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An alum () is a type of
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
, usually a
hydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
d
double A double is a look-alike or doppelgänger; one person or being that resembles another. Double, The Double or Dubble may also refer to: Film and television * Double (filmmaking), someone who substitutes for the credited actor of a character * Th ...
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ar ...
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 quantitie ...
of
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
with the general
formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...
, where is a monovalent
cation 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 convent ...
such as
potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...
or
ammonium The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...
. By itself, "alum" often refers to
potassium alum Potassium alum, potash alum, or potassium aluminium sulfate is a chemical compound: the double sulfate of potassium and aluminium, with chemical formula KAl(SO4)2. It is commonly encountered as the dodecahydrate, KAl(SO4)2·12H2O. It crystalli ...
, with the formula . Other alums are named after the monovalent ion, such as
sodium alum Sodium aluminium sulfate is the inorganic compound with the chemical formula NaAl(SO4)2·12H2O (sometimes written Na2SO4·Al2(SO4)3·24H2O). Also known as soda alum, sodium alum, or SAS, this white solid is used in the manufacture of baking powd ...
and
ammonium alum Ammonium aluminium sulfate, also known as ammonium alum or just alum (though there are many different substances also called "alum"), is a white crystalline double sulfate usually encountered as the dodecahydrate, formula (NH4)Al(SO4)2·12H2O. It ...
. The name "alum" is also used, more generally, for salts with the same formula and structure, except that aluminium is replaced by another
trivalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with other atoms when it forms chemical compounds or molecules. Description The combining capacity, or affinity of an ...
metal ion like
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hardne ...
, and/or sulfur is replaced by another
chalcogen The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the radioact ...
like
selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
. The most common of these analogs is
chrome alum Chrome alum or Chromium(III) potassium sulfate is the potassium double sulfate of chromium. Its chemical formula is KCr(SO4)2 and it is commonly found in its dodecahydrate form as KCr(SO4)2·12(H2O). It is used in leather tanning. Production a ...
. In most industries, the name "alum" (or "papermaker's alum") is used to refer to
aluminium sulfate Aluminium sulfate is a salt with the chemical formula, formula aluminium, Al2sulfate, (SO4)3. It is soluble in water and is mainly used as a Coagulation (water treatment), coagulating agent (promoting particle collision by neutralizing charge) in ...
, , which is used for most industrial
flocculation Flocculation, in the field of chemistry, is a process by which colloidal particles come out of suspension to sediment under the form of floc or flake, either spontaneously or due to the addition of a clarifying agent. The action differs from pr ...
(the variable is an integer whose size depends on the amount of water absorbed into the alum). In
medicine Medicine is the science and practice of caring for a patient, managing the diagnosis, prognosis, prevention, treatment, palliation of their injury or disease, and promoting their health. Medicine encompasses a variety of health care pract ...
, "alum" may also refer to
aluminium hydroxide Aluminium hydroxide, Al(OH)3, is found in nature as the mineral gibbsite (also known as hydrargillite) and its three much rarer polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is amphoteric, i.e., it has both basic and ...
gel used as a
vaccine adjuvant In immunology, an adjuvant is a substance that increases or modulates the immune response to a vaccine. The word "adjuvant" comes from the Latin word ''adiuvare'', meaning to help or aid. "An immunologic adjuvant is defined as any substance that ...
.


