Misplaced Pages

#996003

55-412: A Hantzsch–Widman name will always contain a prefix, which indicates the type of heteroatom present in the ring, and a stem, which indicates both the total number of atoms and the presence or absence of double bonds . The name may include more than a one prefix, if more than one type of heteroatom is present; a multiplicative prefix if there are several heteroatoms of the same type; and locants to indicate

110-449: A lighter based on hydrogen and a platinum sponge, which became a commercial success in the 1820s that lives on today. Humphry Davy discovered the use of platinum in catalysis. In the 1880s, Wilhelm Ostwald at Leipzig University started a systematic investigation into reactions that were catalyzed by the presence of acids and bases, and found that chemical reactions occur at finite rates and that these rates can be used to determine

165-409: A liquid or gaseous reaction mixture . Important heterogeneous catalysts include zeolites , alumina , higher-order oxides, graphitic carbon, transition metal oxides , metals such as Raney nickel for hydrogenation, and vanadium(V) oxide for oxidation of sulfur dioxide into sulfur trioxide by the contact process . Diverse mechanisms for reactions on surfaces are known, depending on how

220-598: A facet (edge, surface, step, etc.) of a solid. Most of the volume but also most of the surface of a heterogeneous catalyst may be catalytically inactive. Finding out the nature of the active site is technically challenging. For example, the catalyst for the Haber process for the synthesis of ammonia from nitrogen and hydrogen is often described as iron . But detailed studies and many optimizations have led to catalysts that are mixtures of iron-potassium-calcium-aluminum-oxide. The reacting gases adsorb onto active sites on

275-422: A heteroatom record (HETATM) describes an atom as belonging to a small molecule cofactor rather than being part of a biopolymer chain. In the context of zeolites , the term heteroatom refers to partial isomorphous substitution of the typical framework atoms ( silicon , aluminium , and phosphorus ) by other elements such as beryllium , vanadium , and chromium . The goal is usually to adjust properties of

330-452: A high surface area, most commonly alumina , zeolites or various kinds of activated carbon . Specialized supports include silicon dioxide , titanium dioxide , calcium carbonate , and barium sulfate . In the context of electrochemistry , specifically in fuel cell engineering, various metal-containing catalysts are used to enhance the rates of the half reactions that comprise the fuel cell. One common type of fuel cell electrocatalyst

385-401: A higher specific activity (per gram) on support. Sometimes the support is merely a surface on which the catalyst is spread to increase the surface area. More often, the support and the catalyst interact, affecting the catalytic reaction. Supports can also be used in nanoparticle synthesis by providing sites for individual molecules of catalyst to chemically bind. Supports are porous materials with

440-406: A kinetic barrier. The catalyst may increase the reaction rate or selectivity, or enable the reaction at lower temperatures. This effect can be illustrated with an energy profile diagram. In the catalyzed elementary reaction , catalysts do not change the extent of a reaction: they have no effect on the chemical equilibrium of a reaction. The ratio of the forward and the reverse reaction rates

495-562: A non-standard valence state for a heteroatom but, in practice, this is rare. The choice of stem is quite complicated, and not completely standardised. The main criteria are: Notes on table: Hantzsch–Widman nomenclature is named after the German chemist Arthur Hantzsch and the Swedish chemist Oskar Widman , who independently proposed similar methods for the systematic naming of heterocyclic compounds in 1887 and 1888 respectively. It forms

550-409: A one-pot reaction. In autocatalysis , the catalyst is a product of the overall reaction, in contrast to all other types of catalysis considered in this article. The simplest example of autocatalysis is a reaction of type A + B → 2 B, in one or in several steps. The overall reaction is just A → B, so that B is a product. But since B is also a reactant, it may be present in the rate equation and affect

605-399: A process, is derived from Greek καταλύειν , meaning "to annul", or "to untie", or "to pick up". The concept of catalysis was invented by chemist Elizabeth Fulhame and described in a 1794 book, based on her novel work in oxidation–reduction reactions. The first chemical reaction in organic chemistry that knowingly used a catalyst was studied in 1811 by Gottlieb Kirchhoff , who discovered

