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Family unit of double sulfate salts of aluminium

This article is almost the form of double sulfates of aluminium. For the specific representative chemical compound, encounter potassium alum. For the chromium analogs, see chrome alum. For papermakers alum, see aluminium sulfate. For other uses, see Alum (disambiguation).

For a graduate or former student of an educational institution, see Alumnus.

Bulk potassium alum KAl(So
four )
two ·12H
2 O.

An alum () is a type of chemical compound, usually a hydrated double sulfate salt of aluminium with the general formula XAl(And so
iv )
two ·12 H
2 O, where X is a monovalent cation such as potassium or ammonium.[i] By itself, "alum" often refers to potassium alum, with the formula KAl(Then
iv )
2 ·12 H
2 O. Other alums are named after the monovalent ion, such as sodium alum and ammonium alum.

The proper noun "alum" is also used, more generally, for salts with the aforementioned formula and structure, except that aluminium is replaced by another trivalent metal ion like chromiumIii, and/or sulfur is replaced past another chalcogen similar selenium.[1] The most common of these analogs is chrome alum KCr(SO
4 )
2 ·12 H
ii O.

In most industries, the proper noun "alum" (or "papermaker's alum") is used to refer to aluminium sulfate, Al
ii  (SO
4 )
3 ·nH
two O , which is used for near industrial flocculation[ane] : 766 (the variable n is an integer, whose size depends on the amount of water absorbed into the alum). In medicine, "alum" may also refer to aluminium hydroxide gel used as a vaccine adjuvant.[two]

History [edit]

Alum found at archaeological sites [edit]

The western desert of Egypt was a major source of alum substitutes in artifact. These evaporites were mainly FeAl
two (And then
4 )
4 ·22 H
two O, MgAl
ii (SO
4 )
4 ·22 H
2 O, NaAl(So
iv )
two ·6 H
two O, MgSO
4 ·7H
two O and Al
two (SO
4 )
three ·17 H
2 O.[3] [four] The Ancient Greek Herodotus mentions Egyptian alum as a valuable article in The Histories.[5]

The production of potassium alum from alunite is archaeologically attested on the isle Lesbos.[six] The site was abandoned in the 7th century CE, but dates dorsum at least to the 2nd century CE. Native alumen from the island of Melos appears to have been a mixture mainly of alunogen (Al
two (Then
4 )
three ·17 H
2 O) with potassium alum and other minor sulfates.[seven]

Alumen in Pliny and Dioscorides [edit]

A detailed description of a substance called alumen occurs in the Roman Pliny the Elder'due south Natural History.[eight]

By comparing Pliny's description with the account of stupteria given past Dioscorides,[9] it is obvious the two are identical. Pliny informs u.s. that a form of alumen was found naturally in the earth, and calls it salsugoterrae.

Pliny wrote that different substances were distinguished by the proper name of alumen, but they were all characterised by a certain caste of astringency, and were all employed in dyeing and medicine. Pliny wrote that at that place is another kind of alum that the Greeks call schiston, and which "splits into filaments of a whitish color".[8] From the name schiston and the way of formation, it appears that this kind was the common salt that forms spontaneously on certain salty minerals, as alum slate and bituminous shale, and consists chiefly of sulfates of iron and aluminium.[ citation needed ] 1 kind of alumen was a liquid, which was apt to be adulterated; merely when pure it had the property of blackening when added to pomegranate juice. This property seems to narrate a solution of feII sulfate in water; a solution of ordinary (potassium) alum would possess no such property. Contamination with fe sulfate was greatly disliked as this darkened and dulled dye colours. In some places the iron sulfate may accept been lacking, and so the salt would exist white and would be suitable, according to Pliny, for dyeing bright colors.

Pliny describes several other types of alumen but it is not clear as to what these minerals are. The alumen of the ancients, then, was not always potassium alum, not even an alkali aluminum sulfate.[ten] :  766–767

Alum described in medieval texts [edit]

Alum and green vitriol (iron sulfate) both have sweetish and astringent taste, and they had overlapping uses. Therefore, through the Middle Ages, alchemists and other writers do not seem to accept discriminated the two salts accurately from each other. In the writings of the alchemists we find the words misy, sory, and chalcanthum applied to either compound; and the name atramentum sutorium, which i might await to belong exclusively to greenish vitriol, applied indifferently to both.

