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Current Opinion in Colloid & Interface Science 15 (2010) 119–124

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Current Opinion in Colloid & Interface Science


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c o c i s

The history of electrokinetic phenomena


Staffan Wall ⁎
Department of Chemistry/Physical Chemistry, University of Gothenburgh, SE 412 96 Gothenburgh, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Electrokinetic phenomena comprise the phenomena where a liquid moves tangentially to a charged surface.
Received 25 August 2009 Well-known phenomena of this kind are electrophoresis, electro-osmosis, streaming potential and
Received in revised form 9 December 2009 sedimentation potential. A historical review is given here, starting with their discovery by F.F. Reuss in
Accepted 11 December 2009
1808 and continuing with the early investigators including G. Wiedemann, G.Quincke, E. Dorn and U. Saxén.
Available online 16 December 2009
It is also discussed how electrokinetic phenomena gave rise to the concept electrical double layer in colloid
Keywords:
science. The development of the theory starting with H. Helmholtz, continuing with M. Smoluchowski is
Electrophoresis described. Extension of the theory including relaxation and surface conduction is included. Finally the history
Electro-osmosis of other kinds of electrokinetic phenomena such as electroacoustics and diffusiophoresis is treated.
Streaming potential © 2009 Elsevier Ltd. All rights reserved.
Sedimentation potential

1. Introduction importance for the development of the understanding of electrical


phenomena. Among the electrical experiments were those performed
Electrokinetic phenomena belong to the oldest areas of surface and in1808 in Moscow by Ferdinand Friedrich Reuss, a German scientist
colloid science. Only surface tension and related concepts have a born in Tübingen in 1788, who was attracted by the generous scientific
longer history, dating from the time of Francis Hauksbee, Newton's conditions in Russia at that time. He published [1] his discovery in 1809
assistant at the Royal Society. The discovery of the electrokinetic in “Mémoires de la Societé Impériale des Naturalistes de Moskou”, in an
phenomena electrophoresis, electro-osmosis, and streaming potential, article entitled “Sur un Novel Effet de l'Électricité Galvanique”.
gave rise to the concept of the electrical double layer, which, in turn, Reuss carried out two types of simple experiments with an
has played an important role in the understanding of colloidal stability. apparatus consisting of a U-tube with two electrodes connected to a
Studying the history and how the pioneering scientists thought about Volta pile containing 92 silver coins and with the same number of zinc
electrokinetic phenomena, gives a deeper understanding of several plates. In his first set of experiments he put a plug of clay in the U-
colloidal phenomena. In this short review the very start of electroki- tube, and discovered that when he applied a voltage, the water level
netics will be described, followed by some lines of developments. rose in one part of the tube. With modern knowledge we understand
that he observed electro-osmosis. In another type of experiment he
2. The discovery of electrokinetic phenomena put quartz sand above the clay plug and found that the clay particles
migrated through the sand layer, that is, the clay particles migrated by
In the eighteenth century the methods for producing a well defined electrophoresis.
electric current, or electric potential, were very limited. Instruments like These very simple experiments marked the genesis of a very
friction generators and Leyden jars had to be used to perform electrical important branch of surface and colloid science, later called electro-
investigations. In 1798, Alessandro Volta invented a reliable and stable kinetic phenomena. The explanation of experimental electrokinetic
source of electricity, the well-known Volta pile, which was based on zinc results necessitated the introduction of the concept of the electrical
and silver plates, connected with paper soaked in brine. This was a double layer, which is of crucial importance for the understanding of
readily available source of constant electrical potential and an important the electrostatic repulsion between charged colloidal particles and
tool for various electrical investigations. Many scientists utilized this colloidal stability. Electrokinetic phenomena also offer numerous
remarkable invention, among them Jöns Jakob Berzelius and Humphrey applications that are of great importance in many industrial activities.
