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c
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a27 049
Tin, Tin Alloys, and Tin Compounds 1
Tin, Tin Alloys, and Tin Compounds
G¨unter G. Graf
, Freiberg, Federal Republic of Germany
1. History
. . . . . . . . . . . . . . . . .
2
2. Properties
. . . . . . . . . . . . . . . .
2
3. Occurrence; Ore Extraction andBeneficiation
. . . . . . . . . . . . . .
5
3.1. Minerals
. . . . . . . . . . . . . . . .
5
3.2. Deposits
. . . . . . . . . . . . . . . . .
5
3.3. Mining
. . . . . . . . . . . . . . . . . .
6
3.4. Ore Beneficiation
. . . . . . . . . . .
7
4. Smelting
. . . . . . . . . . . . . . . . .
8
4.1. Fundamental Theory of Smelting
8
4.2. Special Aspects of the Winning of Tin from its Ores
. . . . . . . . . . .
10
4.3. Production of Crude Tin
. . . . . .
114.3.1. General Aspects
. . . . . . . . . . . .
114.3.2. Ore Preparation prior to Reduction 114.3.2.1. Pyrometallurgical Enrichmentof Low-Grade Concentrates
. . . . .
114.3.2.2. Roasting
. . . . . . . . . . . . . . . . .
124.3.2.3. Leaching
. . . . . . . . . . . . . . . . .
134.3.3. Reduction
. . . . . . . . . . . . . . . .
144.3.3.1. Reduction in a Shaft Kiln
. . . . . .
144.3.3.2. Reduction in a ReverberatoryFurnace
. . . . . . . . . . . . . . . . .
154.3.3.3. Reduction in Rotary Kilns
. . . . . .
164.3.3.4. Reduction in an Electric Furnace
. .
174.3.3.5. Other Reduction Processes
. . . . .
184.3.4. Slag Processing
. . . . . . . . . . . .
18
5. Refining
. . . . . . . . . . . . . . . . .
20
5.1. Pyrometallurgical Refining
. . . .
205.1.1. Removal of Iron
. . . . . . . . . . . .
205.1.2. Removal of Copper
. . . . . . . . . .
215.1.3. Removal of Arsenic
. . . . . . . . . .
215.1.4. Removal of Lead
. . . . . . . . . . . .
225.1.5. Removal of Bismuth
. . . . . . . . .
22
5.2. Electrorefining
. . . . . . . . . . . .
225.2.1. Electrorefining in Acid Medium
. .
225.2.2. Electrorefining in an AlkalineMedium
. . . . . . . . . . . . . . . . .
235.2.3. Other Methods of Electrorefining
.
23
6. Recovery of Tin from ScrapMaterials and Residues
. . . . . . .
23
7. Analysis
. . . . . . . . . . . . . . . . .
24
7.1. Analysis ofOres and Concentrates
24
7.2. Analysis of Metallic Tin
. . . . . .
25
8. Economic Aspects
. . . . . . . . . .
25
9. Tin Alloys and Coatings
. . . . . .
26
10. Inorganic Tin Compounds
. . . . .
28
10.1. Tin(II) Compounds
. . . . . . . . .
28
10.2. Tin(IV) Compounds
. . . . . . . . .
29
11. Organic Compounds of Tin
. . . .
30
11.1. Properties of OrganotinCompounds
. . . . . . . . . . . . . .
31
11.2. Production of OrganotinCompounds
. . . . . . . . . . . . . .
31
11.3. Industrially ImportantCompounds
. . . . . . . . . . . . . .
32
11.4. Analysis of OrganotinCompounds
. . . . . . . . . . . . . .
33
11.5. Storage and Shipping of Organotin Compounds
. . . . . . .
33
11.6. Pattern of Productionand Consumption
. . . . . . . . . .
33
12. Toxicology
. . . . . . . . . . . . . . .
33
13. References
. . . . . . . . . . . . . . .
34
1. History
[1–4], [6], [11], [15]Because of its luster and softness, tin was usu-allyassignedtotheplanetJupiter,morerarelytoVenus. The name of the element is derived fromthe Old High German
zin
and the Norse
tin
. ThesymbolSnfromtheLatin
stannum
wasproposedby
Berzelius
. Historically tin is of major cul-tural importance, being an essential componentof the copper alloy bronze which gave its nameto the Bronze Age. The first bronze objects ap-peared in Egyptian tombs dating from the endof the 4th millennium
b
.
c
.PuretinwasfirstproducedinChinaandJapanaround 1800
b
.
c
. Around 600
b
.
