INSTRUMENTAL ANALYSIS

ELECTROANALYTICAL CHEMISTRY

GABRIEL ENGONGA OBIANG

20180767101
 1. INSTRUMENTAL ANALYSIS
The instrumental analysis course will provide us with the tools to obtain qualitative and quantitative
information on a sample from various sources using the use of laboratory equipment.

The course is designed to acquire the basic foundations to carry out methods of separation before
chemical analysis, while learning the basics of management instrumental analysis techniques and
methodologies for developing protocols analysis.

2. ELECTROANALYTICAL CHEMISTRY
Electroanalytical chemistry encompasses a group of quantitative analytical methods that are
based upon the electrical properties of a solution of the analyte when it is made part of an
electrochemical cell.
Electroanalytical methods have certain general advantages over other types of procedures:
– often specific for a particular oxidation state of an element.
– Instrumentation is relatively inexpensive.
– Provide information about activities rather than concentrations of
chemical species.
Types of Electroanalytical Methods
Voltammetry:
- measures current as a function of applied potential under conditions that keep a working
electrode polarized.
Coulometer:
- measures the electricity required to drive an electrolytic oxid. /red. to completion.
Potentiometer:
- measure the potential of electrochemical cells without drawing substantial current.
ELECTROCHEMICAL CELLS
A dc electrochemical cell consists of two electrical conductors called electrodes,
each immersed in a suitable electrolyte solution. For a current to develop in a cell, it
is necessary
(1) that the electrodes be connected externally by means of a metal conductor,
(2) that the two electrolyte solutions be in contact to permit movement of ions
from one to the other, and
(3) that an electron transfer reaction can occur at each of the two electrodes.

Conduction in a Cell:
Charge is conducted by three distinct processes in various parts of the cell:
1. In the copper and Zinc electrodes, as well as in the external conductor, electrons serve as
carriers, moving from the zinc through the conductor to the copper.
2. Within the solutions the flow of electricity involves migration of both cations and anions.
3. A third process occurs at the two electrode surfaces. Here, an oxidation or a reduction
reaction provides a mechanism to provide a complete circuit for the flow of charge. The two
electrode processes are described by the equations.
Galvanic and Electrolytic Cells
The net cell reaction that occurs in the cell shown in Fig. 22-1 is the sum of the two half-cell
reactions.
Zn(s) + Cu2+ Zn2+ + Cu(s)
Cells, that are operated in a way that produces electrical energy are called galvanic cells.
Electrolytic cells consume electrical energy, e.g. the cell under discussion could be made
electrolytic by connecting the negative terminal of a dc power supply to the zinc electrode and
the positive terminal to the copper electrode. If the output of this supply was made somewhat
greater than 1.1 V, the two electrode reactions would be reversed and the net cell reaction
would become:
Cu(s) + Zn2+ Cu2+ + Zn(s)
A cell in which reversing the direction of the current simply reverses the reactions at the two
electrodes is termed a chemically reversible cell.
Faradaic and No Faradaic Currents
Two types of processes can conduct currents across an electrode/solution interface.

One kind involves a direct transfer of electrons via an oxidation reaction at one electrode and a
reduction reaction at the other. Processes of this type are called faradaic processes because they are
governed by Faraday’s law, which states that the amount of chemical reaction at an electrode is
proportional to the current; the resulting currents are called faradaic currents.

To understand the basic difference between a faradaic and a no faradaic current, imagine an electron
traveling down the external circuit to an electrode surface.

When the electron reaches the solution interface, it can do one of only two things.

It can remain at the electrode surface and increase the charge on the double layer, which constitutes a
no faradaic current.

Alternatively, it can leave the electrode surface and transfer to a species in the solution, thus becoming
a part of a faradaic current.

The Thermodynamics of Cell Potentials

The potential of an electrochemical cell is related to the activities of the reactants and products of the
cell reaction and indirectly to their molar concentrations. The relationship between the activity of a
chemical species and its concentration is given by
 aX = X [X]

Here, X is the activity coefficient of solute X and the bracketed term is the molar concentration of X.
When the activity coefficient approaches unity, the molar concentration and the activity of a species are
identical.

2AgCl(s) + H2 (g) 2Ag(s) + 2Cl- + 2H+

The equilibrium constant K for this reaction is given by where, as are the activities of the various species
indicated by the subscripts and pH2 is the partial pressure of hydrogen in atmospheres.

Nernst equation. The standard potential is equal to the cell potential when the reactants and products
are at unit activity and pressure.