Davy. Using a huge Volta pile, Davy succeeded in producing metallic
sodium by electrolysis. Later, John Daniell (1836) and William Groove 3. Early experiments
(1839) invented other electrochemical elements which were of great
After Reuss' discovery many qualitative experiments were carried
out, mainly involving electro-osmosis. The simple reason for this was,
⁎ Tel.: +46 317722836; fax: +46 317721394. of course, that these experiments were relatively easy to carry out.
E-mail address: wall@chem.gu.se. Several well-known scientists became involved in this field, for

1359-0294/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2009.12.005
120 S. Wall / Current Opinion in Colloid & Interface Science 15 (2010) 119–124

instance William Wollaston, Robert Porrett, John Napier, and Michael 4. The origin of the surface charge and the electrical double layer
Faraday. John Daniell also carried out experiments with porous
earthenware, which is a porous solid. These experiments were It was immediately clear, even for Reuss, that the clay particles he
important because they showed that electro-osmosis could be used were charged, but how the charge arose was not understood. Many
observed with many different systems. However, the basic mecha- experimental data were gathered through investigation by electro-
nism remained enigmatic. osmosis and streaming potential, but despite all the experimental data
The first quantitative experiments were made by Gustav Wiede- the progress towards an understanding was very slow. The charge on
mann, a well-known physicist, whose first paper [2] on electro- particles and surfaces usually seemed to be negative when the particle
osmosis was published in 1852. He investigated electro-osmosis in surface was in contact with water. Instead of the term electrophoresis,
tubes and found, for instance, that the ratio m/I is independent of the the word cataphoresis was therefore often used. For positively charged
applied voltage and the inner diameter of the tube; here m is the mass particles the word anaphoresis should be used. The observations
of the transported water, and I is the electric current. This is of course regarding the signs of charges led Alfred Coehn [9] to formulate the
in line with Smoluchowski's equation which was derived around following empirical rule: “Stoffe von höherer Dielektrizitätskonstante
60 years later. Wiedemann's investigations were important steps laden sich positive bei Berührung mit Stoffen von niederer Dielektrizi-
towards the quantitative understanding of electro-osmosis. tätskonstante”, or, in a translation by Harold Abramson in his book [6]
The next important step was reported in 1859 by the physicist about electrokinetic phenomena: “A substance having a high dielectric
Georg Quincke [3], then working in Berlin. In addition to experiments constant is positively charged when in contact with another substance
on electro-osmosis he also carried out the reverse experiment. That is having a lower dielectric constant.” Coehn's rule is now mainly of
he pumped water through a tube and could measure an electrical historical interest because it works only in systems without free charges.
potential difference between the ends of the tube. This meant the We now know that hence it has many violations. For instance, in
discovery of streaming potentials. Quincke formed a plug, or tube, aqueous media colloidal particles of metal oxides are usually positively
comprised of several different materials, including glass, sand, charged at low pH and negatively charged at high pH. It is interesting to
sulphur, talk, graphite, silk, linen, and ivory. He found that the note that Coehn worked at Walther Nernst's department of physical
magnitude of the potential difference varied between the various chemistry in Göttingen. For Coehn and his contemporary free ions in
systems but had the same sign. This last conclusion results of course water and other liquids were evidently unknown concepts.
from the fact that many natural materials tend to be negatively It was not until Jacobus van't Hoff showed in 1886 that the osmotic
charged in aqueous solution. pressure of a simple monovalent salt solution (such as sodium chloride)
He also discovered that the potential difference was independent was in fact twice the expected value for the undissociated salt, that the
of the cross section and the thickness of the plug and that the dissociation of salts into ions in aqueous media became, somewhat
streaming potential varied linearly with the applied pressure. reluctantly, accepted. This concept of the dissociation of electrolytes
Amongst other important observations he found that addition of had, however, been proposed earlier by Svante Arrhenius in 1884.
sodium chloride lowered the streaming potential. Quincke also Quinke's and Helmholtz' double layer model is very primitive; it
performed extensive investigations of other, then known, electroki- consisted of a charged flat surface and a spatial countercharge with
netic phenomena. These discoveries led him to postulate the existence opposite sign as compared to that of the surface.
of a space charge outside the charged surface, of which the sign of the Louis-Georges Gouy's theory for a double layer came in 1910
charge was opposite to that on the surface. The existence of this space [10,11]; it included a diffuse space charge. David Leonard Chapman
charge was necessary for Quincke to qualitatively explain both the independently formulated an equivalent theory in 1913 [12].
electro-osmosis and the streaming potential. Quincke's introduction Smoluchowski mentioned Gouy's theory in a footnote but did not
of the space charge was of crucial importance for colloid science utilize this knowledge. It can be noted that Helmholtz–Smoluchows-
because it was the discovery of the electrical double layer. This ki's theory for electro-osmosis is not dependent on the precise
concept is indispensable for modern treatment of colloidal stability. structure of the diffuse layer. The derivation only requires Poisson's
In 1879 Hermann Helmholtz derived a quantitative theory for equation. Otherwise a reasonably correct expression could not have
electrokinetic phenomena on the basis of Quincke's idea of electrical been derived by Helmholtz and Smoluchowski. Helmholtz published
double layers. his theory 1879 and Smoluchowski published an improved version
The next important discovery was also made by a physicist, Ernst 1903 [13]. This means that the theories by Helmholtz and Smolu-
Dorn [4], who worked in the German city of Breslau. In a paper chowski antedates Gouy's double layer theory.
published in 1880 he wrote: “Man durfte nach einem allgemein The Gouy–Chapman model for the diffuse layer gave rise to a very
gültigen Princip die reciproken Erscheinung erwarten, also einen important parameter characterising the thickness of the diffuse layer
galvanischen Strom bei Bewegung fremder Theilchen durch eine usually denoted by κ and given by
Flüssigkeit”. His experimental system was washed sand grains which
he sedimented in a vertical glass tube filled with water. At two levels 2 31
∑ðci Þo z2i e2o 2
in this tube electrodes were melted into the glass, one at each level. 6 7
κ=4 i 5: ð1Þ
During the sedimentation process he was able to measure a potential εεo kT
difference between the two electrodes. This potential difference is
nowadays called the sedimentation potential or Dorn effect.
By 1880 all the classical electrokinetic phenomena had been Here (ci)o is the bulk concentration of the i:th ion in the bulk phase
discovered, namely; electrophoresis, electro-osmosis, streaming poten- and zi is its valency. κ− 1 has the dimensions of a length and is called
tial and sedimentation potential. However, during the twentieth century the Debye length. It has a fundamental importance in the theory for
other kinds of these interesting phenomena were to be discovered. electrokinetic phenomena usually in combination with the particle
Very important sources of information about the early investiga- radius a, usually as κa. At that time scientists began to connect
tions of electrokinetic phenomena are the book by Harold Abramson colloidal stability with electrophoresis. The main issue was whether
[5] and the paper by Stanislav Dukhin [6]. Another important source is the particles, including their space charges, were electroneutral or not.
the book edited by H.R. Kruyt entitled Colloid Science. The chapter However, Quincke, Helmholtz and Smoluchowski considered the
about electrokinetic phenomena is written by J.Th.G. Overbeek [7]. colloidal particles as electroneutral, despite the fact that they migrate
Much historical information can also be found in the handbook in an electrical field and can form a stable colloidal system. This led
Fundamentals of Interface and colloid Science by J.Lyklema [8]. many other scientists to claim that colloidal particles could not be
S. Wall / Current Opinion in Colloid & Interface Science 15 (2010) 119–124 121

completely electroneutral. One of these was Jean Billitzer[14,15], who without any derivation. The electroviscous effect is the contribution to
also was one of Walther Nernst's co-workers in Göttingen. Only much the viscosity when a charged particle rotates in a shear field and the
later did it become clear that the repulsive free energy between two electrical double layer is deformed. It can be noted that Smoluchowski
colloidal particles comes from the decrease in entropy when their two treated practically all the then known electrokinetic phenomena
diffuse layers overlap. Neither Helmholtz nor Smoluchowski could theoretically.
