Lithium sulfate

Last updated
Lithium sulfate
Lithium sulfate.svg
Lithiumsulfat.png
__ Li +__ S 6+__ O 2−
Lithium sulfate (1).JPG
Names
IUPAC name
Lithium sulfate
Other names
Lithium sulphate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.734 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • OJ6419000
UNII
  • InChI=1S/2Li.H2O4S/c;;1-5(2,3)4/h;;(H2,1,2,3,4)/q2*+1;/p-2 X mark.svgN
    Key: INHCSSUBVCNVSK-UHFFFAOYSA-L X mark.svgN
  • InChI=1/2Li.H2O4S/c;;1-5(2,3)4/h;;(H2,1,2,3,4)/q2*+1;/p-2
    Key: INHCSSUBVCNVSK-NUQVWONBAF
  • [Li+].[Li+].[O-]S(=O)(=O)[O-]
Properties [1]
Li2SO4
Molar mass 109.94 g/mol
AppearanceWhite crystalline solid, hygroscopic
Density 2.221 g/cm3 (anhydrous)
2.06 g/cm3 (monohydrate)
Melting point 859 °C (1,578 °F; 1,132 K)
Boiling point 1,377 °C (2,511 °F; 1,650 K)
monohydrate:
34.9 g/100 mL (25 °C)
29.2 g/100 mL (100 °C)
Solubility insoluble in absolute ethanol, acetone and pyridine
-40.0·10−6 cm3/mol
1.465 (β-form)
Structure [2]
Primitive monoclinic
P 21/a, No. 14
a = 8.239 Å, b = 4.954 Å, c = 8.474 Å
α = 90°, β = 107.98°, γ = 90° [2]
328.9 Å3
4
Tetrahedral at sulfur
Thermochemistry
1.07 J/g K
Std molar
entropy
(S298)
113 J/mol K
−1436.37 kJ/mol
-1324.7 kJ/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
0
0
Lethal dose or concentration (LD, LC):
613 mg/kg (rat, oral) [3]
Related compounds
Other anions
Lithium chloride
Other cations
Sodium sulfate

Potassium sulfate
Rubidium sulfate
Caesium sulfate

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Lithium sulfate is a white inorganic salt with the formula Li 2 S O 4. It is the lithium salt of sulfuric acid.

Contents

Properties

Laboratory derivation of Lithium Sulfate

Physical properties

Lithium sulfate is soluble in water, though it does not follow the usual trend of increasing solubility of most salts with temperature. To the contrary, its solubility in water decreases with increasing temperature, as its dissolution is an exothermic process. This relatively unusual property, also called retrograde solubility, is shared with few inorganic compounds, such as calcium hydroxide (portlandite, an important mineral phase of hydrated cement paste), the calcium sulfates (gypsum, bassanite, and anhydrite) and lanthanoid sulfates whose dissolution reactions are also exothermic. The retrograde solubility is common for gases dissolution in water, but less frequently encountered for the dissolution of solids. Calcium carbonate also exhibits a retrograde solubility, but it also depends on the behavior of CO2 dissolution in the calco-carbonate equilibria.

Lithium sulfate crystals, being piezoelectric, are also used in ultrasound-type non-destructive testing because they are very efficient sound receivers. However, they do suffer in this application because of their water solubility.

Since it has hygroscopic properties, the most common form of lithium sulfate is lithium sulfate monohydrate. Anhydrous lithium sulfate has a density of 2.22 g/cm3 but, weighing lithium sulfate anhydrous can become cumbersome as it must be done in a water lacking atmosphere.