Alum was the nigh mutual mordant used in the dye industry in the Islamic eye ages. It was the master export of the Republic of chad region, from where information technology was transported to the markets of Egypt and Kingdom of morocco, and then on to Europe. Other, less significant, sources were found in Egypt and Republic of yemen.[eleven]

Modern understanding of the alums [edit]

In the early 1700s, G.E. Stahl claimed that reacting sulfuric acrid with limestone produced a sort of alum.[12] [a] [b] [13] The error was soon corrected past J.H. Pott and A.S. Marggraf, who showed that the precipitate obtained when an brine is poured into a solution of alum, namely alumina, is quite unlike from lime and chalk, and is one of the ingredients in mutual clay.[14] [c] [15] : 41–66

Marggraf also showed that perfect crystals with backdrop of alum tin can be obtained past dissolving alumina in sulfuric acrid and adding potash or ammonia to the concentrated solution.[10] : 766 [15] : 31–xl In 1767, Torbern Bergman observed the demand for potassium or ammonium sulfates to convert aluminium sulfate into alum, while sodium or calcium would not piece of work.[16] [d] [10] : 766

The composition of common alum was finally adamant by Vauquelin in 1797. As soon as Klaproth discovered the presence of potassium in leucite and lepidolite,[17] [18] [east] Vauquelin demonstrated that mutual alum is a double table salt, composed of sulfuric acid, alumina, and potash.[xix] In the same journal volume, Chaptal published the analysis of four unlike kinds of alum, namely, Roman alum, Levant alum, British alum, and an alum manufactured past himself,[xx] confirming Vauquelin's consequence.[10]

Product [edit]

Some alums occur as minerals, the virtually important being alunite.

The well-nigh important alums – potassium, sodium, and ammonium – are produced industrially. Typical recipes involve combining aluminium sulfate and the sulfate monovalent cation.[21] The aluminium sulfate is unremarkably obtained by treating minerals like alum schist, bauxite and cryolite with sulfuric acid.[10] : 767

Types [edit]

Crystal of potassium alum

Aluminium-based alums are named by the monovalent cation. Unlike the other alkali metals, lithium does not class alums; a fact attributed to the pocket-size size of its ion.

The most of import alums are

  • Potassium alum, KAl(SO
    four     )
    ii     ·12 H
    ii     O    , also chosen "potash alum" or simply "alum".
  • Sodium alum, NaAl(And then
    4     )
    2     ·12 H
    ii     O    , also chosen "soda alum" or "SAS".
  • Ammonium alum, NH
    4     Al(SO
    4     )
    2     ·12 H
    2     O    .

Chemical properties [edit]

Aluminium-based alums have a number of mutual chemical backdrop. They are soluble in water, have a sweetish gustatory modality, react equally acrid past turning blue litmus to ruby-red, and crystallize in regular octahedra. In alums each metal ion is surrounded by six water molecules. When heated, they liquefy, and if the heating is continued, the h2o of crystallization is driven off, the salt froths and swells, and at last an amorphous powder remains.[10] : 766 They are astringent and acidic.

Crystal structure [edit]

Alums crystallize in ane of 3 unlike crystal structures. These classes are called α-, β- and γ-alums. The first Ten-ray crystal structures of alums were reported in 1927 by James Chiliad. Cork and Lawrence Bragg, and were used to develop the phase retrieval technique isomorphous replacement.[22]

Solubility [edit]

The solubility of the various alums in water varies greatly, sodium alum beingness readily soluble in water, while caesium and rubidium alums are but sparingly soluble. The various solubilities are shown in the post-obit tabular array.[10] : 767

At temperature T, 100 parts h2o deliquesce:

T Ammonium
alum 		Potassium
alum 		Rubidium
alum 		Caesium
alum
0 °C 2.62 3.90 0.71 0.nineteen
x °C 4.fifty ix.52 i.09 0.29
50 °C fifteen.9 44.eleven iv.98 1.235
80 °C 35.xx 134.47 21.60 5.29
100 °C seventy.83 357.48

   ···

   ···

Uses [edit]

Aluminium-based alums accept been used since antiquity, and are notwithstanding important in many industrial processes. The most widely used alum is potassium alum. It has been used since antiquity as a flocculant to clarify turbid liquids, as a mordant in dyeing, and in tanning. It is all the same widely used in water treatment, in medicine, for cosmetics (in deodorant), in food preparation (in baking pulverisation and pickling), and to fire-proof newspaper and cloth.