have understood this because of their lack of knowledge about the In 1924, some years after Smoluchowski's review paper was
structure of the electrical double layer. published, Debye and Hückel [20] developed Smoluchowski's
A scientist with a good insight into the charging process of colloids approach for application to small particles and derived an equation,
was the Englishman William Hardy, a physiologist working with differing only by a factor of 2/3 from the Helmholtz–Smoluchowski
biological systems such as proteins. In a paper dated 1905 [16], on equation for relatively large particles. This well-known equation
globulins produced from oxblood serum, he coined the word reads
isoelectric point, that is the pH where the amounts of positive and
negative electrokinetic charge on a colloidal particle are the same. 2 εεo ς
u= : ð3Þ
3 η
5. Quantitative theories
Nowadays it is called the Hückel–Onsager equation. Onsager's
In 1879, Herrmann Helmholtz published a paper [17] entitled name was added because of some contributions made by him in this
“Studien über electrische Grenzschichten”, in which he formulated a field. Debye's name has disappeared because it already appears in
theory for electro-osmosis and derived an equation which described several other equations about electrolytes. The Debye–Hückel paper
the connection between the electro-osmosis in a tube and the referred to above was not very clearly written, the assumptions were
electrical potential on the inner surface of the tube. The equation not clearly stated and it contained much mathematics. At that time
was in the same form as the well-known Smoluchowski equation, the discrepancy between the Helmholtz–Smoluchowski and Hückel–
except that Helmholtz had neglected the dielectric constant. In effect Onsager equations gave rise to a debate because they seemingly
he had put it equal to 1. This was corrected by the French physicist addressed the same phenomenon. This was settled in 1931 in a paper
Henri Pellat and reported by Jean Perrin [18]. by D. C. Henry [21]. A discussion concerning this discrepancy can be
At the end of the nineteenth century Marian Smoluchowski began found in the book published in 1929 [22], by Wolfgang (Joseph) Pauli
to work with electrokinetic phenomena and wrote a number of papers and EmerichValkó in a book entitled “ Elektrochemie der Kolloide”
on this subject. He made an improved derivation of the Helmholtz which also is an excellent source on how people thought about
equation for electro-osmosis [13], which therefore bears the name charging processes before 1929. Wolfgang Pauli was the father of the
Helmholtz–Smoluchowski's equation. In its modern SI-form it reads more well-known Wolfgang (Ernst) Pauli who discovered the
exclusion principle in quantum mechanics.
Henry [21] redid the analysis and paid attention to the extent to
v εε ζ
= o : ð2Þ which the applied electrical field is deformed by the particle. He found
E η
that if the electrical field is not deformed by the particle, the Hückel–
Onsager formula is valid. If the particle is relatively big and an
Here v is the electroosmotic velocity, E the applied field strength, insulator the electrical field is deformed, making the electrical field
ε the relative dielectric constant of the liquid medium, εo the lines parallel with the particle surface. This last case leads to the
permittivity of vacuum, ζ the zeta potential, and η the viscosity of Helmholtz–Smoluchowski equation. In Henry's treatments the
the dispersion medium. This equation is given in many textbooks on assumptions of low potentials and spherical symmetry were also
colloid science. Equations for electrophoresis, streaming potential and made, limiting the range of applicability of this equation. Henry
sedimentation potential were also derived by Smoluchowski, that is, showed that Smoluchowski's and Hückel–Onsager's equations were
for all the classical electrokinetic phenomena. the limiting cases for κa >> 1 and κa < <1 respectively.
