Zeta potential

Zeta potential is a scientific term for electrokinetic potential[1] in

colloidal dispersions. In the colloidal chemistry literature, it is
usually denoted using the Greek letter zeta (), hence -potential.
From a theoretical viewpoint, the zeta potential is the electric
potential in the interfacial double layer (DL) at the location of the
slipping plane relative to a point in the bulk fluid away from the
interface. In other words, zeta potential is the potential difference
between the dispersion medium and the stationary layer of fluid
attached to the dispersed particle.

The zeta potential is caused by the net electrical charge contained

within the region bounded by the slipping plane, and also depends on
the location of that plane. Thus it is widely used for quantification of
the magnitude of the charge. However, zeta potential is not equal to Diagram showing the ionic concentration and
the Stern potential or electric surface potential in the double layer,[2] potential difference as a function of distancefrom
because these are defined at different locations. Such assumptions of the charged surface of a particle suspended in a
dispersion medium.
equality should be applied with caution. Nevertheless, zeta potential
is often the only available path for characterization of double-layer
properties.

The zeta potential is a key indicator of the stability of colloidal dispersions. The magnitude of the zeta potential indicates the degree
of electrostatic repulsion between adjacent, similarly charged particles in a dispersion. For molecules and particles that are small
enough, a high zeta potential will confer stability, i.e., the solution or dispersion will resist aggregation. When the potential is small,
attractive forces may exceed this repulsion and the dispersion may break and flocculate. So, colloids with high zeta potential
(negative or positive) are electrically stabilized while colloids with low zeta potentials tend to coagulate or flocculate as outlined in
the table.[3][4]

Zeta potential [mV] Stability behavior of the colloid

from 0 to 5, Rapid coagulation or flocculation
from 10 to 30 Incipient instability
from 30 to 40 Moderate stability
from 40 to 60 Good stability
more than 61 Excellent stability

Contents
1 Measurement
1.1 Electrokinetic phenomena
1.1.1 Electrophoresis
1.2 Electroacoustic phenomena
2 Calculation
3 References
Measurement
Zeta potential is not measurable directly but it can be calculated using theoretical models and an experimentally-determined
electrophoretic mobilityor dynamic electrophoretic mobility.

Electrokinetic phenomena and electroacoustic phenomena are the usual sources of data for calculation of zeta potential. See Zeta
potential titration.

Electrokinetic phenomena
Electrophoresis is used for estimating zeta potential of particulates, whereas streaming potential/currentis used for porous bodies and
flat surfaces. In practice, the Zeta potential of dispersion is measured by applying an electric field across the dispersion. Particles
within the dispersion with a zeta potential will migrate toward the electrode of opposite charge with a velocity proportional to the
magnitude of the zeta potential.

This velocity is measured using the technique of the laserDoppler anemometer. The frequency shift or phase shift of an incident laser
beam caused by these moving particles is measured as the particle mobility, and this mobility is converted to the zeta potential by
inputting the dispersant viscosity and dielectric permittivity [5]
, and the application of the Smoluchowski theories (see below).

Electrophoresis
Electrophoretic mobilityis proportional to electrophoretic velocity, which is the measurable parameter. There are several theories that
link electrophoretic mobility with zeta potential. They are briefly described in the article on electrophoresis and in details in many
books on colloid and interface science.[6][7][8][9] There is an IUPAC Technical Report[10] prepared by a group of world experts on the
electrokinetic phenomena.

From the instrumental viewpoint, there are two different experimental techniques: microelectrophoresis and electrophoretic light
scattering. Microelectrophoresis has the advantage of yielding an image of the moving particles. On the other hand, it is complicated
by electro-osmosis at the walls of the sample cell. Electrophoretic light scattering is based on dynamic light scattering. It allows
measurement in an open cell which eliminates the problem of electro-osmotic flow for the case of an Uzgiris, but not a capillary cell.
And, it can be used to characterize very small particles, but at the price of the lost ability to display images of moving particles.

Both these measuring techniques may require dilution of the sample. Sometimes this dilution might affect properties of the sample
and change zeta potential. There is only one justified way to perform this dilution - by using equilibrium supernatant. In this case the
interfacial equilibrium between the surface and the bulk liquid would be maintained and zeta potential would be the same for all
volume fractions of particles in the suspension. When the diluent is known (as is the case for a chemical formulation), additional
diluent can be prepared. If the diluent is unknown, equilibrium supernatant is readily obtained by centrifugation.

Electroacoustic phenomena
There are two electroacoustic effects that are widely used for characterizing zeta potential: colloid vibration currentand electric sonic
amplitude, see reference.[8] There are commercially available instruments that exploit these effects for measuring dynamic
electrophoretic mobility, which depends on zeta potential.

Electroacoustic techniques have the advantage of being able to perform measurements in intact samples, without dilution. Published
and well-verified theories allow such measurements at volume fractions up to 50%, see reference. Calculation of zeta potential from
the dynamic electrophoretic mobility requires information on the densities for particles and liquid. In addition, for larger particles
exceeding roughly 300 nm in size information on the particle size required as well.

Calculation
The most known and widely used theory for calculating zeta potential from experimental data is that developed by Marian
Smoluchowski in 1903.[11] This theory was originally developed for electrophoresis; however, an extension to electroacoustics is
now also available.[8] Smoluchowski's theory is powerful because it is valid for dispersed particles of any shape and any
concentration. However, it has its limitations:

Detailed theoretical analysis proved that Smoluchowski's theory are valid only for a suf
ficiently thin double layer,
when the Debye length, 1/, is much smaller than the particle radiusa:

{\kappa
}\cdot
The model of the "thin double layer" offers tremendous simplifications not only for
electrophoresis theory but for many other electrokinetic and electroacoustic theories. This
model is valid for most aqueous systems because the Debye length is typically only a few
nanometers in water. The model breaks only for nano-colloids in a solution with ionic
strength approaching that of pure water.