History


Alum found at archaeological sites

The western desert of Egypt was a major source of alum substitutes in antiquity. These
evaporite An evaporite () is a water-soluble sedimentary mineral deposit that results from concentration and crystallization by evaporation from an aqueous solution. There are two types of evaporite deposits: marine, which can also be described as ocea ...
s were mainly , , , and . The
Ancient Greek Ancient Greek includes the forms of the Greek language used in ancient Greece and the ancient world from around 1500 BC to 300 BC. It is often roughly divided into the following periods: Mycenaean Greek (), Dark Ages (), the Archaic peri ...
Herodotus Herodotus ( ; grc, , }; BC) was an ancient Greek historian and geographer from the Greek city of Halicarnassus, part of the Persian Empire (now Bodrum, Turkey) and a later citizen of Thurii in modern Calabria ( Italy). He is known f ...
mentions Egyptian alum as a valuable commodity in ''The Histories''. The production of potassium alum from
alunite Alunite is a hydroxylated aluminium potassium sulfate mineral, formula K Al3( S O4)2(O H)6. It was first observed in the 15th century at Tolfa, near Rome, where it was mined for the manufacture of alum. First called ''aluminilite'' by J.C. Del ...
is archaeologically attested on the island
Lesbos Lesbos or Lesvos ( el, Λέσβος, Lésvos ) is a Greek island located in the northeastern Aegean Sea. It has an area of with approximately of coastline, making it the third largest island in Greece. It is separated from Anatolia, Asia Minor ...
. The site was abandoned in the 7th century CE, but dates back at least to the 2nd century CE. Native ''alumen'' from the island of
Melos Milos or Melos (; el, label=Modern Greek, Μήλος, Mílos, ; grc, Μῆλος, Mêlos) is a volcanic Greek island in the Aegean Sea, just north of the Sea of Crete. Milos is the southwesternmost island in the Cyclades group. The ''Venus d ...
appears to have been a mixture mainly of alunogen () with potassium alum and other minor sulfates.


Alumen in Pliny and Dioscorides

A detailed description of a substance called ''alumen'' occurs in the
Roman Roman or Romans most often refers to: *Rome, the capital city of Italy *Ancient Rome, Roman civilization from 8th century BC to 5th century AD *Roman people, the people of ancient Rome *''Epistle to the Romans'', shortened to ''Romans'', a letter ...
Pliny the Elder Gaius Plinius Secundus (AD 23/2479), called Pliny the Elder (), was a Roman author, naturalist and natural philosopher, and naval and army commander of the early Roman Empire, and a friend of the emperor Vespasian. He wrote the encyclopedic '' ...
's '' Natural History''. By comparing Pliny's description with the account of ''stupteria'' given by
Dioscorides Pedanius Dioscorides ( grc-gre, Πεδάνιος Διοσκουρίδης, ; 40–90 AD), “the father of pharmacognosy”, was a Greek physician, pharmacologist, botanist, and author of ''De materia medica'' (, On Medical Material) —a 5-vol ...
, it is obvious the two are identical. Pliny informs us that a form of ''alumen'' was found naturally in the earth, and calls it ''salsugoterrae''. Pliny wrote that different substances were distinguished by the name of ''alumen'', but they were all characterised by a certain degree of
astringency An astringent (sometimes called adstringent) is a chemical that shrinks or constricts body tissues. The word derives from the Latin ''adstringere'', which means "to bind fast". Calamine lotion, witch hazel, and yerba mansa, a Californian plant ...
, and were all employed in dyeing and medicine. Pliny wrote that there is another kind of alum that the
Greeks The Greeks or Hellenes (; el, Έλληνες, ''Éllines'' ) are an ethnic group and nation indigenous to the Eastern Mediterranean and the Black Sea regions, namely Greece, Cyprus, Albania, Italy, Turkey, Egypt, and, to a lesser extent, oth ...
call ''schiston'', and which "splits into filaments of a whitish colour". From the name ''schiston'' and the mode of formation, it appears that this kind was the salt that forms spontaneously on certain salty minerals, as alum
slate Slate is a fine-grained, foliated, homogeneous metamorphic rock derived from an original shale-type sedimentary rock composed of clay or volcanic ash through low-grade regional metamorphism. It is the finest grained foliated metamorphic rock. ...
and bituminous
shale Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4) and tiny fragments (silt-sized particles) of other minerals, especial ...
, and consists chiefly of sulfates of iron and aluminium. One kind of ''alumen'' was a liquid, which was apt to be adulterated; but when pure it had the property of blackening when added to
pomegranate The pomegranate (''Punica granatum'') is a fruit-bearing deciduous shrub in the family Lythraceae, subfamily Punicoideae, that grows between tall. The pomegranate was originally described throughout the Mediterranean Basin, Mediterranean re ...
juice. This property seems to characterize a
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Soluti ...
of
iron sulfate Iron sulfate may refer to: * Ferrous sulfate, Iron(II) sulfate Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula Fe SO4·''x''H2O. These compounds exist most commonly as the hept ...
in water; a solution of ordinary (potassium) alum would possess no such property. Contamination with iron sulfate was greatly disliked as this darkened and dulled dye colours. In some places the iron sulfate may have been lacking, so the salt would be 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.


Alum described in medieval texts

Alum and
green vitriol Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula Fe SO4·''x''H2O. These compounds exist most commonly as the hepta hydrate (''x'' = 7) but several values for x are kno ...
(iron sulfate) both have sweetish and astringent taste, and they had overlapping uses. Therefore, through the
Middle Ages In the history of Europe, the Middle Ages or medieval period lasted approximately from the late 5th to the late 15th centuries, similar to the post-classical period of global history. It began with the fall of the Western Roman Empire a ...
, alchemists and other writers do not seem to have discriminated the two salts accurately from each other. In the writings of the
alchemists Alchemy (from Arabic: ''al-kīmiyā''; from Ancient Greek: χυμεία, ''khumeía'') is an ancient branch of natural philosophy, a philosophical and protoscientific tradition that was historically practiced in China, India, the Muslim world, ...
we find the words ''misy'', ''sory'', and ''chalcanthum'' applied to either compound; and the name ''atramentum sutorium'', which one might expect to belong exclusively to green vitriol, applied indifferently to both. Alum was the most common
mordant A mordant or dye fixative is a substance used to set (i.e. bind) dyes on fabrics by forming a coordination complex with the dye, which then attaches to the fabric (or tissue). It may be used for dyeing fabrics or for intensifying stains in ...
(substance used to set dyes on fabrics) used in the dye industry in the Islamic middle ages. It was the main export of the
Chad Chad (; ar, تشاد , ; french: Tchad, ), officially the Republic of Chad, '; ) is a landlocked country at the crossroads of North and Central Africa. It is bordered by Libya to the north, Sudan to the east, the Central African Republic ...
region, from where it was transported to the markets of
Egypt Egypt ( ar, مصر , ), officially the Arab Republic of Egypt, is a transcontinental country spanning the northeast corner of Africa and southwest corner of Asia via a land bridge formed by the Sinai Peninsula. It is bordered by the Mediter ...
and
Morocco Morocco (),, ) officially the Kingdom of Morocco, is the westernmost country in the Maghreb region of North Africa. It overlooks the Mediterranean Sea to the north and the Atlantic Ocean to the west, and has land borders with Algeria to ...
, and then on to
Europe Europe is a large peninsula conventionally considered a continent in its own right because of its great physical size and the weight of its history and traditions. Europe is also considered a Continent#Subcontinents, subcontinent of Eurasia ...
. Other, less significant, sources were found in Egypt and
Yemen Yemen (; ar, ٱلْيَمَن, al-Yaman), officially the Republic of Yemen,, ) is a country in Western Asia. It is situated on the southern end of the Arabian Peninsula, and borders Saudi Arabia to the Saudi Arabia–Yemen border, north and ...
.


Modern understanding of the alums

In the early 1700s, G.E. Stahl claimed that reacting sulfuric acid with limestone produced a sort of alum. The error was soon corrected by J.H. Pott and A.S. Marggraf, who showed that the
precipitate In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a super-saturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading ...
obtained when an alkali is poured into a solution of alum, namely alumina, is quite different from
lime Lime commonly refers to: * Lime (fruit), a green citrus fruit * Lime (material), inorganic materials containing calcium, usually calcium oxide or calcium hydroxide * Lime (color), a color between yellow and green Lime may also refer to: Botany ...
and
chalk Chalk is a soft, white, porous, sedimentary carbonate rock. It is a form of limestone composed of the mineral calcite and originally formed deep under the sea by the compression of microscopic plankton that had settled to the sea floor. Chalk ...
, and is one of the ingredients in common
clay Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4). Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
. Marggraf also showed that perfect crystals with properties of alum can be obtained by dissolving alumina in
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
and adding
potash Potash () includes various mined and manufactured salts that contain potassium in water-soluble form.
or
ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
to the concentrated solution. In 1767,
Torbern Bergman Torbern Olaf (Olof) Bergman (''KVO'') (20 March 17358 July 1784) was a Swedish chemist and mineralogist noted for his 1775 ''Dissertation on Elective Attractions'', containing the largest chemical affinity tables ever published. Bergman was the ...
observed the need for potassium or ammonium sulfates to convert
aluminium sulfate Aluminium sulfate is a salt with the chemical formula, formula aluminium, Al2sulfate, (SO4)3. It is soluble in water and is mainly used as a Coagulation (water treatment), coagulating agent (promoting particle collision by neutralizing charge) in ...
into alum, while sodium or calcium would not work. : The composition of common alum was finally determined by Vauquelin in 1797. As soon as Klaproth discovered the presence of potassium in
leucite Leucite is a rock-forming mineral of the feldspathoid group, silica-undersaturated and composed of potassium and aluminium tectosilicate KAlSi2O6. Crystals have the form of cubic icositetrahedra but, as first observed by Sir David Brewster in 18 ...
and
lepidolite Lepidolite is a lilac-gray or rose-colored member of the mica group of minerals with chemical formula . It is the most abundant lithium-bearing mineral and is a secondary source of this metal. It is the major source of the alkali metal rubidium. ...
, Vauquelin demonstrated that common alum is a
double salt A double salt is a salt that contains two or more different cations or anions. Examples of double salts include alums (with the general formula ) and Tutton's salts (with the general formula ). Other examples include potassium sodium tartrate, ammo ...
, composed of sulfuric acid, alumina, and potash. In the same journal volume, Chaptal published the analysis of four different kinds of alum, namely, Roman alum, Levant alum, British alum, and an alum manufactured by himself, confirming Vauquelin's result.


Production

Some alums occur as minerals, the most important being
alunite Alunite is a hydroxylated aluminium potassium sulfate mineral, formula K Al3( S O4)2(O H)6. It was first observed in the 15th century at Tolfa, near Rome, where it was mined for the manufacture of alum. First called ''aluminilite'' by J.C. Del ...
. The most important alums – potassium, sodium, and ammonium – are produced industrially. Typical recipes involve combining
aluminium sulfate Aluminium sulfate is a salt with the chemical formula, formula aluminium, Al2sulfate, (SO4)3. It is soluble in water and is mainly used as a Coagulation (water treatment), coagulating agent (promoting particle collision by neutralizing charge) in ...
and the sulfate monovalent cation. The aluminium sulfate is usually obtained by treating minerals like alum
schist Schist ( ) is a medium-grained metamorphic rock showing pronounced schistosity. This means that the rock is composed of mineral grains easily seen with a low-power hand lens, oriented in such a way that the rock is easily split into thin flakes o ...
,
bauxite Bauxite is a sedimentary rock with a relatively high aluminium content. It is the world's main source of aluminium and gallium. Bauxite consists mostly of the aluminium minerals gibbsite (Al(OH)3), boehmite (γ-AlO(OH)) and diaspore (α-AlO(O ...
and
cryolite Cryolite ( Na3 Al F6, sodium hexafluoroaluminate) is an uncommon mineral identified with the once-large deposit at Ivittuut on the west coast of Greenland, mined commercially until 1987. History Cryolite was first described in 1798 by Danish vete ...
with sulfuric acid.


Types

Aluminium-based alums are named by the monovalent cation. Unlike the other
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
s,
lithium Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid el ...
does not form alums; a fact attributed to the small size of its ion. The most important alums are *
Potassium alum Potassium alum, potash alum, or potassium aluminium sulfate is a chemical compound: the double sulfate of potassium and aluminium, with chemical formula KAl(SO4)2. It is commonly encountered as the dodecahydrate, KAl(SO4)2·12H2O. It crystalli ...
, , also called "potash alum" or simply "alum" *
Sodium alum Sodium aluminium sulfate is the inorganic compound with the chemical formula NaAl(SO4)2·12H2O (sometimes written Na2SO4·Al2(SO4)3·24H2O). Also known as soda alum, sodium alum, or SAS, this white solid is used in the manufacture of baking powd ...
, , also called "soda alum" or "SAS" *
Ammonium alum Ammonium aluminium sulfate, also known as ammonium alum or just alum (though there are many different substances also called "alum"), is a white crystalline double sulfate usually encountered as the dodecahydrate, formula (NH4)Al(SO4)2·12H2O. It ...
,


Chemical properties

Aluminium-based alums have a number of common chemical properties. They are soluble in
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
, have a sweetish taste, react as
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
by turning blue
litmus Litmus is a water-soluble mixture of different dyes extracted from lichens. It is often absorbed onto filter paper to produce one of the oldest forms of pH indicator, used to test materials for acidity. It is a purple dye that is extracted fro ...
to red, and
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
lize in regular
octahedra In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at ea ...
. In alums each metal ion is surrounded by six water molecules. When heated, they liquefy, and if the heating is continued, the
water of crystallization In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is ...
is driven off, the salt froths and swells, and at last an amorphous powder remains. They are
astringent An astringent (sometimes called adstringent) is a chemical that shrinks or constricts body tissues. The word derives from the Latin ''adstringere'', which means "to bind fast". Calamine lotion, witch hazel, and yerba mansa, a Californian plant ...
and acidic.