Alum is as well used equally a styptic, in styptic pencils bachelor from pharmacists, or equally an alum block, bachelor from hairdresser shops and gentlemen's outfitters, to stalk bleeding from shaving nicks;[23] and as an severe. An alum block can exist used straight as a perfume-costless deodorant (antiperspirant), and unprocessed mineral alum is sold in Indian bazaars for but that purpose. Throughout Island Southeast Asia, potassium alum is near widely known as tawas and has numerous uses. It is used as a traditional antiperspirant and deodorant, and in traditional medicine for open up wounds and sores. The crystals are usually ground into a fine powder before using.[24] [25]

In the Victorian Era, Alum was used along with other substances like Plaster of Paris to adulterate certain nutrient products, particularly staff of life. It was used to make lower-course flour appear whiter, allowing the producers to spend less on whiter flour. And because it retains water, it would make the bread heavier, pregnant that merchants could accuse more for it in their shops. The amount of Alum present in each loaf of bread could reach levels that would be toxic to humans and cause chronic diarrhea which could lead to death in young children.[26]

Alum is used every bit a mordant in traditional textiles;[27] and in Indonesia and the Philippines, solutions of tawas, salt, borax, and organic pigments were used to alter the color of gold ornaments.[28] In the Philippines, alum crystals were also burned and allowed to baste into a bowl of water by babaylan (shamans) for divination. It is likewise used in other rituals in the animistic anito religions of the islands.[29] [xxx] [31] [32] In traditional Japanese fine art, alum and animate being glue were dissolved in water, forming a liquid known as dousa (ja:礬水), and used as an undercoat for paper sizing.

Alum in the grade of potassium aluminium sulphate or ammonium aluminium sulfate in a concentrated bathroom of hot water is regularly used by jewelers and machinists to deliquesce hardened steel drill bits that take broken off in items made of aluminum, copper, brass, gold (any karat), silvery (both sterling and fine) and stainless steel. This is because alum does not react chemically to any significant degree with any of these metals, simply will corrode carbon steel. When heat is applied to an alum mixture holding a slice of work that has a drill bit stuck in it, if the lost scrap is minor enough, it tin can sometimes exist dissolved / removed within hours.[33]

[edit]

Many trivalent metals are capable of forming alums. The full general course of an alum is XY (And then
four )
two ·n H
2 O, where 10 is an element of group i or ammonium, Y is a trivalent metal, and due north often is 12. The most important case is chrome alum, KCr(SO
four )
two ·12 H
2 O, a dark violet crystalline double sulfate of chromium and potassium, was used in tanning.

In general, alums are formed more easily when the alkali metal atom is larger. This rule was first stated by Locke in 1902,[34] who found that if a trivalent metal does not class a caesium alum, information technology neither will class an alum with any other brine metal or with ammonium.

Selenate-containing alums [edit]

Selenium or selenate alums are besides known that contain selenium in place of sulfur in the sulfate anion, making selenate (SeO 2−
iv ) instead.[35] They are potent oxidizing agents.

Mixed alums [edit]

In some cases, solid solutions of alums with different monovalent and trivalent cations may occur.

Other hydrates [edit]

In addition to the alums, which are dodecahydrates, double sulfates and selenates of univalent and trivalent cations occur with other degrees of hydration. These materials may also be referred to every bit alums, including the undecahydrates such equally mendozite and kalinite, hexahydrates such as guanidinium [CH
6 Due north +
3 ] and dimethylammonium [(CH
3 )2NH +
2 ] "alums", tetrahydrates such as goldichite, monohydrates such as thallium plutonium sulfate and anhydrous alums (yavapaiites). These classes include differing, but overlapping, combinations of ions.