Smoluchowski's theory neglects the contribution ofsurface conductivity. This is expressed in modern theories as the
condition of a small Dukhin number:

Du\ll 1

The development of electrophoretic and electroacoustic theories with a wider range of validity was a purpose of many studies during
the 20th century. There are several analytical theories that incorporate surface conductivity and eliminate the restriction of the small
Dukhin number for both the electrokinetic and electroacoustic applications.

[12] and Booth.[13]

Early pioneering work in that direction dates back to Overbeek

Modern, rigorous electrokinetic theories that are valid for any zeta potential and often any a, stem mostly from Soviet Ukrainian
(Dukhin, Shilov and others) and Australian (O'Brien, White, Hunter and others) schools. Historically, the first one was Dukhin-
Semenikhin theory.[14] A similar theory was created 10 years later by O'Brien and Hunter.[15] Assuming a thin double layer, these
theories would yield results that are very close to the numerical solution provided by O'Brien and White.[16] There are also general
electroacoustic theories that are valid for any values ofDebye length and Dukhin number.[8][9]

References
1. Definition of electrokinetic potential (http://goldbook.iupac.org/E01968.html)in "IUPAC. Compendium of Chemical
Terminology", 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific
Publications, Oxford (1997). XML on-line corrected version:http://goldbook.iupac.org(2006-) created by M. Nic, J.
Jirat, B. Kosata; updates compiled by A. Jenkins.ISBN 0-9678550-9-8. doi:10.1351/goldbook (https://doi.org/10.135
1%2Fgoldbook).
2. Kirby, B.J. (2010). Micro- and Nanoscale Fluid Mechanics: T
ransport in Microfluidic Devices.(http://www.kirbyresearc
h.com/textbook) Cambridge University Press.ISBN 978-0-521-11903-0.
3. Greenwood, R; Kendall, K (1999). "Electroacoustic studies of moderately concentrated colloidal suspensions".
Journal of the European Ceramic Society. 19 (4): 479488.
4. Hanaor, D.A.H.; Michelazzi, M.; Leonelli, C.;Sorrell, C.C. (2012). "The effects of carboxylic acids on the aqueous
dispersion and electrophoretic deposition of ZrO2" (http://www.sciencedirect.com/science/article/pii/S095522191100
4171). Journal of the European Ceramic Society. 32 (1): 235244. doi:10.1016/j.jeurceramsoc.2011.08.015(https://d
oi.org/10.1016%2Fj.jeurceramsoc.2011.08.015) .
5. Zeta Potential Using Laser Doppler Electrophoresis - Malvern.com(http://www.malvern.com/LabEng/technology/zeta
_potential/zeta_potential_LDE.htm)
6. Lyklema, J. "Fundamentals of Interface and Colloid Science"(https://books.google.com/books?id=bX4_GQGPzrgC&
pg=SA3-PA31), vol.2, page.3.208, 1995ISBN 0-12-460529-X
7. Russel, W.B., Saville, D.A. and Schowalter, W.R. "Colloidal Dispersions"(https://books.google.com/books?id=FZIh-V
1Asn8C&printsec=frontcover), Cambridge University Press, 1992ISBN 0-521-42600-6
 8. Dukhin, A.S. and Goetz, P.J. "Ultrasound for characterizing colloids"(https://books.google.com/books?id=8UwuPmW
MbE0C&printsec=frontcover), Elsevier, 2002 ISBN 0-444-51164-4
9. Hunter, R.J. "Foundations of Colloid Science", Oxford University Press, 1989ISBN 0-19-855189-4
10. A. V. Delgado; F. Gonzalez-Caballero; R. J. Hunter; L. K. Koopal; J. yLklema (2005). "Measurement and
Interpretation of Electrokinetic Phenomena"(http://www.iupac.org/publications/pac/2005/pdf/7710x1753.pdf) (IUPAC
Technical Report). Pure Appl. Chem. 77 (10): 17531850. doi:10.1351/pac200577101753(https://doi.org/10.1351%2
Fpac200577101753).
11. von Smoluchowski, M.Bull. Int. Acad. Sci. Cracovie, 184 (1903)
12. Overbeek, J.Th.G (1943). "Theory of electrophoresis The relaxation ef
fect". Koll. Bith.: 287.
13. Booth, F. (1948). "Theory of Electrokinetic Effects". Nature. 161 (4081): 836. Bibcode:1948Natur.161...83B (http://a
dsabs.harvard.edu/abs/1948Natur.161...83B). PMID 18898334 (https://www.ncbi.nlm.nih.gov/pubmed/18898334).
doi:10.1038/161083a0 (https://doi.org/10.1038%2F161083a0).
14. Dukhin, S.S. and Semenikhin, N.M.Koll. Zhur., 32, 366 (1970)
15. O'Brien, R.W. and Hunter, R.J. (1981). "The electrophoretic mobility of large colloidal parti
cles". Can. J. Chem. 59:
1878. doi:10.1139/v81-280 (https://doi.org/10.1139%2Fv81-280).
16. O'Brien, Richard W.; White, Lee R. (1978). "Electrophoretic mobility of a spherical colloidal particle".Journal of the
Chemical Society, Faraday Transactions 2. 74: 1607. doi:10.1039/F29787401607(https://doi.org/10.1039%2FF2978
7401607).

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