Smoluchowski also wrote a valuable review on electrokinetic Already in 1888 [23], Horace Lamb remarked that the mobility of
phenomena in “Handbuch der Elektrizität und des Magnetismus”, particles was independent of the particle size. Many subsequent
edited by L. Graetz and published in 1921 [19]. It appeared four years experimental investigations by, for instance, Abramson [5] and Henry,
after Smoluchowski's untimely death in 1917. In this review he also confirmed that the electrophoretic mobility is independent (or
discussed important contributions to the theory and experiments on approximately independent) of the size and shape of the particles,
electrokinetics covering the literature until 1913. It is an essential provided that, for the differently sized particles, the material in the
reading matter for those who are interested in the development of particles and the dispersion medium are the same. This was a very
electrokinetics in the nineteenth century, and in the first years of the much discussed issue in the literature. A related phenomenon was
twentieth century. In this review Smoluchowski gave an interesting that the electro-osmosis seemed to be independent of the radius of
discussion on the retarding forces on the migrating particles. He the capillary. The radius independence was consistent with Helm-
understood that the applied electrical field is tangential to the particle holtz–Smoluchowski's, Hückel–Onsager's, and Henry's equations,
surface when κa >> 1. That is, the applied electrical field transports none of which contain the particle radius. On the other hand,
the diffuse layer along the particle surface more or less oppositely streaming potential measurements seemed to give capillary radius-
directed to the direction of the migration of the particle. This flow of dependent results, which at that time was not understood.
the diffuse layer gives rise to a counteracting force which is nowadays
called electrophoretic retardation. 6. Deviations from Helmholtz–Smoluchowski and
Smoluchowski also discussed the possibility of a viscous resistance Henry's equations
of the Stokes type, but did not bring this discussion to completion. This
would have led to an equation of the Hückel–Onsager type discussed Henry showed that the limiting cases κa >> 1 and κa < <1 were
below. correctly described by Helmholtz–Smoluchowski and Hückel Onsa-
Smoluchowski also made important contributions to the study of ger's equations respectively. This was in fact already stated by Mooney
surface conductivity. in 1931 [24] independently of Henry's work. In the same paper
A less familiar electrokinetic phenomenon, the electroviscous Mooney discussed many possible effects which could give deviations
effect, was mentioned by him and an equation was postulated from the Helmholtz–Smoluchowski and the Hückel–Onsager
122 S. Wall / Current Opinion in Colloid & Interface Science 15 (2010) 119–124

equation, including the relaxation effect and surface conductivity. In 7. The zeta potential and the stagnant layer
addition he also noted that the viscosity and dielectric constant of the
dispersion medium close to the surface of the particle or tube could Following Quincke, early researchers accepted the existence of a
considerably deviate from their bulk values. However, his theoretical potential jump across the space charge around charged particles. Even
treatment gave only little substantial progress in the understand- Smoluchowski considered this to be the complete potential jump
ing of the phenomena although his discussion was an important between particle and solution in his electrokinetic equations. He
contribution. denoted this potential jump as ϕi − ϕa where ϕi is the electrical
Surface conductivity Kσ is caused by a higher ion concentration in the potential in the bulk phase, and ϕa is the potential at the surface.
solution part of the double layer as compared to the bulk phase. A Nowadays we know that there is a stagnant layer of solvent molecules
consequence of this is that the applied electrical field is much lower close to the surface. The shear plane separates the stagnant layer from
close to the particles and, consequently, the electrophoretic mobility is the moving liquid layer, which introduces the problem of slip between
reduced. This effect was first quantitatively treated by Jacob J. Bikerman the liquid and the particle. Horacio Lamb, a well-known hydrody-
[25,26] for the case that the counterlayer is purely diffuse. Interestingly, namicist, began to discuss this issue as early as 1888 [23].
