T. W.

Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

Ficks Diffusion Experiments Revisited

T. W. Patzek Department of Civil and Environmental Engineering University of California at Berkeley 591 Evans Hall Berkeley, CA 94720 Patzek@patzek.berkeley.edu

Abstract
In this paper, we revisit Ficks original diffusion experiments and reconstruct the geometry of his inverted funnel. We show that Ficks experimental approach was sound and measurements were accurate despite his own claims to the contrary. Using the standard modern approach, we predict Ficks cylindrical tube measurements with a high degree of accuracy. We calculate that the salt reservoir at the bottom of the inverted funnel must have been about 5 cm in height and the unreported depth of the deepest salt concentration measurement by Fick was yet another 3 cm above the reservoir top. We verify the latter calculation by using Ficks own calculated concentration profiles and show that the modern diffusion theory predicts the inverted funnel measurements almost as well as those in the cylindrical tube. We also append a translation of Ficks discussion of diffusion in liquids in the first edition of his three-volume monograph on Medical Physics published in 1856, one year after his seminal Pogendorffs Annalen paper On Diffusion.

1 Introduction
Ficks classical diffusion equation is so much a part of the scientific folklore that I decided to revisit its original derivation and the underlying experiments in a graduate course taught at Cal. To my surprise, Ficks own experiments turned out to be remarkably accurate and the geometry of his funnel experiments could be adequately reconstructed. While searching for Ficks original publications, a student in the class found on the Web an antique book dealer who had the first edition of Ficks handbook on medical physics,

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

which I quickly purchased. I then asked my neighbor who is German by birth and education to help me in the translation of the relevant sections of the book and she kindly agreed. The book was written by Fick as an account of physics applicable to medicine and it brings interesting insights into Ficks way of thinking about diffusion and osmosis, see Appendix A. The book section on the diffusion in liquids is more personal and somewhat different from the two famous papers published one year earlier (Fick 1855; Fick 1855). This paper is a simple evaluation of Ficks original experiments based on the theory of diffusion presented so well in (Hirschfelder 1954) and (Bird 1960). For an exquisite and brief discussion of the various theories of diffusion developed over the decades by Maxwell, Stefan, Onsager, Chapman and Enskog, Eckart and Meixner, and many others, one may refer to (Truesdell 1962). Ficks theory of diffusion is almost as old as the theories of heat conduction by Fourier (Fourier 1807; Fourier 1822) and viscosity by Newton. While originally it was too primitive to reveal any ideas of principle, Maxwell soon 1 gave it a rational basis in his kinetic theory of gas mixtures and Stefan (Stefan 1871) cleared away the specifically kinetic details to achieve an inclusive phenomenological theory, see (Truesdell 1966) for further details.

2 Background
For convenience, a few pertinent equations describing diffusion will be listed here. A full derivation may be found in, e.g., (Bird 1960). Let vB denote the velocity of constituent 2 B of a fluid mixture with respect to a stationary coordinate system, and define this velocity as by taking a snapshot of instantaneous velocities of the molecules of B. For a mixture of N c constituents, we define the local mass-average velocity as

Maxwell published four important papers on gas theory, the first of which, Illustrations of the Dynamical Theory of Gases, appeared in 1860, and contained Maxwells first theory of diffusion. See (Garber 1986) for details. 2 Constituent denotes a chemical species or a pseudo-component.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

v=

B =1 Nc B =1

Nc

B B

v
B

B =1

Nc

B B

(1)

Thus v is the local rate at which mass passes through a unit area perpendicular to v . Similarly, we may define a local molar average velocity as

v =
*

cB v B
B =1 Nc

Nc

c
B =1

c v
i =1

Nc

B B

(2)

Thus cv * is the local rate at which moles pass through a unit area perpendicular to v * . In flow systems one is often interested in the velocity of a given constituent with respect to v or v * , rather than with respect to a stationary coordinate system. This leads to the following definition of the diffusion velocities:

v( D ) B vB v = diffusion velocity of B relative to v v(*D ) B vB v * = diffusion velocity of B relative to v *

(3)

These velocities measure the motion of constituent B in a fluid relative to the local mean motion of the fluid. Now we can define the different mass and molar fluxes. The mass or molar flux of constituent B is defined as a vector whose magnitude is equal to the mass or moles of constituent B that pass through a unit area per unit time. The motion may be referred to stationary coordinates, to the local mass-average velocity, v , or to the local molaraverage velocity, v * . Thus the mass and molar flux densities relative to stationary coordinates are
j( m ) B = B vB j( n ) B = cB vB

mass,

molar

(4)

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

The mass and molar flux densities relative to the mass-average velocity v are
j( m|v ) B = b v( D ) B j( n|v ) B = cB v( D ) B

mass,

molar

(5)

and the mass and molar flux densities relative to the molar-average velocity v * are

j( m|v* ) B = B v(*D ) B

mass,

j( n|v* ) B = cB v(*D ) B

molar

(6)

Again, one should remember that the definition of a mass flux density is incomplete until both the units and the frame of reference are given.

By analogy with the flux of energy in one-dimensional systems:

q y =

d ( c pT ) (Fourier's law for constant c p ), dy

(7)

one may define the mass flux of constituent 1 in a binary system 12 as

j y1 = D12

d ( 1 ) (Fick's law for constant ) dy

(8)

Note that the total mass density, , of the mixture is uniform, i.e., constant given a constant temperature. Here is the thermal diffusivity, c p is the heat capacity, D12 is the diffusion coefficient, and 1 is the mass density of constituent 1. If the fluid density is not uniform, one defines the mass diffusivity D12 = D21 in a binary system in an analogous fashion:

j( m|v )1 = D12w1

mass,

j( n|v* )1 = cD12x1

molar

(9)

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

Note that Eq. (9) is purely kinematic, i.e., it involves only the dimensions of length and time, and it must be justified from an independent dynamic theory that invokes forces.

It may easily be shown (Bird 1960) that the mass or molar diffusion fluxes in Eq. (9) are also given by

j( m|v )1 = j( m )1 w1 j( m ) B = D12w1
B =1 2

j( n|v* )1 = j( n )1 x1 j( n ) B = cD12x1
B =1

(10)

These two relationships are of special importance for this paper.

3 Ficks cylindrical tube experiment

Ficks experiment (Fick 1855) in a cylindrical tube is shown in Figure 1. At z = L , salt (1) diffuses into fresh water (2), while solid salt in a salt reservoir dissolves, replenishing the diffusing salt, and maintaining the saturated salt concentration at z = 0 . A stream of fresh water sweeps the salt emerging from the tube, keeping the zero salt concentration at z = L . The whole system is at constant (albeit unknown) temperature and pressure. The mixture of salt and water is assumed ideal, i.e., each component activity is equal to its mole fraction.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

Liquid stream of water (2) and salt (1) from tube

z=L

j( n )1 ( z + dz )

dz

j( n )1 ( z )
z=0
Saturated salt solution and solid salt

Figure 1 Ficks diffusion experiment in a cylindrical tube with a salt reservoir at the bottom and flowing fresh water at the top.

