Arsenates
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The arsenate ion is . An arsenate (compound) is any
compound Compound may refer to: Architecture and built environments * Compound (enclosure), a cluster of buildings having a shared purpose, usually inside a fence or wall ** Compound (fortification), a version of the above fortified with defensive struc ...
that contains this ion. Arsenates are
salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quant ...
s or
ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ...
s of
arsenic acid Arsenic acid or trihydrogen arsenate is the chemical compound with the formula . More descriptively written as , this colorless acid is the arsenic analogue of phosphoric acid. Arsenate and phosphate salts behave very similarly. Arsenic acid as su ...
. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate resembles
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phosph ...
in many respects, since
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, b ...
and
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...
occur in the same group (column) of the
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
. Arsenates are moderate oxidizers, with an
electrode potential In electrochemistry, electrode potential is the electromotive force of a galvanic cell built from a standard reference electrode and another electrode to be characterized. By convention, the reference electrode is the standard hydrogen electrode ...
of +0.56  V for reduction to
arsenite In chemistry, an arsenite is a chemical compound containing an arsenic oxyanion where arsenic has oxidation state +3. Note that in fields that commonly deal with groundwater chemistry, arsenite is used generically to identify soluble AsIII anions. ...
s.


Occurrence

Arsenates occur naturally in a variety of
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
s. Those minerals may contain
hydrated Drinking is the act of ingesting water or other liquids into the body through the mouth, proboscis, or elsewhere. Humans drink by swallowing, completed by peristalsis in the esophagus. The physiological processes of drinking vary widely among o ...
or
anhydrous A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achi ...
arsenates. Unlike phosphates, arsenates are not lost from a mineral during
weathering Weathering is the deterioration of rocks, soils and minerals as well as wood and artificial materials through contact with water, atmospheric gases, and biological organisms. Weathering occurs '' in situ'' (on site, with little or no movement ...
. Examples of arsenate-containing minerals include
adamite Adamite is a zinc arsenate hydroxide mineral, Zn2 As O4O H. It is a mineral that typically occurs in the oxidized or weathered zone above zinc ore occurrences. Pure adamite is colorless, but usually it possess yellow color due to Fe compounds ...
, alarsite, annabergite,
erythrite Erythrite or red cobalt is a secondary hydrated cobalt arsenate mineral with the formula . Erythrite and annabergite, chemical formula , or nickel arsenate form a complete series with the general formula . Erythrite crystallizes in the monocli ...
and
legrandite Legrandite is a rare zinc arsenate mineral, Zn2(AsO4)(OH)·(H2O). It is an uncommon secondary mineral in the oxidized zone of arsenic bearing zinc deposits and occurs rarely in granite pegmatite. Associated minerals include: adamite, paradami ...
. Where two arsenate ions are required to balance the charge in a formula, it is called diarsenate for example trizinc diarsenate, Zn3(AsO4)2.


Ions

The word arsenate is derived from
arsenic acid Arsenic acid or trihydrogen arsenate is the chemical compound with the formula . More descriptively written as , this colorless acid is the arsenic analogue of phosphoric acid. Arsenate and phosphate salts behave very similarly. Arsenic acid as su ...
, H3AsO4. This moderately strong acid converts to dihydrogen arsenate (), hydrogen arsenate (), and arsenate (), depending on pH. The quantitative relationship between these species is defined by the acid dissociation constants: :H3AsO4 + H2O + H3O+(log ''K''1 = −2.19) : + H2O + H3O+(log ''K''2 = −6.94) : + H2O + H3O+(log ''K''3 = −11.5) These values are similar to those of the hydrogen phosphates. Hydrogen arsenate and dihydrogen arsenate predominate in aqueous solution near neutral pH.


Arsenate poisoning

Arsenate can replace inorganic
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phosph ...
in the step of
glycolysis Glycolysis is the metabolic pathway that converts glucose () into pyruvate (). The free energy released in this process is used to form the high-energy molecules adenosine triphosphate (ATP) and reduced nicotinamide adenine dinucleotide (NADH ...
that produces
1,3-bisphosphoglycerate 1,3-Bisphosphoglyceric acid (1,3-Bisphosphoglycerate or 1,3BPG) is a 3-carbon organic molecule present in most, if not all, living organisms. It primarily exists as a metabolic intermediate in both glycolysis during respiration and the Calvin cy ...
from
glyceraldehyde 3-phosphate Glyceraldehyde 3-phosphate, also known as triose phosphate or 3-phosphoglyceraldehyde and abbreviated as G3P, GA3P, GADP, GAP, TP, GALP or PGAL, is a metabolite that occurs as an intermediate in several central pathways of all organisms.Nelson, D ...
. This yields 1-arseno-3-phosphoglycerate instead, which is unstable and quickly hydrolyzes, forming the next intermediate in the pathway,
3-phosphoglycerate 3-Phosphoglyceric acid (3PG, 3-PGA, or PGA) is the conjugate acid of 3-phosphoglycerate or glycerate 3-phosphate (GP or G3P). This glycerate is a biochemically significant metabolic intermediate in both glycolysis and the Calvin-Benson cycle. The ...
. Therefore, glycolysis proceeds, but the ATP molecule that would be generated from
1,3-bisphosphoglycerate 1,3-Bisphosphoglyceric acid (1,3-Bisphosphoglycerate or 1,3BPG) is a 3-carbon organic molecule present in most, if not all, living organisms. It primarily exists as a metabolic intermediate in both glycolysis during respiration and the Calvin cy ...
is lost – arsenate is an uncoupler of glycolysis, explaining its toxicity. As with other arsenic compounds, arsenite binds to
lipoic acid Lipoic acid (LA), also known as α-lipoic acid, alpha-lipoic acid (ALA) and thioctic acid, is an organosulfur compound derived from caprylic acid (octanoic acid). ALA is made in animals normally, and is essential for aerobic metabolism. It i ...
, inhibiting the conversion of
pyruvate Pyruvic acid (CH3COCOOH) is the simplest of the alpha-keto acids, with a carboxylic acid and a ketone functional group. Pyruvate, the conjugate base, CH3COCOO−, is an intermediate in several metabolic pathways throughout the cell. Pyruvic a ...
into
acetyl-CoA Acetyl-CoA (acetyl coenzyme A) is a molecule that participates in many biochemical reactions in protein, carbohydrate and lipid metabolism. Its main function is to deliver the acetyl group to the citric acid cycle (Krebs cycle) to be oxidized for ...
, blocking the
Krebs cycle The citric acid cycle (CAC)—also known as the Krebs cycle or the TCA cycle (tricarboxylic acid cycle)—is a series of chemical reactions to release stored energy through the oxidation of acetyl-CoA derived from carbohydrates, fats, and protein ...
and therefore resulting in further loss of ATP.


See also

* :Arsenates


References

{{Reflist Oxyanions * Arsenic(V) compounds