Crystal structure

Alums crystallize in one of three different crystal structures. These classes are called α-, β- and γ-alums. The first X-ray crystal structures of alums were reported in 1927 by James M. Cork and
Lawrence Bragg Sir William Lawrence Bragg, (31 March 1890 – 1 July 1971) was an Australian-born British physicist and X-ray crystallography, X-ray crystallographer, discoverer (1912) of Bragg's law, Bragg's law of X-ray diffraction, which is basic for t ...
, and were used to develop the
phase retrieval Phase retrieval is the process of algorithmically finding solutions to the phase problem. Given a complex signal F(k), of amplitude , F (k), , and phase \psi(k): ::F(k) = , F(k), e^ =\int_^ f(x)\ e^\,dx where ''x'' is an ''M''-dimensional spatia ...
technique
isomorphous replacement Multiple isomorphous replacement (MIR) is historically the most common approach to solving the phase problem in X-ray crystallography studies of proteins. For protein crystals this method is conducted by soaking the crystal of a sample to be analyze ...
.


Solubility

The solubility of the various alums in water varies greatly, sodium alum being readily soluble in water, while
caesium Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
and
rubidium Rubidium is the chemical element with the symbol Rb and atomic number 37. It is a very soft, whitish-grey solid in the alkali metal group, similar to potassium and caesium. Rubidium is the first alkali metal in the group to have a density higher ...
alums are only sparingly soluble. The various solubilities are shown in the following table. At temperature , 100 parts water dissolve: :