When this dissolving salt system attains a steady state, there is a net motion of salt away from the salt reservoir and the water in the tube is stationary. Hence we can use expression (10)2 for the molar flux of salt relative to a stationary frame of reference:
j( n|v* )1 ( z ) = j( n )1 ( z ) x1 j( n )1 ( z ) x1 0 = cD12x1 j( n )1 ( z ) = cD12 dx1 1 x1 dz

(11)

The salt mass balance over an incremental column height, dz states that at steady state

dj( n )1 ( z ) dz

=0

(12)

Substitution of Eq. (11) into Eq. (12) gives

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

d cD12 dx1 =0 dz 1 x1 dz

(13)

We shall assume that D12 is nearly independent of concentration. Indeed the literature data show that D12 1 cm 2 /day for 0.1-1 normal salt solutions. The saturated salt concentration is about 36g NaCl/100g of water or 26g NaCl/100g solution at room temperatures of 10-20 degrees C. From Appendix B, we can calculate the total concentration of water and salt at 20 deg C. This calculation is summarized in Table 1. The percent coefficient of variation is generally less than 1%; therefore, the total concentration can be assumed constant.
Table 1 Total concentration of aqueous salt solutions, see Appendix B. c1-water 99 98 96 94 92 90 88 86 84 82 80 78 76 74 c5-water 55.2915 55.1087 54.7360 54.3790 53.9682 53.5350 53.0787 52.5986 52.0893 51.5643 51.0133 50.4400 49.8391 49.2182 Total c 55.4635 55.4551 55.4386 55.4478 55.4133 55.3667 55.3075 55.2353 55.1446 55.0498 54.9405 54.8208 54.6856 54.5433 C.V. 0.5408 0.5255 0.4956 0.5123 0.4498 0.3653 0.2579 0.1270 -0.0372 -0.2091 -0.4072 -0.6243 -0.8693 -1.1273

The coefficient of variation is defined as C.V. =

c c 100% c

Thus, we can recast the steady state diffusion mass balance of salt, Eq. (13), as

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

d 1 dx1 =0 dz 1 x1 dz x1 (0) = 0.0976, x1 ( L) = 0

(14)

This equation can be easily solved (Bird 1960) and the result is

1 x1 ( L) L 1 x1 = 1 x1 (0) 1 x1 (0)

(15)

The density-mole concentration data from Table 1 and Table 3 are summarized in Table 2. The latter table can be used in conjunction with the excess gravities reported by Fick to convert his gravity versus depth results into the salt mole fraction versus depth. This was implemented as linear interpolation.
Table 2 Salt solution density at 20 deg C and the mole fraction of salt g/cc 1.0053 1.0122 1.0263 1.0413 1.0559 1.0707 1.0857 1.1009 1.1162 1.1319 1.1478 1.1640 1.1804 1.1972 x1 0.0031 0.0062 0.0127 0.0193 0.0261 0.0331 0.0403 0.0477 0.0554 0.0633 0.0715 0.0799 0.0886 0.0976

The results are shown in Figure 2. Agreement between the theory and experiment is excellent.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

Fick's Cylindrical Tube Experiment 25

20

Elevation above salt reservoir, cm

15

10

0.01

0.02

0.03

0.04 0.05 0.06 Mole fraction of salt, x1

0.07

0.08

0.09

0.1

Figure 2 Ficks cylindrical tube excess gravities (+) have been converted to mole fractions of salt versus depth by linear interpolation of data in Table 2. The theoretical curve given by Eq. (15) is the solid line. Note excellent agreement between theory and experiment.
Fick's Cylindrical Tube Experiment 25

20

Elevation above salt reservoir, cm

15

10

0.02

0.04

0.06

0.08 0.1 0.12 Excess gravity, g/cc

0.14

0.16

0.18

0.2

Figure 3 This is how Fick would interpret his cylindrical tube experiment. Note the systematic deviation between the data and the straight line drawn by Fick.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

10

3.1 Remarks Figure 3 shows the profile of excess gravity that would have been calculated by Fick for the cylindrical tube experiment. Note that there is a systematic deviation of the calculation from the experimental data. Fick himself said (Fick 1855): That the degrees of concentration in the lower layers decrease a little more slowly than in the upper ones, is easily explained by the consideration, that the stationary condition had not been perfectly attained. Similar excuses have been used by experimentalists ever since.

4 Ficks conical funnel experiment

The conical funnel data obtained by Fick (Fick 1855) are more difficult to decipher because of the incomplete reporting of the experiment. The most likely experiment geometry may be inferred from Figure 6. In an inverted conical funnel, and in the absence of gravity, the salt concentration contours would be sections of concentric spheres centered on the salt reservoir at the funnel tip. One may argue that in the gravitational field the spherical concentration profiles of salt will be flattened vigorously by buoyancy force 3 . The denser salt solution near the funnel axis will sink, while the less dense solution near the walls will be buoyed. The concentration profiles will then become almost perfectly horizontal. With help of Figure 4, this assertion can be proven as follows. For the salt profile flattening to happen, the ratio of the characteristic time of diffusion, D spreading the salt radially, and convection, C , tumbling the more concentrated salt solution down a hill of height h, must be much more than one:

Fick's Number Fi =

D >> 1 , C

(16)

i.e., buoyancy flattens the constant salt concentration profiles before diffusion propagates them as sections of concentric spheres.

Fick was aware of this phenomenon, see the underlined sentences in Appendix A, Section 24.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

11

Liquid stream of water (2) and salt (1) from cone

2L

Saturated salt solution and solid salt

Figure 4 Geometry of flattening of diffusion front.

The characteristic diffusion time scale can be obtained from the diffusion coefficient, D12 , and the distance, h:

h2 D12

(17)

Assuming no viscous dissipation, the shortest convection time scale can be obtained from the balance of potential and kinetic energy:

gh = vC ,max

1 2 vC ,max 2 2 / gh L

(18)

vC ,max / 2

From elementary geometry, it also follows that

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

12

L = r sin , h = r (1 cos )

(19)

By combining Eqs. (16) - (19), one obtains the following criterion h 2 / D12 r 3/ 2 (1 cos )5 / 2 2 g g = >> 1, g 2sin D12 2 L / 2 g h 2 D sin 12 5 2 g (1 cos )
3/ 2

Fi

(20)

r >> rcrit

The plot of the critical distance from the salt reservoir with the most conservative

g = 0.01g is given in Figure 5. It is obvious that at distances of more than 1 mm above

the salt reservoir, the salt concentration profiles are essentially flat.
10
-2

10 Critical distance, cm 10

-3

-4

10

-5

10

15 20 Funnel half-angle, degrees

25

30

Figure 5 The critical distance from the salt reservoir at the tip of an inverted conical funnel versus the funnel half-angle. At distances much greater than the critical distance, the salt concentration profiles will be essentially flat.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

13

The geometry of Ficks cemented funnel experiments is shown in Figure 6. The junction between the funnel and the salt reservoir is at an unknown elevation z1 at which the salt solution is saturated. Because the deepest reported salt density is far from the density of the saturated salt solution, there is an unknown offset z between z1 and the deepest measurement.

1 ( z = z2 , t ) = 0
j( m )1 ( z + dz )

dz
j( m )1 ( z )
Offset of deepest measurement

A( z + dz )

A( z )

1 ( z = z1 , t ) = sat

Figure 6 Geometry of Ficks funnel experiment.

In the cylindrical-polar coordinate system in Figure 6, the vertical diffusion flux is

j( n|v* )1 ( z ) = j( n )1 ( z ) x1 j( n )1 ( z ) x1 0 = cD12x1 j( n )1 ( z ) = cD12 dx1 1 x1 dz

(21)

The salt mass balance over a cylinder with the base of r 2 ( z ) and height dz , states that at steady state

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

14

d 2 ( r ( z ) j( n )1 ( z ) ) = 0, dz . d 2 ( z j( n )1 ( z ) ) = 0 dz

(22)

Substitution of Eq. (21) into Eq. (22) and assumption of constant cD12 give
d 2 1 dx1 z = 0, dz 1 x1 dz x1 ( z1 ) = 0.0976, x1 ( z2 ) = 0.

(23)

Equation (23) can be readily solved (Bird 1960) and the result is
1/ z1 1/ z

1 x1 ( z ) 1 x1 ( z2 ) 1/ z1 1/ z2 = 1 x1 ( z1 ) 1 x1 ( z1 )
Fick's Conical Funnel Experiment 22

(24)

20

Radial distance from salt reservoir, cm

18

16

14

12

10

0.005

0.01

0.015

0.02 0.025 0.03 Mole fraction of salt, x1

0.035

0.04

0.045

0.05

Figure 7 Ficks conical funnel excess gravities (+) have been converted to mole fractions of salt versus by linear interpolation of data in Table 2. The theoretical curve given by Eq. (24) is the solid line. Note excellent agreement between the theory and Ficks experiment.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

15

To match Ficks results with the theoretical curve (24), one needs to find the lower elevation
z1

and

the

measurement

offset

z.

Then

z2 = z1 + z + (155.4 27.7) /10 cm . The resulting two-parameter optimization problem

has been solved using the Nelder-Mead amoeba algorithm and the solution is:
z1 = 4.985 5 cm,

z = 3.0848 3 cm,
z2 = 20.84 21 cm.