Definition of Electrode Potential

Electrode potentials are defined as cell potentials for a cell consisting of the electrode acting as a
cathode and the standard hydrogen electrode acting as an anode. The electrode potential for the half-
reaction

M2+ + 2e ↔ M(s)

Here, the half-cell on the right (the cathode) consists of a strip of the metal M in contact with a solution
of M2+. The half-cell on the left (the anode) is standard hydrogen electrode. By definition, the potential
E observed on the voltage measuring device is the electrode potential for the M/ M2+ couple. If we
assume that the activity of M2+ in the solution is exactly 1.00, the potential is called the standard
electrode potential for the system and is given the symbol E0. That is, the standard electrode potential
for a half-reaction is the electrode potential when the reactants and products are all at unit activity.

Calculation of Cell Potentials from Electrode Potentials

An important use of standard electrode potentials is the calculation of the potential obtainable from a
galvanic cell or the potential required to operate an electrolytic cell. The electromotive force of a cell is
obtained by combining half-cell potentials as follows:

Ecell = Ecathode – Eanode

Currents in Electrochemical Cells

Except potentiometric methods all electroanalytical methods involve electrical currents and current
measurements. We need to consider the behavior of cells when significant currents are present.
Electricity is carried within a cell by the movement of ions. With small currents, Ohm’s law is usually
obeyed, and we may write E = IR where E is the potential difference in volts responsible for movement
of the ions, I is the current in amperes, and R is the resistance in ohms of the electrolyte to the current.

The measured cell potential normally departs from that derived from theoretical thermodynamic
calculation. This departure can be traced to a number of phenomena, including:

ohm potential and several polarization effects, such as:

charge-transfer polarization, concentration polarization, diffusion overvoltage, and crystallization
overvoltage.

Generally, these phenomena have the effect of reducing the potential of a galvanic cell or increasing the
potential needed to develop a current in an electrolytic cell.

Ohm Potential; IR Drop

To develop a current in either a galvanic or an electrolytic cell, a driving force in the form of a potential is
required to overcome the resistance of the ions to movement toward the anode and the cathode.

This force follows Ohm’s law and is equal to the product of the current in amperes and the resistance of
the cell in ohms. The force is generally referred to as the ohm potential, or the IR drop.

The net effect of IR drop is to increase the potential required to operate an electrolytic cell and to
decrease the measured potential of a galvanic cell. Therefore, the IR drop is always subtracted from the
theoretical cell potential.

Eapplied = Ecathode – Eanode – IR

Diffusion
Whenever there is a concentration difference between two regions of a solution, as happens when a
species is reduced at a cathode surface (or oxidized at an anode surface), diffusion causes ions or
molecules to move from the more concentrated region to the more dilute. The rate of diffusion is given
by dc / dt = k ( c-c0 ) c

is the reactant concentration in the bulk of the solution, Co is its equilibrium concentration at the
electrode surface, and k is a proportionality constant. As shown earlier, the value of C0 is fixed by the
potential of the electrode and can be calculated from the Nernst equation. As increasingly higher
potentials are applied to the electrode, C0 becomes smaller and smaller, and the diffusion rate becomes
greater and greater. Ultimately, however, C0 becomes negligible with respect to c, and the rate then
becomes constant. That is, when C0  0, dc / dt = k c

Under this condition, concentration polarization is said to be complete, and the electrode operates as an
ideal polarized electrode Diffusion Convection is the transport of ions or molecules through a solution as
a result of stirring, vibration, or temperature gradients. Thus, forced convection, such as stirring or
agitation, tends to decrease concentration polarization. Migration is the process by which ions move
under the influence of an electrostatic field. It is often the primary mass-transfer process in the bulk of
the solution in a cell. The electrostatic attraction (or repulsion) between a particular ionic species and
the electrode becomes smaller as the total electrolyte concentration of the solution becomes greater. It
may approach zero when the reactive species is only a small fraction, say 1/100, of the total
concentration of ions with a given charge. To summarize, concentration polarization is observed when
diffusion, migration, and convection are insufficient to transport the reactant to or from an electrode
surface at a rate demanded by the theoretical current. Because of concentration polarization, a larger
potential must he applied to an electrolytic cell than the value predicted from the thermodynamic
potential and the IR drop.
 3. LEARNING EXPERIENCE
This class I have learned basic foundations to carry out separation before chemical analysis, while
learning the basics of management instrumental analysis techniques and methodologies for developing
protocols analysis. I have learned techniques based on electrochemical phenomena, the techniques
spectrophotometric and chromatographic techniques. These techniques are elementary for carry out
determinations of pollutants, drugs, toxic substances and organic matter, so they will be very useful in
the toxicology course, in the research and professional activities. Thank you teacher for the time and the
concerns about our learning we really appreciate it. It was hard sometimes to take this class online
because of many different teachers and methods but in the end I learn something new in my life.

My suggestion is if we have the change to take this class again we should do more practices because like
this we learn faster and understand what we are learning.