Uses

Aluminium-based alums have been used since antiquity, and are still important in many industrial processes. The most widely used alum is
potassium alum Potassium alum, potash alum, or potassium aluminium sulfate is a chemical compound: the double sulfate of potassium and aluminium, with chemical formula KAl(SO4)2. It is commonly encountered as the dodecahydrate, KAl(SO4)2·12H2O. It crystalli ...
. It has been used since antiquity as a flocculant to clarify turbid liquids, as a
mordant A mordant or dye fixative is a substance used to set (i.e. bind) dyes on fabrics by forming a coordination complex with the dye, which then attaches to the fabric (or tissue). It may be used for dyeing fabrics or for intensifying stains in ...
in
dyeing Dyeing is the application of dyes or pigments on textile materials such as fibers, yarns, and fabrics with the goal of achieving color with desired color fastness. Dyeing is normally done in a special solution containing dyes and particular ...
, and in
tanning Tanning may refer to: *Tanning (leather), treating animal skins to produce leather *Sun tanning, using the sun to darken pale skin **Indoor tanning, the use of artificial light in place of the sun **Sunless tanning, application of a stain or dye t ...
. It is still widely used in
water treatment Water treatment is any process that improves the Water quality, quality of water to make it appropriate for a specific end-use. The end use may be drinking water, drinking, industrial water supply, irrigation, river flow maintenance, water recrea ...
, in medicine, for cosmetics (in
deodorant A deodorant is a substance applied to the body to prevent or mask body odor due to bacterial breakdown of perspiration or vaginal secretions, for example in the armpits, groin, or feet. A subclass of deodorants, called antiperspirants, prevents s ...
), in food preparation (in
baking powder Baking powder is a dry chemical leavening agent, a mixture of a carbonate or bicarbonate and a weak acid. The base and acid are prevented from reacting prematurely by the inclusion of a buffer such as cornstarch. Baking powder is used to increase ...
and
pickling Pickling is the process of preserving or extending the shelf life of food by either anaerobic fermentation in brine or immersion in vinegar. The pickling procedure typically affects the food's texture and flavor. The resulting food is called a ...
), and to fire-proof paper and cloth. Alum is also used as a
styptic An antihemorrhagic (antihæmorrhagic) agent is a substance that promotes hemostasis (stops bleeding). It may also be known as a hemostatic (also spelled haemostatic) agent. Antihemorrhagic agents used in medicine have various mechanisms of action: ...
, in styptic pencils available from pharmacists, or as an alum block, available from barber shops and gentlemen's outfitters, to stem bleeding from shaving nicks; and as an
astringent An astringent (sometimes called adstringent) is a chemical that shrinks or constricts body tissues. The word derives from the Latin ''adstringere'', which means "to bind fast". Calamine lotion, witch hazel, and yerba mansa, a Californian plant ...
. An alum block can be used directly as a perfume-free deodorant (antiperspirant), and unprocessed mineral alum is sold in Indian bazaars for just that purpose. Throughout
Island Southeast Asia Maritime Southeast Asia comprises the countries of Brunei, Indonesia, Malaysia, the Philippines, Singapore, and East Timor. Maritime Southeast Asia is sometimes also referred to as Island Southeast Asia, Insular Southeast Asia or Oceanic Sout ...
, potassium alum is most widely known as ''tawas'' and has numerous uses. It is used as a traditional antiperspirant and deodorant, and in traditional medicine for open wounds and sores. The crystals are usually ground into a fine powder before using. In the
Victorian era In the history of the United Kingdom and the British Empire, the Victorian era was the period of Queen Victoria's reign, from 20 June 1837 until her death on 22 January 1901. The era followed the Georgian period and preceded the Edwardia ...
, alum was used along with other substances like
plaster of Paris Plaster is a building material used for the protective or decorative coating of walls and ceilings and for moulding and casting decorative elements. In English, "plaster" usually means a material used for the interiors of buildings, while "re ...
to adulterate certain food products, particularly bread. It was used to make lower-grade flour appear whiter, allowing the producers to spend less on whiter flour. Because it retains water, it would make the bread heavier, meaning that merchants could charge 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.Phillips, Suzanne, director
''The Hidden Killers of the Victorian Home''
Sterling Documentaries, 27 Jan. 2018. Accessed 9 Oct. 2021.
Alum is used as a mordant in traditional textiles; and in
Indonesia Indonesia, officially the Republic of Indonesia, is a country in Southeast Asia and Oceania between the Indian and Pacific oceans. It consists of over 17,000 islands, including Sumatra, Java, Sulawesi, and parts of Borneo and New Guine ...
and the
Philippines The Philippines (; fil, Pilipinas, links=no), officially the Republic of the Philippines ( fil, Republika ng Pilipinas, links=no), * bik, Republika kan Filipinas * ceb, Republika sa Pilipinas * cbk, República de Filipinas * hil, Republ ...
, solutions of ''tawas'',
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 quantitie ...
,
borax Borax is a salt (ionic compound), a hydrated borate of sodium, with chemical formula often written . It is a colorless crystalline solid, that dissolves in water to make a basic solution. It is commonly available in powder or granular form, ...
, and organic pigments were used to change the color of
gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile met ...
ornaments. In the Philippines, alum crystals were also burned and allowed to drip into a basin of water by ''
babaylan Filipino shamans, commonly known as (also ''Balian'' or , among many other names), were shamans of the various ethnic groups of the pre-colonial Philippine islands. These shamans specialized in communicating, appeasing, or harnessing the spir ...
'' (shamans) for
divination Divination (from Latin ''divinare'', 'to foresee, to foretell, to predict, to prophesy') is the attempt to gain insight into a question or situation by way of an occultic, standardized process or ritual. Used in various forms throughout histor ...
. It is also used in other rituals in the
animistic Animism (from Latin: ' meaning 'breath, spirit, life') is the belief that objects, places, and creatures all possess a distinct spiritual essence. Potentially, animism perceives all things—animals, plants, rocks, rivers, weather systems, hum ...
anito ''Anito'', also spelled ''anitu'', refers to ancestor spirits, nature spirits, and deities in the indigenous Philippine folk religions from the precolonial age to the present, although the term itself may have other meanings and associati ...
religions of the islands. In traditional
Japanese art Japanese art covers a wide range of art styles and media, including ancient pottery, sculpture, ink painting and calligraphy on silk and paper, ''ukiyo-e'' paintings and woodblock prints, ceramics, origami, and more recently manga and anime. It ...
, alum and
animal glue Animal glue is an adhesive that is created by prolonged boiling of animal connective tissue in a process called rendering. In addition to being used as an adhesive it is used for coating and sizing, in decorative composition ornaments, and as a ...
were dissolved in water, forming a liquid known as ''dousa'' ( ja, 礬水), and used as an undercoat for paper
sizing Sizing or size is a substance that is applied to, or incorporated into, other materials—especially papers and textiles—to act as a protective filler or glaze. Sizing is used in papermaking and textile manufacturing to change the absorption ...
. Alum in the form of potassium aluminium sulphate or ammonium aluminium sulfate in a concentrated bath of hot water is regularly used by jewelers and machinists to dissolve hardened steel drill bits that have broken off in items made of aluminum, copper, brass, gold (any karat), silver (both sterling and fine) and stainless steel. This is because alum does not react chemically to any significant degree with any of these metals, but will corrode carbon steel. When heat is applied to an alum mixture holding a piece of work that has a drill bit stuck in it, if the lost bit is small enough, it can sometimes be dissolved / removed within hours.