(25)

Without invoking a nonzero offset, Ficks experimental results cannot be matched. Thus, the funnel-salt reservoir junction corresponds to the elevation of 5 cm above the funnel tip and the deepest gravity measurement was preformed 3 cm above that junction. The resulting fit of Ficks funnel data is shown in Figure 7. A little bit of scientific sleuthing has resulted in excellent agreement with Ficks experimental data a handsome reward indeed!

5 Discussion of Ficks equation

On no basis beyond an asserted analogy to Fouriers analysis of the flow of heat, Fick proposed that in a binary mixture the diffusion mass flux density vector is proportional to the gradient of mass density:

j( m|v ) B B v( D ) B = D B , B = 1, 2, D > 0,

(26)

where D is a phenomenological coefficient which may depend upon the densities and the temperature. From Eq. (9) we now know that Eq. (26) holds only if the solution density is constant: j( m|v ) B B v( D ) B = DwB = D( B / ) = D B , B = 1 (salt), B = 2 (water), D > 0, = const

(27)

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

16

Because densities of Ficks salt solutions varied by almost 20%, Fick in fact was mistaken in asserting Eq. (26). His subsequent diffusion equation was derived from a shell mass balance between two horizontal planes dz apart. Based on the mass balance shown in Figure 6, Fick derived the following equation: 1 = j( m )1 ( z, t ) A( z ) j( m )1 ( z + dz , t ) A( z + dz ) t 1 1 = ( A( z) j(m)1 ( z, t ) ) t A( z ) z A( z )dz

(28)

Instead of inserting the salt mass flux density from Eq. (10) (he did not know this equation), Fick asserted Eq. (26), and obtained the following equation:
2 1 1 dA 1 = D 21 + . t A( z ) dz z z

(29)

At steady state, and in the conical funnel whose radius is given as r ( z ) = (tan ) z , Fick simplified equation (29) and solved it: d 2 1 2 d 1 + =0 dz 2 z dz , C2 1 ( z ) = C1 z

(30)

The two constants C1 and C2 are to be so determined, that for a certain z (where the cone is cut off and rests upon the salt reservoir 4 ) 1 is equal to perfect

Fick used y instead of 1 and x instead of z. So his certain distance x becomes z = z1 in our notation.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

17

saturation; and for a certain value of z which corresponds to the base of the funnel 5 , 1 becomes =0. Thus

1 ( z = z2 ) = 0, 1 ( z = z1 ) = sat = 0.196 g/cc.

(31)

If Fick knew about Eq. (10), then instead of Eq. (30) he would have probably written:
d 1 dx1 d 2 1 dx1 A( z ) = z = 0, dz 1 x1 dz dz 1 x1 dz

cD

(32)

and he would have obtained Eq. (23).

Fick's Conical Funnel Experiment 22 Fick's data Fick's calculation TWP's calculation with r1 and r 20

18 Elevation over cone tip, cm

16

14

12

10

0.02

0.04

0.06 Excess gravity, g/cc

0.08

0.1

0.12

Figure 8 Ficks excess gravity data (+) in the conical funnel, his calculated salt density profile (upper curve), and the profile reconstructed here with use of the previously obtained values of z1 and z .

Equal to the outer elevation z2 in our notation.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

18

Because Fick does not report these certain values of z, to obtain the two constants we must use the elevation of the funnel base, and the offset of the deepest measurement calculated above. The two constants in Eq. (30) are then readily calculated as C1 = -0.0616, C 2 = 1.2843 . In the paper, however, Fick lists his calculated salt density profile! The raw data, Ficks calculation and the present calculation are shown in Figure 8. Agreement between the reconstructed solution and Ficks exact calculation is very good indeed. The latter comparison confirms validity of the elevations (or axial distances) listed in Eq. (25). Of course, because of the incorrect form of the governing equation, the solutions shown in Figure 8 are nowhere nearly as good as the solution shown in Figure 7.

6 Conclusions
In general, Ficks equation (29) is not entirely correct. For the concentrated salt solutions, one may not assert that mass density 1 is the appropriate unit of concentration, and that = const . As it stands, after the sign correction, Ficks original equation can only be applied to dilute solutions and to such tubes of variable crosssection whose walls are orthogonal to the surfaces of constant concentration. This does not detract however from Ficks great physical insight, and from his creative and quite accurate 6 experimental technique!

7 Acknowledgements
The financial support for this work was provided by PV Technologies, Inc. I would like to thank Ms. Karin Lloyd-Mumford for her patience and tenacity in translating Ficks difficult prose. I am grateful to Prof. T. N. Narasimhan for sharing his insights into the theories of diffusion and copies of the out-of-print books and papers. I would also like to thank Dr. Mark Jellinek for sketching the gravitational equilibration equations (16)(18). Finally, I would like to thank the Spring 2000, E241 Class for the excellent questions about diffusion.

Fick remained modest about his approach: This method (of weighing an immersed glass bulb to determine density) creates little confidence at first sight, nevertheless preliminary experiments showed it to be sufficiently accurate.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

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8 References
Achmatowicz, O., et al., Ed. (1954). Chemical Calendar, Vol. I (in Polish). Warsaw, PWN. Achmatowicz, O., et al., Ed. (1954). Chemical Calendar, Vol. 2, Part II (in Polish). Warsaw, PWN. Bird, R. B., Stewart, W. E., and Lightfoot, E. N. (1960). Transport Phenomena. New York, John Wiley & Sons, Inc. Fick, A. (1855). On Liquid Diffusion. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science 10 - Fourth Series(July-September): 3039. Fick, A. (1855). Ueber Diffusion (On Diffusion). Annalen der Physik und Chemie von J. C. Pogendorff 94: 59-86. Fourier, J. B. J. (1807). Thorie des mouvements de la chaleur dans le corps solides. French Academy. Fourier, J. B. J. (1822). Theory of Heat (Thorie Analytique del la Chaleur). Paris, F. Didot. Garber, E., Brush, S. G., and Everitt, C. W. F., Ed. (1986). Maxwell on Molecules and Gases. Cambridge, Massachusetts, MIT Press. Hirschfelder, J. O., Curtiss, C. F., and Bird, R. B. (1954). Molecular Theory of Gases and Liquids. New York, John Wiley & Sons, Inc. Stefan, J. (1871). ber das Gleichgewicht und die Bewegung, insbesondere die Diffusion von Gasmengen. Wiener Sitzungsberichte 63: 63-124. Truesdell, C. (1962). Mechanical basis of diffusion. J. Chem. Phys. 37. Truesdell, C. (1966). The Elements of Continuum Mechanics. New York, SpringerVerlag.

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Appendix A Laws of Diffusions

Section 1, Molecular Physics, Chapter 2, in Medical Physics, Parts I and II, by Dr. Adolf Fick, Anatomy Demonstrator in Zrich, Printing Press and Publishing Company of Friedrich Vieweg and Son, Braunschweig, 1856. This translation of Ficks discourse on laws of diffusion in liquid mixtures in direct contact and separated by permeable membranes (Articles 23-39) was performed by Karin Mumford 7 with help from Tad W. Patzek. The figure numbers follow Ficks book. The book was typeset in German gothic, Figure 9, and Ficks painfully long compound sentences did not make the translation any easier.

23

Now all thats left are those molecular

movements that occur on contact with heterogeneous liquids. The essence of this is given the name liquid diffusion. At this point one has to remember the commonly known fact that in contrast to gases in each case of
Figure 9 Cover of Ficks Medical Physics

contact

of

heterogeneous

molecular

aggregates, diffusion currents will occur regardless of hydrostatic equilibrium. Liquid diffusion operates in much more heterogeneous liquids, which on contact are absolutely indifferent against each other, so that in no location flow will prevail as soon as each of the liquids by itself is in a state of hydrostatic equilibrium. Examples of these indifferent characteristics are combinations of fatty oils with water, or mercury with most other liquids. To explain this one cannot assume that the heterogeneous molecules in question reject each other entirely, rather it is sufficient to assume that the attraction between each two heterogeneous molecules is less than that between two homogeneous of one as well as of the other aggregate. If attraction between the heterogeneous molecules is stronger than between a pair of homogeneous
7

6638 Longwalk, Oakland, CA 94611, lmumford@dnai.com.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

21

molecules, a molecular movement happens immediately at the interface, which develops the diffusion current in a manner analogous to the gas process. Therefore, both processes have in common that none of them comes to rest and attains final equilibrium until a uniform equilibrium distribution is produced in the entire space that is occupied by both diffusing substances, meaning until in each part of this space the same condition is obtained for each of the substances.

