A voltameter or coulometer is a scientific instrument used for measuring electric charge (quantity of electricity) through electrolytic action. The SI unit of electric charge is the coulomb.
The voltameter should not be confused with a voltmeter, which measures electric potential. The SI unit for electric potential is the volt.
Michael Faraday used an apparatus that he termed a "volta-electrometer"; subsequently John Frederic Daniell called this a "voltameter". [1]
The voltameter is an electrolytic cell and the measurement is made by weighing the element deposited or released at the cathode in a specified time.
This is the most accurate type. It consists of two silver plates in a solution of silver nitrate. When current is flowing, silver dissolves at the anode and is deposited at the cathode. The cathode is initially massed, current is passed for a measured time and the cathode is massed again.
This is similar to the silver voltameter but the anode and cathode are copper and the solution is copper sulfate, acidified with sulfuric acid. It is cheaper than the silver voltameter, but slightly less accurate.
In this device, mercury is used to determine the amount of charges transformed during the following reaction:
These oxidation/reduction processes have 100% efficiency with the wide range of the current densities. Measuring of the quantity of electricity (coulombs) is based on the changes of the mass of the mercury electrode. Mass of the electrode can be increased during cathodic deposition of the mercury ions or decreased during the anodic dissolution of the metal.
The anode and cathode are platinum and the solution is dilute sulfuric acid. Hydrogen is released at the cathode and collected in a graduated tube so that its volume can be measured. The volume is adjusted to standard temperature and pressure and the mass of hydrogen is calculated from the volume. This kind of voltameter is sometimes called Hofmann voltameter.
A coulometer is a device to determine electric charges. The term comes from the unit of charge, the coulomb. There can be two goals in measuring charge:
Coulometers can be devices that are used to determine an amount of substance by measuring the charges. The devices do a quantitative analysis. This method is called coulometry, and related coulometers are either devices used for a coulometry or instruments that perform a coulometry in an automatic way.
Coulometers can be used to determine electric quantities in the direct current circuit, namely the total charge or a constant current. These devices invented by Michael Faraday were used frequently in the 19th century and in the first half of the 20th century. In the past, the coulometers of that type were named voltameters.
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 out 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 "-" (minus) is the anode.
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, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit. Electrodes are essential parts of batteries that can consist of a variety of materials depending on the type of battery.
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.
In electrochemistry, standard electrode potential, or , is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as: "the value of the standard emf of a cell in which molecular hydrogen under standard pressure is oxidized to solvated protons at the left-hand electrode".
Coulometry determines the amount of matter transformed during an electrolysis reaction by measuring the amount of electricity consumed or produced. It can be used for precision measurements of charge, and the amperes even used to have a coulometric definition. However, today coulometry is mainly used for analytical applications. Coulometry is a group of techniques in analytical chemistry. It is named after Charles-Augustin de Coulomb.
The copper coulometer is a one application for the copper-copper(II) sulfate electrode. Such a coulometer consists of two identical copper electrodes immersed in slightly acidic pH-buffered solution of copper(II) sulfate. Passing of current through the element leads to the anodic dissolution of the metal on anode and simultaneous deposition of copper ions on the cathode. These reactions have 100% efficiency over a wide range of current density.
A mercury coulometer is an electroanalytical chemistry device using mercury to determine the amount of matter transformed during the following reaction:
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.
A Hofmann voltameter is an apparatus for electrolysing water, invented by August Wilhelm von Hofmann (1818–1892) in 1866. It consists of three joined upright cylinders, usually glass. The inner cylinder is open at the top to allow addition of water which contains a low concentration of a compound such as sulfuric acid to improve conductivity and complete the circuit. A platinum electrode is placed inside the bottom of each of the two side cylinders, connected to the positive and negative terminals of a source of electricity. When current is run through Hofmann's voltameter, gaseous oxygen forms at the anode and gaseous hydrogen at the cathode. Each gas displaces water and collects at the top of the two outer tubes.
Electrochemistry, a branch of chemistry, went through several changes during its evolution from early principles related to magnets in the early 16th and 17th centuries, to complex theories involving conductivity, electric charge and mathematical methods. The term electrochemistry was used to describe electrical phenomena in the late 19th and 20th centuries. In recent decades, electrochemistry has become an area of current research, including research in batteries and fuel cells, preventing corrosion of metals, the use of electrochemical cells to remove refractory organics and similar contaminants in wastewater electrocoagulation and improving techniques in refining chemicals with electrolysis and electrophoresis.
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.
In electrochemistry, Faraday efficiency describes the efficiency with which charge (electrons) is transferred in a system facilitating an electrochemical reaction. The word "Faraday" in this term has two interrelated aspects: first, the historic unit for charge is the faraday (F), but has since been replaced by the coulomb (C); and secondly, the related Faraday's constant correlates charge with moles of matter and electrons. This phenomenon was originally understood through Michael Faraday's work and expressed in his laws of electrolysis.
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.
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:
