One and a Half Century of Diffusion FICK, EINSTEIN before and beyond

Jean Philibert
Diffusion Fundamentals I, Leipzig September 2005

Some MILESTONES
Thomas Graham A Scottish Chemist 1830 (gas) 1863 (liquids) Adolf Fick 1855 A German Physiologist Josef Stefan 1879 An Austrian Physicist W.C. Roberts-Austen 1896 An English
Metallurgist

G. Von Hevesy 1920 A Hungarian Physicist

Random Walk
Robert Brown 1828 J.C. Maxwell 1867 Albert Einstein 1905 Maryan Smoluchowski 1906 Jean Perrin 1912 J. Bardeen , C. Herring 1950

Temperature dependence
Svante Arrhenius 1889 Henry Eyring 1935 / 1941 C. Wert, C. Zener 1949 G.H. Vineyard 1957

Fruitful as the miscibility of the gases has been an interesting speculation,the experimental information we possess on the subject amounts to little more than the well established fact, that gases of different nature, when brought into contact, do not arrange themselves according to their density, . but they spontaneouly diffuse, mutually and equally, through each other and so remain in the intimate state of mixture for any length of time. Thomas Graham, 1829

Adolf FICK
1829-1901

Ficks experimental Set-up

Ficks results (tube)

FICK ( cylindrical tube) 1.2 y = 1.0045 + 0.00088321x R= 0.99908

1.15
specific gravity

1.1

1.05

1 0 50 100 150 200 250

depth under surface (mm)

FICK / funnel
d ln A dc d 2c = 2 dx dx dx Cone : 2 dc d 2c = 2 x + dO dx dx dO d c(x) = 1+ d dO x + dO c sat

Ficks results (funnel)

250 mm is a guess for the position of the cone apex
Fick (funnel)
0.12 0.1 0.08
Specific gravity (-1)

y = -0.078707 + 17.248x R= 0.99922

0.06 0.04 0.02 0

-0.02 0.004 0.005 0.006 0.007 0.008 0.009 0.01 0.011

(250-depth) -1 ( mm -1 )

Fick revisited
Theory and Simulation of Ficks historical verification of the 2nd Law M.E. Glicksman, R. DiDomizio, A. Lupulescu
This Conference

Ficks Diffusion Experiments revisited

T.W. Patzak,
unpublished, available at

http://petroleum.berkeley.edu/papers/patzek/Fick%20 Revisited%20V2.pdf

Joseph Fourier
1768-1830

Josef STEFAN
1836-1893

Is solid state diffusion possible ?

Corpora non agunt nisi soluta

Gay-Lussac, 1846

However, diffusion in solids has been used for centuries in many metallurgical processes : e.g. cementation described by the Roman author PLINY.

W.C. ROBERTS-AUSTEN Chemist and essayer, The Mint, London

Bakerian Lecture on the Diffusion in Metals 1) Diffusion of molten Metals 2) Diffusion of solid Metals
London, 1896
To make accurate experiments on diffusion is one of the most difficult problems in practical physics Ostwald, 1891 My long connection with Grahams researches made it almost a duty to attempt to extend is work on liquide diffusionto metals Roberts-Austen, 1896

W. C. ROBERTS-AUSTEN

Diffusion of Gold In Lead

The evidence gathered by the metallurgist of active atomic movements in fluid and solid metals sustain hope of the Physiologist that

he will ultimately be able to measure the atomic movements upon which vitality and thought depend.
Roberts-Austen

 Robert BROWN 1773-1858

Robert Brown
Havingfound mo in the particles of the pollen of allthe living plants which I tion had exa mined, I was led next to inquire whether this property continuedafter the death of the plant, and for what length of time it was retained In p lants, either dried or imm ersed in spirit for a fe days only, the particles of pollen of bo w th kinds were found in mo equ evident w that observed in the li ing plant tion ally ith v ; specimens of several pl nts, some o wh had been driedand preserved n an a f ich i herbarium for upwards of twenty years, and others not less than a century, still exhibitedthe mo es or. smaller spherical particle in consider num lecul s able bers, and in evident motion,

Albert EINSTEIN
1879-1955

Drunkards walk
from G. GAMOW

Jean PERRIN
1870-1942

Fractal trajectory D =2
Si on faisait des points des intervalles de temps 100 fois plus rapprochs, chaque segment serait remplac par un contour polygonal relativement aussi compliqu que le dessin entier, et ainsi de suite. On voit comment svanouit la notion de trajectoire. Jean Perrin

Gyrgy HEVESY
1885-1966 1920: natural radioactive Lead Pb*/PbCl2 1935: artificial 32P