a consideration of surface conductance introduces a dependence of A closely related historical question is when and by whom the
the tube radius for electro-osmosis and streaming potential and concept of zeta potential was introduced. The earliest use of the
a dependence on the particle size for electrophoresis. The surface notation zeta potential I have found is in the book by Herbert
 −1
conductance introduces the factor 1 + 2K
σ
= ð1 + 2DuÞ−1 for all Freundlich, entitled “Kapillarchemie” (second edition), published in
aKL
1922 [31]. Freundlich's book on surface and colloid science was widely
the mentioned electrokinetic phenomena. a is the tube radius and KL is used and considered as a reliable source of information, and the

the conductivity in the bulk. The Dukhin number Du = aK L
has been general use of the symbol ζ for the electrical potential at the slip plane
introduced here. A careful investigation of the radius-dependence of the is probably derived from this book. The issue of slip plane and its
streaming potential was published 1940 by Arend Joan Rutgers [27] physical significance is still actively discussed and will certainly be so
working in Gent. for many more years to come.
Another effect which affects the electrophoretic mobility is the Choosing zeta potentials for interpreting the stability of colloidal
relaxation effect, that is, the polarisation of the double layer. dispersions continues to be common practice, often for lack of
Helmholtz and Smoluchowski assumed that the distribution of ions alternatives. However many scientists were rather sceptical. For
was unaffected by the applied electrical field. instance Verwey and Overbeek [32] in their famous book Theory of
In the Netherlands Hugo Rudolph Kruyt had started his scientific the Stability of Lyophobic Colloids, published 1948, wrote: It is no
career with investigations on the phase properties of sulphur. In 1914 exaggeration to state that at this moment practically none of the values of
he published his first papers on colloid science; subsequently he and ζ-potentials, as found in the literature can be relied upon to give
his co-workers wrote many papers in this field. He began working in fundamental information on the double layer. In view of the latest
Utrecht where he started a colloid laboratory. Surface electrical investigations in this field, it may be hoped that in a few years time the
phenomena, including electrokinetic phenomena, were important situation will somewhat improve, but in the meantime we think it better
activities in the Utrecht laboratory. The colloid tradition continued to forego the use of ζ-potentials for our purposes, the dangers of
with Kruyt's successor, Theo Overbeek. We will now come back to our misinterpretation being too great. Indeed, at the time of Verwey and
story of electrokinetics, with emphasis on the relaxation effect, which Overbeek several aspects of the interpretation of electrokinetic
is related to the polarisation or the deformation of the diffuse part of potentials were not yet established; for instance, as the role of surface
the double layer of a colloidal particle. conduction was not yet clear, is seemed as if different electrokinetic
This effect was thoroughly treated in the thesis of Overbeek in methods gave rise to different ζ-potentials. So, the choice for the
1941, with the title “Het relaxatie-effect” (The Relaxation Effect) and surface potential was well-established. However, with a touch of
it was shown to be of great importance for many cases, especially for irony, this choice gave rise to the important misconception that the
multivalent counterions, and also for high zeta potentials. Overbeek coagulation concentration of lyophobic colloids was proportional to
also published a comprehensive paper in Kolloid Zeitschrift in 1943 the inverse sixth power of the counterion valence. Had the, much
[28]. At that time the calculations had to be performed analytically lower, ζ-potential been taken instead of the surface potential, this
and the numerical calculations had to be made by hand, which would have led to a z− 2 dependence.
necessitated more or less crude approximations. However, Overbeek's Many years later, in 1966, the situation was clearer but still a
work was of great importance and showed that important deviations matter of considerable concern. In a contribution to a Discussion of the
from Henry's theory could be expected in many situations. Later on Faraday Society by R.H. Ottewill and J.N. Shaw [33] the coagulation
Overbeek, in co-operation with a PhD student Pieter Wiersema, kinetics of latex particles was studied. The surface electrical properties
repeated these calculations with the same theoretical model but now were characterized by electrophoresis and the zeta potentials were
with an electronic computer which very much facilitated the calculated and compared with the colloidal stability. A comprehensive
calculations. Now the general picture was confirmed with much discussion of the paper was also published. Among the discussion
more accurate calculations. Wiersema's thesis entitled “On the Theory participants was Johannes Lyklema who pointed out the difficulty in
of Electrophoresis” was published in 1964 [29]. using the zeta potential for the estimation of the colloidal stability.