Related compounds

Many trivalent metals are capable of forming alums. The general form of an alum is , where is an
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
or
ammonium The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...
, is a trivalent metal, and often is 12. The most important example is
chrome alum Chrome alum or Chromium(III) potassium sulfate is the potassium double sulfate of chromium. Its chemical formula is KCr(SO4)2 and it is commonly found in its dodecahydrate form as KCr(SO4)2·12(H2O). It is used in leather tanning. Production a ...
, , a dark violet crystalline double sulfate of chromium and potassium, was used in
tanning Tanning may refer to: *Tanning (leather), treating animal skins to produce leather *Sun tanning, using the sun to darken pale skin **Indoor tanning, the use of artificial light in place of the sun **Sunless tanning, application of a stain or dye t ...
. In general, alums are formed more easily when the alkali metal atom is larger. This rule was first stated by Locke in 1902, who found that if a trivalent metal does not form a caesium alum, it neither will form an alum with any other alkali metal or with ammonium.


Selenate-containing alums

''Selenium'' or ''selenate alums'' are also known that contain
selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
in place of
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
in the
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ar ...
anion, making
selenate The selenate ion is . Selenates are analogous to sulfates and have similar chemistry. They are highly soluble in aqueous solutions at ambient temperatures. Unlike sulfate, selenate is a somewhat good oxidizer; it can be reduced to selenite o ...
() instead. They are strong
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...
s.


Mixed alums

In some cases,
solid solution A solid solution, a term popularly used for metals, is a homogenous mixture of two different kinds of atoms in solid state and have a single crystal structure. Many examples can be found in metallurgy, geology, and solid-state chemistry. The word ...
s of alums with different monovalent and trivalent cations may occur.


Other hydrates

In addition to the alums, which are dodecahydrates, double
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ar ...
s and
selenate The selenate ion is . Selenates are analogous to sulfates and have similar chemistry. They are highly soluble in aqueous solutions at ambient temperatures. Unlike sulfate, selenate is a somewhat good oxidizer; it can be reduced to selenite o ...
s of univalent and trivalent cations occur with other degrees of hydration. These materials may also be referred to as alums, including the undecahydrates such as mendozite and
kalinite Kalinite is a mineral composed of hydrated potassium aluminium sulfate (a type of alum). It is a fibrous monoclinic alum, distinct from isometric potassium alum,American Mineralogist (1923) 8:15 named in 1868. Its name comes from ''kalium'' ...
, hexahydrates such as
guanidinium Guanidine is the compound with the formula HNC(NH2)2. It is a colourless solid that dissolves in polar solvents. It is a strong base that is used in the production of plastics and explosives. It is found in urine predominantly in patients experien ...
and
dimethylammonium Dimethylamine is an organic compound with the formula (CH3)2NH. This secondary amine is a colorless, flammable gas with an ammonia-like odor. Dimethylamine is commonly encountered commercially as a solution in water at concentrations up to aroun ...
"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

