History & Etymology

Tinisoneoftheoldestmetalsknownbyman.Therearedomesticutensilsand
armsmadeofbrass(copperwithabout15%oftin),datingfrom3500BC.The
Phoenicianshadaveryimportantroleinthespreadofbrassutensilsduetoits
commercialtradeswithBritain,SpainandtheMiddleEast.

TheTinoftheBible([kassiteros]intheGreekversion)
correspondstotheHebrew[bdil],whichisreallyaCopperalloyknownas
earlyas1600BCinEgypt.

"AndElea'zarthepriestsaiduntothemenofwarwhichwenttothebattle,This
istheordinanceofthelawwhichtheLORDcommandedMoses;onlythegold,
andthesilver,thebrass,theiron,thetin,andthelead,everythingthatmayabide
thefire,yeshallmakeitgothroughthefire,anditshallbeclean:neverthelessit
shallbepurifiedwiththewaterofseparation:andallthatabidethnotthefireye
shallmakegothroughthewater."(Numbers31:2123).

TheGreeksimportedTinfromtheCasseterides("Tinislands"),islandsinthe
West.ThepreciselocationoftheCassiteridesor"tinislands"isunknown,butitis
suggestedtheyaretheBritishIsles.ThemostimportantoreofTinisTinoxide,
Cassiterite(SnO2).AspecimenfromCornwallisillustratedhere.Theimportance
oftintotheGreekswasitsimmensevalueinalloyingcopper,whichwasmined
fromancienttimesinCyprus.Copperbyitselfisverydifficulttocast,butwiththe
additionofabouttenpercentoftin,itflowsnicelyinthemoltenstate,andhas
greaterhardnessthancopper.The"BronzeAge"wasdependentontinfromits
veryinception.

FromPlinyswritingsitappearsthattheRomansinhistimedidnotrealizethe
distinctionbetweenTinandLead.HereferredtoTinasplumbumalbum(white
lead)todistinguishitfromLeadwhichwascalledplumbumnigrum(blacklead).
PlinyreferredtotheexistenceofTinandLeadalloys,whatwenowknowas
solder,aswellasrecipientsoftinnedcopper.Hewrotethatthebestmirrorswere
madeatBrundisiumfromamixtureofCopperand"stagnum".BytheRomans,the
termstannumwasmostlyusedforanalloyofLeadandSilverobtainedinthe
winningofSilver.NotuntilthesixthcenturywasitappliedtoTin,butthereafter
wascommonlyusedinthissense.
 BytheearlyGreekalchemiststhemetalwasnamedHermes,butataboutthe
beginningofthe6thcentury,itwastermedZeusorJupiter.Itwasalsoreferredto
asdiabolusmetallorum(devilamongmetals),onaccountofthebrittlealloys
whichitformed.

Inastrologyalchemythesevenheavenlybodiesknowntotheancientswere
associatedwithsevenmetalsalsoknowninantiquity:

Chemistianity 1873
Tinstone (Tin Dioxide) found in Mines and Streams
In Cornwall, produces Bar- and Grain-Tin.
It is our only native source for Tin.

Althoughnotasmuchasfortheothersixantiquemetals,thenameforthemetal
tinhasavarietyofrootsinthevariouslanguages.Themostimportantare:

1.Stannum<Tin
TheLatin nameStannumisconnected
to"stagnum" and"stag"(IndoEuropean)
fordripping becausetinmeltseasily.The
worddefinitely assumeditspresentmeaning
inthe4th century(H.Kopp).
According toMeyers
 KonversationslexikonStannumisderivedfromCornishstean(present
orthographysten),andisproofthatCornwallinthefirstcenturiesADwas
themainsourceofTin.(othersources,however,seetheCornishsteanasa
derivationfromtheLatinstannum![Eedle]).TheLatinStannumbecamethe
sourceformostEuropeanwords.InSpanish(estao)evolved
fromstannumbyfirstbecomingstanno(the"m"neverwasstrongly
pronouncedinLatin,andmostlynasalizedthe"u").ThentheGothshad
problemswith"st"soitbecameestanno.Finally,thedouble"n"mergedinto
""whenthespellingwasregularized,andwehavethefinalform.
Italianstagnosufferedasimilartransformation(gn=).TheFrenchtainis
closertotheEnglish(andDutch)Tin.Indeed,thesecondsyllablewouldbe
prounouncedjustas"Tin"wouldbe.
AccordingtoSMIthemetalisnamedafteranEtruscangod,Tinia.

