experimental data in good agreement with the theoretical predictions.

NOMENCLATURE F Rate of transfer of diffusing substance (salt) (kg/m 2 s) A mathematical function which gives a diffusion coefficient as a function of concentration Diffusion coefficient (mE/s) Concentration of the diffusing substance (salt) (kg/m 3) Distance from the surface of the salt stratified column (m) Depth of the salt stratified column (m) Number of the initially stacked, uniform salinity, layers Dimensionless time (= (Tz/L)2Dt) Time (s)

f
D C
x

L
m

T
t

* Now at: Commercial Bank of Greece, 11 Sophocleous Street, Athens, Greece. All correspondence to Dr Tsilingiris at: E. Venizelou 43, 17123 Nea Smirni, Athens, Greece. 57 Applied Energy 0306-2619/88/$03-50 Elsevier Applied Science Publishers Ltd, England, 1988. Printed in Great Britain

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L. B. Mullett, P. T. Tsilingiris

INTRODUCTION One o f the most widely-used methods of salt-gradient establishment, especially for small-scale systems, is that of stacking a number o f equal depth layers of decreasing salinity. After a day or so, depending on the parameters, and mainly as an effect of salt diffusion, a uniform salt gradient is formed. The recently introduced method o f establishing a salt gradient by redistribution, 1'2 which involves the selective injection of fresh water into a saline solution, can be either a continuous process or one also proceeding through a step-wise salinity profile smoothed by diffusion. Results from a numerical treatment of the problem are discussed and compared in this paper with those from previously reported analyses. The treatment is also applied to the calculation of diffusion across sharp salinity steps. It was also possible to compare the analytical predictions with laboratory measurements obtained from NaCl-stratified tanks.

2 ANALYSIS AND COMPARISON WITH EARLIER PUBLISHED WORK The rate of transfer o f the diffusing substance through a unit cross-section is proportional to the concentration gradient normal to the section, i.e.,

F=-D--

8C Ox

The solar pond can be treated adequately as one dimensional, with salt diffusion governed by the diffusion equation

8C 82C 8t -- D 8x 2

(1)

The b o u n d a r y conditions were the obvious ones, that no salt should cross the water boundaries at the top and b o t t o m of the tank, i.e., 8C =0

~x~O
and
0)( x=L = 0

As an initial condition, the salinity distribution along the axis o f the liquid column at time t = O, when diffusion starts, m a y be used.

Molecular diffusion of salt in salt-gradient solar ponds

59

The first analytical treatment o f this problem was given by Mowbray, 3 who derived an analytical solution as the summation C= C1 1 + re(m-- 1)

421
n=l

n- exp{--(nrc/L)2Dt}cot(n~/2m)cos(nrtx/L)

where m is the total n u m b e r of layers, D the constant diffusion coefficient within the isothermal column, which is of total depth L, and n = 1,3,5 ..... oQ. In a previously published study, 4 the above analytical solution was used to derive plots for the smoothing of a staircase salinity profile at various dimensionless times, for the case o f stacking two, three, six, ten and twenty layers o f uniform salinity. The steps get progressively out-of-phase with increasing depth, as can be seen by comparison with the plotted results from Mowbray. 3 Here, the salt transport equation was solved numerically, because the m e t h o d offers greater freedom to readily incorporate various initial conditions and possible variations o f the diffusion coefficient with concentration. The depth o f the liquid column o f 0"30 m was subdivided into 60 increments, each having a particular (i.e. an average) salt concentration, and ihe salt-balance equation was translated into a backward finitedifference scheme. The C r a n k - N i c k o l s o n approximation was selected since it is inherently stable and gives the least accumulated truncation error, as discussed, for example, in References 5 and 6. The computer program for the numerical solution o f eqn (1) has the option to accept data for the function D = t i C ) at a fixed temperature. A literature survey showed that the available data are few and incomplete, somelimes being based on early investigations. Rough estimates from published tables 7 using data from the US Office o f Saline Waters, show that the salt diffusion coefficient is a weak function of concentration, initially decreasing and then increasing with concentration, with a m i n i m u m in the range of very small salt concentrations. The variation does not exceed 7% o f its m e a n value over the whole range o f concentrations. According to International Critical Tables data, 8 the salt diffusion coefficient has a m i n i m u m near 20 kg/m 3 and a variation of not larger than 20% over the whole range o f concentration. Also, a small variation of less than 5.5%, was indicated by a few measurements of Stiles, 9 even though the diffusion coefficient appeared to be a monotonically decreasing function of concentration. It was therefore decided to ignore the variation of the diffusion coefficient and to fix its value as 1.4 x 10 - 9 m 2 / s , corresponding roughly to that at ambient conditions.