SECTION 10

#1732793818997

660-401: A type of catalysis where the catalyst can be toggled between different ground states possessing distinct reactivity, typically by applying an external stimulus. This ability to reversibly switch the catalyst allows for spatiotemporal control over catalytic activity and selectivity. The external stimuli used to switch the catalyst can include changes in temperature, pH, light, electric fields, or

715-427: Is a good reagent for dihydroxylation, but it is highly toxic and expensive. In Upjohn dihydroxylation , the sacrificial catalyst N-methylmorpholine N-oxide (NMMO) regenerates OsO 4 , and only catalytic quantities of OsO 4 are needed. Catalysis may be classified as either homogeneous or heterogeneous . A homogeneous catalysis is one whose components are dispersed in the same phase (usually gaseous or liquid) as

770-466: Is a stable molecule that resembles the transition state of a chemical reaction can function as weak catalysts for that chemical reaction by lowering its activation energy. Such catalytic antibodies are sometimes called " abzymes ". Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture. In 2005, catalytic processes generated about $ 900 billion in products worldwide. Catalysis

825-476: Is applied is in the oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid . Many heterogeneous catalysts are in fact nanomaterials. Heterogeneous catalysts are typically " supported ", which means that the catalyst is dispersed on a second material that enhances the effectiveness or minimizes its cost. Supports prevent or minimize agglomeration and sintering of small catalyst particles, exposing more surface area, thus catalysts have

880-408: Is based upon nanoparticles of platinum that are supported on slightly larger carbon particles. When in contact with one of the electrodes in a fuel cell, this platinum increases the rate of oxygen reduction either to water or to hydroxide or hydrogen peroxide . Homogeneous catalysts function in the same phase as the reactants. Typically homogeneous catalysts are dissolved in a solvent with

935-513: Is one of the largest-scale and most energy-intensive processes. In the Haber process nitrogen is combined with hydrogen over an iron oxide catalyst. Methanol is prepared from carbon monoxide or carbon dioxide but using copper-zinc catalysts. Bulk polymers derived from ethylene and propylene are often prepared via Ziegler-Natta catalysis . Polyesters, polyamides, and isocyanates are derived via acid-base catalysis . Most carbonylation processes require metal catalysts, examples include

990-407: Is produced, and if there is no energy barrier, there is no need for a catalyst. Then, removing the catalyst would also result in a reaction, producing energy; i.e. the addition and its reverse process, removal, would both produce energy. Thus, a catalyst that could change the equilibrium would be a perpetual motion machine , a contradiction to the laws of thermodynamics. Thus, catalysts do not alter

1045-475: Is regenerated. The overall rate is the rate of the slow step An example of heterogeneous catalysis is the reaction of oxygen and hydrogen on the surface of titanium dioxide (TiO 2 , or titania ) to produce water. Scanning tunneling microscopy showed that the molecules undergo adsorption and dissociation . The dissociated, surface-bound O and H atoms diffuse together. The intermediate reaction states are: HO 2 , H 2 O 2 , then H 3 O 2 and

1100-412: Is so pervasive that subareas are not readily classified. Some areas of particular concentration are surveyed below. Petroleum refining makes intensive use of catalysis for alkylation , catalytic cracking (breaking long-chain hydrocarbons into smaller pieces), naphtha reforming and steam reforming (conversion of hydrocarbons into synthesis gas ). Even the exhaust from the burning of fossil fuels

1155-401: Is the effect of catalysts on air pollution and reducing the amount of carbon monoxide. Development of active and selective catalysts for the conversion of carbon monoxide into desirable products is one of the most important roles of catalysts. Using catalysts for hydrogenation of carbon monoxide helps to remove this toxic gas and also attain useful materials. The SI derived unit for measuring

SECTION 20

#1732793818997

1210-659: Is treated via catalysis: Catalytic converters , typically composed of platinum and rhodium , break down some of the more harmful byproducts of automobile exhaust. With regard to synthetic fuels, an old but still important process is the Fischer-Tropsch synthesis of hydrocarbons from synthesis gas , which itself is processed via water-gas shift reactions , catalyzed by iron. The Sabatier reaction produces methane from carbon dioxide and hydrogen. Biodiesel and related biofuels require processing via both inorganic and biocatalysts. Fuel cells rely on catalysts for both

