● Sometimes ch.nges exist in the electrode / electrolyte interf.

ce without
ch.rge tr.nsfer t.king pl.ce. These ch.nges .re due to processes such .s
.dsorption .nd desorption. Such processes .re c.lled nonf.r.d.ic
process.

● Nonf.r.d.ic process: No electrons flow through the electrode / electrolyte

interf.ce during nonf.r.d.ic process. However, tr.nsient extern.l currents
c.n be gener.ted by nonf.r.d.ic processes

● Current .ppe.r bcs of the loss of .n electron. The current observed is

proportion.l to concentr.tion. Once oxidized, the potenti.l is reversed .nd
we c.n see the reduction pe.k.

!. Cyclic Volt*mmogr*m
At the beginning of the gr.phs, when . potenti.l lower th.n the form.l
potenti.l is .pplied, no re.ction will occur, for . while. Any current observed is
due to the migr.tion of the ions .nd the electric.l double l.yer. When the
potenti.l sc.n re.ches the form.l potenti.l .n onset of current c.n be
observed, .nd .s higher potenti.l is .pplied (higher driving force) more .n.lyte
will diffuse to the surf.ce .nd re.ct resulting in . higher current. However .s
the potenti.l incre.ses, the current pe.ks bec.use the r.te of diffusion limits
the over.ll re.ction r.te. After th.t the current then drops due to depletion of
the oxidizing species from the diffusion l.yer. When the switching potenti.l (D)
is re.ched, the sc.n direction is reversed, .nd the potenti.l is sc.nned in the
neg.tive (c.thodic) direction. While the concentr.tion of Fe2+ .t the electrode
surf.ce w.s depleted, the concentr.tion of Fe3+ .t the electrode surf.ce
incre.sed, s.tisfying the Nernst equ.tion. The Fe3+ present .t the electrode
surf.ce is reduces b.ck to Fe2+ .s the .pplied potenti.l becomes more
neg.tive. The two pe.ks .re sep.r.ted due to the diffusion of the .n.lyte to
.nd from the electrode.

Sc*n r*te
The sc.n r.te of the experiment controls how f.st the .pplied potenti.l is
sc.nned. F.ster sc.n r.te le.d to .n incre.se in pe.k current for two re.sons:
– F.ster sc.n r.tes le.d to . decre.se in the size of the diffusion l.yer. This
will c.use the del.y of the diffusion control .nd m.ke it e.sier for the
.n.lyte to diffuse into the diffusion l.yer. As . consequence, higher
currents .re observed.
– For the s.me potenti.l window, the energy .pplied to the system should be
the s.me, however if the sc.n r.te is incre.sed the tot.l re.ction time will
decre.se, which me.ns th.t the .mount of re.gent re.cted per unit time
will incre.se which will c.use the current to incre.se.
ip-v^(1/2)
R.ndles−Sevcik equ.tion describes how the pe.k current ip (A) incre.ses
line.rly with the squ.re root of the sc.n r.te υ.

P. Chrono*mperometry
When . potenti.l step l.rge enough to c.use .n electrochemic.l re.ction is
.pplied to .n electrode, the current ch.nges with time.

Assume: Ox + ne- <---> Red

Potenti.l is set so reduction goes to completion .t the electrode surf.ce.
– Current decre.ses bec.use Ox is used up .t electrode surf.ce .nd Ox is
only replenished by diffusion.
– This dec.ys .lso described by Cottrell eq

Wh.t c.use d.t. to differ from Cottrell eq:

Occurrence of coupled chemic.l rxn ex:
Ox +ne- ---> red
2red ---> A
A + ne- <---> B
This c.n .ffect the sh.pe of the current time curve

Q. Rot*ting Disk Volt*mmetry

Ne.r to the equilibrium potenti.l (when the curve becomes .lmost vertic.l), the
electrodic re.ctions .re controlled by ch.rge tr.nsfer .nd the currents .re
independent of rot.tion speed. When the overpotenti.ls .re incre.sed, the
system enters the region of mixed control, .nd the current becomes gr.du.lly
more dependent on the rot.tion speed. Fin.lly, .t high enough overpotenti.ls,
the current is tot.lly independent of the RDE potenti.l. This illustr.tes how the
RDE m.y be used to r.pidly distinguish between the kinetics of ch.rge-
tr.nsfer, mixed, .nd m.ss-tr.nsport controlled regions.

This pl.te.u is .lso known .s the m.ss tr.nsfer limited region of the
volt.mmetry profile where the r.te of the re.ction is limited by the .v.il.bility
of the re.gent .t the electrode surf.ce.

The l.min.r flow .t . rot.ting disk electrode conveys . ste.dy stre.m of

m.teri.l from the bulk solution to the electrode surf.ce. While the bulk solution
f.r .w.y from the electrode rem.ins well-stirred by the convection induced by
rot.tion, the portion of the solution ne.rer to the electrode surf.ce tends to
rot.te with the electrode. Thus, if the solution is viewed from the fr.me of
reference of the rot.ting electrode surf.ce, then the solution .ppe.rs rel.tively
st.gn.nt. This rel.tively st.gn.nt l.yer is known .s the hydrodyn.mic
bound.ry l.yer
In .ctu.l “re.l world” experiments, the w.ve m.y be observed on top of .
b.ckground current, .nd furthermore, the b.ckground current m.y be slightly
sloped (see Figure 10.5). This (undesired) b.ckground current m.y be due to
interference from oxid.tion or reduction of impurities or of the solvent itself.
The b.ckground current m.y .lso be due to c.p.citive ch.rging .nd
disch.rging of the ionic double l.yer th.t forms next to the pol.rized electrode
surf.ce.

When the oxidized form ( O ) .nd the reduced form ( R ) of . molecule or ion
.re both present in . solution .t the s.me time, the volt.mmogr.m is likely to
exhibit both . c.thodic .nd .n .nodic limiting current. It c.n be very difficult to
me.sure the limiting current properly in this c.se, especi.lly if there is .lso .
sloping b.ckground current. For this re.son, most experiments with rot.ting
electrodes .re conducted in solutions where only one form of the molecule or
ion is initi.lly present.

The slope of the bold line represent devi.tion from Levich line .nd tend
tow.rds the limit limω√→∞, i=iK. The higher the speed of rot.tion is, the less is
the electrode re.ction limited by m.ss-tr.nsfer effects.