60

L. B. Mullett, P. T. Tsilingiris

Moreover, the coefficient is an extremely sensitive function of temperature; even the few degrees deviation from isothermal fluid conditions due to diurnal variations of ambient temperature (usually unavoidable under experimental conditions), results in larger variations than those due to concentration changes. 2.1 Diffusion smoothing across a staircase profile with equal salinity steps The diffusion equation was solved having as initial condition a staircase profile with equal salinity steps. The results from the numerical predictions presented here, are shown in Figs 1, 2, 3 and 4, corresponding to the initial condition of two, three, six and
~'~ 300
z -- 2BO

~z 260

2~

220

200

180

160

1~.0

120

ijr?i
." /: ,., ,,: .. ,;
r / [

I:

100

BO

60

~0

0
0.00
l .... I 1........

/," .." 1. ./I

!i

I'"
0"08 0"10

0'02

0'0 t,

0"06

0.12

0.1/,

0.16 '

0.1B '

o.L2o

0"22 '

0"2~, '

O.'26

0 !28 0-30 DEPTH (m }

Fig. 1.

C o m p u t e d diffusion s m o o t h i n g across the boundary of two fluid layers of uniform salinity.

Molecular diffusion of salt in salt-gradient solar ponds

61

3OO

280

260

' r'"

.............. 7: :

24.O

220 2O0 180 160

140 120

100 80 60 ~)

/ .." ,i/
20

/:ii

0 000

0.02

0'04

006

0"08

0"10

0"12

0.1/,,

0"1(.

0"18

0"20

0"22

0'24

026

0.28, 030 DEPTH(m)

Fig. 2. Computed diffusion smoothing across the boundaries of three fluid layers of

uniform salinity. ten stacked layers o f equal thickness, respectively, and decreasing density in a 0-30m depth pond, for 2, 9, 18, 90 and 180h after filling, corresponding to dimensionless times (~z/L)2Dt, equal to 0"0011, 0-00497, "009 94, 0-0497 and 0-0994. It can be clearly seen from these plots how the smoothing time increases progressively, as the n u m b e r o f similar initially stacked layers is reduced from ten, as in these experiments, to only two. Also, comparing the results

62
300

L. B. Mullett, P. T. Tsilingiris

_g
g

280
:t

260
240

,;j!!

220

200

180

160

140

120

100

60

20

i!;iiiiii:it ,
O. O0 0.02 0.04 0.06 0.08

0. I0

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.26

0.28 0.30 DEPTH {m)

Fig. 3.

Computed diffusion smoothing across the boundaries of six fluid layers of uniform salinity.

with previously performed analyses, there is good agreement in terms o f the corresponding salt-concentration profiles. 2.2 The effect of a larger salinity step on the required time for smoothing The diffusion equation was solved numerically after a slight modification for the initial condition, so as to allow for a large salinity step near the surface and a thicker stagnant layer at the bottom. The results are shown in Fig. 5 for 2, 9, 18, 90 and 180 hours after the instantaneous simultaneous establishment o f the layers. The molecular saltdiffusion coefficient is taken to be 1.4 x 10- 9 mZ/sas previously used, i.e. that corresponding to ambient conditions.