1265-439: Is unaffected (see also thermodynamics ). The second law of thermodynamics describes why a catalyst does not change the chemical equilibrium of a reaction. Suppose there was such a catalyst that shifted an equilibrium. Introducing the catalyst to the system would result in a reaction to move to the new equilibrium, producing energy. Production of energy is a necessary result since reactions are spontaneous only if Gibbs free energy

1320-586: The Monsanto acetic acid process and hydroformylation . Many fine chemicals are prepared via catalysis; methods include those of heavy industry as well as more specialized processes that would be prohibitively expensive on a large scale. Examples include the Heck reaction , and Friedel–Crafts reactions . Because most bioactive compounds are chiral , many pharmaceuticals are produced by enantioselective catalysis (catalytic asymmetric synthesis ). (R)-1,2-Propandiol,

1375-514: The catalytic activity of a catalyst is the katal , which is quantified in moles per second. The productivity of a catalyst can be described by the turnover number (or TON) and the catalytic activity by the turn over frequency (TOF), which is the TON per time unit. The biochemical equivalent is the enzyme unit . For more information on the efficiency of enzymatic catalysis, see the article on enzymes . In general, chemical reactions occur faster in

1430-423: The reactant 's molecules. A heterogeneous catalysis is one where the reaction components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Similar mechanistic principles apply to heterogeneous, homogeneous, and biocatalysis. Heterogeneous catalysts act in a different phase than the reactants . Most heterogeneous catalysts are solids that act on substrates in

1485-551: The acid-catalyzed conversion of starch to glucose. The term catalysis was later used by Jöns Jakob Berzelius in 1835 to describe reactions that are accelerated by substances that remain unchanged after the reaction. Fulhame , who predated Berzelius, did work with water as opposed to metals in her reduction experiments. Other 18th century chemists who worked in catalysis were Eilhard Mitscherlich who referred to it as contact processes, and Johann Wolfgang Döbereiner who spoke of contact action. He developed Döbereiner's lamp ,

1540-478: The activity of enzymes (and other catalysts) including temperature, pH, the concentration of enzymes, substrate, and products. A particularly important reagent in enzymatic reactions is water, which is the product of many bond-forming reactions and a reactant in many bond-breaking processes. In biocatalysis , enzymes are employed to prepare many commodity chemicals including high-fructose corn syrup and acrylamide . Some monoclonal antibodies whose binding target

1595-421: The addition of chemical agents. A true catalyst can work in tandem with a sacrificial catalyst . The true catalyst is consumed in the elementary reaction and turned into a deactivated form. The sacrificial catalyst regenerates the true catalyst for another cycle. The sacrificial catalyst is consumed in the reaction, and as such, it is not really a catalyst, but a reagent. For example, osmium tetroxide (OsO 4 )

1650-442: The adsorption takes place ( Langmuir-Hinshelwood , Eley-Rideal , and Mars- van Krevelen ). The total surface area of a solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger the surface area for a given mass of particles. A heterogeneous catalyst has active sites , which are the atoms or crystal faces where the substrate actually binds. Active sites are atoms but are often described as

1705-502: The anodic and cathodic reactions. Catalytic heaters generate flameless heat from a supply of combustible fuel. Some of the largest-scale chemicals are produced via catalytic oxidation, often using oxygen . Examples include nitric acid (from ammonia), sulfuric acid (from sulfur dioxide to sulfur trioxide by the contact process ), terephthalic acid from p-xylene, acrylic acid from propylene or propane and acrylonitrile from propane and ammonia. The production of ammonia

Hantzsch–Widman nomenclature - Misplaced Pages Continue

1760-479: The backbone of the molecular structure. Typical heteroatoms are nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), chlorine (Cl), bromine (Br), and iodine (I), as well as the metals lithium (Li) and magnesium (Mg). It can also be used with highly specific meanings in specialised contexts. In the description of protein structure, in particular in the Protein Data Bank file format,

1815-405: The basis for many common chemical names, such as dioxin and benzodiazepine . Heteroatom In chemistry , a heteroatom (from Ancient Greek heteros  'different' and atomos  'uncut') is, strictly, any atom that is not carbon or hydrogen . In practice, the term is mainly used more specifically to indicate that non-carbon atoms have replaced carbon in

1870-462: The early 2000s, these organocatalysts were considered "new generation" and are competitive to traditional metal (-ion)-containing catalysts. Organocatalysts are supposed to operate akin to metal-free enzymes utilizing, e.g., non-covalent interactions such as hydrogen bonding . The discipline organocatalysis is divided into the application of covalent (e.g., proline , DMAP ) and non-covalent (e.g., thiourea organocatalysis ) organocatalysts referring to

1925-407: The environment by increasing the efficiency of industrial processes, but catalysis also plays a direct role in the environment. A notable example is the catalytic role of chlorine free radicals in the breakdown of ozone . These radicals are formed by the action of ultraviolet radiation on chlorofluorocarbons (CFCs). The term "catalyst", broadly defined as anything that increases the rate of

1980-431: The equilibrium constant. (A catalyst can however change the equilibrium concentrations by reacting in a subsequent step. It is then consumed as the reaction proceeds, and thus it is also a reactant. Illustrative is the base-catalyzed hydrolysis of esters , where the produced carboxylic acid immediately reacts with the base catalyst and thus the reaction equilibrium is shifted towards hydrolysis.) The catalyst stabilizes

2035-405: The final "a" is elided when the prefix comes before a vowel. The heteroatom is assumed to have its standard bonding number for organic chemistry while the name is being constructed. The halogens have a standard bonding number of one, and so a heterocyclic ring containing a halogen as a heteroatom should have a formal positive charge. In principle, lambda nomenclature could be used to specify

2090-414: The iron particles. Once physically adsorbed, the reagents partially or wholly dissociate and form new bonds. In this way the particularly strong triple bond in nitrogen is broken, which would be extremely uncommon in the gas phase due to its high activation energy. Thus, the activation energy of the overall reaction is lowered, and the rate of reaction increases. Another place where a heterogeneous catalyst

2145-401: The material (e.g., Lewis acidity ) to optimize the material for a certain application (e.g., catalysis ). Catalysis Catalysis ( / k ə ˈ t æ l ə s ɪ s / ) is the increase in rate of a chemical reaction due to an added substance known as a catalyst ( / ˈ k æ t əl ɪ s t / ). Catalysts are not consumed by the reaction and remain unchanged after it. If

2200-497: The precursor to the antibacterial levofloxacin , can be synthesized efficiently from hydroxyacetone by using catalysts based on BINAP -ruthenium complexes, in Noyori asymmetric hydrogenation : One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) of fats using nickel catalyst to produce margarine . Many other foodstuffs are prepared via biocatalysis (see below). Catalysis affects

2255-1085: The preferred catalyst- substrate binding and interaction, respectively. The Nobel Prize in Chemistry 2021 was awarded jointly to Benjamin List and David W.C. MacMillan "for the development of asymmetric organocatalysis." Photocatalysis is the phenomenon where the catalyst can receive light to generate an excited state that effect redox reactions. Singlet oxygen is usually produced by photocatalysis. Photocatalysts are components of dye-sensitized solar cells . In biology, enzymes are protein-based catalysts in metabolism and catabolism . Most biocatalysts are enzymes, but other non-protein-based classes of biomolecules also exhibit catalytic properties including ribozymes , and synthetic deoxyribozymes . Biocatalysts can be thought of as an intermediate between homogeneous and heterogeneous catalysts, although strictly speaking soluble enzymes are homogeneous catalysts and membrane -bound enzymes are heterogeneous. Several factors affect

Hantzsch–Widman nomenclature - Misplaced Pages Continue

2310-444: The prefix that is lower on the list. For example, "oxa" (for oxygen ) always comes before "aza" (for nitrogen ) in a name. The priority order is the same as that used in substitutive nomenclature , but Hantzsch–Widman nomenclature is recommended only for use with a more restricted set of heteroatoms (see also below). All of the prefixes end in "a": In Hantzsch–Widman nomenclature (but not in some other methods of naming heterocycles),

2365-428: The presence of a catalyst because the catalyst provides an alternative reaction mechanism (reaction pathway) having a lower activation energy than the non-catalyzed mechanism. In catalyzed mechanisms, the catalyst is regenerated. As a simple example occurring in the gas phase, the reaction 2 SO 2 + O 2 → 2 SO 3 can be catalyzed by adding nitric oxide . The reaction occurs in two steps: The NO catalyst

