Hydrodynamic Techniques

Jerry A Fereiro
1
School of Chemistry – IISER TVM
 Hydrodynamic methods
The rate at which reactants travel to the electrode surface from the bulk electrolyte is known as mass transport, while
the rate at which electrons transfer across the interface is known as charge transfer. There are three basic forms of
mass transport that can influence the rate of an electrochemical reaction:

• Diffusion, defined as the movement of a species due to a concentration gradient.

• Convection, defined as the movement of a species in the bulk electrolyte by mechanical or other forces. Convection
can be natural or forced.

• Migration, defined as the movement of ions in an electrolyte due to a potential gradient.

Hydrodynamic methods studies the effects of mass transport, particularly as a result of forced convection on
electrochemical reactions
 Hydrodynamic Devices
➢ Hydrodynamic devices: These devices use convection to enhance and control the rate of mass transport to the
electrode surface. Detectable currents are increased and the sensitivity of voltammetric measurements is
enhanced.
➢ Two approaches are possible: The electrode is held in a fixed position and the solution is flowed over the electrode
surface by an applied force, usually an applied pressure gradient (e.g. wall-jet electrode). The electrode is designed
to move which acts to mix the solution via convection

Two different types of fluid flow:

Laminar flows are smooth and streamlined, whereas turbulent flows are irregular and chaotic.

Reynolds number below the critical value indicates laminar flow while a high Reynolds number indicates turbulent flow.
 Hydrodynamic Devices
Reynolds number

Note that:
ρ is the density of the fluid
V is the fluid velocity
D is the hydraulic diameter (of pipe, tube, or duct).
μ is the fluid viscosity

Important takeaways from the Reynolds number (for a flow in a pipe):

➢ A flow is considered laminar if the Reynolds number is up to 2300. Viscous force is more prominent due to the
slower flow rate.
➢ A flow is considered turbulent if the Reynolds number is greater than 3500. A faster and irregular flow path
maximizes the inertial force in the system.
➢ Flow regime for the Reynolds number between 2300 to 3500 is considered transitional flow.

In order to be able to perform a quantitative analysis of the electrode processes, the introduced convection must be
predictable. The flow of the solution must be laminar rather than turbulent in order to lead to well-defined,
reproducible results.
 Forced convection hydrodynamic methods

The advantage of hydrodynamic methods is that a steady state is attained rather quickly and moreover double-layer
charging does not enter the measurement

➢ To determine the diffusion coefficient of a quasi-reversible redox couple, it is suggested that a RDE be employed.

The most convenient and widely used system is the rotating disk electrode

This electrode is rather simple to construct and consists of a disk of the electrode material embedded in a rod of insulating
material. For example, a commonly used form involves a platinum wire sealed in glass tubing with the sealed end ground
smooth and perpendicularly to the rod axis. More frequently, the metal is embedded into teflon, epoxy resin, or another
plastic
 Rotating Disk electrode

A RDE encounters a steady-state flux of analyte to the electrode surface, thus leading to the case where the current at a
given potential is no longer dependent upon time.

Due to the steady-state mass transport in RDEs, current−potential curves

are S-shaped as opposed to the typical duck-shape of stationary (unstirred)
CVs that rely on the growth of the diffusion layer thickness and diffusion of
the reactive analytes to, and redox products from, the electrode
throughout the scan
Rotating Disk electrode
Rotating Disk electrode
 Rotating Disk electrode
The mass-transport-limited diffusion current does not depend on either the electrode potential or the rate of the
reaction but only on diffusion and the rotation rate

From the steady state:

What controls the thickness of the diffusion layer?

According to the model, there exist a thin stationary layer immediately adjacent to the electrode surface called the Nernst
diffusion layer (δ) where diffusion alone controls the mass transport of reactant species due to the presence of a
concentration gradient; outside this layer, the concentration of the species is maintained at a constant value by the
stirring/convective transfer

The results from linear sweep voltammetry

indicate, that δ is now controlled by convection
and not by diffusion!
 Rotating Disk electrode

Let’s look at an example:

 Rotating Disk electrode
A deviation of a plot of I vs. ω1/2 from a straight line intersecting the origin suggests that a kinetic limitation is
involved in the electron-transfer reaction.

Let’s look at an example:

 Koutecky-levich analysis
The Koutecky–Levich equation (KL) can be used to separate the mass transport and the kinetic contributions to the
process(es) occurring at the electrode (Levich analysis) while the rotation rate is varied.