Molecular diffusion of salt in salt-gradient solar ponds

63

% ~o
_ g

300

260 8 2~
220

180

160

. f f f S~:/
1~0

120
/"i" //

,,$:;;:f:;;;';;:"

100

80 60

40 20

--

0.00

002 0.04 0106 o!oe 0110 0'-12 ;.'1~ 0116 o.'la o!20 0'2~ 0'2~ 0'26 o12s 0~0
DEPTH (m)

Fig. 4. Computed diffusion smoothing across the boundaries of ten fluid layers of uniform salinity. 2.3 Salt transport along a linear salinity gradient and diffusion smoothing of sharp salinity steps across the interface between a uniform salinity layer and a gradient zone
Equation (1) was solved for four different initial conditions. The first was a linear salinity profile from the surface to the b o t t o m o f the tank without uniform salinity zones. The second was a linear salinity profile with a b o t t o m zone of uniform salinity and no step at the interface between the gradient and lower convecting zone. The third was also a linear profile, with a sharp salinity step o f 5 0 k g / m 3, and the fourth with a step of 150kg/m 3 at the interface between the zones. The results are shown in Figs 6, 7, 8 and 9, respectively, for 2, 9, 18, 90 and 180 h after the (hypothetical) instantaneous

64

L. B. Mullett, P. T. Tsilingiris
300 280

--

5
~z

260

240

220 20O 180

160

140 120 IO0 /' : ..' .,i"

80
6o

.:'!i //!):

20 0

-"

o.oo o!oz 0'04 0'06 0108 o.'~o 0!~2 o!14 0'.16 o!1~ o.'2o o'zz o-2~ o'-26 0!z8 0.30
DEPTH {m)

Fig. 5. Computed effect of a double layer. establishment The diffusion coefficient in the calculations was fixed at its ambient condition value. In Fig. 8, the computed smoothing o f the net salinity step of 50 kg/m 3 is presented for ambient conditions. Appreciable smoothing can be observed to occur between 18 and 90 h.

3 COMPARISON BETWEEN ANALYTICAL AND EXPERIMENTAL RESULTS AND DISCUSSION For comparison of the behaviour of the system with the theoretical predictions, a series of experiments with a model pond were carried out in the laboratory. Various concentration gradients were set up during the

Molecular diffusion of salt in salt-gradient solar ponds

3OO

65

280

5
260

240

220

200

180

140

120

100

80

o0

40

20

/
i i i i i i i
i

O. O0

0.02

0.04

0.0o

0.00

0.10

0.12

0.14

0.16

0.10

O. 20

0.22

0.24

0.26

0.28 0.30 DEPTH (m)

Fig. 6.

Computed diffusion through a constant salt-gradient.

experiments. The tank in which the pond was housed was 0-42 m in diameter and 0"5 m in height. The gradient zone, of 0.3 m thickness, was set up by stacking ten equal layers of decreasing salinity, falling to zero at the top layer, over a thick zone o f dense brine at the bottom o f the tank. Appropriate quantities of dense brine of maximum salinity were mixed with plain water in a separate mixing tank, to form equal quantities of mixtures of decreasing salinity. Great care was taken not to disturb the layers during filling. The mixture was discharged into the experimental tank using a controlling flow pipe and a specially designed floating horizontal diffuser. The diffuser was balanced such that its thin horizontal slit was always at the water level. The filling process usually took about two hours. The salt concentration was measured by a buoyancy probe in the nearly isothermal

66

L. B. Mullett, P. T. Tsilingiris

3o0
280 z 260
/

2~0 22O

200 180 160 14.0 120

100

80 60

~.0

20
0

i
-

0.06

0.02

0'04

0.06

OOB

0'10

0.12

01&

0"16

018

0"20

0"22 0.2&

0"26

028 0'30 DEPTH (m)

Fig. 7.

Computed diffusion through a salt gradient over a thick layer of uniform salinity.

liquid column. The mechanically-driven probe, described elsewhere, 1 scanned the liquid column with an adjacent moving thermocouple junction, simultaneously producing continuous temperature and salinity scans. The finite size of the salinity probe gave a vertical resolution better than 0-5 cm. A typical pair of salinity/temperature scans in almost isothermal conditions, immediately following stacking, can be seen in Fig. 10(a). The deviation from isothermal conditions was due to the layers near the surface being laid down at slightly higher temperatures. The corresponding pair of salinity and temperature profiles after 13"5 h can be seen in Fig. 10(b). It can be clearly seen that the stepwise salinity profile had been adequately smoothed within about 14h from filling. Taking all the experimental evidence, it can be seen that a virtually uniform gradient is obtained within about 14 h from filling for ten or eleven initially stacked layers of uniform

Molecular diffusion of salt in salt-gradient solar ponds

300 _oz 280
z260
...... ........... .....