Lithium sulfate has pyroelectric properties. When aqueous lithium sulfate is heated, the electrical conductivity also increases. The molarity of lithium sulfate also plays a role in the electrical conductivity; optimal conductivity is achieved at 2 M and then decreases. [4]

When solid lithium sulfate is dissolved in water it has an endothermic disassociation. This is different from sodium sulfate which has an exothermic disassociation. However, the exact energy of disassociation is difficult to quantify as it seems also to depend on the quantity (number of mols) of the salt added to water. Small amounts of dissolved lithium sulfate induce a much greater temperature change per mol than large amounts. [5]

Crystal properties

Lithium sulfate has two different crystal phases. In common phase II form, Lithium sulfate has a sphenoidal monoclinic crystal system that has edge lengths of a = 8.23Å b = 4.95Å c = 8.47Å β = 107.98°. When lithium sulfate is heated passed 130 °C it changes to a water free state but retains its crystal structure. It is not until 575 °C when there is a transformation from phase II to phase I. The crystal structure changes to a face centered cubic crystal system, with an edge length of 7.07Å. [6] During this phase change, the density of lithium sulfate changes from 2.22 to 2.07 g/cm3. [7]

Uses

Lithium sulfate is used to treat bipolar disorder (see lithium pharmacology).

Lithium sulfate is researched as a potential component of ion conducting glasses. Transparent conducting film is a highly investigated topic as they are used in applications such as solar panels and the potential for a new class of battery. In these applications, it is important to have a high lithium content; the more commonly known binary lithium borate (Li₂O · B₂O₃) is difficult to obtain with high lithium concentrations and difficult to keep as it is hygroscopic. With the addition of lithium sulfate into the system, an easily produced, stable, high lithium concentration glass is able to be formed. Most of the current transparent ionic conducting films are made of organic plastics, and it would be ideal if an inexpensive stable inorganic glass could be developed. [8]

Lithium sulfate has been tested as an additive for Portland cement to accelerate curing with positive results. Lithium sulfate serves to speed up the hydration reaction (see Cement) which decreases the curing time. A concern with decreased curing time is the strength of the final product, but when tested, lithium sulfate doped Portland cement had no observable decrease in strength. [9]

Lithium-ion batteries

Lithium sulphate monohydrate (Li
2
SO
4
· H
2
O
) containing around 10% lithium is a useful chemical for the production of lithium hydroxide for the lithium-ion battery materials supply chain. It is a less reactive material than LiOH, and hence can be more easily stored and transported. [10] [11]

Feedstock of hard-rock spodumene concentrate is processed by acid roasting, followed by water leaching, achieving a lithium recovery of 84-88%. Evaporation is then applied to the purified leach solution resulting in a primary lithium sulphate solid product made up mostly of lithium sulphate monohydrate (Li
2
SO
4
· H
2
O
).

Medication

Lithium ion (Li+) is used in psychiatry for the treatment of mania, endogenous depression, and psychosis, and also for treatment of schizophrenia. Usually lithium carbonate (Li
2
CO
3
) is applied, but sometimes lithium citrate (Li
3
C
6
H
5
O
7
), lithium sulfate or lithium oxy-butyrate are used as alternatives. [12] Li+ is not metabolized. Because of Li+ chemical similarity to sodium (Na+) and potassium (K+) cations, it may interact or interfere with the biochemical pathways of these substances and displace these cations from intra- or extracellular compartments of the body. Li+ seems to be transported out of nerve and muscle cells by the active sodium pump, although less efficiently.

Lithium sulfate has a rapid gastrointestinal absorption rate (within a few minutes), and complete following oral administration of tablets or the liquid form. [12] It quickly diffuses into the liver and kidneys but requires 8–10 days to reach a body equilibrium. Li+ produces many metabolic and neuroendocrine changes, but no conclusive evidence favors one particular mode of action. [12] For example, Li+ interacts with neurohormones, particularly the biogenic amines, serotonin (5-hydroxy tryptamine) and norepinephrine, which provides a probable mechanism for the beneficial effects in psychiatric disorders, e.g. manias. In the central nervous system (CNS), Li+ affects nerve excitation, synaptic transmission, and neuronal metabolism. [13] Li+ stabilizes serotoninergic neurotransmission.