c
., the ancientEgyptians occasionally placed pure tin artifactsin mummies’ tombs. Tin is not only an essen-tial constituent of tin bronze, but is also a con-stituent of lead alloys for solders and tin plating.Tin and especially its alloys have shaped the de-velopment of many geographical regions, e.g.,China, Indochina, Indonesia, India, the NearEast, North Africa, and Europe.The cultural and historical importance of tinfrom the Middle Ages to early modern times lay
 
2 Tin, Tin Alloys, and Tin Compounds
initsuseforsacredobjects,articlesofdailyuse,and jewelry.There is no historical evidence concerningthe oldest methods of tin extraction. It is fairlycertain that in 100
b
.
c
. in Cornwall, England,tin was smelted from very pure ore over woodfiresinpitsandlaterinsmallfurnaces.Uptothe1200s, Cornwall provided most of Europe’s tin.Today, these deposits are virtually exhausted.Tin was probably produced in Bohemia around1150. Also, the first tin mines were opened inSaxony at this time, and these supplied Euro-pean requirements until they were destroyed inthe Thirty Years War. Then, as these various de-positsgraduallybecameexhaustedandasoceantransport developed, tin from overseas becamedominant.ThelargesttinminesareinAsia,themostim-portant ore-supplying countries in the world be-ing Malaysia and Indonesia, followed by China.The second largest tin-producing region in-cludes Brazil and Bolivia. The countries export-ingthelargestquantitiesoftinoresalsoproducethe most tin metal.World annual production has developed asfollows:
ca. 1800 9100tca. 1850 19000tca. 1900 91900tca. 1950 172100t1980 243600t1990 225600t
The principal consumer countries are theUnited States, Japan, China, and Russia.
2. Properties
Physical Properties
[1], [2], [4], [16–19],[20]. Tin, Sn, exists in two crystalline modifica-tions, the
α
- and
β 
-forms. A third modificationmay also exist. Some physical properties of 
α
-and
β 
-tin are listed in the following. (see rightcolumn)In the periodic table, tin lies on the bound-ary between metals and nonmetals. The trans-formation of the
α
- to the
β 
-modification isaccompanied by a complete change of latticestructure, affecting the physical, chemical, andmechanical properties. Also, at 170
◦
C there isa secondorder transformation accompanied by adiscontinuous change in the lattice parametersand thermomechanical properties. A tetragonalhighpressuremodificationoftin,stablebetween3500 and 11000MPa, is described in the litera-ture, the lattice constants being
a
=381pm and
b
=348pm.
Natural isotopes 10Relative atomic mass 118.69Crystal structure
α
-Sn (gray tin) fcc (A
4
) diamond type
β
-Sn (white tin) tetragonal (A
5
)Transformation temperature
α
-Sn
↔
β
-Sn286.2KEnthalpy of transformation 1966J/molLattice constants at 25
◦
C
α
-Sn
a
=648.92pm
β
-Sn
a
=583.16pm
c
=318.13pmDensity of 
β
-tin20
◦
C 7.286g/cm
3
100
◦
C 7.32g/cm
3
230
◦
C 7.40g/cm
3
Density of 
α
-tin 5.765g/cm
3
Density of liquid tin240
◦
C 6.992g/cm
3
400
◦
C 6.879g/cm
3
800
◦
C 6.611g/cm
3
1000
◦
C 6.484g/cm
3
Molar heat capacity of 
β
-tin25
◦
C 27.0Jmol
−
1
K
−
1
230
◦
C 30.7Jmol
−
1
K
−
1
Liquid 28.5Jmol
−
1
K
−
1
Melting point 505.06KEnthalpy of fusion 7029J/molBoiling point 2876KEnthalpy of vaporization 295763J/molVapor pressure1000K 9.8
×
10
−
4
Pa1800K 750Pa2100K 8390Pa2400K 51200PaCubic coefficient of expansion
α
-tin at
−
130
◦
C to +10
◦
C 14.1
×
10
−
6
K
−
1
to 4.7
×
10
−
6
K
−
1
β
-tin at 0
◦
C 59.8
×
10
−
6
K
−
1
β
-tin at 50
◦
C 69.2
×
10
−
6
K
−
1
β
-tin at 100
◦
C 71.4
×
10
−
6
K
−
1
β
-tin at 150
◦
C 80.2
×
10
−
6
K
−
1
Molten tin at 700
◦
C 105.0
×
10
−
6
K
−
1
Coefficient of thermal conductivity of 
β
-tin at 0
◦
C0.63Wcm
−
1
K
−
1
Surface tension232
◦
C 0.53–0.62N/m400
◦
C 0.52–0.59N/m800
◦
C 0.51–0.52N/m1000
◦
C 0.49N/mDynamic viscosity232
◦
C 2.71
×
10
−
3
Pa
·
s400
◦
C 1.32
×
10
−
3
Pa
·
s1000
◦
C 0.80
×
10
−
3
Pa
·
sSpecific electrical resistivity
α
-tin at 0
◦
C 5
×
10
−
6
Ω
m
β
-tin at 25
◦
C 11.15
×
10
−
6
Ω
mTransition temperature forsuperconductivity3.70KMagnetic susceptibility of 
β
-Sn 2.6
×
10
−
11
m
3
 /kg
 
Tin, Tin Alloys, and Tin Compounds 3
Thetransformationof 
β 
-tin(whitetin)into
α
-tin (gray tin) is of practical importance, as it in-volves a volume increase of 21%. The transfor-mation process requires a high energy of activa-tion,andcanbeverystronglyhindered.White
β 
-tincanthereforeexistformanyyearsat
−
30
◦
C.The presence of 
α
-tin seed crystals is impor-tant for the transformation process, and theseare formed by repeated phase transitions. For-eign “elements” also affect the transformationtemperatureandrate.Thesecanconsistofimpu-rities and deformations. The effect of impuritieson transformation behavior is described in [21].Tin vapor consists of Sn
2
molecules.
Mechanical Properties
[1], [2], [4], [20–23]. Mechanical properties are not of great rele-vance to most applications of pure tin. The mostimportant are listed in the following:
Yield strength at 25
◦
C 2.55N/mm
2
Ultimate tensile strength
−
120
◦
C 87.6N/mm
2
15
◦
C 14.5N/mm
2
200
◦
C 4.5N/mm
2
Brinell hardness (10mm,3000N, 10s)0
◦
C 4.12100
◦
C 2.26200
◦
C 0.88Modulus of elasticity
E 
−
170
◦
C 65000N/mm
2
−
20
◦
C 50000N/mm
2
0
◦
C 52000N/mm
2
40
◦
C 49300N/mm
2
100
◦
C 44700N/mm
2
200C 26000N/mm
2
Chemical Properties
[1], [2], [4], [20]. Tinhas the atomic number50 and is a member of group14 of the periodic table. The electronicconfiguration is 1
s
2
2
s
2
 p
6
3
s
2
 p
6
d 
10
4
s
2
 p
4
d 
10
5
s
2
 p
2
. Tin can be di- or tetravalent. It is sta-ble in dry air, but is considerably more rapidlyoxidized at a relative humidity of 80%. Brightmetallic tin becomes dull within 100d evenin indoor atmospheres. Oxygen is rapidly andirreversibly chemisorbed, and the oxide layerformed grows at an exponentially increasingrate. Typical impurities present after metallurgi-cal production (e.g., Sb, Tl, Bi, and Fe) promoteoxidation. Treatment with carbonate or chro-mate solutions leads to passivation.Molten tin at temperatures up to ca. 500
◦
Cpicks up oxygen from the air at a rate that obeysa parabolic law, a result of the compact layer of oxide formed.Gaseous water and nitrogen do not dissolvein solid tin. Dissolution in molten tin only oc-curs at high temperatures (ca.
>
1000
◦
C). Un-der the conditions of electrochemical reductionin hydrochloric acid solutions, atomic hydro-gen forms SnH
4
, and elemental nitrogen formsSn
3
N
4
.Tin is stable towards fluorine at room tem-perature, but SnF
2
or SnF
4
are formed at highertemperatures.Rapid and vigorous reactions occur withchlorine, bromine, and iodine, these reactionsbeingacceleratedbymoistureandelevatedtem-peratures. The reaction products are SnCl
4
,SnBr
4
, SnI
2
, and SnI
4
.Sulfur reacts rapidly with molten tin at
>
600
◦
C to form the sulfides SnS, Sn
2
S
3
, andSnS
2
. The reaction rate is lower above 900
◦
C,and only SnS is formed.Reaction with hydrogen sulfide is slow andonlyoccursinthepresenceofoxygenandmois-ture. Sulfur dioxide reacts with molten tin toform SnO
2
and S, and a molten solution of tinin copper reacts with SO
2
to form SnO
2
andCu
2
S(animportantreactioninpyrometallurgy).Tin is stable towards pure hot water, steam, anddry ammonia. Nitrogen oxides only react withmolten tin.Tin is amphoteric, reacting with both strongbases and strong acids with evolution of hy-drogen. Having a normal electrode potential of 
−
0.136V,tinliesbetweennickelandleadintheelectrochemical series.With sodium hydroxide solution, tin formsNa
2
[Sn(OH)
6
], and with potassium hydroxidesolution K
2
[Sn(OH)
6
].Tin reacts slowly with acids in the absenceof oxygen. The high hydrogen overvoltage iscausedbyalayerofatomichydrogenatthemetalsurface preventing further attack. Vigorous re-actions occur with nitric acid, the rate depend-ing on the acid concentration. The reactions arevery vigorous with 35% acid, but complete pas-sivationcanoccuratconcentrations
>
80%.Tinis stable towards fuming nitric acid. While hy-drogenfluoridedoesnotattacktin,hydrochloricacidreactsevenataconcentrationof0.05%andtemperatures below 0
◦
C. Tin is not attacked bysulfurous acid or by
<
80% sulfuric acid.
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