24

In the currently still inadequate understanding of the structure of molecules, it

would be useless to try to demonstrate this course of events. We have to restrict ourselves to just demonstrating here the known laws from our experience. Until now, from all possible cases, only the ones where the touching liquid solutions of the same solid in the same solvent, which only differed in their concentrations, were subject to a specific test. This is the reason for us to start this case with the governing law, but not without mentioning immediately that other cases with a probability bordering certainty are subject to the same law, if one only interprets or modifies terms of their mathematical description. To avoid unnecessary notation and at the same time deal with fixed concepts, we will simply name the dissolved solid salt and the solvent water. The governing law for the spreading of salt in a water mass is, to say it very briefly, the same as the one that rules the spreading of heat in a heat-conducting body, on which Fourier based his famous mathematical theory of heat, and that was extended by Ohm, as we know with great success, to the flow of electricity in a conductor. Avoiding the shorthand language of mathematical analysis, we must express the same as follows. One has to think of two very thin horizontal solvent layers on top of each other, the lower one contains more salt and its concentration is = k; in the top one we will assume the lesser concentration k . If now the separation of both layers is = d, all these quantities will somehow retain the same values during a certain time interval . The diffusion current, caused by the heterogeneity (concentration difference) between both layers during the imagined time interval, conveys a quantity of salt through the unit area of the dividing surface from the concentrated lower layer to the thinner upper one that is C

k k . Here C is a quantity d

depending on the chemical nature of the relevant salt and the temperature alone, and

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

22

therefore for the present consideration it is considered constant. If Q were the total surface area of both layers, the total amount of salt delivered to the upper would be =

C.Q

k k . At the same time, a water mass will be added from the upper layer to the d

bottom layer, which occupies the same volume so that the volumes of both layers together will not be altered during the process. The special assumption of horizontal layers with constant concentration was necessary to make, because only in this case a hydrostatic equilibrium remains in the liquid mass. It also had to be assumed, as we did just now, that the change of the concentration from one horizontal layer to the other one only takes place if the upper layer is more diluted than the lower layer. Only then, meaning that always when a less dense layer rests upon a heavier one, the hydrostatic equilibrium is stabilized. Hydrostatic equilibrium must also hold in the liquid mass if the diffusion current shall be achieved untroubled by hydrodynamic currents 8 . One can derive through integration of the just formulated law that directly represents the elementary process, how the concentrations in a finite mass will change after elapse of a finite time, if initially they were distributed in a given manner. By comparing the thus achieved results with the observational facts, one can recognize the accuracy or inaccuracy of the assumed governing law.

25

At this point, we shall discuss in more detail a case that can be perceived without

application of the higher analysis. We think namely of a cylinder filled with liquid whose density from bottom to top in elevation

C M m N

above the ground is proportionally reduced in such a way that if one looked at the concentration of a given layer as ordinate of a curve of which the abscise would be the height of the same above the lower end surface, this curve would

Q
Fig. 7.

make a straight line 9 . In this geometry, of

8 9

Text underlined by TWP. Hence, Fick wrote Eq. (30), text underlined by TWP.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

23

course, the given concentration difference of two arbitrarily chosen layers is always proportional to their distance, and the constant proportion of these two quantities can namely be expressed through the proportion of the concentration difference between the lower- and upper-end cross-section to the length of the whole cylinder. Figure 7 further makes this assertion graphically clear. It means namely, AB is the length of the whole cylinder and CB is a line, the ordinates of which denote the concentrations of the layers, so that for example over a distance AP from the lower end cross-section the concentration PM occurs. At Q, in comparison, the concentration QN is located. By looking at the figure, one recognizes immediately that PM-QN or Mm has a constant proportion to the distance of the layers PQ or mN. This distance is arbitrary, and specifically the latter proportion is the same as the proportion of the difference of the concentration A (AC) and B (zero is the assumed value of the liquid concentration at the upper end of the cylinder) to the full length of the cylinder, therefore =

AC . The same ratio has to hold AB

between the infinitely small differences of concentrations in two immediately adjacent layers at the just as infinitely small distance from each other. One may take the same proportion at whichever section of the cylinder one chooses. As to how from this proportion the salt and water exchange between consecutive layers depends on the assumed governing law. This exchange is just as intense in all parts of the cylinder; that means that each layer receives as much salt from the previous one during a given small time interval as it distributes to the following one. Thus, the concentration (in each layer) remains the same. If therefore the concentration AC of the lower-end cross-section and the zero concentration of the upper end during a finite time interval could be kept constant by any means, the concentration in all of the cylinder would remain constant during the entire time. This way a stationary diffusion current is formed, which moves the same amount of salt from bottom to top in each time instant through all cross-sections, which according to our law has to be = C.Q

AC . In due time, the stationary distribution AB

of the concentration in the cylinder evolves, it could have been in the beginning or otherwise, one only needs to keep the concentration of the two end cross-sections constant. This condition can be accomplished easily in an experiment. One keeps the

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

24

lower-end cross-section of the cylinder temporarily filled with any saturated solution in contact with solid salt, the upper one though in contact with (fresh) water. This way the lowest layer always maintains total saturation by constantly being able to dissolve salt, the top one constantly delivers each trace of salt it receives from the bottom through diffusion immediately to the surrounding water and its concentration remains constant = zero.

Temperature during the processes

10

C calculated from the amount of salt delivered

The longest tube 15.8-14.8 15.5-16 16-16.5 17.5-18.5 18-19 20 19-22 20-21 10.79 10.71 11.14 11.44 11.89 9.67

The medium tube 9.7 9.57 9.94

The shortest tube 9.30

11.08

10.50 11.02

11.33 11.12

In fact, experiments took place 11 in part to prove the law, and in part to determine the constant C. So far, though, only experiments with kitchen salt and water are at hand. The experimental setup is as follows. A cylinder filled with a salt solution was cemented into a salt reservoir, and the whole unit was sunk into a huge water container. The same amount of salt, which passed through each cross-section of the cylinder after achievement of the stationary condition, also had to pass through the end cross-section and pass over into the water container. The difference in the density of both end cross-sections was the value of the total saturation as the subtrahend, the concentration on the upper end was =zero. If the cylinder, the length of which was likewise known, would deliver a salt amount m during the given time interval, all remaining quantities will be known in the
10

In centigrades.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

25

equation m = C.Q

AC , so that C can be found from it. The numeric results for the AB

combination of cooking salt and water are compiled in the following table. We remark that each time three tubes of different length were set up at the same time and from the delivered salt in each one C was calculated. The three values of C of course had to be the same and in fact corresponded so perfectly as is to be expected in similar experiments anywhere.