Organic chemistry synthesis

Lithium sulfate is being used as a catalyst for the elimination reaction for transforming n-butyl bromide to 1-butene at close to 100% yields at a range of 320 °C to 370 °C. The yields of this reaction change dramatically if heated beyond this range as higher yields of 2-butene is formed. [14]

Related Research Articles

<span class="mw-page-title-main">Lithium carbonate</span> Chemical compound

Lithium carbonate is an inorganic compound, the lithium salt of carbonic acid with the formula Li
2
CO
3
. This white salt is widely used in processing metal oxides. It is on the World Health Organization's List of Essential Medicines for its efficacy in the treatment of mood disorders such as bipolar disorder.

<span class="mw-page-title-main">Calcium carbonate</span> Chemical compound

Calcium carbonate is a chemical compound with the chemical formula CaCO3. It is a common substance found in rocks as the minerals calcite and aragonite, most notably in chalk and limestone, eggshells, gastropod shells, shellfish skeletons and pearls. Materials containing much calcium carbonate or resembling it are described as calcareous. Calcium carbonate is the active ingredient in agricultural lime and is produced when calcium ions in hard water react with carbonate ions to form limescale. It has medical use as a calcium supplement or as an antacid, but excessive consumption can be hazardous and cause hypercalcemia and digestive issues.

<span class="mw-page-title-main">Solubility</span> Capacity of a substance to dissolve in a solvent in a homogeneous way

In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.

<span class="mw-page-title-main">Sodium carbonate</span> Chemical compound

Sodium carbonate is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, odourless, water-soluble salts that yield alkaline solutions in water. Historically, it was extracted from the ashes of plants grown in sodium-rich soils, and because the ashes of these sodium-rich plants were noticeably different from ashes of wood, sodium carbonate became known as "soda ash". It is produced in large quantities from sodium chloride and limestone by the Solvay process, as well as by carbonating sodium hydroxide which is made using the Chlor-alkali process.

<span class="mw-page-title-main">Potassium hydroxide</span> Inorganic compound (KOH)

Potassium hydroxide is an inorganic compound with the formula KOH, and is commonly called caustic potash.

<span class="mw-page-title-main">Magnesium sulfate</span> Chemical compound with formula MgSO4

Magnesium sulfate or magnesium sulphate (in English-speaking countries other than the US) is a chemical compound, a salt with the formula MgSO4, consisting of magnesium cations Mg2+ (20.19% by mass) and sulfate anions SO2−4. It is a white crystalline solid, soluble in water but not in ethanol.

<span class="mw-page-title-main">Calcium hydroxide</span> Inorganic compound of formula Ca(OH)2

Calcium hydroxide (traditionally called slaked lime) is an inorganic compound with the chemical formula Ca(OH)2. It is a colorless crystal or white powder and is produced when quicklime (calcium oxide) is mixed with water. It has many names including hydrated lime, caustic lime, builders' lime, slaked lime, cal, and pickling lime. Calcium hydroxide is used in many applications, including food preparation, where it has been identified as E number E526. Limewater, also called milk of lime, is the common name for a saturated solution of calcium hydroxide.

<span class="mw-page-title-main">Copper(II) sulfate</span> Chemical compound

Copper(II) sulfate, also known as copper sulphate, is an inorganic compound with the chemical formula CuSO4. It forms hydrates CuSO4·nH2O, where n can range from 1 to 7. The pentahydrate (n = 5), a bright blue crystal, is the most commonly encountered hydrate of copper(II) sulfate. Older names for the pentahydrate include blue vitriol, bluestone, vitriol of copper, and Roman vitriol. It exothermically dissolves in water to give the aquo complex [Cu(H2O)6]2+, which has octahedral molecular geometry. The structure of the solid pentahydrate reveals a polymeric structure wherein copper is again octahedral but bound to four water ligands. The Cu(II)(H2O)4 centers are interconnected by sulfate anions to form chains. Anhydrous copper sulfate is a light grey powder.

<span class="mw-page-title-main">Lithium hydroxide</span> Chemical compound

Lithium hydroxide is an inorganic compound with the formula LiOH. It can exist as anhydrous or hydrated, and both forms are white hygroscopic solids. They are soluble in water and slightly soluble in ethanol. Both are available commercially. While classified as a strong base, lithium hydroxide is the weakest known alkali metal hydroxide.

<span class="mw-page-title-main">Calcium sulfate</span> Laboratory and industrial chemical

Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO4 and related hydrates. In the form of γ-anhydrite (the anhydrous form), it is used as a desiccant. One particular hydrate is better known as plaster of Paris, and another occurs naturally as the mineral gypsum. It has many uses in industry. All forms are white solids that are poorly soluble in water. Calcium sulfate causes permanent hardness in water.

<span class="mw-page-title-main">Sodium sulfate</span> Chemical compound with formula Na2SO4

Sodium sulfate (also known as sodium sulphate or sulfate of soda) is the inorganic compound with formula Na2SO4 as well as several related hydrates. All forms are white solids that are highly soluble in water. With an annual production of 6 million tonnes, the decahydrate is a major commodity chemical product. It is mainly used as a filler in the manufacture of powdered home laundry detergents and in the Kraft process of paper pulping for making highly alkaline sulfides.

<span class="mw-page-title-main">Potassium sulfate</span> Chemical compound

Potassium sulfate (US) or potassium sulphate (UK), also called sulphate of potash (SOP), arcanite, or archaically potash of sulfur, is the inorganic compound with formula K2SO4, a white water-soluble solid. It is commonly used in fertilizers, providing both potassium and sulfur.

<span class="mw-page-title-main">Lithium aluminate</span> Chemical compound

Lithium aluminate, also called lithium aluminium oxide, is an inorganic chemical compound, an aluminate of lithium. In microelectronics, lithium aluminate is considered as a lattice matching substrate for gallium nitride. In nuclear technology, lithium aluminate is of interest as a solid tritium breeder material, for preparing tritium fuel for nuclear fusion. Lithium aluminate is a layered double hydroxide (LDH) with a crystal structure resembling that of hydrotalcite. Lithium aluminate solubility at high pH is much lower than that of aluminium oxides. In the conditioning of low- and intermediate level radioactive waste (LILW), lithium nitrate is sometimes used as additive to cement to minimise aluminium corrosion at high pH and subsequent hydrogen production. Indeed, upon addition of lithium nitrate to cement, a passive layer of LiH(AlO
2
)
2
· 5 H
2
O
is formed onto the surface of metallic aluminium waste immobilised in mortar. The lithium aluminate layer is insoluble in cement pore water and protects the underlying aluminium oxide covering the metallic aluminium from dissolution at high pH. It is also a pore filler. This hinders the aluminium oxidation by the protons of water and reduces the hydrogen evolution rate by a factor of 10.

<span class="mw-page-title-main">Nickel(II) sulfate</span> Chemical compound

Nickel(II) sulfate, or just nickel sulfate, usually refers to the inorganic compound with the formula NiSO4(H2O)6. This highly soluble blue green coloured salt is a common source of the Ni2+ ion for electroplating.

<span class="mw-page-title-main">Mercury(I) sulfate</span> Chemical compound

Mercury(I) sulfate, commonly called mercurous sulphate (UK) or mercurous sulfate (US) is the chemical compound Hg2SO4. Mercury(I) sulfate is a metallic compound that is a white, pale yellow or beige powder. It is a metallic salt of sulfuric acid formed by replacing both hydrogen atoms with mercury(I). It is highly toxic; it could be fatal if inhaled, ingested, or absorbed by skin.

Lithium nitrite is the lithium salt of nitrous acid, with formula LiNO2. This compound is hygroscopic and very soluble in water. It is used as a corrosion inhibitor in mortar. It is also used in the production of explosives, due to its ability to nitrosate ketones under certain conditions.

<span class="mw-page-title-main">Concrete degradation</span> Damage to concrete affecting its mechanical strength and its durability

Concrete degradation may have many different causes. Concrete is mostly damaged by the corrosion of reinforcement bars due to the carbonatation of hardened cement paste or chloride attack under wet conditions. Chemical damages are caused by the formation of expansive products produced by various chemical reactions, by aggressive chemical species present in groundwater and seawater, or by microorganisms. Other damaging processes can also involve calcium leaching by water infiltration and different physical phenomena initiating cracks formation and propagation. All these detrimental processes and damaging agents adversely affects the concrete mechanical strength and its durability.

<span class="mw-page-title-main">Green rust</span> Generic name for various green-colored iron compounds

Green rust is a generic name for various green crystalline chemical compounds containing iron(II) and iron(III) cations, the hydroxide (HO
) anion, and another anion such as carbonate (CO2−
3
), chloride (Cl
), or sulfate (SO2−
4
), in a layered double hydroxide structure. The most studied varieties are

Oilfield scale inhibition is the process of preventing the formation of scale from blocking or hindering fluid flow through pipelines, valves, and pumps used in oil production and processing. Scale inhibitors (SIs) are a class of specialty chemicals that are used to slow or prevent scaling in water systems. Oilfield scaling is the precipitation and accumulation of insoluble crystals (salts) from a mixture of incompatible aqueous phases in oil processing systems. Scale is a common term in the oil industry used to describe solid deposits that grow over time, blocking and hindering fluid flow through pipelines, valves, pumps etc. with significant reduction in production rates and equipment damages. Scaling represents a major challenge for flow assurance in the oil and gas industry. Examples of oilfield scales are calcium carbonate (limescale), iron sulfides, barium sulfate and strontium sulfate. Scale inhibition encompasses the processes or techniques employed to treat scaling problems.

AFt Phases refer to the calcium Aluminate Ferrite trisubstituted, or calcium aluminate trisubstituted, phases present in hydrated cement paste (HCP) in concrete.

References

  1. Patnaik, Pradyot (2002). Handbook of Inorganic Chemicals. McGraw-Hill. ISBN   0-07-049439-8.
  2. 1 2 Nord, A. G. (1976). "Crystal structure of β-Li2SO4". Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry. 32 (3): 982–983. doi:10.1107/S0567740876004433.
  3. Chambers, Michael. "ChemIDplus - 10377-48-7 - INHCSSUBVCNVSK-UHFFFAOYSA-L - Lithium sulfate - Similar structures search, synonyms, formulas, resource links, and other chemical information". chem.sis.nlm.nih.gov. Retrieved 12 October 2018.
  4. Angel C.; Sobron F.; Jose I. (1995). Density, viscosity, and electrical conductivity of aqueous solutions of lithium sulfate. J. Chem. Eng., 40, 987–991.
  5. Thomson T. P.; Smith D. E.; Wood R. H. (1974). Enthalpy of dilution of aqueous Na2SO4 and Li2SO4. J. Chem. Eng., 19, 386–388.
  6. Rao C. N. R.; Prakash B. Crystal Structure Transformations in Inorganic sulfates, Phosphates, Perchlorates, and Chromates. NSRDS. 1975, 56, 2-12
  7. Fordland, T.; Keogh, M. J. The structure of the High temperature Modification of lithium Sulfate. 1957, 565-567
  8. E. I. Chemists; M. A. Karakassides; G. D. Chryssikos. A Vibrational Study of Lithium Sulfate Based Fast Ionic Conducting Borate Glasses. J. Phys. Chem. 1986, 90 4528-4533
  9. Yuhai D.; Changing Z.; Xiaosheng W. Influence of lithium sulfate addition on the properties of Portland cement paste. Construction and Building 2014, 50, 457-462
  10. "Metallurgical test work confirms Manono Primary Lithium Sulphate suitable for battery production feedstock" (PDF). AVZ Minerals Limited. 13 January 2021. Retrieved 25 March 2021.{{cite web}}: External link in |author-link= (help)
  11. "AVZ Minerals Limited". AVZ Minerals. Retrieved 25 March 2021.
  12. 1 2 3 Haddad, L.M., Winchester, J.F. Clinical Management of Poisoning and Drug Overdose. 1990 2nd ed, 656-665
  13. Poisindex, Thomson Micromedex 2005
  14. Noller, H., Rosa-Brusin, M. and Andréu, P. (1967), Stereoselective Synthesis of 1-Butene with Lithium Sulfate as Elimination Catalyst. Angew. Chem. Int. Ed. Engl., 6: 170–171. doi:10.1002/anie.196701702