Around this time computers began to develop very quickly and the There are three different electrical potentials which play a role, viz. the
possibilities of performing more complex and accurate calculations surface potential ψo at the proper surface, ψd and ζ. None of these
were facilitated. In Canberra Lee White and Richard O'Brien [30] quantities can be directly determined. The zeta potential must be
performed numerical calculations on the standard model. This meant calculated via a more or less artificial and approximate model. The
that the Navier–Stokes and the Poisson equation, together with the surface potential ψo can be determined via various titration methods
conservation laws for mass and charge, were solved. These calcula- which primarily determine the surface charge and require a reference
tions were published in 1978. Since then Lee White et al. have worked potential. ψd the potential at the outer Helmholtz plane requires some
with more elaborate models. model. The situation is still roughly the same when these lines are
However, there are still more details to be included. For instance, written, although experience has shown that equating ζ to ψd is the
Lee White has not included ion correlations in the diffuse layer, which most promising.
is very important for multivalent ions but fortunately of relatively The Stern model [34] which includes the diffuse layer theory by
small significance for univalent ions. Gouy [11] has been very successful in describing electrical double
S. Wall / Current Opinion in Colloid & Interface Science 15 (2010) 119–124 123

layers. The Stern layer is the innermost non-diffuse part of the 9. Other types of electrokinetic phenomena:
counterlayer which may contain adsorbed ions. The diffuse layer is electroacoustics, diffusiophoresis
generic while the Stern layer is strongly dependent of the nature of the
substances involved. There are a few experimental ways to reveal the After the discovery of the classical electrokinetic phenomena,
structure of an electrical double layer, a combination of electrokinetic electrophoresis, electro-osmosis, streaming potential and sedimenta-
and titration techniques is one of these. Electrokinetic phenomena of tion potential a number of other electrokinetic phenomena have been
various kinds contain often a component of surface conductivity which discovered and investigated. In 1947 [42] the famous Russian colloid
becomes relatively more prominent when the electrolyte content is science group, under Boris Vladimirovitch Derjaguin, discovered an
relatively low. As surface conductivity occurs both above and below electrokinetic phenomenon called diffusiophoresis, which is the move-
the surface of shear this is a possible probe to obtain information about ment of colloidal particles in a concentration gradient of an electrolyte.
the properties of the outer and inner sides of electrical double layers. Due to the different thickness of the diffuse layer on opposite sides of the
J Lyklema et al. [35] have developed many methods to measure colloidal particle the diffuse layer become polarised. This gives rise to a
and utilize surface conduction to investigate these properties. MD- net electrical field acting on the particle. A theory was given in 1961 by
simulations have been performed by Lyklema et al. [36] to extract Stanislav Dukhin [43].
information about the dynamic properties of the stagnant layer. Dukhin, together with Shilov, also gave a comprehensive treatise
on electrophoretic phenomena in alternating electrical fields [44].
8. The work of Uno Saxén and the connection with Onsager's In 1933 Peter Debye [45] published a theoretical paper where
reciprocity relations he predicted that, if an electrolyte solution was exposed to a high
frequency acoustic field, a high frequency electrical field .develops
An interesting investigation was made by a Finnish student, Uno across the solution. The aim of the paper was to give a base for the
Saxén, who worked in Wiedemann's laboratory for a short period of experimental determination of the mass of ions in solution. A
time. He investigated electro-osmosis and streaming potentials in glass necessary condition was that the masses of the two ions (the cation
capillaries, concentrating on researching the reciprocity relations which and the anion) are sufficiently different. However, the realization of
exist between various electrokinetic phenomena [37]. These relations such experiments appeared to be very difficult. In a short letter A.J.
