We are examining reductions. In controlled current, can add a cathodic depolarizer.

Cu(II) is
reduced in the presence of Pb(II). As the potential shifts to more negative potential, Pb(II) will be
simultaneously reduced. Add nitrate ion. It will be reduced before Pb(II) and will not co-deposit
like Pb would with Cu. Hydrogen ion can serve this role.
• 11.4.2
  Coulometric methods (constant current)

 is applied current and is electrolysis time (100 % efficiency)

 Consider oxidation of Fe(II) to Fe(II)
o When applied current > limiting current, efficiency falls below 100 %.
o Some of current would go to oxygen evolution due to oxidation of water.
o The charge would not correspond correctly to amount of Fe(II)
o Add Ce(III)
o When current efficiency falls below 100 %, Ce(III) is oxidized to Ce(IV)
o The Ce(IV) can then oxidize Fe(II) (indirectly)
o Current efficiency is maintained
• 11.4.2 Coulometric methods (constant current) continued

 Need a way to know when all Fe(II) has been oxidized

 An indicator when Ce(IV) starts to build up and doesn’t indirectly oxidize Fe(II)
• A popular reaction for titration is reaction of olefins with electrochemically
generated bromine (titrant)
Analyte is A, we are generating B
which is the titrant. Our current
efficiency can be predicted as shown in
the graph where S is current in the
absence of analyte.
 11.5 Electrometric End Point Detection
• 11.5.1 Classification
 2 electrodes….potentiometric
o a) i = 0, one nonpolarizable (ordinary pontentiometry)
o b) constant applied current one polarizable electrode (one-electrode potentiometry)
o c) constant applied current, two polarizable electrodes (two-electrode potentiometry)
 Amperometric, one can be nonpolarizable (ref electrode) and one polarizable or both
polarizable
o a) constant applied voltage, one polarizable electrode (one-electrode amperometry)
o b) constant applied voltage, two polarizable electrodes (two-electrode amperometry)
 The polarizable or indicator electrode can be a steady-state voltammetric electrode, a platinum
electrode in a stirred solution or and RDE.
 Reference electrode can be an SCE
• 11.5.2 Current potential curves during titration
 f is fraction of analyte converted (analogous to titrant volume)
 Figure 11.5.1 on next slide
 11.5 Electrometric
End Point Detection

• 11.5.3 Potentiometric
Methods
• 11.5.4 Amperometric
Methods
 one electrode and two
electrode amperometry.
 We are going to have our
indicator electrode at a
potential (E1). One
electrode is shown in
Figure 11.5.5
 For two electrode, we will
have a difference in
potential applied to two
identical indicator
electrodes or ΔE. The
signal is shown in Figure
11.5.6
 11.6 Flow Electrolysis
• 11.6.1 Introduction: See Figure 11.6.1 on next slide
• 11.6.2 Math treatment L is electrode length (cm), A is cross sectional area (cm2), v is
flow rate in cm3/s. Linear velocity of stream U (cm/s) is
• Assume 100 % efficiency for
•• 11.6.2
  Math treatment continued
 Inlet concentration of O is (in) and (in) is zero
 Overall conversion of O to R in passage through electrode is (mol/s) or (mol/cm 3)
 R is the fraction converted (I don’t like capital R) R = 0, no conversion, R = 1, 100 % conversion

 Need an expression for current based on flow velocity and electrode parameters. Total internal area of
electrode is a (cm2) which includes all internal pore surface area, etc.
 Specific area s is:

 I am not going to go through all the math but:

mass transfer coefficient is a function of flow
velocity and b (proportionality factor) and α with
values of 0.33 to 0.5 for laminar flow and close to 1
for turbulent flow.
•• 11.6.2
  Math treatment continued
 With

 Current and R equations become

 Note R, conversion efficiency, increases with decreasing flow velocity

 Current density is highest at the front

 Decreases exponentially with x.

 Figure 11.6.3 (next slide) considers open area of the pores () and porosity (ε)

 Interstitial velocity (W) is a function of liner velocity (U) and flow velocity (v)

 A volume element enters at t = 0 will be at x at time t.

•• 11.6.2
  Math treatment continued

 Similar to batch electrolysis: (compared to )

 L (length) required for given R is

 Residence time τ.

 For a porous electrode, t’ is the time it takes for O to move from center of pore with radius r to the wall.

 Time it take to move down (through) the pore (in the x direction) is

 If t’ < t, then R = 1.

 For high conversion:

• 11.6.2
  Math treatment continued
• Consider: Porous Ag electrode with these parameters

For A = 0.2 cm2, ε = 0.5, L = 50 μm, r = 0.25 μm, DO = 5 x 10-6 cm2/s, ap = εA = 0.1 cm2
for R ≈~1, maximum flow velocity is 0.1 cm3/s and residence time in the electrode of
~ 5 ms.

Neglected
o Resistive drops in the electrode and solution in the pores
o Kinetic limitations to electron-transfer process
o Current efficiency less than 1

For R = 1, measure current is proportional to analyted undergoing electrolysis

Dual electrode flow cells will be discuss in the context of LC-EC