2420-464: The presence of a catalyst such as manganese dioxide this reaction proceeds much more rapidly. This effect is readily seen by the effervescence of oxygen. The catalyst is not consumed in the reaction, and may be recovered unchanged and re-used indefinitely. Accordingly, manganese dioxide is said to catalyze this reaction. In living organisms, this reaction is catalyzed by enzymes (proteins that serve as catalysts) such as catalase . Another example

2475-484: The reactant, or heterogeneous , whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture. The term "catalyst" is derived from Greek καταλύειν , kataluein , meaning "loosen" or "untie". The concept of catalysis

2530-409: The reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. The rate increase occurs because the catalyst allows

2585-415: The reaction product ( water molecule dimers ), after which the water molecule desorbs from the catalyst surface. Catalysts enable pathways that differ from the uncatalyzed reactions. These pathways have lower activation energy . Consequently, more molecular collisions have the energy needed to reach the transition state . Hence, catalysts can enable reactions that would otherwise be blocked or slowed by

2640-419: The reaction rate. As the reaction proceeds, the concentration of B increases and can accelerate the reaction as a catalyst. In effect, the reaction accelerates itself or is autocatalyzed. An example is the hydrolysis of an ester such as aspirin to a carboxylic acid and an alcohol . In the absence of added acid catalysts, the carboxylic acid product catalyzes the hydrolysis. Switchable catalysis refers to

2695-426: The reaction to occur by an alternative mechanism which may be much faster than the non-catalyzed mechanism. However the non-catalyzed mechanism does remain possible, so that the total rate (catalyzed plus non-catalyzed) can only increase in the presence of the catalyst and never decrease. Catalysis may be classified as either homogeneous , whose components are dispersed in the same phase (usually gaseous or liquid) as

2750-499: The reaction. For example, Wilkinson's catalyst RhCl(PPh 3 ) 3 loses one triphenylphosphine ligand before entering the true catalytic cycle. Precatalysts are easier to store but are easily activated in situ . Because of this preactivation step, many catalytic reactions involve an induction period . In cooperative catalysis , chemical species that improve catalytic activity are called cocatalysts or promoters . In tandem catalysis two or more different catalysts are coupled in

2805-401: The relative positions of the different atoms. Hantzsch–Widman names may be combined with other aspects of organic nomenclature, to indicate substitution or fused-ring systems. The Hantzsch–Widman prefixes indicate the type of heteroatom(s) present in the ring. They form a priority series: If there is more than one type of heteroatom in the ring, the prefix that is higher on the list comes before

SECTION 50

#1732793818997

2860-500: The substrates. One example of homogeneous catalysis involves the influence of H on the esterification of carboxylic acids, such as the formation of methyl acetate from acetic acid and methanol . High-volume processes requiring a homogeneous catalyst include hydroformylation , hydrosilylation , hydrocyanation . For inorganic chemists, homogeneous catalysis is often synonymous with organometallic catalysts . Many homogeneous catalysts are however not organometallic, illustrated by

2915-474: The transition state more than it stabilizes the starting material. It decreases the kinetic barrier by decreasing the difference in energy between starting material and the transition state. It does not change the energy difference between starting materials and products (thermodynamic barrier), or the available energy (this is provided by the environment as heat or light). Some so-called catalysts are really precatalysts . Precatalysts convert to catalysts in

2970-617: The use of cobalt salts that catalyze the oxidation of p-xylene to terephthalic acid . Whereas transition metals sometimes attract most of the attention in the study of catalysis, small organic molecules without metals can also exhibit catalytic properties, as is apparent from the fact that many enzymes lack transition metals. Typically, organic catalysts require a higher loading (amount of catalyst per unit amount of reactant, expressed in mol% amount of substance ) than transition metal(-ion)-based catalysts, but these catalysts are usually commercially available in bulk, helping to lower costs. In

3025-431: Was invented by chemist Elizabeth Fulhame , based on her novel work in oxidation-reduction experiments. An illustrative example is the effect of catalysts to speed the decomposition of hydrogen peroxide into water and oxygen : This reaction proceeds because the reaction products are more stable than the starting compound, but this decomposition is so slow that hydrogen peroxide solutions are commercially available. In

#996003