Electrolyte

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An electrolyte is a medium containing ions that are electrically conductive through the movement of those ions, but not conducting electrons. [1] [2] [3] This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dissolving, the substance separates into cations and anions, which disperse uniformly throughout the solvent. [4] Solid-state electrolytes also exist. In medicine and sometimes in chemistry, the term electrolyte refers to the substance that is dissolved. [5] [6]

Contents

Electrically, such a solution is neutral. If an electric potential is applied to such a solution, the cations of the solution are drawn to the electrode that has an abundance of electrons, while the anions are drawn to the electrode that has a deficit of electrons. The movement of anions and cations in opposite directions within the solution amounts to a current. Some gases, such as hydrogen chloride (HCl), under conditions of high temperature or low pressure can also function as electrolytes.[ clarification needed ] Electrolyte solutions can also result from the dissolution of some biological (e.g., DNA, polypeptides) or synthetic polymers (e.g., polystyrene sulfonate), termed "polyelectrolytes", which contain charged functional groups. A substance that dissociates into ions in solution or in the melt acquires the capacity to conduct electricity. Sodium, potassium, chloride, calcium, magnesium, and phosphate in a liquid phase are examples of electrolytes.

In medicine, electrolyte replacement is needed when a person has prolonged vomiting or diarrhea, and as a response to sweating due to strenuous athletic activity. Commercial electrolyte solutions are available, particularly for sick children (such as oral rehydration solution, Suero Oral, or Pedialyte) and athletes (sports drinks). Electrolyte monitoring is important in the treatment of anorexia and bulimia.

In science, electrolytes are one of the main components of electrochemical cells. [2]

In clinical medicine, mentions of electrolytes usually refer metonymically to the ions, and (especially) to their concentrations (in blood, serum, urine, or other fluids). Thus, mentions of electrolyte levels usually refer to the various ion concentrations, not to the fluid volumes.

Etymology

The word electrolyte derives from Ancient Greek ήλεκτρο- (ēlectro-), prefix related to electricity, and λυτός (lytos), meaning "able to be untied or loosened". [7]

History

Svante Arrhenius, father of the concept of electrolyte dissociation in aqueous solution for which he received the Nobel Prize in Chemistry in 1903 Arrhenius2.jpg
Svante Arrhenius, father of the concept of electrolyte dissociation in aqueous solution for which he received the Nobel Prize in Chemistry in 1903

In his 1884 dissertation, Svante Arrhenius put forth his explanation of solid crystalline salts disassociating into paired charged particles when dissolved, for which he won the 1903 Nobel Prize in Chemistry. [8] [9] [10] [11] Arrhenius's explanation was that in forming a solution, the salt dissociates into charged particles, to which Michael Faraday (1791-1867) had given the name "ions" many years earlier. Faraday's belief had been that ions were produced in the process of electrolysis. Arrhenius proposed that, even in the absence of an electric current, solutions of salts contained ions. He thus proposed that chemical reactions in solution were reactions between ions. [9] [10] [11]

Shortly after Arrhenius's hypothesis of ions, Franz Hofmeister and Siegmund Lewith [12] [13] [14] found that different ion types displayed different effects on such things as the solubility of proteins. A consistent ordering of these different ions on the magnitude of their effect arises consistently in many other systems as well. This has since become known as the Hofmeister series.

While the origins of these effects are not abundantly clear and have been debated throughout the past century, it has been suggested that the charge density of these ions is important [15] and might actually have explanations originating from the work of Charles-Augustin de Coulomb over 200 years ago.

Formation

Electrolyte solutions are normally formed when salt is placed into a solvent such as water and the individual components dissociate due to the thermodynamic interactions between solvent and solute molecules, in a process called "solvation". For example, when table salt (sodium chloride), NaCl, is placed in water, the salt (a solid) dissolves into its component ions, according to the dissociation reaction[ citation needed ]

NaCl(s) → Na+(aq) + Cl(aq)

It is also possible for substances to react with water, producing ions. For example, carbon dioxide gas dissolves in water to produce a solution that contains hydronium, carbonate, and hydrogen carbonate ions.[ citation needed ]

Molten salts can also be electrolytes as, for example, when sodium chloride is molten, the liquid conducts electricity. In particular, ionic liquids, which are molten salts with melting points below 100 °C, [16] are a type of highly conductive non-aqueous electrolytes and thus have found more and more applications in fuel cells and batteries. [17]

An electrolyte in a solution may be described as "concentrated" if it has a high concentration of ions, or "dilute" if it has a low concentration. If a high proportion of the solute dissociates to form free ions, the electrolyte is strong; if most of the solute does not dissociate, the electrolyte is weak. The properties of electrolytes may be exploited using electrolysis to extract constituent elements and compounds contained within the solution.[ citation needed ]

Alkaline earth metals form hydroxides that are strong electrolytes with limited solubility in water, due to the strong attraction between their constituent ions. This limits their application to situations where high solubility is required. [18]

In 2021 researchers have found that electrolyte can "substantially facilitate electrochemical corrosion studies in less conductive media". [19]

Physiological importance

In physiology, the primary ions of electrolytes are sodium (Na+), potassium (K+), calcium (Ca2+), magnesium (Mg2+), chloride (Cl), hydrogen phosphate (HPO42−), and hydrogen carbonate (HCO3). [20] [ failed verification ] The electric charge symbols of plus (+) and minus (−) indicate that the substance is ionic in nature and has an imbalanced distribution of electrons, the result of chemical dissociation. Sodium is the main electrolyte found in extracellular fluid and potassium is the main intracellular electrolyte; [21] both are involved in fluid balance and blood pressure control. [22]

All known multicellular lifeforms require a subtle and complex electrolyte balance between the intracellular and extracellular environments. [20] In particular, the maintenance of precise osmotic gradients of electrolytes is important. Such gradients affect and regulate the hydration of the body as well as blood pH, and are critical for nerve and muscle function. Various mechanisms exist in living species that keep the concentrations of different electrolytes under tight control. [23]

Both muscle tissue and neurons are considered electric tissues of the body. Muscles and neurons are activated by electrolyte activity between the extracellular fluid or interstitial fluid, and intracellular fluid. Electrolytes may enter or leave the cell membrane through specialized protein structures embedded in the plasma membrane called "ion channels". For example, muscle contraction is dependent upon the presence of calcium (Ca2+), sodium (Na+), and potassium (K+). Without sufficient levels of these key electrolytes, muscle weakness or severe muscle contractions may occur.[ citation needed ]

Electrolyte balance is maintained by oral, or in emergencies, intravenous (IV) intake of electrolyte-containing substances, and is regulated by hormones, in general with the kidneys flushing out excess levels. In humans, electrolyte homeostasis is regulated by hormones such as antidiuretic hormones, aldosterone and parathyroid hormones. Serious electrolyte disturbances, such as dehydration and overhydration, may lead to cardiac and neurological complications and, unless they are rapidly resolved, will result in a medical emergency.

Measurement

Measurement of electrolytes is a commonly performed diagnostic procedure, performed via blood testing with ion-selective electrodes or urinalysis by medical technologists. The interpretation of these values is somewhat meaningless without analysis of the clinical history and is often impossible without parallel measurements of renal function. The electrolytes measured most often are sodium and potassium. Chloride levels are rarely measured except for arterial blood gas interpretations since they are inherently linked to sodium levels. One important test conducted on urine is the specific gravity test to determine the occurrence of an electrolyte imbalance.[ citation needed ]

Rehydration

In oral rehydration therapy, electrolyte drinks containing sodium and potassium salts replenish the body's water and electrolyte concentrations after dehydration caused by exercise, excessive alcohol consumption, diaphoresis (heavy sweating), diarrhea, vomiting, intoxication or starvation. Athletes exercising in extreme conditions (for three or more hours continuously, e.g. a marathon or triathlon) who do not consume electrolytes risk dehydration (or hyponatremia). [24]

A home-made electrolyte drink can be made by using water, sugar and salt in precise proportions. [25] It is important to include glucose (sugar) to utilise the co-transport mechanism of sodium and glucose. Commercial preparations are also available [26] for both human and veterinary use.

Electrolytes are commonly found in fruit juices, sports drinks, milk, nuts, and many fruits and vegetables (whole or in juice form) (e.g., potatoes, avocados).

Electrochemistry

When electrodes are placed in an electrolyte and a voltage is applied, the electrolyte will conduct electricity. Lone electrons normally cannot pass through the electrolyte; instead, a chemical reaction occurs at the cathode, providing electrons to the electrolyte. Another reaction occurs at the anode, consuming electrons from the electrolyte. As a result, a negative charge cloud develops in the electrolyte around the cathode, and a positive charge develops around the anode. The ions in the electrolyte neutralize these charges, enabling the electrons to keep flowing and the reactions to continue.[ citation needed ]

Electrolytic cell producing chlorine (Cl2) and sodium hydroxide (NaOH) from a solution of common salt Chloralkali membrane.svg
Electrolytic cell producing chlorine (Cl2) and sodium hydroxide (NaOH) from a solution of common salt

For example, in a solution of ordinary table salt (sodium chloride, NaCl) in water, the cathode reaction will be

2 H2O + 2e → 2 OH + H2

and hydrogen gas will bubble up; the anode reaction is

2 NaCl → 2 Na+ + Cl2 + 2e

and chlorine gas will be liberated into solution where it reacts with the sodium and hydroxyl ions to produce sodium hypochlorite - household bleach. The positively charged sodium ions Na+ will react toward the cathode, neutralizing the negative charge of OH there, and the negatively charged hydroxide ions OH will react toward the anode, neutralizing the positive charge of Na+ there. Without the ions from the electrolyte, the charges around the electrode would slow down continued electron flow; diffusion of H+ and OH through water to the other electrode takes longer than movement of the much more prevalent salt ions. Electrolytes dissociate in water because water molecules are dipoles and the dipoles orient in an energetically favorable manner to solvate the ions.

In other systems, the electrode reactions can involve the metals of the electrodes as well as the ions of the electrolyte.

Electrolytic conductors are used in electronic devices where the chemical reaction at a metal-electrolyte interface yields useful effects.

Solid electrolytes

Solid electrolytes can be mostly divided into four groups described below.

Gel electrolytes

Gel electrolytes – closely resemble liquid electrolytes. In essence, they are liquids in a flexible lattice framework. Various additives are often applied to increase the conductivity of such systems. [27] [29]

Polymer electrolytes

Dry polymer electrolytes – differ from liquid and gel electrolytes in the sense that salt is dissolved directly into the solid medium. Usually it is a relatively high dielectric constant polymer (PEO, PMMA, PAN, polyphosphazenes, siloxanes, etc.) and a salt with low lattice energy. In order to increase the mechanical strength and conductivity of such electrolytes, very often composites are used, and inert ceramic phase is introduced. There are two major classes of such electrolytes: polymer-in-ceramic, and ceramic-in-polymer. [30] [31] [32]

Ceramic electrolytes

Solid ceramic electrolytes – ions migrate through the ceramic phase by means of vacancies or interstitials within the lattice. There are also glassy-ceramic electrolytes.

Organic plastic electrolytes

Organic ionic plastic crystals – are a type organic salts exhibiting mesophases (i.e. a state of matter intermediate between liquid and solid), in which mobile ions are orientationally or rotationally disordered while their centers are located at the ordered sites in the crystal structure. [28] They have various forms of disorder due to one or more solid–solid phase transitions below the melting point and have therefore plastic properties and good mechanical flexibility as well as improved electrode|electrolyte interfacial contact. In particular, protic organic ionic plastic crystals (POIPCs), [28] which are solid protic organic salts formed by proton transfer from a Brønsted acid to a Brønsted base and in essence are protic ionic liquids in the molten state, have found to be promising solid-state proton conductors for fuel cells. Examples include 1,2,4-triazolium perfluorobutanesulfonate [28] and imidazolium methanesulfonate. [33]

See also

Related Research Articles

<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">Salt (chemistry)</span> Chemical compound involving ionic bonding

In chemistry, a salt or ionic compound is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a neutral compound with no net electric charge. The constituent ions are held together by electrostatic forces termed ionic bonds.

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

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."

The term chloride refers to a compound or molecule that contains either a chlorine ion, which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond. Many inorganic chlorides are salts. Many organic compounds are chlorides. The pronunciation of the word "chloride" is.

<span class="mw-page-title-main">Aqueous solution</span> Solution in which the solvent is water

An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, also known as sodium chloride (NaCl), in water would be represented as Na+(aq) + Cl(aq). The word aqueous means pertaining to, related to, similar to, or dissolved in, water. As water is an excellent solvent and is also naturally abundant, it is a ubiquitous solvent in chemistry. Since water is frequently used as the solvent in experiments, the word solution refers to an aqueous solution, unless the solvent is specified.

The self-ionization of water (also autoionization of water, and autodissociation of water, or simply dissociation of water) is an ionization reaction in pure water or in an aqueous solution, in which a water molecule, H2O, deprotonates (loses the nucleus of one of its hydrogen atoms) to become a hydroxide ion, OH. The hydrogen nucleus, H+, immediately protonates another water molecule to form a hydronium cation, H3O+. It is an example of autoprotolysis, and exemplifies the amphoteric nature of water.

In chemistry, the common-ion effect refers to the decrease in solubility of an ionic precipitate by the addition to the solution of a soluble compound with an ion in common with the precipitate. This behaviour is a consequence of Le Chatelier's principle for the equilibrium reaction of the ionic association/dissociation. The effect is commonly seen as an effect on the solubility of salts and other weak electrolytes. Adding an additional amount of one of the ions of the salt generally leads to increased precipitation of the salt, which reduces the concentration of both ions of the salt until the solubility equilibrium is reached. The effect is based on the fact that both the original salt and the other added chemical have one ion in common with each other.

<span class="mw-page-title-main">Nafion</span> Brand name for a chemical product

Nafion is a brand name for a sulfonated tetrafluoroethylene based fluoropolymer-copolymer discovered in the late 1960s by Dr. Walther Grot of DuPont. Nafion is a brand of the Chemours company. It is the first of a class of synthetic polymers with ionic properties that are called ionomers. Nafion's unique ionic properties are a result of incorporating perfluorovinyl ether groups terminated with sulfonate groups onto a tetrafluoroethylene (PTFE) backbone. Nafion has received a considerable amount of attention as a proton conductor for proton exchange membrane (PEM) fuel cells because of its excellent chemical and mechanical stability in the harsh conditions of this application.

<span class="mw-page-title-main">Ionic liquid</span> Salt in the liquid state

An ionic liquid (IL) is a salt in the liquid state at ambient conditions. In some contexts, the term has been restricted to salts whose melting point is below a specific temperature, such as 100 °C (212 °F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions. These substances are variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.

<span class="mw-page-title-main">Molten-salt battery</span> Type of battery that uses molten salts

Molten-salt batteries are a class of battery that uses molten salts as an electrolyte and offers both a high energy density and a high power density. Traditional non-rechargeable thermal batteries can be stored in their solid state at room temperature for long periods of time before being activated by heating. Rechargeable liquid-metal batteries are used for industrial power backup, special electric vehicles and for grid energy storage, to balance out intermittent renewable power sources such as solar panels and wind turbines.

Beta-alumina solid electrolyte (BASE) is a fast ion conductor material used as a membrane in several types of molten salt electrochemical cell. Currently there is no known substitute available. β-Alumina exhibits an unusual layered crystal structure which enables very fast ion transport. β-Alumina is not an isomorphic form of aluminium oxide (Al2O3), but a sodium polyaluminate. It is a hard polycrystalline ceramic, which, when prepared as an electrolyte, is complexed with a mobile ion, such as Na+, K+, Li+, Ag+, H+, Pb2+, Sr2+ or Ba2+ depending on the application. β-Alumina is a good conductor of its mobile ion yet allows no non-ionic (i.e., electronic) conductivity. The crystal structure of the β-alumina provides an essential rigid framework with channels along which the ionic species of the solid can migrate. Ion transport involves hopping from site to site along these channels. Since the 1970's this technology has been thoroughly developed, resulting in interesting applications. Its special characteristics on ion and electrical conductivity make this material extremely interesting in the field of energy storage.

<span class="mw-page-title-main">Hofmeister series</span>

The Hofmeister series or lyotropic series is a classification of ions in order of their lyotrophic properties, which is the ability to salt out or salt in proteins. The effects of these changes were first worked out by Franz Hofmeister, who studied the effects of cations and anions on the solubility of proteins.

<span class="mw-page-title-main">Fast-ion conductor</span>

In materials science, fast ion conductors are solid conductors with highly mobile ions. These materials are important in the area of solid state ionics, and are also known as solid electrolytes and superionic conductors. These materials are useful in batteries and various sensors. Fast ion conductors are used primarily in solid oxide fuel cells. As solid electrolytes they allow the movement of ions without the need for a liquid or soft membrane separating the electrodes. The phenomenon relies on the hopping of ions through an otherwise rigid crystal structure.

Sodium atoms have 11 electrons, one more than the stable configuration of the noble gas neon. As a result, sodium usually forms ionic compounds involving the Na+ cation. Sodium is a reactive alkali metal and is much more stable in ionic compounds. It can also form intermetallic compounds and organosodium compounds. Sodium compounds are often soluble in water.

<span class="mw-page-title-main">ZEBRA battery</span>

The ZEBRA battery is a type of rechargeable molten salt battery based on commonly available and low-cost materials – primarily nickel metal, the sodium and chloride from conventional table salt, as well beta-alumina solid electrolyte. It is technically known as the sodium–nickel–chloride battery, and sometimes as a sodium–metal–halide battery. The common name comes from its development under the Zeolite Battery Research Africa (ZEBRA) project, started in South Africa in 1985.

<span class="mw-page-title-main">Ion</span> Particle, atom or molecule with a net electrical charge

An ion is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convention. The net charge of an ion is not zero because its total number of electrons is unequal to its total number of protons.

<span class="mw-page-title-main">Solid state ionics</span>

Solid-state ionics is the study of ionic-electronic mixed conductor and fully ionic conductors and their uses. Some materials that fall into this category include inorganic crystalline and polycrystalline solids, ceramics, glasses, polymers, and composites. Solid-state ionic devices, such as solid oxide fuel cells, can be much more reliable and long-lasting, especially under harsh conditions, than comparable devices with fluid electrolytes.

<span class="mw-page-title-main">Conductivity (electrolytic)</span> Measure of the ability of a solution containing electrolytes to conduct electricity

Conductivity or specific conductance of an electrolyte solution is a measure of its ability to conduct electricity. The SI unit of conductivity is siemens per meter (S/m).

<span class="mw-page-title-main">NASICON</span> Class of solid materials

NASICON is an acronym for sodium (Na) super ionic conductor, which usually refers to a family of solids with the chemical formula Na1+xZr2SixP3−xO12, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements. NASICON compounds have high ionic conductivities, on the order of 10−3 S/cm, which rival those of liquid electrolytes. They are caused by hopping of Na ions among interstitial sites of the NASICON crystal lattice.

<i>N</i>,<i>N</i>-Diethylmethylamine Organic compound, industrial chemical

N,N-Diethylmethylamine (diethylmethylamine, DEMA) is a tertiary amine with the formula C5H13N. N,N-Diethylmethylamine is a clear, colorless to pale yellow liquid at room temperature, and is used in various industrial and scientific applications including water desalination as well as analytical and organic chemistry.

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