A pseudo alum is a double sulfate of the typical formula , where : is a divalent metal ion, such as ::
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
( wupatkiite),
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
( apjohnite),
magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
( pickingerite) or
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
(
halotrichite Halotrichite, also known as ''feather alum'', is a highly hydrated sulfate of aluminium and iron. Its chemical formula is FeAl2(SO4)4·22H2O. It forms fibrous monoclinic crystals. The crystals are water-soluble. It is formed by the weathering and ...
or feather alum), and : is a trivalent metal ion. Double
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ar ...
s with the general formula are also known, where : is a monovalent
cation 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 convent ...
such as ::
sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
,
potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...
,
rubidium Rubidium is the chemical element with the symbol Rb and atomic number 37. It is a very soft, whitish-grey solid in the alkali metal group, similar to potassium and caesium. Rubidium is the first alkali metal in the group to have a density higher ...
,
caesium Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
, or
thallium Thallium is a chemical element with the Symbol (chemistry), symbol Tl and atomic number 81. It is a gray post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Chemists W ...
, or a compound cation such as
ammonium The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...
(), methylammonium (), hydroxylammonium () or
hydrazinium Hydrazinium is the cation with the formula . This cation has a methylamine-like structure (). It can be derived from hydrazine by protonation (treatment with a strong acid). Hydrazinium is a weak acid with p''K''a = 8.1. Salts of hydrazinium ar ...
() : is a trivalent metal ion, such as ::
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
,
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hardne ...
,
titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
,
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
,
vanadium Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer ( pas ...
,
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
,
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
,
gallium Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in group 13 of the periodic table and is similar to the other metals of the group (aluminiu ...
,
molybdenum Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...
,
indium Indium is a chemical element with the symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts p ...
,
ruthenium Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
,
rhodium Rhodium is a chemical element with the symbol Rh and atomic number 45. It is a very rare, silvery-white, hard, corrosion-resistant transition metal. It is a noble metal and a member of the platinum group. It has only one naturally occurring isoto ...
, or
iridium Iridium is a chemical element with the symbol Ir and atomic number 77. A very hard, brittle, silvery-white transition metal of the platinum group, it is considered the second-densest naturally occurring metal (after osmium) with a density of ...
. Analogous
selenate The selenate ion is . Selenates are analogous to sulfates and have similar chemistry. They are highly soluble in aqueous solutions at ambient temperatures. Unlike sulfate, selenate is a somewhat good oxidizer; it can be reduced to selenite o ...
s also occur. The possible combinations of univalent cation, trivalent cation, and
anion 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 convent ...
depends on the sizes of the
ion 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 conven ...
s. A
Tutton salt Tutton's salts are a family of salts with the formula M2M'(SO4)2(H2O)6 (sulfates) or M2M'(SeO4)2(H2O)6 (selenates). These materials are double salts, which means that they contain two different cations, M+ and M'2+ crystallized in the same regular ...
is a double sulfate of the typical formula , where is a univalent cation, and a
divalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with other atoms when it forms chemical compounds or molecules. Description The combining capacity, or affinity of an ...
metal ion. Double sulfates of the composition , where : is a univalent cation and : is a divalent metal ion are referred to as
langbeinite Langbeinite is a potassium magnesium sulfate mineral with the chemical formula K2Mg2(SO4)3. Langbeinite crystallizes in the isometric-tetartoidal (cubic) system as transparent colorless or white with pale tints of yellow to green and violet cry ...
s, after the prototypical potassium magnesium sulfate.


See also

*
Alunite Alunite is a hydroxylated aluminium potassium sulfate mineral, formula K Al3( S O4)2(O H)6. It was first observed in the 15th century at Tolfa, near Rome, where it was mined for the manufacture of alum. First called ''aluminilite'' by J.C. Del ...
*
List of minerals This is a list of minerals for which there are articles on Wikipedia. Minerals are distinguished by various chemical and physical properties. Differences in chemical composition and crystal structure distinguish the various ''species''. Within a m ...
*
Gum bichromate Gum bichromate is a 19th-century photographic printing process based on the light sensitivity of dichromates. It is capable of rendering painterly images from photographic negatives. Gum printing is traditionally a multi-layered printing process, ...
– photo prints and other similar processes use alums, sometimes as
colloid A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend ...
(gelatin, albumen) hardeners


Footnotes


References


External links

* {{Authority control * Sulfates Sulfate minerals Traditional medicine Astringent flavors