were special cases of Onsager's reciprocity relations published in 1931 Rutgers [46] pointed out that a sol of silver iodide particles could be a
[38,39]. Saxén's work in Wiedemann's laboratory was the basis of his suitable system. Colloidal silver iodide particles could be considered
doctoral thesis entitled, “Experimentelle Bestätigung einer die Recipro- as a very asymmetric electrolyte, the colloidal particle acting as the
cität der electrischen Endosmose und Strömungsströme–Erscheinungen one ion, the other ions being the counterions. The Debye effect should
betreffenden Gleichung” published in Helsingfors in 1892. Nowadays in this case be much stronger than for an ordinary electrolyte. In a
these reciprocity relations are called Saxén's laws. following paper [47] Rutgers et al. demonstrated the effect for a
Saxén also made another very important observation. At that time colloidal dispersion consisting of arsenic trisulphide. They called the
there was a discussion whether the potential jumps ζo and ζS across effect the supersonic vibration potential. After this pioneering work,
Quincke's postulated space charge were the same for electro-osmosis electroacoustic methods have become useful and popular methods
and streaming potential. For a cylindrical capillary these phenomena to measure both electrophoretic mobility and particle sizes. Both
can be written by equations derived by Smoluchowski in the following the application of an acoustic field on a colloidal dispersion and
form application of a high frequency electrical field have been utilized.
The application of an electrical field gives rise to an acoustic wave.
QEO εε ζ Nowadays the acronyms UVP, CVP and ESA are used. UVP stands for
= o o ðElectro−osmosisÞ ð4Þ
I ηKL Ultrasonic Vibration Potential, CVP stands for Colloidal Vibration
Potential and ESA stands for Electrophoretic Sonic Amplitude. UVP
Ustr εε ζ
= o S ðStreaming potentialÞ ð5Þ and CVP refer to the situation when an acoustic wave applied to a
ΔP ηKL colloidal dispersion give rise to an acoustic field and ESA is the
reverse situation when an applied electrical field gives rise to an
Here the equations are written in a modern form with SI-units; acoustic field.
where QEO is the liquid flow caused by the electro-osmosis, I the
electrical current, KL the conductivity of the liquid, Ustr streaming 10. Electrophoresis as a separation method
potential, ΔP the pressure difference, and ε, εo and η having their
usual meaning. If the potential jump, now written as ζo and ζS, is the Perhaps the most spectacular application of electrokinetic
same, the value of the expression phenomena is its use in separation techniques for proteins and
DNA. A start was made in Svedberg's laboratory in Uppsala. After
QEO ΔP some initial experiments by The Svedberg, Arne Tiselius [48]
ð6Þ
I Ustr continued this work very successfully. It led to Tiselius being
awarded the Nobel Prize in 1948. As proteins cannot be observed
must be one, provided the classical electrokinetic equations hold. with an optical microscope, the moving boundary technique must be
Saxén showed that this expression was indeed equal to one for used. Knowledge about proteins and DNA is of fundamental
several kinds of salt solutions and concentrations of these salts. The importance in biochemistry. This field developed into an indepen-
experimental errors were, at most, 3%. Thus Saxén showed that the dent field of research. Here the electrophoresis usually occurs in gels,
potential jump or zeta potential, with a modern nomenclature, was which make the theories and techniques rather different from
independent of the kind of electrokinetic phenomenon used, at least the forms of electrophoresis utilized in traditional colloid science.
for electro-osmosis and streaming potential. In order to keep this account reasonably short, here this field is
Saxen's laws re-appeared in 1946 in a paper by Overbeek and therefore not elaborated on any further in the current context. Those
Wijga [40]. Later, in co-operation with P. Mazur and S.R. de Groot [41], interested in the historical development of electrokinetic phenom-
Overbeek published a paper utilizing Onsager's reciprocity relations ena utilized as separation methods, can read a review article written
for a description of electrokinetic phenomena. Since then electroki- by P.G.Righetti [49].
netic phenomena have been a standard component in elementary Several of the themes discussed in this historical introduction
accounts on non-equilibrium thermodynamics. recur in the following chapters of the present issue of COCIS.
124 S. Wall / Current Opinion in Colloid & Interface Science 15 (2010) 119–124

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