Electrogravimetry

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Electrogravimetry apparatus EG4.JPG
Electrogravimetry apparatus

Electrogravimetry is a method used to separate and quantify ions of a substance, usually a metal. In this process, the analyte solution is electrolyzed. Electrochemical reduction causes the analyte to be deposited on the cathode. The mass of the cathode is determined before and after the experiment, and the difference is used to calculate the mass of analyte in the original solution. Controlling the potential of the electrode is important to ensure that only the metal being analyzed will be deposited on the electrode.

The process is similar to electroplating.

The phenomenon of polarization exerts a back EMF in electrolysis, which reduces the actual EMF of the cell. Thus electrolysis of an electrolyte is possible only when this back EMF is overcome. If two separated platinum electrodes are placed in a dilute solution of copper sulfate and if a source of potential is applied, no appreciable current will flow through the system, until some minimum potential is applied after which the current will increase as the applied potential increases. The applied voltage which is just sufficient to overcome the back EMF due to polarization and also to bring about the electrolysis of an electrolyte without any hindrance is known as decomposition potential.

The decomposition potential Ed is composed of various potentials and is given by:

Ea (min)= Ed= Eb+ Es+ Ev

where:

The origins of electrogravimetry date back to the 19th century, when Oliver Wilcott Gibbs, an American chemist, studied the electrolytic precipitation of copper and nickel. This procedure was the first of its kind until Carl Luckow did similar research on electric metal analysis. Today, these two are credited with the invention of the electrogravimetry, known at the time as “electrochemical analysis,” “electroanalysis,” or “electrolytic analysis”. [1]

All methods of electrogravimetry involve a traditional quartz crystal microbalance (QCM) system in which a sensor is used from an AT cut quartz crystal[ clarification needed ]. The groundwork of the QCM is built upon the notion that any mass delivered on the quartz electrode's interfacial region can be detected through the resonating frequency of the vibrating quartz crystal. While most vibrational modes occurring in the AT cut quartz are negligible, the vibration mode is known as thickness shear mode. [2] These vibrations are extremely sensitive, which permits accurate detection of atomic interactions near the sensor, allowing these techniques to be used in analytical chemistry [ further explanation needed ].

Through combining the techniques of QCM with classic electrochemical techniques, the electrochemical quartz crystal microbalance (EQCM) was created. EQCM is a new device used to perform the process of electrogravimetry. This device employs a high frequency acoustic wave generated by a piezoelectric resonator to store and dissipate energy infused into the device's interfacial region. [3]

Electrogravimetry has been useful in polymer studies, copper electrodeposition, gold oxidation in an acidic medium, and passivity of iron in a sulfuric medium, as well as Ionic insertion in WO3. [4]

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An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ACID, for "anode current into device". The direction of conventional current in a circuit is opposite to the direction of electron flow, so electrons flow from the anode of a galvanic cell, into an outside or external circuit connected to the cell. For example, the end of a household battery marked with a "+" is the cathode.

<span class="mw-page-title-main">Cathode</span> Electrode where reduction takes place

A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic CCD for Cathode Current Departs. A conventional current describes the direction in which positive charges move. Electrons have a negative electrical charge, so the movement of electrons is opposite to that of the conventional current flow. Consequently, the mnemonic cathode current departs also means that electrons flow into the device's cathode from the external circuit. For example, the end of a household battery marked with a + (plus) is the cathode.

<span class="mw-page-title-main">Electrochemistry</span> Branch of chemistry

Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference and identifiable chemical change. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.

<span class="mw-page-title-main">Electrochemical cell</span> Electro-chemical device

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<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

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<span class="mw-page-title-main">Galvanic cell</span> Electrochemical device

A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous Oxidation-Reduction reactions. A common apparatus generally consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane.

<span class="mw-page-title-main">Electrolytic cell</span> Cell that uses electrical energy to drive a non-spontaneous redox reaction

An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to force a chemical reaction that would otherwise not occur. The external energy source is a voltage applied between the cell's two electrodes; an anode and a cathode, which are immersed in an electrolyte solution. This is in contrast to a galvanic cell, which itself is a source of electrical energy and the foundation of a battery. The net reaction taking place in a galvanic cell is a spontaneous reaction, i.e., the Gibbs free energy remains -ve, while the net reaction taking place in an electrolytic cell is the reverse of this spontaneous reaction, i.e., the Gibbs free energy is +ve.

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<span class="mw-page-title-main">Chronoamperometry</span> Analytical method in electrochemistry

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<span class="mw-page-title-main">Voltameter</span> Instrument for measuring electric charge

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<span class="mw-page-title-main">Electrochemical quartz crystal microbalance</span>

Electrochemical quartz crystal microbalance (EQCM) is the combination of electrochemistry and quartz crystal microbalance, which was generated in the eighties. Typically, an EQCM device contains an electrochemical cells part and a QCM part. Two electrodes on both sides of the quartz crystal serve two purposes. Firstly, an alternating electric field is generated between the two electrodes for making up the oscillator. Secondly, the electrode contacting electrolyte is used as a working electrode (WE), together with a counter electrode (CE) and a reference electrode (RE), in the potentiostatic circuit constituting the electrochemistry cell. Thus, the working electrode of electrochemistry cell is the sensor of QCM.

References

  1. Lubert, Karl-Heinz; Kalcher, Kurt (2010). "History of Electroanalytical Methods". Electroanalysis. John Wiley & Sons, Inc. 22 (17–18): 1937–1946. doi:10.1002/elan.201000087 . Retrieved 9 April 2021.
  2. Torres, Róbinson; Arnau, Antonio; Perrot, Hubert. "ELECTRONIC SYSTEM FOR EXPERIMENTATION IN AC ELECTROGRAVIMETRY I: TECHNIQUE FUNDAMENTALS" (PDF). Universidad EIA. Retrieved 9 April 2021.
  3. Hillman, Robert (2011). "The EQCM: electrogravimetry with a light touch". Journal of Solid State Electrochemistry. Springer Nature Switzerland AG. 15 (7–8): 1647–1660. doi:10.1007/s10008-011-1371-2. S2CID   97029963 . Retrieved 9 April 2021.
  4. Gabrielli, C.; Keddam, M.; Nadi, N.; Perrot, H. "Ions and solvent transport across conducting polymers investigated by ac electrogravimetry. Application to polyaniline". Elsevier. doi:10.1002/elan.201000087 . Retrieved 9 April 2021.