67

2t~O

220
2OO 180

160

1~0 120 100

6O 40 2O 0

000 0.'02 0'.04 0!06 o.'oB 0'~10 o'n

0'1~ 0!16 o'.lB 0'~0 0'-22 0'.2~ 0126 o'.zB o'30

OEPTH (m)

Fig. 8. Computed diffusion smoothing through a salt gradient with a sharp salinity step of 50 kg/m 3 over a thick layer of uniform salinity. salinity, irrespective of the m a x i m u m salt concentration at the bottom of the tank. During the course of one of the experiments, a double-size salinity step was stacked near the surface of the tank. It was thus possible to observe the effect of such a step on the smoothing process. Figure 1 l(a) shows the salinity and temperature profiles after 2-5 h from the start of filling. At 15.5 h, as can be seen in Fig. 1 l(b), the large step still persisted, with the rest of the salinity profile being adequately smoothed. At this time the solar simulator was turned on, resulting in the immediate development o f a transient temperature profile with an appreciably increased diffusion rate, due to the increase of the diffusion coefficient with temperature. Nevertheless, the salinity step was still visible for a further 35 h.

68
~ - - 300

L. B. Mullett, P. 7". Tsilingiris

~8o

2[0 24O

220

200 1B0

160 1~0

120
/

./
" .: /"

/7

100 80

60 40

_.........x_ 0.00 002

0.04

006

0.08

0'10

0.12

0.14

0.16

0'18

0'20

0"2~'

0.2 t,,

0"26

0"28 0.30 DEPTH (rn)

Fig. 9.

Computed diffusion smoothing through a salt gradient with a sharp salinity step of 150kg/m 3 over a thick layer of uniform salinity.

In practice, of course, smoothing starts with the laying down of the first layer and will have proceeded for about two hours by the completion of the stack. Profiles from the experimental runs, at the completion of stacking, already show the effect of diffusion in the earliest (i.e. the bottom) layers. The derivation of further details is limited by the finite resolution of the scanning system. According to theoretical predictions, the required smoothing time for the large salinity step should be about 90 h, as compared with the 50 h observed. This is believed to be due to the marked increase of the molecular saltdiffusion coefficient with temperature, after turning on the radiation input at time t = 15-5h. During the course of laboratory experiments, once the initial salt

Molecular diffusion o f salt in salt-gradient solar ponds

69

(b)

0.4

04
S T

0.2

'

100 200 0 CONCEN TRA TION(KG/H 3)

100

200

CONCEN TRA TION (KG/H ~)

Fig. 10. Measured diffusion smoothing across eleven layers of uniform salinity: (a) salinity and temperature profiles immediately after filling and (b) salinity and temperature profiles 14 hours from filling.

(QI

O3 T O2 S C12

0.1

0.1

TEI~.~ALE
' A I I I

%
Ill

20

CONCENTRATION (KG/M 3)

40

~o

2'o

'

CONCENTRATION (KG/f4 )

do

~,o

Fig. l I. Measured diffusion smoothing showing the effect of a double layer: (a) salinity and temperature profiles immediately after filling and (b) salinity and temperature profile after 15'5 hours.

