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Fig. 5.53 Anodic processes at an iron electrode. (According to K. J. Vetter)

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380 migration control this transport when the electric field in the film is not very strong. If the electrochemical potential of an ion in the film in the steady state decreases with increasing distance from the surface of the electrode, then the current passing through the film (cf. Eq. 2.5.23) is given as (5.8.20) where \ix is the electrochemical potential of the ion at the film-electrolyte interface, JU2 is the value at the metal-film interface and / is the thickness of the film. If the film is insoluble then

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PPP is by far the dominant point-to-point protocol in use in modern networks. The frame itself is fairly simple and, in fact, has several fields that are not actually used. The reason for this is that the frame is derived from the frame for the High Level data link layer Control (HDLC) protocol designed by IBM. HDLC is still in use, but primarily only for connections to IBM mainframes. Some of the fields in the PPP header are relevant for HDLC but not for PPP and are retained mainly as historical artifacts. The PPP frame is shown in Figure 3.3, and the relevant fields are described in the following list.

(5.8.21)

Figure 3.3 The PPP frame header. The address and control fields are not used by PPP and are always set to default values.

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Solution of the differential equation obtained by combining Eqs (5.8.20) and (5.8.21) yields the Wagner parabolic law of film growth, I2 = kt (5.8.22)

The relevant fields in the PPP frame are: Flag The first flag field indicates the start of a PPP frame. It always has the value 01111110 binary (0x7E hexadecimal or 126 decimal). The last flag field indicates the end of a PPP frame. It always has the value 01111110 binary (0x7E hexadecimal or 126 decimal). Address In HDLC this is the address of the destination of the frame but has no meaning in PPP. Therefore, it is always set to 11111111 (0xFF or 255 decimal), which is equivalent to a broadcast (it means all stations ).

A strong electric field is formed in very thin films (with a thickness of about 10~5cm) during current flow. If the average electrochemical potential difference between two neighbouring ions in the lattice is comparable with their energy of thermal motion, kT, then Ohm's law is no longer valid for charge transport in the film. Verwey, Cabrera, and Mott developed a theory of ion transport for this case. If the energy of an ion in the lattice is a periodic function of the interionic distance, then the minima of this function correspond to stable positions in the lattice and the maxima to the most unstable positions. The maxima are situated approximately half-way between two neighbouring stable positions. If there is an electric field in the film, A0//, where A0 is the electric potential difference between the two edges of the film, then a potential energy difference of zFaA(p/l is formed between two neighbouring ions. In these expressions, z is the charge number and a is the distance between two neighbouring ions. The energies corresponding to the transfer of an ion from two neighbouring rest positions to the energy maximum are the activation energies for transport of an ion in the direction and against the direction of the field. Analogous considerations to those employed in the derivation of the basic relationship for electrode kinetics (Section 5.2) yield the relationship for the current density, given by the difference between the rates of these two processes: