Tin(II) chloride

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Tin(II) chloride
Tin(II) chloride.jpg
Names
IUPAC names
Tin(II) chloride
Tin dichloride
Other names
Stannous chloride
Tin salt
Tin protochloride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
DrugBank
ECHA InfoCard 100.028.971 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 231-868-0
E number E512 (acidity regulators, ...)
PubChem CID
RTECS number
  • XP8700000 (anhydrous)
    XP8850000 (dihydrate)
UNII
UN number 3260
  • InChI=1S/2ClH.Sn/h2*1H;/q;;+2/p-2 X mark.svgN
    Key: AXZWODMDQAVCJE-UHFFFAOYSA-L X mark.svgN
  • InChI=1/2ClH.Sn/h2*1H;/q;;+2/p-2
    Key: AXZWODMDQAVCJE-NUQVWONBAJ
  • Cl[Sn]Cl
Properties
SnCl2
Molar mass 189.60 g/mol (anhydrous)
225.63 g/mol (dihydrate)
AppearanceWhite crystalline solid
Odor odorless
Density 3.95 g/cm3 (anhydrous)
2.71 g/cm3 (dihydrate)
Melting point 247 °C (477 °F; 520 K) (anhydrous)
37.7 °C (dihydrate)
Boiling point 623 °C (1,153 °F; 896 K) (decomposes)
83.9 g/100 ml (0 °C)
Hydrolyses in hot water
Solubility soluble in ethanol, acetone, ether, Tetrahydrofuran
insoluble in xylene
69.0·10−6 cm3/mol
Structure
Layer structure
(chains of SnCl3 groups)
Trigonal pyramidal (anhydrous)
Dihydrate also three-coordinate
Bent (gas phase)
Thermochemistry
325 kJ/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Irritant, dangerous for aquatic organisms
GHS labelling: [1]
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H290, H302+H332, H314, H317, H335, H373, H412
P260, P273, P280, P303+P361+P353, P304+P340+P312, P305+P351+P338+P310
NFPA 704 (fire diamond)
3
0
0
Lethal dose or concentration (LD, LC):
700 mg/kg (rat, oral)
10,000 mg/kg (rabbit, oral)
250 mg/kg (mouse, oral) [2]
Safety data sheet (SDS) ICSC 0955 (anhydrous)
ICSC 0738 (dihydrate)
Related compounds
Other anions
Tin(II) fluoride
Tin(II) bromide
Tin(II) iodide
Other cations
Germanium dichloride
Tin(IV) chloride
Lead(II) chloride
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 ?)

Tin(II) chloride, also known as stannous chloride, is a white crystalline solid with the formula Sn Cl 2. It forms a stable dihydrate, but aqueous solutions tend to undergo hydrolysis, particularly if hot. SnCl2 is widely used as a reducing agent (in acid solution), and in electrolytic baths for tin-plating. Tin(II) chloride should not be confused with the other chloride of tin; tin(IV) chloride or stannic chloride (SnCl4).

Contents

Chemical structure

SnCl2 has a lone pair of electrons, such that the molecule in the gas phase is bent. In the solid state, crystalline SnCl2 forms chains linked via chloride bridges as shown. The dihydrate has three coordinates as well, with one water on the tin and another water on the first. The main part of the molecule stacks into double layers in the crystal lattice, with the "second" water sandwiched between the layers.

Structures of tin(II) chloride and related compounds SnCl2 structure.svg
Structures of tin(II) chloride and related compounds
Ball-and-stick models of the crystal structure of SnCl2 Tin(II)-chloride-xtal-1996-3D-balls-front.png
Ball-and-stick models of the crystal structure of SnCl2

Chemical properties

Tin(II) chloride can dissolve in less than its own mass of water without apparent decomposition, but as the solution is diluted, hydrolysis occurs to form an insoluble basic salt:

SnCl2 (aq) + H2O (l) Sn(OH)Cl (s) + HCl (aq)

Therefore, if clear solutions of tin(II) chloride are to be used, it must be dissolved in hydrochloric acid (typically of the same or greater molarity as the stannous chloride) to maintain the equilibrium towards the left-hand side (using Le Chatelier's principle). Solutions of SnCl2 are also unstable towards oxidation by the air:

6 SnCl2 (aq) + O2 (g) + 2 H2O (l) → 2 SnCl4 (aq) + 4 Sn(OH)Cl (s)

This can be prevented by storing the solution over lumps of tin metal. [4]

There are many such cases where tin(II) chloride acts as a reducing agent, reducing silver and gold salts to the metal, and iron(III) salts to iron(II), for example:

SnCl2 (aq) + 2 FeCl3 (aq) → SnCl4 (aq) + 2 FeCl2 (aq)

It also reduces copper(II) to copper(I).

Solutions of tin(II) chloride can also serve simply as a source of Sn2+ ions, which can form other tin(II) compounds via precipitation reactions. For example, reaction with sodium sulfide produces the brown/black tin(II) sulfide:

SnCl2 (aq) + Na2S (aq) → SnS (s) + 2 NaCl (aq)

If alkali is added to a solution of SnCl2, a white precipitate of hydrated tin(II) oxide forms initially; this then dissolves in excess base to form a stannite salt such as sodium stannite:

SnCl2(aq) + 2 NaOH (aq) → SnO·H2O (s) + 2 NaCl (aq)
SnO·H2O (s) + NaOH (aq) → NaSn(OH)3 (aq)

Anhydrous SnCl2 can be used to make a variety of interesting tin(II) compounds in non-aqueous solvents. For example, the lithium salt of 4-methyl-2,6-di-tert-butylphenol reacts with SnCl2 in THF to give the yellow linear two-coordinate compound Sn(OAr)2 (Ar = aryl). [5]

Tin(II) chloride also behaves as a Lewis acid, forming complexes with ligands such as chloride ion, for example:

SnCl2 (aq) + CsCl (aq) → CsSnCl3 (aq)

Most of these complexes are pyramidal, and since complexes such as SnCl3 have a full octet, there is little tendency to add more than one ligand. The lone pair of electrons in such complexes is available for bonding, however, and therefore the complex itself can act as a Lewis base or ligand. This seen in the ferrocene-related product of the following reaction :

SnCl2 + Fe(η5-C5H5)(CO)2HgCl → Fe(η5-C5H5)(CO)2SnCl3 + Hg

SnCl2 can be used to make a variety of such compounds containing metal-metal bonds. For example, the reaction with dicobalt octacarbonyl:

SnCl2 + Co2(CO)8 → (CO)4Co-(SnCl2)-Co(CO)4

Preparation

Anhydrous SnCl2 is prepared by the action of dry hydrogen chloride gas on tin metal. The dihydrate is made by a similar reaction, using hydrochloric acid:

Sn (s) + 2 HCl (aq) → SnCl2 (aq) + H2 (g)

The water then carefully evaporated from the acidic solution to produce crystals of SnCl2·2H2O. This dihydrate can be dehydrated to anhydrous using acetic anhydride. [6]

Uses

A solution of tin(II) chloride containing a little hydrochloric acid is used for the tin-plating of steel, in order to make tin cans. An electric potential is applied, and tin metal is formed at the cathode via electrolysis.

Tin(II) chloride is used as a mordant in textile dyeing because it gives brighter colours with some dyes e.g. cochineal. This mordant has also been used alone to increase the weight of silk.

In recent years, an increasing number of tooth paste brands have been adding Tin(II) chloride as protection against enamel erosion to their formula, e. g. Oral-B or Elmex.

It is used as a catalyst in the production of the plastic polylactic acid (PLA).

It also finds a use as a catalyst between acetone and hydrogen peroxide to form the tetrameric form of acetone peroxide.

Tin(II) chloride also finds wide use as a reducing agent. This is seen in its use for silvering mirrors, where silver metal is deposited on the glass:

Sn2+ (aq) + 2 Ag+ → Sn4+ (aq) + 2 Ag (s)

A related reduction was traditionally used as an analytical test for Hg 2+ (aq). For example, if SnCl2 is added dropwise into a solution of mercury(II) chloride, a white precipitate of mercury(I) chloride is first formed; as more SnCl2 is added this turns black as metallic mercury is formed. Stannous chloride can be used to test for the presence of gold compounds. SnCl2 turns bright purple in the presence of gold (see Purple of Cassius ).

When mercury is analyzed using atomic absorption spectroscopy, a cold vapor method must be used, and tin (II) chloride is typically used as the reductant.

In organic chemistry, SnCl2 is mainly used in the Stephen reduction, whereby a nitrile is reduced (via an imidoyl chloride salt) to an imine which is easily hydrolysed to an aldehyde. [7]

The reaction usually works best with aromatic nitriles Aryl-CN. A related reaction (called the Sonn-Müller method) starts with an amide, which is treated with PCl5 to form the imidoyl chloride salt.

The Stephen reduction SnCl2 Stephen reduction.png
The Stephen reduction

The Stephen reduction is less used today, because it has been mostly superseded by diisobutylaluminium hydride reduction.

Additionally, SnCl2 is used to selectively reduce aromatic nitro groups to anilines. [8]

Aromatic nitro group reduction using SnCl2 SnCl2 Nitro Reduction Scheme.png
Aromatic nitro group reduction using SnCl2

SnCl2 also reduces quinones to hydroquinones.

Stannous chloride is also added as a food additive with E number E512 to some canned and bottled foods, where it serves as a color-retention agent and antioxidant.

SnCl2 is used in radionuclide angiography to reduce the radioactive agent technetium-99m-pertechnetate to assist in binding to blood cells.

Aqueous stannous chloride is used by many precious metals refining hobbyists and professionals as an indicator of gold and platinum group metals in solutions. [9]

Molten SnCl2 can be oxidised to form highly crystalline SnO2 nanostructures. [10] [11]

Notes

Related Research Articles

<span class="mw-page-title-main">Acid–base reaction</span> Chemical reaction

An acid–base reaction is a chemical reaction that occurs between an acid and a base. It can be used to determine pH via titration. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their application in solving related problems; these are called the acid–base theories, for example, Brønsted–Lowry acid–base theory.

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

Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations Na+ and hydroxide anions OH.

<span class="mw-page-title-main">Aqua regia</span> Mixture of nitric acid and hydrochloric acid in a 1:3 molar ratio

Aqua regia is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but it turns yellow, orange or red within seconds from the formation of nitrosyl chloride and nitrogen dioxide. It was named by alchemists because it can dissolve the noble metals gold and platinum, though not all metals.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. What exactly this can mean depends on which definitions of acids and bases are being used.

<span class="mw-page-title-main">Sodium hypochlorite</span> Chemical compound (known in solution as bleach)

Sodium hypochlorite is an inorganic chemical compound with the formula NaOCl, comprising a sodium cation and a hypochlorite anion. It may also be viewed as the sodium salt of hypochlorous acid. The anhydrous compound is unstable and may decompose explosively. It can be crystallized as a pentahydrate NaOCl·5H
2
O
, a pale greenish-yellow solid which is not explosive and is stable if kept refrigerated.

Iron(III) chloride is the inorganic compound with the formula FeCl3. Also called ferric chloride, it is a common compound of iron in the +3 oxidation state. The anhydrous compound is a crystalline solid with a melting point of 307.6 °C. The colour depends on the viewing angle: by reflected light the crystals appear dark green, but by transmitted light they appear purple-red.

<span class="mw-page-title-main">Zinc chloride</span> Chemical compound

Zinc chloride is the name of inorganic chemical compounds with the formula ZnCl2 and its hydrates. Zinc chlorides, of which nine crystalline forms are known, are colorless or white, and are highly soluble in water. This salt is hygroscopic and even deliquescent. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

<span class="mw-page-title-main">Barium chloride</span> Chemical compound

Barium chloride is an inorganic compound with the formula BaCl2. It is one of the most common water-soluble salts of barium. Like most other water-soluble barium salts, it is a white powder, highly toxic, and imparts a yellow-green coloration to a flame. It is also hygroscopic, converting to the dihydrate BaCl2·2H2O, which are colourless crystals with a bitter salty taste. It has limited use in the laboratory and industry.

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

Lead(II) chloride (PbCl2) is an inorganic compound which is a white solid under ambient conditions. It is poorly soluble in water. Lead(II) chloride is one of the most important lead-based reagents. It also occurs naturally in the form of the mineral cotunnite.

<span class="mw-page-title-main">Aluminium chloride</span> Chemical compound

Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both are colourless crystals, but samples are often contaminated with iron(III) chloride, giving a yellow color.

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

Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations.

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

Cobalt(II) chloride is an inorganic compound of cobalt and chlorine, with the formula CoCl
2
. The compound forms several hydrates CoCl
2
·nH
2
O
, for n = 1, 2, 6, and 9. Claims of the formation of tri- and tetrahydrates have not been confirmed. The anhydrous form is a blue crystalline solid; the dihydrate is purple and the hexahydrate is pink. Commercial samples are usually the hexahydrate, which is one of the most commonly used cobalt compounds in the lab.

