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![Electroanalytical Chemistry: Electroanalytical Chemistry en- compasses a group of quantita-](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-1.jpg)
Electroanalytical Chemistry:
Electroanalytical Chemistry en-
compasses a group of quantita-
tive analytical
methods that are based upon the electrical properties of a analyte solution when it is part of an electrochemical cell.
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![Electrochemical cell](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-2.jpg)
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![Potential and Concentration: The Nernst equation indicates the relationship between](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-3.jpg)
Potential and Concentration:
The Nernst equation indicates the relationship between the activity
of species in solution and the potential (E) produced by a half-cell involving those species.
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![The potential of a electrochemical cell is given as: Ecell = Ec – Ea](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-4.jpg)
The potential of a electrochemical cell is given as:
Ecell = Ec
– Ea
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![The simplest division is between: bulk methods, which measure properties](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-5.jpg)
The simplest division is between:
bulk methods, which measure properties of the
whole solution (Conductometric methods)
Interfacial methods, in which the signal is a function of phenomena occurring at the interface between an electrode and the solution in contact with the electrode.
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![Interfacial Electrochemical Methods](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-6.jpg)
Interfacial Electrochemical Methods
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![Ohm’s law The statement that the current moving through a](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-7.jpg)
Ohm’s law
The statement that the current moving through a circuit is
proportional to the applied potential and inversely proportional to the circuit’s resistance:
E = iR
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![potentiostat potentiostat A device used to control the potential in an electrochemical cell.](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-8.jpg)
potentiostat
potentiostat
A device used to control the potential in
an electrochemical cell.
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![Three principal sources for the analytical signal: Potential Current charge](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-9.jpg)
Three principal sources for the analytical signal:
Potential
Current
charge
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![Galvanostat galvanostat A device used to control the current in an electrochemical cell.](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-10.jpg)
Galvanostat
galvanostat
A device used to control the current in
an electrochemical cell.
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![Three main Electroanalytical methods are: Potentiometry Voltammetry Coulometry](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-11.jpg)
Three main Electroanalytical methods are:
Potentiometry
Voltammetry
Coulometry
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![Potentiometry The electrochemical technique called potentiometry measures the potential developed](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-12.jpg)
Potentiometry
The electrochemical technique called potentiometry measures the potential developed by a
cell consisting of an indicator electrode and a reference electrode.
E(total) = E(indicator) - E(reference)
Accurate determination of the potential developed by a cell requires a negligi-
ble current flow during measurement.
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![Potentiometer: A device for measuring the potential of an electrochemical](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-13.jpg)
Potentiometer:
A device for measuring the potential of an electrochemical cell
without drawing a current or altering the cell’s composition.
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![Electrochemical measuring System:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-14.jpg)
Electrochemical measuring System:
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![Electrodes in Potentiometry: 1- Reference Electrodes: The Saturated Calomel Electrode](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-15.jpg)
Electrodes in Potentiometry:
1- Reference Electrodes:
The Saturated Calomel Electrode (SCE)
The Silver/Silver Chloride
Electrode
2-Indicator Electrodes:
Metallic Electrodes
Membrane Electrodes
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![Calomel Electrode (SCE)](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-16.jpg)
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![Silver / Silver chloride electrode](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-17.jpg)
Silver / Silver chloride electrode
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![Metallic indicator electrodes: 1- First kind 2- Second kind 3- Redox electrode](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-18.jpg)
Metallic indicator electrodes:
1- First kind
2- Second kind
3- Redox electrode
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![Electrode of the First kind](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-19.jpg)
Electrode of the First kind
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![Electrode of the Second kind](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-20.jpg)
Electrode of the Second kind
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![Redox Electrode](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-21.jpg)
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![Membrane Electrodes ( Ion Selective Electrodes or ISE) : Membrane](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-22.jpg)
Membrane Electrodes ( Ion Selective Electrodes or ISE) :
Membrane electrodes are
a class of electrodes that respond selectively to ions by the development of a potential difference across a membrane that separates the analyte solution from a reference solution.
