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:
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]
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.
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.
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.
An electrochemical cell is a device that generates electrical energy from chemical reactions. Electrical energy can also be applied to these cells to cause chemical reactions to occur. Electrochemical cells which generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells.
In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".
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.
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.
A regenerative fuel cell or reverse fuel cell (RFC) is a fuel cell run in reverse mode, which consumes electricity and chemical B to produce chemical A. By definition, the process of any fuel cell could be reversed. However, a given device is usually optimized for operating in one mode and may not be built in such a way that it can be operated backwards. Standard fuel cells operated backwards generally do not make very efficient systems unless they are purpose-built to do so as with high-pressure electrolysers, regenerative fuel cells, solid-oxide electrolyser cells and unitized regenerative fuel cells.
In electrochemistry, cyclic voltammetry (CV) is a type of potentiodynamic measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV experiment, the working electrode's potential is ramped in the opposite direction to return to the initial potential. These cycles of ramps in potential may be repeated as many times as needed. The current at the working electrode is plotted versus the applied voltage to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution or of a molecule that is adsorbed onto the electrode.
A quartz crystal microbalance (QCM) measures a mass variation per unit area by measuring the change in frequency of a quartz crystal resonator. The resonance is disturbed by the addition or removal of a small mass due to oxide growth/decay or film deposition at the surface of the acoustic resonator. The QCM can be used under vacuum, in gas phase and more recently in liquid environments. It is useful for monitoring the rate of deposition in thin-film deposition systems under vacuum. In liquid, it is highly effective at determining the affinity of molecules to surfaces functionalized with recognition sites. Larger entities such as viruses or polymers are investigated as well. QCM has also been used to investigate interactions between biomolecules. Frequency measurements are easily made to high precision ; hence, it is easy to measure mass densities down to a level of below 1 μg/cm2. In addition to measuring the frequency, the dissipation factor is often measured to help analysis. The dissipation factor is the inverse quality factor of the resonance, Q−1 = w/fr ; it quantifies the damping in the system and is related to the sample's viscoelastic properties.
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram, which plots the current produced by the analyte versus the potential of the working electrode.
In electrochemistry, chronoamperometry is an analytical technique in which the electric potential of the working electrode is stepped and the resulting current from faradaic processes occurring at the electrode is monitored as a function of time. The functional relationship between current response and time is measured after applying single or double potential step to the working electrode of the electrochemical system. Limited information about the identity of the electrolyzed species can be obtained from the ratio of the peak oxidation current versus the peak reduction current. However, as with all pulsed techniques, chronoamperometry generates high charging currents, which decay exponentially with time as any RC circuit. The Faradaic current - which is due to electron transfer events and is most often the current component of interest - decays as described in the Cottrell equation. In most electrochemical cells, this decay is much slower than the charging decay-cells with no supporting electrolyte are notable exceptions. Most commonly a three-electrode system is used. Since the current is integrated over relatively longer time intervals, chronoamperometry gives a better signal-to-noise ratio in comparison to other amperometric techniques.
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically-determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.
A voltameter or coulometer is a scientific instrument used for measuring electric charge through electrolytic action. The SI unit of electric charge is the coulomb.
Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical cell containing the analyte. These methods can be broken down into several categories depending on which aspects of the cell are controlled and which are measured. The four main categories are potentiometry, amperometry, coulometry, and voltammetry.
Bulk electrolysis is also known as potentiostatic coulometry or controlled potential coulometry. The experiment is a form of coulometry which generally employs a three electrode system controlled by a potentiostat. In the experiment the working electrode is held at a constant potential (volts) and current (amps) is monitored over time (seconds). In a properly run experiment an analyte is quantitatively converted from its original oxidation state to a new oxidation state, either reduced or oxidized. As the substrate is consumed, the current also decreases, approaching zero when the conversion nears completion.
Within surface science, a quartz crystal microbalance with dissipation monitoring (QCM-D) is a type of quartz crystal microbalance (QCM) based on the ring-down technique. It is used in interfacial acoustic sensing. Its most common application is the determination of a film thickness in a liquid environment. It can be used to investigate further properties of the sample, most notably the layer's softness.
In chemistry, ion transport number, also called the transference number, is the fraction of the total electric current carried in an electrolyte by a given ionic species i:
A biotransducer is the recognition-transduction component of a biosensor system. It consists of two intimately coupled parts; a bio-recognition layer and a physicochemical transducer, which acting together converts a biochemical signal to an electronic or optical signal. The bio-recognition layer typically contains an enzyme or another binding protein such as antibody. However, oligonucleotide sequences, sub-cellular fragments such as organelles and receptor carrying fragments, single whole cells, small numbers of cells on synthetic scaffolds, or thin slices of animal or plant tissues, may also comprise the bio-recognition layer. It gives the biosensor selectivity and specificity. The physicochemical transducer is typically in intimate and controlled contact with the recognition layer. As a result of the presence and biochemical action of the analyte, a physico-chemical change is produced within the biorecognition layer that is measured by the physicochemical transducer producing a signal that is proportionate to the concentration of the analyte. The physicochemical transducer may be electrochemical, optical, electronic, gravimetric, pyroelectric or piezoelectric. Based on the type of biotransducer, biosensors can be classified as shown to the right.
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.