This technique uses the limiting current, the regime with no changes in the current as the potential is scanned, where all
processes are slower due to mass transport limitation of the kinetics. This is represented by plotting the square root of the
rotation rate versus the reciprocal of the current.

A plot of 1/I vs 1/ ω1/2 should be linear and can be extrapolated to ω-1/2 =0 to yield 1/I K.

Here, IK represents the current in the absence of any

mass-transfer effects, that is, the current that would
flow under the kinetic limitation if the mass transfer
were efficient enough to keep the concentration at the
electrode surface equal to the bulk value, regardless of
the electrode reaction
Koutecky-levich analysis
 How to extract the kinetic information?

Determine the Tafel slope and exchange current density

Rotating Ring Disk Electrode
 Rotating Ring Disk Electrode
Calibration of the ring
Proper calibration of the ring is an essential step prior to any RRDE experiment, especially when the collection of a
reduced species is important. As part of the calibration, a collection experiment is performed.

This is one where the disk potential is varied as the ring potential is held constant. Each manufactured RRDE
has a specific collection efficiency (N), which is a measure of how well the ring will collect the reduced species
from the disk to oxidize it.

N=−(I R/I D)

where i R and i D are the limiting currents of the ring and disk respectively.

N also depends on the distance and separation between the disk and the ring. The determination of the collection
efficiency is an important parameter for studying reaction mechanisms.
 Rotating Ring Disk Electrode
When performing a collection experiment, the disk potential is swept linearly while the ring potential is held constant. While
rotating the electrode, the disk potential is swept to more negative potentials until a limiting current is reached, such that
mass transport limitations are observed.

As the species come into contact with the disk they become reduced. The reduced species are then diffused towards the ring
and collected. The ring is held at a sufficiently positive potential so the reduced species are immediately oxidized upon
contact with the ring. Thus, the ring regenerates the original analyte.

Through this technique, the researcher can monitor both the ring and disk currents as a function of the disk potential
 Rotating Ring Disk Electrode
❖ A well-defined electrochemical process is often used for the calibration, classically the potassium (II/III)
hexacyanoferrate reaction as the potential is swept negatively, Fe3+ species become reduced at the disk:
[Fe(CN)6]4−+e− ⇄ [Fe(CN)6]3−

❖ The reduced form of Fe2+ migrates out to the ring via rotation of the electrode, which is held at a positive
enough potential where Fe2+ will be oxidized during the diffusion of the species to the ring:
[Fe(CN)6]3− ⇄ [Fe(CN)6] 4−+e−

The measured collection efficiency defines how efficiently the Fe2+ generated at the disk is collected and
oxidized back to Fe3+ at the ring, and this gives the determination of the percentage of species that can be
detected at the ring.

Typical values of collection efficiency are anywhere from 20 to 40%.

It is important to note that the area of the ring is considerably smaller than that of the disk. Thus, all of
the reduced species produced will not be oxidized at the ring.

The size of the ring and the diffusion of the analyte to the ring directly effects how much of a species
can be collected at the ring.
Data analysis from the RRDE experiment with the hexacyanoferrate redox couple. A) RRDE ring currents from the
potassium (II/III) hexacyanoferrate redox couple at a scan rate of 10 mV s-1 in 1 M KNO3 at 25 °C B) RRDE disk
currents from the potassium (II/III) hexacyanoferrate redox couple at a scan rate of 10 mV s-1 in 1 M KNO3 at 25 °C C)
Levich plot of potassium (II/III) hexacyanoferrate redox couple at 0.1 V vs RHE D) Koutecky-Levich plot of potassium
(II/III) hexacyanoferrate redox couple at 0.1 V vs RHE.
 Dropping Mercury Electrode
Historically, this is the first used hydrodynamic technique
 Microelectrodes
Microelectrodes (often referred to as ultramicroelectrodes, UMEs) are electrodes with at least one dimension
below 100 μm.

While microelectrodes may appear merely as smaller versions of their larger ‘macro’ counterparts, their small
size leads to characteristically different electrochemical behaviours, creating advantages far beyond
measurement in smaller volumes.

Radial diffusion leads to much higher mass transport rates and current densities, which facilitates the
measurement of faster processes

The limiting current of a microelectrode is not dependent on the scan rate