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![Ion Selective Electrode](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-23.jpg)
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![Types of Ion – Selective Membrane Electrodes: Glass Ion Selective](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-24.jpg)
Types of Ion – Selective Membrane Electrodes:
Glass Ion Selective electrodes
Crystalline
Solid-State Electrodes
Liquid Membrane ISEs
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![Glass ion selective electrodes](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-25.jpg)
Glass ion selective electrodes
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![Crystalline Solid-State Electrodes ( Flouride Ion Selective Electrode):](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-26.jpg)
Crystalline Solid-State Electrodes
( Flouride Ion Selective Electrode):
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![Liquid Membrane ISEs: The ion-exchanger may be a cation exchanger,](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-27.jpg)
Liquid Membrane ISEs:
The ion-exchanger may be a cation exchanger, an anion
exchanger, or a neutral complexing agent.
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![Analytical applications of Potentiometry: A ) Direct Potetiometry B) Potentiometric Titrations](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-28.jpg)
Analytical applications of Potentiometry:
A ) Direct Potetiometry
B) Potentiometric Titrations
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![A ) Direct Potetiometry 1- Direct Determination 2- Calibration Curve 3- Standard addition Method](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-29.jpg)
A ) Direct Potetiometry
1- Direct Determination
2- Calibration Curve
3- Standard addition Method
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![Direct Determination Measurement of Ag+ Ion Concentration: E(cell) = E(Ag+) - E(SCE)](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-30.jpg)
Direct Determination
Measurement of Ag+ Ion Concentration:
E(cell) = E(Ag+) -
E(SCE)
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![LIKE AAS ANALYTICAL METHODS 2- Calibration Curve 3- Standard addition Method](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-31.jpg)
LIKE AAS ANALYTICAL METHODS
2- Calibration Curve
3- Standard addition Method
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![B) Potentiometric Titrations Potentiometry is a useful way to determine](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-32.jpg)
B) Potentiometric Titrations
Potentiometry is a useful way to determine the endpoint
in many titrations. For example, the concentration of Ag+ ion in solution can be used to determine the equivalence point in the titration of Ag+ with Cl- . In this titration the following reaction takes place:
Ag+ + Cl - AgCl(s) ( precipitation)
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![Potentiometric Titration Curves:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-33.jpg)
Potentiometric Titration Curves:
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![Voltammetry: Determination of the concentrations of trace metals in a](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-34.jpg)
Voltammetry:
Determination of the concentrations of trace metals in a variety
of Clinical, Environmental, food, steels and other alloys, gasoline, gunpowder, residues, and pharmaceuticals matrices.
Quantitative analysis of organics, particularly in the pharmaceutical industry
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![Voltammetry Voltametry comprises a group of electroanalytical methods in which](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-35.jpg)
Voltammetry
Voltametry comprises a group of electroanalytical methods in which information
about the analyte is derived from the measurement of current as a function of applied potential under conditions that encourage polarization of an indicator or working microelectrode.
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![Controlling and Measuring Current and Potential: Voltammetric measurements are made](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-36.jpg)
Controlling and Measuring Current and Potential:
Voltammetric measurements are made in an
electrochemical cell:
indicator electrode
The electrode whose potential is a function of the analyte’s concentration (also known as the working electrode).
counter electrode
The second electrode in a two-electrode cell that completes the circuit.
reference electrode
An electrode whose potential remains constant and against which other potentials can be measured.
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![Typical cell for Voltammetry:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-37.jpg)
Typical cell for Voltammetry:
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![Voltammetric Techniques: Polarography (NPP, DPP) Cyclic Voltammetry Normal pulse voltammetry](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-38.jpg)
Voltammetric Techniques:
Polarography (NPP, DPP)
Cyclic Voltammetry
Normal pulse voltammetry (NPV)
Differential pulse Voltammetry
(DPV)
Staircase Voltammetry
Square Wave Voltammetry (SWV)
Stripping Voltammetry
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![Polarography( Voltammetry with Dropping Mercury Electrode): Potential excitation signal Polarogram the Ilikovic equation imax = 706nD1/2m2/3t1/6CA](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-39.jpg)
Polarography( Voltammetry with Dropping Mercury Electrode):
Potential excitation signal Polarogram
the Ilikovic
equation
imax = 706nD1/2m2/3t1/6CA
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![Polarographic Cell and three electrode circuit](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-40.jpg)
Polarographic Cell and three electrode circuit
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![Different types of Hg electrodes: 1- hanging mercury drop electrode](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-41.jpg)
Different types of Hg electrodes:
1- hanging mercury drop electrode
An electrode in
which a drop of Hg is suspended from a capillary tube.
2- dropping mercury electrode
An electrode in which successive drops of Hg form at the end of a capillary tube as a result of gravity, with each drop providing a fresh electrode surface.