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

Copper(II) chloride is the chemical compound with the chemical formula CuCl2. The anhydrous form is yellowish brown but slowly absorbs moisture to form a blue-green dihydrate.

<span class="mw-page-title-main">Chromium(III) chloride</span> Chemical compound

Chromium(III) chloride (also called chromic chloride) describes any of several chemical compounds with the formula CrCl3 · xH2O, where x can be 0, 5, and 6. The anhydrous compound with the formula CrCl3 is a violet solid. The most common form of the trichloride is the dark green hexahydrate, CrCl3 · 6 H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

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

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

<span class="mw-page-title-main">Gold(III) chloride</span> Chemical compound

Gold(III) chloride, traditionally called auric chloride, is a compound of gold and chlorine with the molecular formula Au2Cl6. The "III" in the name indicates that the gold has an oxidation state of +3, typical for many gold compounds. Gold(III) chloride is hygroscopic and decomposes in visible light. This compound is a dimer of AuCl3. This compound has few uses, although it catalyzes various organic reactions.

<span class="mw-page-title-main">Tin(II) oxide</span> Chemical compound, stannous oxide (SnO)

Tin(II) oxide is a compound with the formula SnO. It is composed of tin and oxygen where tin has the oxidation state of +2. There are two forms, a stable blue-black form and a metastable red form.

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

Tin(II) fluoride, commonly referred to commercially as stannous fluoride (from Latin stannum, 'tin'), is a chemical compound with the formula SnF2. It is a colourless solid used as an ingredient in toothpastes.

<span class="mw-page-title-main">Metal halides</span>

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.

<span class="mw-page-title-main">Technetium(IV) oxide</span> Chemical compound

Technetium(IV) oxide, also known as technetium dioxide, is a chemical compound with the formula TcO2 which forms the dihydrate, TcO2·2H2O, which is also known as technetium(IV) hydroxide. It is a radioactive black solid which slowly oxidizes in air.

References

  1. Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  2. "Tin (inorganic compounds, as Sn)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. J. M. Leger; J. Haines; A. Atouf (1996). "The high pressure behaviour of the cotunnite and post-cotunnite phases of PbCl2 and SnCl2". J. Phys. Chem. Solids . 57 (1): 7–16. Bibcode:1996JPCS...57....7L. doi:10.1016/0022-3697(95)00060-7.
  4. H. Nechamkin (1968). The Chemistry of the Elements . New York: McGraw-Hill.
  5. Cetinkaya, B.; Gumrukcu, I.; Lappert, M. F.; et al. (1980-03-01). "Bivalent germanium, tin, and lead 2,6-di-tert-butylphenoxides and the crystal and molecular structures of M(OC6H2Me-4-But2-2,6)2 (M = Ge or Sn)". Journal of the American Chemical Society . 102 (6): 2088–2089. doi:10.1021/ja00526a054. ISSN   0002-7863.
  6. Armarego, W. L. F.; Chai, C. L. L. (2009). Purification of Laboratory Chemicals. www.abebooks.com. Burlington: Elsevier, Butterwoth-Heinemann. doi:10.1016/B978-1-85617-567-8.50009-3. ISBN   9780080878249 . Retrieved 2022-02-03.
  7. Williams, J. W. (1955). "β-Naphthaldehyde". Organic Syntheses .; Collective Volume, vol. 3, p. 626
  8. F. D. Bellamy & K. Ou (1984). "Selective reduction of aromatic nitro compounds with stannous chloride in non acidic and non aqueous medium". Tetrahedron Letters . 25 (8): 839–842. doi:10.1016/S0040-4039(01)80041-1.
  9. How To Make Stannous Chloride for Testing Gold Solutions , retrieved 2023-02-10
  10. Kamali, Ali Reza, Divitini, Giorgio, Ducati, Caterina, Fray, Derek J (2014). "Transformation of molten SnCl2 to SnO2 nano-single crystals". CERI Ceramics International. 40 (6): 8533–8538. doi:10.1016/j.ceramint.2014.01.067. ISSN   0272-8842. OCLC   5902254906.
  11. Kamali, Ali Reza (2014). "Thermokinetic characterisation of tin(II) chloride". Journal of Thermal Analysis and Calorimetry. 118 (1): 99–104. doi:10.1007/s10973-014-4004-z. ISSN   1388-6150. OCLC   5690448892. S2CID   98207611.