Other double sulfates [edit]

A pseudo alum is a double sulfate of the typical formula 10SO
4 · Y(2 SO
iv )
3 ·22 H
2 O, where

X is a divalent metallic ion, such every bit
cobalt (wupatkiite), manganese (apjohnite), magnesium (pickingerite) or iron (halotrichite or feather alum), and
Y is a trivalent metal ion.[36]

Double sulfates with the general formula 10
2 And so
4 · Y
2 (SO
4 )
three ·24 H
two O are likewise known, where

X is a monovalent cation such as
sodium, potassium, rubidium, caesium, or thalliumI, or a compound cation such every bit ammonium (NH +
4 ), methylammonium (CH3NH +
iii ), hydroxylammonium (HONH +
3 ) or hydrazinium (North
two H +
five )
Y is a trivalent metal ion, such as
aluminium, chromium, titanium, manganese, vanadium, ironIii, cobaltIII, gallium, molybdenum, indium, ruthenium, rhodium, or iridium.[37]

Analogous selenates besides occur. The possible combinations of univalent cation, trivalent cation, and anion depends on the sizes of the ions.

A Tutton salt is a double sulfate of the typical formula X
2 So ·
4 Y  So
4 ·6H
2 O, where X is a univalent cation, and Y a divalent metal ion.

Double sulfates of the composition X
2 So
4 ·2 Y  So
four , where

X is a univalent cation and
Y is a divalent metallic ion are referred to equally langbeinites, subsequently the prototypical potassium magnesium sulfate.

Run into besides [edit]

  • Alunite
  • List of minerals
  • Gum bichromate - photograph prints and other similar processes utilise alums, sometimes as colloid (gelatin, albumen) hardeners

Footnotes [edit]

  1. ^ CVII. Vitriolum, Creta præcipitari potest, ut omissa metallica sua substantia, aluminosum evadat.
    [107.   Sulfuric acid [and] chalk can [class a] precipitate, as its liberated metal substance, alum, escapes.]
    Ausführliche Betrachtung und zulänglicher Beweiss von den Saltzen, daß diesselbe aus einer zarten Erde, mit Wasser innig verbunden, bestehen
    [Detailed treatment and acceptable proof of salts, that they consist of a subtile earth intimately bound with water]
    — G.East. Stahl (1703)[12]
  2. ^ Wäysenhaus, Halle
    ... wie aus Kreide und Vitriole-Spiritu, ein rechter Alaun erwächset: ...
    [... as from chalk and sulfuric acid, a real alum arises ...]
    — G.E. Stahl (1723)[xiii]
  3. ^ Concentrirt human hingegen diese solution gelinde, und läßt sie crystallisiren, then schiessen harte und mercklich adstringente und hinter her etwas süßliche crystallen an, die allen Umständen nach in der Haupt-Sach nichts anders sind als ein formaler Alaun. Diese Entdeckung ist in der physicalischen Chymie von Wichtigkeit. Human chapeau bishero geglaubt, die Grund-Erde des Alauns sey eine in acido Vitrioli solvirte kalckige ... Erde, ...
    [On the other mitt, if one gently concentrates this solution, and lets it crystallize, so there precipitate hard, noticeably severe crystals with a somewhat sweet palatableness, which in all circumstances are mainly nothing other than a grade of alum. This discovery is of importance to chemistry. One had hitherto believed [that] the primal earth of alum is a calcareous ... earth dissolved in sulfuric acid, ...]
    — J.H. Pott (1746)[14]
  4. ^ Later acknowledging that Marggraf had noticed that potash caused alum to crystallize from a solution of alumina and sulfuric acid, Bergman adds
    "Notatu quoque dignum est, quod hoc cristallisationis obstaculum alcali volatili aeque tollatur, non vero alkali minerali et calce."
    [It is significant too that past [utilize of] the volatile alkali (i.e., ammonia) this obstacle to crystallization is similarly removed, but not [in the cases of] mineral brine]
    (i.east., sodium carbonate and lime).
    — Bergman (1767)[xvi]
  5. ^ "On the contrary, I was surprised in an unexpected manner, by discovering in information technology some other constituent part, consisting of a substance, the beingness of which, certainly, no one person would accept conjectured within the limits of the mineral kingdom ... This constituent function of leucite ... is no other than pot-ash, which, hitherto, has been thought exclusively to belong to the vegetable kingdom, and has, on this business relationship, been called vegetable alkali.
    This discovery, which I retrieve of groovy importance, cannot fail to occasion considerable changes in the systems of natural history, ... ." — 1000.H. Klaproth (1801)[xviii]

References [edit]

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  2. ^ "Alhydrogel". InvivoGen (invivogen.com). Alum vaccine adjuvant for research. Retrieved 2018-06-08 .
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External links [edit]

  • Media related to Alum at Wikimedia Eatables

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Source: https://en.wikipedia.org/wiki/Alum

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