3- static mercury drop electrode
An electrode in which successive drops of Hg form at the end of a capillary tube as the result of a mechanical plunger, with each drop providing a fresh electrode surface.
4- amalgam
A metallic solution of mercury with another metal.
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![Hg electrodes](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-42.jpg)
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![Cyclic voltammetry: i E E time](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-43.jpg)
Cyclic voltammetry:
i
E
E
time
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![Normal pulse voltammetry:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-44.jpg)
Normal pulse voltammetry:
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![Differential pulse Voltammetry:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-45.jpg)
Differential pulse Voltammetry:
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![Staircase Voltammetry:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-46.jpg)
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![Square Wave Voltammetry:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-47.jpg)
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![Stripping Voltammetry: This method is composed of three related techniques: anodic, cathodic, and adsorptive stripping voltammetry.](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-48.jpg)
Stripping Voltammetry:
This method is composed of three related techniques:
anodic, cathodic,
and adsorptive stripping voltammetry.
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![Simultaneous Determination:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-49.jpg)
Simultaneous Determination:
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![Analytical methods of Voltammetry: Calibration Curve Standard addition Method](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-50.jpg)
Analytical methods of Voltammetry:
Calibration Curve
Standard addition Method
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![Cyclic and Square Wave Voltammograms:](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-51.jpg)
Cyclic and Square Wave Voltammograms:
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![Voltammograms of Standard solutions of Methyl parathion Calibration curve for Standard solutions of Methyl parathion](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-52.jpg)
Voltammograms of Standard solutions of Methyl parathion
Calibration curve for Standard
solutions of Methyl parathion
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![Voltammograms of Standard solutions of Atrazine Calibration curve for Standard solutions of Atrazine](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-53.jpg)
Voltammograms of Standard solutions of Atrazine
Calibration curve for Standard solutions
of Atrazine
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![Evaluation: Scale of Operation: Voltammetry is routinely used to analyze](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-54.jpg)
Evaluation:
Scale of Operation:
Voltammetry is routinely used to analyze samples
at the parts-per-million (ppm) level and, in some cases, can be used to detect analytes at the parts-per-billion (ppb) or parts-per-trillion level.
Accuracy and Precisoin:
The accuracy of a voltammetric analysis often is limited by the ability to correct for residual currents, ppm level, accuracies of ±1–3%. Under most experimental conditions, precisions of ±1–3% .
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![Evaluation Precision is generally limited by the uncertainty in measuring](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-55.jpg)
Evaluation
Precision is generally limited by the uncertainty in measuring the limiting
or peak current. Under most experimental conditions, precisions of ±1–3% . One exception is the analysis of ultratrace analytes in complex matrices by stripping voltammetry,(precisions as poor as ±25%).
Sensitivity In many voltammetric experiments, sensitivity can be improved by adjusting the experimental conditions.
Selectivity Selectivity in voltammetry is determined by the difference between half-wave potentials or peak potentials, with minimum differences of ±0.2–0.3 V required for a linear potential scan, and ±0.04–0.05 V for differential pulse voltammetry.
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![Evaluation Time, Cost and Equipment: Commercial instrumentation for voltammetry ranges](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-56.jpg)
Evaluation
Time, Cost and Equipment: Commercial instrumentation for voltammetry ranges from less
than $1000 for simple instruments to as much as $20,000 for more sophisticated instruments. In general, less expensive instrumentation is limited to linear potential scans, and the more expensive instruments allow for more complex potential-excitation signals using potential pulses.
Except for stripping voltammetry, which uses long deposition times, voltammetric analyses are relatively rapid.
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![Application Clinical Samples: voltammetry and stripping voltammetry have been used](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-57.jpg)
Application
Clinical Samples: voltammetry and stripping voltammetry have been used to determine
the concentration of trace metals in a variety of matrices, including blood, urine, and tissue samples. The determination of lead in blood is of considerable interest due to concerns about lead poisoning.
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![Besides environmental and clinical samples, voltammetry and stripping voltammetry have](/_ipx/f_webp&q_80&fit_contain&s_1440x1080/imagesDir/jpg/325574/slide-58.jpg)
Besides environmental and clinical samples, voltammetry and stripping voltammetry have been
used for the analysis of trace metals in other samples, including food, steels and other alloys, gasoline, gunpowder residues, and pharmaceuticals.
Voltammetry is also an important tool for the quantitative analysis of organics, particularly in the pharmaceutical industry, in which it is used to determine the concentration of drugs and vitamins in formulations.