70

L. B. Mullett, P. T. Tsilingiris

distribution had been smoothed, the radiation input was turned on and a transient temperature profile was developed which resulted in the development of a growing convecting layer. The development of a uniform salt concentration across this growing bottom convecting zone, due to the convective stirring, results in a salt concentration step at the interface between the gradient and lower convection zone. Certainly, the case is only qualitatively similar to isothermal diffusion, which was investigated, because heating is necessary for development of the sharp salinity step. Therefore, from the subsequent simulation experiments 11 it was found that, if the radiation input was turned off overnight, by the following morning, not only had the salinity step disappeared, but the convective layer had shrunk and the gradient zone expanded. These observations are in good agreement with those from other recent investigations,~ 2 - ~4 concerning the direction of movement of the interfacial boundary in solar ponds. Thermal convection mixes the salt to a uniform salinity within the growing convecting zone, producing a sharp salinity step at the boundary, tending to make the zone grow. Under conditions of no insolation, salt diffusion smoothes the boundary and tends to make the zone shrink, showing the dominance of salt diffusion over convective mixing. According to laboratory measurements, there is good agreement between predictions based on diffusion only, and the measured times, and the time is tolerably short for laboratory and full-scale ponds. Interfacial mixing, unavoidable during the process of filling and subsequently, due to the kinetic energy imparted to the fluid column, x5 may be responsible for the observed differences which are ,-~20%.

4 CONCLUSIONS Certainly as far as laboratory conditions are concerned, the widespread view that the smoothing of salinity steps to a uniform salinity gradient is far more rapid than is achieved by molecular diffusion seems unfounded. Rather, it seems that, although the existing analysis of molecular diffusion was correct, the theoretical smoothing times were overestimated. The agreement now found between diffusion theory and experiment seems likely to extend to that for actual salt-gradient ponds. Moreover, the numerical methods used have made it possible to extend the calculations to cases which have not yet been investigated. Specifically, diffusion smoothing of salinity steps across the boundary of a layer of uniform salinity, and a linear salinity gradient is important because

Molecular diffusion of salt in salt-gradient solar ponds

71

m o v e m e n t o f the boundary, between the gradient and convective zones in solar ponds, depends u p o n the relative magnitudes of the temperature and salinity gradients across the interface. Smoothing o f salinity steps by diffusion m a y contribute to the preservation of the vital gradient zone.

REFERENCES 1. F. Zangrando, A simple method to establish salt gradient solar ponds. Solar Energy, 25 (1980), pp. 467-70. 2. L. Wittemberg and M. Harris, Construction and start-up performance of the Miamisburg SGSP. Transactions of ASME, Journal of Solar Energy Engineering, 103 (11) (1981), pp. 11-16. 3. D. E. Mowbray, The use of schlieren and shadowgraph techniques in the study of flow patterns in density stratified liquids. Journal of Fluid Mech., 27 (3) (1967), pp. 595-608. 4. N. Chepurniy and S. Savage, Effect of diffusion on concentration profiles in a solar pond. Solar Energy, 17 (1974), pp. 203-5. 5. D. R. Croft and D. G. Lilley, Heat transfer calculations usingfinite-difference equations. Applied Science Publ. Ltd, London, 1977. 6. R. D. Richtmeyer, Difference methods for initial value problems. Interscience Publishers Inc., New York, 1957. 7. D. L. Elwell, T. H. Short and P. C. Badger, Stability criteria for solar (thermalsaline) ponds. Proc. Annual Meeting oflSES/AS, Orlando, Florida, 6-19 June 1977. 8. International Critical Tables, vol. V, p. 67. McGraw Hill Co., New York, First edn, 1929. 9. W. Stiles, Indicator method for the determination of coefficients of diffusion. Proc. Royal Society, 103, series A (1923), pp. 260-75. 10. P. T. Tsilingiris, A method for prediction of instability in doubly diffusive systems--Development and laboratory testing of a prototype scanner for use with Solar Ponds, International Journal of Physical-Chemical Hydrodynamics, in press. 11. P. T. Tsilingiris and L. B. Mullett, unpublished. 12. C. E. Nielsen, Conditions for absolute stability of salt-gradient solar ponds. International Conference ISES, New Delhi, Jan. 1978, pp. 1176-1180. 13. C. E. Nielsen, Equilibrium thickness of the stable gradient zone in solar ponds. Proc. Annual Meeting ISES/American Section, Denver, Colorado, 1978, pp. 932-35. 14. C. E. Nielsen, Practical zone boundary control in solar ponds. Proc. of International Congress of lSES, Perth, Australia, 1983, pp. 780~. 15. H. Tabor and Z. Weinberger, Non-convecting solar ponds. In Solar Energy Handbook (Ed. F. Kreith), McGraw-Hill, New York, 1978, Ch. 10.