The document discusses several effects that influence ion mobility and conductivity in electrolyte solutions:
1) The relaxation effect occurs when an ion moves through a solution with an electric field, disrupting the spherical symmetry of its ionic atmosphere and slightly retarding its motion.
2) The electrophoretic effect also reduces ion mobility by causing the ionic atmosphere to move in the opposite direction of the ion.
3) The Wien effect shows that at very high electric field strengths, ion mobility increases as the field prevents formation of ionic atmospheres.
4) The Debye-Falkenhagen effect similarly increases conductivity at very high frequencies that do not allow the ionic atmosphere time to adopt an
The document discusses several effects that influence ion mobility and conductivity in electrolyte solutions:
1) The relaxation effect occurs when an ion moves through a solution with an electric field, disrupting the spherical symmetry of its ionic atmosphere and slightly retarding its motion.
2) The electrophoretic effect also reduces ion mobility by causing the ionic atmosphere to move in the opposite direction of the ion.
3) The Wien effect shows that at very high electric field strengths, ion mobility increases as the field prevents formation of ionic atmospheres.
4) The Debye-Falkenhagen effect similarly increases conductivity at very high frequencies that do not allow the ionic atmosphere time to adopt an
The document discusses several effects that influence ion mobility and conductivity in electrolyte solutions:
1) The relaxation effect occurs when an ion moves through a solution with an electric field, disrupting the spherical symmetry of its ionic atmosphere and slightly retarding its motion.
2) The electrophoretic effect also reduces ion mobility by causing the ionic atmosphere to move in the opposite direction of the ion.
3) The Wien effect shows that at very high electric field strengths, ion mobility increases as the field prevents formation of ionic atmospheres.
4) The Debye-Falkenhagen effect similarly increases conductivity at very high frequencies that do not allow the ionic atmosphere time to adopt an
The document discusses several effects that influence ion mobility and conductivity in electrolyte solutions:
1) The relaxation effect occurs when an ion moves through a solution with an electric field, disrupting the spherical symmetry of its ionic atmosphere and slightly retarding its motion.
2) The electrophoretic effect also reduces ion mobility by causing the ionic atmosphere to move in the opposite direction of the ion.
3) The Wien effect shows that at very high electric field strengths, ion mobility increases as the field prevents formation of ionic atmospheres.
4) The Debye-Falkenhagen effect similarly increases conductivity at very high frequencies that do not allow the ionic atmosphere time to adopt an
In Debye-Huckel theory it is assumed that a given ion
(such as a cation) is surrounded by neighbouring ions of opposite charge (anions). These surrounding counter-ions are said to form an ionic atmosphere which can be visualized as a charged cloud surrounding the central ion of interest. In the absence of an electric field the ionic atmosphere is spherically distributed around the central ion.
When an electric field is present the central ion migrates
through the solution and so the ionic atmosphere is no longer spherically symmetric. Because the ions forming the atmosphere do not adjust to the moving ion immediately, the atmosphere is incompletely formed in front of the moving ion, and incompletely decayed behind the moving ion. The net result is the displacement of the centre of charge of the atmosphere behind the moving ion. Because the charge on the ion and the atmosphere are opposite, the result is retardation in the motion of the moving central ion. This reduction in the mobility of the ion is called the relaxation effect. The time-of-relaxation effect originates in a certain time delay (relaxation) required for the renewal of the spherical symmetry of the ionic atmosphere around the central ion moving under the influence of an applied electric field. The disappearance of the ionic atmosphere after removal of the central ion, similar to its formation, is an exponential function of time; in fact, both of these processes are complete after twice the relaxation time, which is of the order of 10-7 to 10-9 s, depending on the electrolyte concentration. If the central ion moves under the influence of an external electric field, it becomes asymmetrically located with respect to the centre of the ionic atmosphere. Thus the time average of the forces of interaction of the ionic atmosphere with the central ion is not equal to zero. The external electric field is decreased by the relaxation electric field, as it is oriented in the opposite direction to the external force. Although the relaxation time is several orders of magnitude smaller than the time required for the central ion to pass through the ionic atmosphere (about10-3 s), its effect is important because the strength of the electric field formed by the ionic atmosphere (~105 V/ cm) is greater than the strength of the external electric field. Thus, even small changes in the symmetry of the ionic atmosphere have measurable effect acting against that of the external electric field.
The moving ion also experiences an enhanced
viscous drag force. This arises because the ionic atmosphere moves in a direction opposite to that of the ion thereby reducing the mobility and hence the conductivity of the latter. This is called the electrophoretic effect. The electrophoretic effect (occurring also in the case of the electrophoretic motion of charged colloidal particles in an electric field) is caused by the simultaneous movement of the ion in the direction of the applied electric field and of the ionic atmosphere in the opposite direction. Both Dr. ARUP KUMAR GHOSH
the central ion and the ions of the ionic atmosphere take the neighbouring solvent molecules with them, which results in a retardation of the movement of the central ion.
The above two effects increase with concentration, hence decreasing the value of equivalent or molar conductance.
Wien Effect The Wien effect is the experimentally-observed increase in ionic mobility or conductivity of electrolytes at very high gradient of electrical potential.
The conductivities of strong electrolytes do not depend on the strength of the electric field for weak fields (of the order of 104V/m). At high electric field strengths (of about 107V/m), Wien observed a significant increase in the conductivity. This effect increases at higher concentrations and at a higher charge number of the electrolyte ions and approaches a limiting value with increasing electric field. This phenomenon is a result of the high ion velocities, preventing rearrangement of the ionic atmospheres during motion. Thus an ionic atmosphere is not formed at all and both the electrophoretic and relaxation effects disappear.
Debye–Falkenhagen Effect The increase in the conductivity of an electrolyte solution when the applied voltage has a very high frequency is known as Debye–Falkenhagen effect.
Debye and Falkenhagen predicted that the ionic atmosphere would not be able to adopt an asymmetric configuration corresponding to a moving central ion if the ion were oscillating in response to an applied electrical field and if the frequency of the applied field were comparable to the reciprocal of the relaxation time of the ionic atmosphere. This was found to be the case at frequencies over 5 MHz where the molar conductivity approaches a value which is somewhat higher. This increase of conductivity is caused by the disappearance of the time-of-relaxation effect, while the electrophoretic effect remains in full force.