The basis of consideration for these units are: the time, one day (24 hours); the length, 1mm; the area, a circle of 10mm radius; and the concentration, complete saturation. One also recognizes from the above table that the quantity C is defined henceforth as the amount of salt that moves through the unit cross section during the unit time interval in a stationary diffusion current. This current owes its existence to a uniform concentration decrease, which, expanded over the whole length, will reduce the concentration from 1 to zero under controlled temperature increase. The constant C is the only true constant for a given solid combination and temperature, which can be comfortably drawn from experiments in the just described order. It is quantity independent from all other conditions, which one can also fittingly name the rule of the diffusivity of the given solid combination at the given temperature. Graham 12 , in his generally well-known work about the subject with which we are dealing here did not proceed to the analysis of the process. He would derive the measure of the diffusivity directly from different experiments which took place in the following manner: He filled two bottles of the same size and shape up to the neck (which has a radius of 1.25 English inches) with the solutions of the solid to be tested. The neck itself was still filled with clear water and then the whole receptacle was sunk into a water container; he determined the amount of the removed solid, which in the course of a certain time was diffused from the bottle into the water of the container. He was convinced that in this formula he had discovered the measure of diffusivity. Following these advanced discussions one may by no means expect that these numbers must be proportional to our C. In the neck of the
Ueber Diffusion, von Dr. Adolph Fick, Annalen der Physik und Chemie, Herausgegeben zu Berlin von J. C. Pogendorff, Vol. CXIV (Vier und Neunzigster Band), Leipzig, 1855, pages 59-86. 12 Annalen b. Chem. u. Pharm., Vol. 77, p. 56.
11

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26

bottle, a stationary diffusion current obviously does not develop, instead a process that would be very difficult to discuss analytically. Nevertheless, these numbers are very interesting whilst they at least grow simultaneously with the diffusivity, though not proportionally, so that in Grahams experiments a solid described by a larger number is more diffusive than one described by a smaller one. Therefore, I will here now list Grahams numerical results, especially that a comparable overall view of different solids has not been reached yet in a different way.

The amount Solution of 20 parts of dehydrated salt per 100 parts of water Sodium chloride Magnesium sulfate Sodium sulfate Aqueous sulfuric acid Specific gravity of solution 1.1265 1.1265 1.185 1.120 1.120 1.108 1.108 Cane sugar Melted cane sugar Starch sugar Syrup of cane sugar Arabian gum Albumen 1.070 1.066 1.061 1.069 1.060 1.053 diffused during 8 days in Grains 58.5 58.87 27.42 52.1 51.02 68.79 69.86 27.74 26.21 26.94 32.55 13.24 3.08

The temperature for all experiments was kept between the limits of 15.5 and 17 degrees Celsius. The diffusion capability of albumen will be increased by the addition of acetic acid. The adding of egg white does not reduce the diffusivity of the salts, just as it does little to that of urea, which incidentally stands very close to that of sodium chloride.

27

Graham also conducted very remarkable experiments with combinations of

different salt solutions, which he filled into his bottles, retaining all other arrangements, and let them diffuse. It was namely found that with the simultaneous presence of the

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

27

other salt the diffusivity of the less soluble one became reduced. If bi-sulfuric acid potash was filled to the bottle, not only this salt diffused out but also still free sulfuric acid, so that therefore a part of this salt decomposed through the diffusion. Under these circumstances, alum will be partly decomposed just as well, whilst more sulfuric acid potash diffuses into the surrounding water than alum is built up by the simultaneously diffusing sulfuric acid aluminum oxide. If Graham mixed sulfuric acid potash (in a very diluted solution to not develop immediate concentration gradient), potassium chloride or sodium chloride with calcium water and let the mixture diffuse against calcium water, the freed alkali would diffuse and the acid would combine with the calcium, which would precipitate if it was in sulfuric acid.

28

It also still seems to follow from Grahams experiments that weak diffusion

currents can cross through each other without any disturbance; because it was found that the diffusion of a 4-percent solution of sodium carbonate took place in the same manner whether the surrounding liquid was pure water or a 4-percent solution of sodium chloride. In addition, with several other different combinations of two salts, the same behavior was observed.

29

The equilibration of heterogeneous liquids still also takes place, just alike the

gases, if they are separated by a porous partition wall of suitable composition, and with it still occur very strange phenomena, which are known under the names of endosmose 13 and exosmose. Without a doubt (the membrane) is the last reason for the equilibration or the driving forces are here the same as in the simpler case of diffusion without a membrane, only the effect is modified through the physical conditions of the liquid molecules in the membrane. Therefore, above all, the attention has to be directed to these if the reason is to discover the diffusion of liquids through membranes. That means one has mainly to examine the way in which the liquids penetrate into those bodies, which used as a partition wall can cause diffusion. Actually, the idea that a substance penetrates
13

The general term osmose (now osmosis) was introduced in 1854 by a British chemist, Thomas Graham. Here we shall use the modern term endosmosis, which is synonymous with motion through, passage, transmission; permeation; penetration, interpenetration; infiltration; endosmose, exosmose (obs); endosmosis (Chem) (Rogets Thesaurus, Project Gutenberg, http://promo.net/pg/).

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

28

into a space that is occupied by another substance cannot create any problems for us. We assume from the atomic picture that each space occupied by an ever so dense substance still leaves enough empty space to grant room for the atoms of another substance, which will store themselves among the atoms of the first one. The penetration of a liquid into certain solids, known by the name of imbibition, can also be thought of in a considerably different way though. One can, 1) imagine the molecules of the imbibed liquid are among themselves in the uniform molecular interstices of the solid body distributed in the same manner. Were this opinion correct, then one might understandably assume very radical differences between the constitution of imbibable and not imbibable bodies; nevertheless, the same chemical substance (i.e., clay) can now have the one and then the other characteristic depending on the mechanical formation of its small (not smallest) particles. Admittedly, the imbibition of a piece of porous clay may still be different in nature from that in a piece of coagulated protein. The difference shows itself immediately if one changes the expression and says swelling instead of imbibition. From a piece of clay, one cannot say that it swells. 2) It also can be thought that a body capable to imbibe is similar to a network or a spongy tissue that besides the molecular interstices also has other gaps that in mechanical sense stand far apart from the interstices, namely much surpassing them in size. These gaps, one could think then, fill themselves during the swelling with the imbibed liquid; meanwhile, no atom penetrates into the space between the molecules that constitute the solid part of the network. This idea offers the immense formal convenience that, if one takes it as a basis of the explanation of the swelling appearances as well as the one of the diffusion through separating walls, one becomes independent of each molecular hypothesis. In fact, most of the researchers in these fields have more or less explicitly adopted the just discussed second theory. By the way, it is still to consider that these two theories do not exclude each other. In particular, Ludwig tends to connect them when he states 14 : As much as we find ourselves in the dark about the special kind of fusion (of the solid substance and the imbibed liquid particles), we may yet still assert that in most of the swollen substances the absorbed liquids partly are present in larger pores, which are

14

Lehrbuch der Physiologie, Vol. I, p 60.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

29

existing between more or less large piles of molecules, but partly are nestling between the molecules themselves.

30

The appearance of the swelling itself is now essentially that a substance capable

of it absorbs a certain quantity from the surrounding liquid in the course of a more or less long time. When this happens, the process reaches equilibrium, whilst no other liquid molecule penetrates into it, may by the way, as much or as little liquid be in store. Through the comparison of the amount of the solid substance and the maximum absorbed liquid (or in the equilibrium after completion of the process), one obtains the swelling ratio. It (this ratio) obviously depends on the nature of the solid body as well as the liquid, so that the same solid body can absorb different amounts of different liquids, and that different amounts of the same liquid penetrate into different solids. Besides that, the swelling ratio varies also with temperature. No extended quantitative series of experiments are available yet on all these aspects. Particularly important for our purposes is the imbibition of saline solutions. First, it has been shown that as far as the imbibition in the swelling body, thus the swelling ratio, is concerned, regularly less liquid is imbibed from the saline solution than from pure water, and from different solutions of the same salts even less, the more concentrated they are. After Liebig, for example, 100 weight parts of dry ox bladder take in 310 weight parts of pure water, 288 parts of a 9% sodium chloride solution, 235 parts of a 13.5%, and 219 parts of 18% solution. After Cloetta, 15 the swelling ratio (the imbibed weight of liquid divided by the weight of the swelling body) of the ox heart bag is 1.35 for 5.4% and 1.01 for 24.3% saline solution, respectively; it is 1.15 for a solution of 3.5% Glaubers salt 16 , and 0.86 for a 11.7% solution of the same salt. Much more remarkable though is the difference in the concentration of the solution imbibed into the swelling body and that of the surrounding liquid from which it originated. Bruecke, relying on other appearances, with which we will soon become acquainted, has proposed the hypothesis that a substance that can cause diffusion of a certain saline solution and consequently is swelling-capable for the same, would exert a

15 16

Experiments with diffusion through membranes with two salts, 1851. Na2SO4 .10H2O - crystalline hydrated sodium sulfate.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

