Electrochemistry

Chapter 4
Mass Transfer in Electrolytes

Electrochemistry
n

is the branch of chemical science that deals with the interrelation of electrical and chemical phenomena. From the very beginning electrochemistry covers two main areas: - the conversion of the energy of chemical reactions into electricity (electrochemical power sources) - the transformations of chemical compounds by the passage of an electric current (electrolysis).

Mass Transfer in Electrolytes

n

Mass transfer refers to mass in transit due to a species concentration gradient in a mixture. Must have a mixture of two or more species for mass transfer to occur.

The species concentration gradient is the driving potential for transfer.

There are three basic mechanisms of mass transport:

o Diffusion o Migration o Convection

o Diffusion
n

The random movement of molecules from a region of high concentration to regions of lower concentration. The rate at which a molecule diffuses is dependent upon the difference in concentration between two points in solution, called the concentration gradient, and on the diffusion coefficient D, which has a characteristic value for a specific solution species at fixed temperature.

This movement of a chemical species under the influence of a concentration gradient is described by Ficks first law.

Jd, j = Dj grad cj

Migration
The movement of charged particles in response to a local electric field is called migration.

Convection
Movement due to changes in density at the electrode solution interface. This occurs due to depletion or addition of a species due to the electrochemical reaction. The movement of fluids is described by hydrodynamics. it applies to electrochemistry is forced movement of solution species by mechanical (stirring) or other means.

Fick's first law

relates the diffusive flux to the concentration under the assumption of steady state. It postulates that the flux goes from regions of high concentration to regions of low concentration, with a magnitude that is proportional to the concentration gradient (spatial derivative). the law is

Jd, j = Dj grad cj

(1)

J The diffusion flux ( measures the amount of substance that will flow through a small area during a small time interval ) D the diffusion coefficient or diffusivity grad c The concentration gradient of diffusing substance

the diffusion of ions in solutions, Eq. (1) is obeyed only at low concentrations of these ions. At higher concentrations the proportionality between flux and concentration gradient is lost (i.e., coefficient Dj ceases to be constant).
A possible reason for the departures from Ficks first law is the fact that the diffusion process tends to level chemical potentials (thermodynamic activities) rather than concentrations of the substances involved. Hence, the equation sometimes is written as

Jd, j =Da, j grad aj

(2)

the equation does not provide a sufficiently accurate description of the experimental results in solutions unless these are highly dilute, and again coefficient Da, j is not constant when the concentration is varied.

Limiting Diffusion Currents in Electrolytes

Diffusion processes in electrochemical systems that are not complicated by migration and convection. - To exclude migration, we consider the behavior of uncharged reaction components. - The condition of a complete absence of convections of the liquid can be realized. the electrode is provided with a porous lining of thickness and filled with the electrolyte. In the small pores of the lining, convection of the liquid is almost impossible.

Diffusion layer of constant thickness.

By powerful stirring of the solution a concentration of the reactant that is sufficiently close to the starting concentration can be maintained at the outer surface of the lining. When current flows in an electrolyte solution, the concentration, of a reactant and/or product close to the electrode surface will change relative to its bulk concentration as a result of the electrode reaction.

The layer of electrolyte where the concentration changes occur and within which the substances are transported by diffusion is called the diffusion layer.

Its thickness, (the diffusion path length), depends on cell design features and on the intensity of convective. The changes in surface concentrations of the components caused by current flow have two important effects: - They produce a change in electrode potential - they imply that there is an upper limit to the cell currents when the diffusion flux attains its limiting value.

Ionic Transport by Migration and Diffusion

The Total Flux Equation The equation for the total flux of ions under the simultaneous effects of an electrostatic field E and a concentration gradient is (the NernstPlanck equation, 1890)

In this equation a minus sign should be used when the direction of the diffusion flux is opposite that of the migration flux.

Convective Transport
Convective transport is the transport of substances with a moving medium (e.g., the transport of a solute in a liquid flow). The convective flux is given by

where is the linear velocity of the medium and cj is the concentration of the substance.

In electrolyte solutions, the convective flux is always electroneutral because of the mediums electroneutrality In electrochemical cells we often find convective transport of reaction components toward (or away from) the electrode surface.

Different ways of convection transport

1- Flow-by Electrodes 2- Rotating-Disk Electrode

3- Rotating RingDisk Electrode

4- Cells with Natural Convection of the Electrolyte

1- Flow-by Electrodes
Flow of the liquid past the electrode is found in electrochemical cells where a liquid electrolyte is agitated with a stirrer or by pumping.

The character of liquid flow near a solid wall depends on the flow velocity , on the characteristic length L of the solid, and on the kinematic viscosity.

2-Rotating-Disk Electrode
At the rotating-disk electrode (RDE), it is the solid electrode and not the liquid that is driven; but from a hydrodynamic point of view this difference is unimportant.

Liquid flows, which in the figure are shown by arrows, are generated in the solution when the electrode is rotated around its vertical axis. The liquid flow impinges on the electrode in the center of the rotating disk, then is diverted by centrifugal forces to the periphery.

3- Rotating RingDisk Electrode