30

larger attraction towards the molecules of water than towards those of the dissolved salt. If this assumption were correct, in each of the pores in which the imbibed liquid is contained, there would be a less concentrated solution against the walls than in the center, whilst the predominant attraction of the wall molecules against the water simply in the proximity of the same has to draw together more water. Ludwig, based on this thought, and also considering that even in the most central part of the pore in any case no larger concentration could occur than in the surrounding liquid, assumed that the concentration in all of the imbibed liquid should be lower than the one in the surrounding liquid from which the imbibed one is taken. It had to be an average result of the lower concentrations in the wall layers and the higher ones in the center layers, the last of which can at best equal the concentration of the surrounding liquid. One therefore understands in one word as the concentration on the imbibed liquid the figure, which expresses the proportion of the imbibed salt amount to the total imbibed liquid mass, regardless of how water and salt are distributed in the pores of the solid body. Ludwig saw himself not deceived by his theory but confirmed it through compelling experiments. If he namely put an ox bladder in a 7.2% solution of Glaubers salt, it imbibed a liquid that contained only 4.4% salt. Did he put the same substance in a 19% kitchen salt solution, it so imbibed a 16.5% solution in its pores.- Cloetta, who continued this line of experiments, ascertained the ratio of the densities of liquids imbibed in the bodies capable of swelling (animal membrane) and the surrounding ones is for kitchen salt constant, in fact =0.84:1, for Glaubers salt though it depends on the solution density of the surrounding liquid.

Experiments with kitchen salt:

Percent content Percent content of surrounding of solution inside liquid 24.002 24.288 6.005 5.540 5.493 swollen solid 20.022 20.427 4.679 4.545 4.512

Experiment time in hrs 76 78 48 76 76

Temperature in deg Reaumur 10 -14 12 -15 9 -14 9 -15 10 -15

Density ratio of inner and outer liquid 0.83 0.84 0.77 0.82 0.82

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

31

Experiments with Glaubers salt:

11.692 6.500 4.831 4.803

4.623 3.578 2.744 2.755

70 70 48 48

8 -13 10 -16 10 -13 8 -12

0.39 0.55 0.56 0.57

In Cloettas experiments with kitchen salt, the density of the surrounding liquid fluctuated between 24 and 5 percent and always turned out in the same proportion. I will place here several numeric results of Cloettas investigation so that the reader can build his own opinion about the degree of accuracy. If one squeezes out the imbibed liquid, as far as this is possible, one receives according to Ludwigs experiments, not a solution of average concentration of the solution that was contained in the pores, but one receives one that corresponds to the density of the original surrounding liquid. Therefore, if the body swelled by dipping it into a 10 % kitchen salt solution, one also squeezes out a 10% kitchen salt solution although if one uses a different way to determine the kitchen salt content in the liquid contained in the pores it results in less than 10%. This at first sight very surprising appearance has absolutely no illogicality if one only remembers that through squeezing the central liquid, mass can only be removed from those pores in which the concentration agrees with the surrounding solution. Whereas the wall layers with less concentration are held tightly by the force of attraction of the wall molecules, so that they cannot be removed by the mechanical compressive force.

31

If a solution containing two salts next to each other imbibes, the presence of one

will modify the imbibing capacity of the other one noticeably. So in particular Cloetta discovered that a piece of ox pericardium has less capability of imbibing Glaubers salt if at the same time the solution contains kitchen salt; and the more kitchen salt it contains the less it will get Glaubers salt. The following table contains the numerical pieces of evidence according to Cloettas experiments.

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

32
Relation of

Temperature Specific gravity imbibed NaS to Percent content of the outer liquid 10.81 Percent content Duration of in deg of inner liquid (outer = 1) 0.71 NaCl NaCl=100 38

of the inner liquid experiment Reaumur

7.838 NaCl 2.972 Na S

6.629 NaCl 7.708 1.079 Na S

72

10 -13

10.817

7.832 NaCl 6.776 NaCl 7.856 2.985 Na S 1.079 Na S

72

10 -15

0.7

38

10.514 NaCl 9.073 NaCl 15.636 10.904 5.122 Na S 1.841 Na S

10.799

48

11 -14

0.69

48

5.813 NaCl 4.646 NaCl 7.030 4.968 Na S 2.384 Na S

6.275

48

9 -12

0.65

85

9.93

5.312 NaCl 4.618 Na S 5.326 NaCl 4.700 Na S

4.093 NaCl 2.182 Na S

46

10 -13

0.63

86

10.026

6.51

4.295 NaCl 2.215 Na S

48

9 -13

0.64

88

32

Now we will imagine two different liquids, which in direct contact would actually

balance out their differences through diffusion currents, separated from each other through a partition wall that dipped into each of the two would swell, which means that its pores could accommodate each of the two liquids. Then we would have all the conditions under which the phenomenon of the endosmosis appears. It is furthermore tacitly assumed that the pores are so tight that filtration is avoided through the attraction between the membrane and the liquid in connection with the cohesion. In addition, even if both sides of the partition wall are moistened, equilibration of the hydrostatic pressure if at all is only possible over a disproportionately long time interval, so that finally within a pore mixing currents through specific gravity differences cannot be produced. When these conditions are met, the heterogeneous solutions will obviously come in direct contact with each other within the partition wall pores and equilibrating diffusion currents will occur immediately. These, of course, cannot come to a stop until each inhomogeneity of the solutions is balanced and so we then see in fact that even with the inclusion of a

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

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partition wall between the two solutions the process will not end until all differences are balanced out. During the process, though, fundamental modifications will be caused by the existence of the partition wall. The important difference between the free diffusion and the diffusion through partition walls is mainly because in the former the equal volumes of the same substances are exchanged between two consecutive layers without any difficulty, so that two equally strong currents in opposite directions are constantly moving. In the latter, as a rule, both currents are not equally strong so that after some time the volume on one side of the partition wall has become larger and on the other side it has become smaller. A theory of the endosmosis has therefore first to be based on explaining how the modification of the diffusion current can be created by the presence of the partition wall. Bruecke carried out the first experiment in this direction, which is already based on the aforementioned idea of the distribution of removed substances in the pores of a body capable of swelling. By going into that in more detail now, it has to be remarked beforehand, that here again we can only rely on the case where solutions of the same salt of different density balance their differences through diffusion. The case is that different mixtures of originally liquid masses (for example alcohol and water) diffuse in one another. However, without hesitation, one can go back to the case that a salt in solution is to be regarded as a liquid itself; its molecules are undoubtfully just as easy to rearrange as the ones of a certain amount of alcohol distributed in water. It therefore actually will be a shortcut expression when we talk about salt and water. If now, in fact, the material of the partition wall has a stronger force of attraction to the water than to the salt, and as a result of that a wall layer of pure water surrounds a central liquid thread within the pores, which can adopt the density of the surrounding solution, the latter one will cause a diffusion current the same way as in the pores which we have imagined previously (see #25). That will distribute as much salt to one side as water to the other side, whereas salt will never be able to penetrate into the wall layer, which can be brought into motion by the attraction of the salt solutions with which it is in touch on both sides. From the side of the concentrated solution, however, works an obviously stronger attraction than from the other side, as here in the same area more attracting salt molecules are facing it. Through the continuing currents, the dilute layer at the wall therefore will be in the process of moving towards the concentrated solution, by replenishing itself

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

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constantly from the less concentrated one. Thus, to the amount of water, reaching through the central thread the concentrated solution (which is the same as the amount of salt traveling to the other side), an additional amount of water is added to the concentrated solution through the peripheral layer for which no salt equivalent travels to the other side. More water therefore has to travel each time from the more dilute solution to the denser one than salt travels in the opposite direction. The volume of the concentrated solution has to grow through the endosmosis. In fact, the success has been observed regularly. In one case, Bruecke was able to substantiate this theoretical analysis by an unambiguous experiment. Turpentine oil has a substantially stronger attraction to glass than tree oil as it forces out completely the latter from a glass surface; therefore a wall layer of turpentine oil and a central layer of a mixture of both liquids will be found in a glass capillary if both can force their way into it. Bruecke manufactured such a capillary surface, which on one side bordered turpentine oil and on the other side tree oil, and discovered according to the theory that more turpentine oil diffused through the capillary to the tree oil than tree oil in the opposite direction.

33

The idea that Bruecke had can be displayed a little farther so that several conclusions of quantitative nature can be drawn out of this. We think about the pores
a

as being cylindrical, and the rectangular cross-section of the separating wall straight through the axial plane would be aa bb (see Fig. 8). If now the separating wall were surrounded by a totally saturated salt solution, according to the above findings, an

Fig. 8.

also saturated solution would only be found in the proximity of the axis of the inner pore (if the pore were extremely tight, probably

not even there). Towards the wall, the concentration would be reduced so that directly at the wall it would be zero. Of course, one concentration would dominate due to the symmetry in a concentric cylindrical layer. The cross-section of such in the plane of the

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

35

figure should be, e.g., and . The saturated solution beneath the separating wall (thought as being horizontal) would now be replaced with pure water, diffusion would start, and we could observe what must happen in particular in the cylindrical volume with the cross-section and . At its lower end, the concentration is kept at the zero level through constant contact with the water. At its upper end, though, the concentration maintains the highest possible level through the contact with the saturated solution. Immediately the stationary concentration distribution occurs in this space. The concentration will grow in proportion to the height above the lower end area ( ). This distribution of the concentration is indicated in the figure by the hatching. Due to the smallness of this volume, stationary condition occurs almost immediately; thus, we can restrict ourselves to its consideration. The concentration distribution now necessitates a stationary diffusion current that moves just as much salt to the bottom as water to the top. One should even be able to calculate the amounts following the above principles (see 26) if the dimensions of the small volume and the maximum possible concentration in it were known. Now, though, the water passing to the top demands a special consideration as well. If the concentration in the small volume (what yet in general has to be presupposed), on which we now have our eyes, has to be lower by a finite amount than the absolute saturation, then a density jump will occur at and from the possible maximum in the small volume to the absolute saturation above the separation wall. This jump would cause an almost infinitely strong diffusion current on the spot, which means almost infinitely large amounts of salt would be driven into the pores and just as large amounts of water would be expelled. Let us suppose for a moment that this has actually happened. The salt amounts could not penetrate because the highest concentration in this particular area already exists at the upper end; they must somehow slip off sidewise. Larger amounts of water though can be delivered from the bottom than the diffusion current, already thought of as established in the cylindrical volume, delivers. A certain water amount is in a way simultaneously being drawn through. This changes the solution density, whilst the water distributes itself generally in the upper liquid, up to a certain distance noticeable from the upper pore opening. In this way, water creates an upward extending conically widening zone (its two cross-sections are shown in simplification in Figure 8 above and ), in which the concentration grows from bottom to top up to the

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total saturation of the upper solution. Immediately, also here a stationary condition comes into effect and causes a diffusion current of the same strength, which brings just as much water to the top as can be distributed in the same time from the upper end of the imagined volume into the reservoir of saturated solution without altering the concentration. Because obviously the imagined zone would extend itself upwards (and through that the intensity of the diffusion current would be reduced), as soon as more water climbed up in this way, the concentration at the upper end of the zone could still be altered. On the other hand, if less water went up, a jump in the concentration increase would occur at some point, which immediately would cause an infinitely strong diffusion current and this way again absorb the relevant water amount.

34

It is now apparent that through all those cylindrical elementary layers, which are

so close to the pore wall that totally saturated solution can no longer exist within them, more water moves to one side than salt moves to other side. As now in a tighter pore proportionally more parts are lying closer to the wall than in a larger one, considerably more of water will be flowing in a tighter pore than in a wider one. One can hardly hope to strongly substantiate this assertion through experiment, as one will hardly find two separation walls that only distinguish themselves from each other by the width of the pores. In any case, though, the following fact speaks for the just established assertion. One has obviously some reason to assume that in the glassy colloidal membrane the pores are unproportionally tighter than in one produced from animal connective tissue (heart pericardium or bladder), so that all other differences against this one are only insignificantly effective. However, it is shown that in fact with a colloidal separation wall, the quantity of water that diffuses towards the concentrated solution is much larger than with an animal bladder. Whilst with the bladder wall approximately 3 to 6 times as much water moves into the solution as salt into the water, approximately 20 times as much water moves through a colloidal separation wall as salt. In most of my experiments only traces of salt had moved through the colloid, while substantial water quantities made it through in the opposite direction. According to the aforementioned idea, the excess of the water above the salt diffusing in the opposite direction must still grow with the increasing mobility of the particles in the

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

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saturated solution above the membrane. The amount of absorbed water, which could spread itself in the reservoir without alteration of the saturation, will be even larger the easier movable the particles are. To prove this theory, I mixed solid particles with the upper solution, which interfered with the mobility; received a positive result though, while the proportion of the diffusing salt and water amounts was not changed.

35

Let us now imagine that instead of the pure water, a solution of the same salt is

located underneath the membrane. Above it there is a completely saturated solution at a certain density c. Counting from the pore wall a number of cylindrical elementary layers will immediately inactive; namely all those in which no higher concentration than that c is possible. Naturally they fill themselves with a uniformly saturated solution, each one with possibly the most concentrated, and on both their ends the absorbing power will be, proportionally to the difference, between the concentration in the solution contained in it and the respective solutions above and under it. As the upper solution is totally saturated, the difference at the upper end and consequently the absorbency is higher, that is why now only water moves from bottom to top through all these characterized elementary layers. The more central layers in which a larger concentration than c is possible are making way for a bilateral diffusion current which will produce itself in the afore described manner even though in less intensity. As in doing this, to the contrary of the first described case, some elementary layers have become passive (dormant) for the salt movement, the surplus of the continuing water flow has to grow. If c were larger than the possible maximum of concentration in the central liquid thread of the pore, the endosmotic current would become unilateral and now only water would be able to move from the thinner solution to the thicker one. In fact, I found out that 11.05 times as much, in a different experiment even 17.05 times as much, water as salt went through a membrane, if the same separated absolutely saturated kitchen salt solution from 22 % one. Only 5 or 6 times as much water as salt went through if the membrane separated the saturated kitchen salt solution from pure water. (Other pieces of evidence in the following table.)

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38

36

Finally we will imagine that there is again pure water below the membrane, above

it though, instead of a saturated solution, there is a solution of the concentration c. Assume that c is not as large as the highest concentration, which is still possible at the axis of the pore. Starting from here a series of elementary layers will now show at their upper ends the concentration c; namely, all up to the one lying so close to a wall that in it the concentration c is no longer possible. In the indicated concentric elementary layers now a completely free two-way diffusion current will develop which will carry the same amounts of salt and water to opposite sides. At the upper end the density jump no longer develops and therefore no reason exists to absorb more of the water. Parts of the pores, which in the first case delivered more water, do not deliver it in this one. One can therefore expect that if an unsaturated solution is present above the membrane, the water surplus will be smaller and even much smaller the more diluted the solution is. Ludwigs experiments on the diffusion of kitchen salt confirm this forecast. Things stand different though with his experiments performed with Glaubers salt. In the following table, the numerical results of his experiments have been put together.

Experiments with kitchen salt: Concentration of originally surrounding liquids

Ratio of transported salt to transported water Upper, % Lower, % XIX XIX XIX 6 8,25 8 Sat. Sat. 4.920 14.329 0.0 0.0 1 : 4.2 1 : 3.2 1 : 1.4

Membrane name

Temperature deg Raumur

XX XX XX

6 8,25 8

Sat. Sat. 4.920

14.329 0.0 0.0

1 : 4.5 1 : 4.3 1 : 1.4

XXI XXI

8 8

Sat. Sat.

14.34 0.0

1 : 4.5 1 : 3.5

T. W. Patzek, Ficks Diffusion Experiments Revisited, 6/22/06

39

XXI

8,25

4.920

0.0

1 : 1.6

X X

9 9,75

Sat. 2.006

22.6 0.0

1 : 7.0 1 : 3.1

XVI XVI

8 8,75

Sat. 2.006

5.0 0.0

1 : 3.6 1 : 1.1

Experiments with Glaubers salt:

XI XI XI 6,5 8 8,5 Sat. 5.358 1.028 0.0 0.0 0.0 1 : 5.9 1 : 8.2 1 : 24.3

XII XII XII

6,5 8 8,5

Sat. 5.359 1.028

0.0 0.0 0.0

1 : 5.5 1 : 8.0 1 : 23.5

XVI XVI XVI

6 7 8

Sat. 5.084 1.028

0.0 0.0 0.0

1 : 5.8 1 : 10.5 1 : 21.6

37

Jolln believed to be able to prove that the proportion between the salt and water

amounts moved back and forth for one particular salt, one particular membrane, and one particular temperature should be a certain constant, might the concentration of the solution above and below the membrane be what it may. He called this proportion the endosmotic equivalent. Jolln has let the density of the solution vary within too narrow limits, therefore he could easily fail to notice the variations of the endosmotic equivalent observed by Ludwig. From the start, by the way, constancy of the endosmotic equivalent was not actually probable. Apart from the particular picture we have drawn ourselves on the basis of Brueckes hypothesis that we explained previously, it is yet this much without a doubt that in endosmosis one does not have to deal with a fundamental phenomenon in which the actual constants, which rely only on the innermost unchanging nature of the participating substances, come out that uncomplicated. Endosmosis is in any case a

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40

course of events fundamentally modified much more through complicated conditions, through the fundamental strength of the matter, though in last instance mechanically caused like all others. I have noticed that for one particular membrane the equivalent came out differently if I brought saturated kitchen salt solution above and pure water underneath it than if I poured saturated kitchen salt solution underneath and pure water over the membrane. In the last case, the endosmosis equivalent was smaller and more salt went through during the time unit than in the first case. Whether the density plays a role in this case or whether the different sides of the membrane which were facing the water were the actual cause, I do not dare to decide after my not adequately numerous experiments. It is known that already Cima and Matteucci have observed phenomena that favor the last interpretation.

38

Very important (especially for the organic process) are the diffusions that occur

when solution mixtures take the place of simple solutions. Theoretically, one can hardly suspect anything about this object. Contrary to that, though, we have an exact and extensive experimental investigation from Cloetta on the diffusion of mixtures of kitchen salt and Glaubers salt solution. This investigation has resulted in the following laws: First, the diffusion equivalent for each of these two salts is, if it diffuses as the mixture, just as large as if it separately diffuses through the same membrane under the same circumstances (particularly therefore in the same solution density). The deviations from this law in the different experiments are insignificant. If for example n and n were the endosmosic equivalents of the two salts for a certain membrane and concentration, and if it were found in an experiment with the mixture that during any given time the amount a of the first salt, and the amount b of the second salt moved across. Then, for the first one a water amount =na, and for the second one a water amount =nb must have moved across. Therefore the equivalent of the mixture =

na + nb should result from it. Thus this a+b

quotient should express the proportion of the entire water amount moved in this experiment counter currently to the simultaneously moved entire salt amount.

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Furthermore, it produced also certain relations between the diffusion velocity of the different salt in itself and in a mixture. If one talks about diffusion velocity, for the moment one must distinguish between the salt and the water current. The velocity of the first would be measurable in each single case by the salt amount that moved through the surface unit of the membrane during a given time. The velocity of the water current would evidently find its measure in the related water amount moved to the opposite side. During experiments with each of the two salts separately, it has become obvious that the salt current for kitchen salt ceteris paribus has approximately twice the velocity as the one for Glaubers salt. The velocity of the water current is for both salts approximately the same. It now became clear that within the mixture the velocity of the salt current remained unchanged while that of Glaubers salt was reduced. The velocity of the total salt current was therefore larger than the one of a mere kitchen salt current, nevertheless it not quite reached the value of the sum of the velocities of a kitchen salt current and a Glaubers salt current. The water current occurs for both salts in the mixture also with the same velocity; understandably, though, the sum of each of the two speeds in itself cannot combine to the velocity of the total water current because the diffusion velocity of the Glaubers salt is reduced in the mixture. When in this manner the diffusions of the two mixed salts are independent of each other, so of course the salt endowed with a higher velocity (or larger diffusion current against water) will remove itself from the container, leaving behind the other one. From these conclusions can be founded about occurrences in the animal body, about which one should read the quoted treatise by Cloetta.

39

In the chronological evolution of the diffusion phenomena, only very few

sentences can be expressed with certainty. Furthermore it is plausible that the equilibration of chemical differences of two liquid masses must take place in a shorter time frame when these masses are contacting each other directly than if they were separated by a porous separation wall. The wall must due to the necessary tightness of the pores, offer delayed resistance to the currents, which cause the equilibration. It can also be asserted with the same evidence that everything else being equal, the time required for equilibration increases with the thickness of the separation wall (length of the pores). Furthermore, the equilibration time depends on the size of the endosmosic equivalent. In

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42

fact, the equilibration happens even faster, the smaller the value of the endosmosic equivalent is (same velocity of the water current presupposed), in other words the more its value approaches unity. If, for example, the equivalent is very large then this means that the water current dominates the opposite salt current by far and will therefore quickly dilute the thicker solution. But the reversed current will hardly thicken the thinner solution; while this would be the case in a more similar measure if the equivalent would not differ so much from unity, i.e., if the strength of both currents would not differ so much. Furthermore, as illuminated from our consideration about the nature of the phenomena (but, apart from this, also would be concluded from every other theoretical idea) and already determined through older experiments (Vierordt 17 ): The liquid amounts exchanged in the same time frame are larger, everything else set equal, the larger is the chemical difference of the masses separated by the membrane. With application of water on one and salt solution on the other side, the transported mass will grow with the salt amount in the solution. Different salts contained in a solution mixture equilibrate themselves with pure water in almost the same amount of time as if they were taken separately with water. The equilibration period of the already less diffusive salt seems to become larger by mixing it with the other one.

17

In the article Endosmosis in the Dictionary of Physiology (Handwrtenbuch der Physiologie).

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43

Appendix B - Different units for salt concentrations

There are several ways of expressing salt concentrations (Achmatowicz 1954): 1. Number of grams of salt per 100 g of solution, c1 2. Number of grams of salt per 100 g of water, c2 3. Number of grams of salt per 1 liter of solution, mass concentration, c3 4. Number of moles of salt per 1000 moles of water, c4 5. Number of moles of salt per 1 liter of solution, molar concentration, c5 6. Number of moles of salt per 1 kg of water, molality, c6 7. Mole fraction of salt in water, c7 Let denote the specific gravity of solution, and M the molecular weight of salt:

c1 = c2 =

c3 cM 100c2 = = 3 10 100 + c2 10 100c1 100c3 cM = = 6 100 c1 1000 c3 10 1000c2 = c5 M 100 + c2 (33)

c3 = 10c1 = c4 =

180.2c2 M c 10 c1 c5 = 3 = M M 10c2 c6 = M c4 c7 = 1000 + c4

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Table 3 Density and concentrations of aqueous NaCl solutions at 20 deg C

c1 %
1 2 4 6 8 10 12 14 16 18 20 22 24 26

20 4 g/l

0.22 0.24 0.28 0.31 0.34 0.37 0.39 0.42 0.44 0.47 0.49 0.51 0.53 0.55

c3
10.053 20.250 41.072 62.478 84.472 107.070 130.284 154.128 178.592 203.742 229.560 256.080 283.296 311.272

c5
0.1720 0.3464 0.7026 1.0688 1.4451 1.8317 2.2288 2.6367 3.0553 3.4855 3.9272 4.3808 4.8465 5.3251

1005.3 1012.2 1026.3 1041.3 1055.9 1070.7 1085.7 1100.9 1116.2 1131.9 1147.8 1164.0 1180.4 1197.2

The concentration units are explained above. The correction is as follows: if the solution density is determined at T1 deg C, then one adds (T2 T1 ) to this density to obtain the corresponding solution density at T2 . The numeric value of specific gravity of a solution relative to the specific gravity of water at 4 degrees C is identical to the numeric value of the solution density in g/cc. Data source is (Achmatowicz 1954).