2.Kassiteros(Greek)
TheGreeknameisalreadyinusesinceHomer.itmeans"the
metalfromthelandoftheKassi(ortheCasseterides)".Theetymologyis
notclear(seeLoma'sabstractbelow).TheCroatiannameisobviously
derivedfromtheGreek.TheArabic[qaSdr]isanoldborrowingfrom
thisGreekword.AlsosomeBalkanSlaviclanguageshasborrowedtheir
wordfromGreek.

AttheXI.FachtagungderIndogermanischenGesellschaft(Halle/S.1723
September2000)AleksandarLomafromBelgradopresentedapaper,Gr.
kassiteros,att.kattiteros:EinfrhesiranischesLehnwort?.Thesummaryis:

Gr.kassiteros,att.kattiteros"Zinn",einWanderwortbislangohne
Etymologie,wirdalsfrheEntlehnungausdemIranischenerklrt
undzusammenmitdenapers.LWimAltindischensisan."Blei",kas
isan."Eisenvitriol"aufdengemeiniranischenAnsatz*katsvi?ra
zurckgefhrt,unterHinweisaufdievonStraboXV,p.724
erwhntenZinngrubeninDrangiana.DieseAnnahmegibtAnlazur
DiskussionberdieabsoluteundrelativeChronologieeinigerfrher
LautwandlungenindenbeidenSprachen.(Source,clickhere).
MoreontheetymologyofKassiterosatEedle'shomepage.
3.Kalay(Turkish)
UsedinmostoftheBalkanlanguages,aswellasintheAltaiclanguages.
4.Alavas(Baltic)
TheBalticAlavasisusedinEasternSlaviclanguages(Russian).In
WesternSlaviclanguagesthisisthenameforLead.
 ApeculiarwebsitefromLavianAmericanAndisKaulins,IndoEuropeanAfro
AsiaticWordsforMetalsCopperLeadTinIronBronzeGoldAmber.Iamnot
surewhattothinkofthevalueofhisunorthodoxinformation,butgiveitforwhat
itisworth.KaulinspresentsthefollowinglistforTin:

Tin(Sn), a chemical element

belonging to the carbon family, Group 14 (IVa) of the periodic table. It is a soft, silvery
white metal with a bluish tinge, known to the ancients in bronze, an alloy with copper.
Tin is widely used for plating steel cans used as food containers, in metals used for
bearings, and in solder.

The origins of tin are lost in antiquity. Bronzes, which are coppertin alloys, were
used by humans in prehistory long before pure tin metal itself was isolated. Bronzes
were common in early Mesopotamia, the Indus valley, Egypt, Crete, Israel, and Peru.
Much of ... (100 of 1,210 words)
SOLID-LIQUID PHASE DIAGRAMS: TIN
AND LEAD

This page explains the relationship between the cooling curves for
liquid mixtures of tin and lead, and the resulting phase diagram. It
also offers a simple introduction to the idea of a eutectic mixture.

Important: This page is only really designed to be an introduction to

the topic suitable for courses for 16-18 year olds such as UK A level
chemistry. Be aware that the phase diagram used is a simplified
version of the real thing. In particular, it ignores the formation of solid
solutions of tin and lead. I will give a link to the correct phase
diagram later.

Cooling curves

Cooling curves for pure substances

Suppose you have some pure molten lead and allow it to cool down
until it has all solidified, plotting the temperature of the lead against
time as you go. You would end up with a typical cooling curve for a
pure substance.
 Note: Just before the liquid freezes, there is sometimes a slight dip
in the curve below the freezing point. This is calledsupercooling. As
soon as some solid forms, the temperature recovers to the normal
freezing point. Supercooling isn't important for the present
discussion, so I'm ignoring it on the diagrams.

Throughout the whole experiment, heat is being lost to the

surroundings - and yet the temperature doesn't fall at all while the
lead is freezing. This is because the freezing process liberates heat
at exactly the same rate that it is being lost to the surroundings.

Energy is released when new bonds form - in this case, the strong
metallic bonds in the solid lead.

If you repeated this process for pure liquid tin, the shape of the
graph would be exactly the same, except that the freezing point
would now be at 232C. (The graph for this is further down the
page.)

Cooling curves for tin-lead mixtures

A sample curve

If you add some tin to the lead, the shape of the cooling curve
changes. The next graph shows what happens if you cool a liquid
mixture containing about 67% lead and 33% tin by mass.

There are lots of things to look at:

Notice that nothing happens at all at the normal freezing

point of the lead. Adding the tin to it lowers its freezing point.

Freezing starts for this mixture at about 250C. You would

start to get some solid lead formed - but no tin. At that point
the rate of cooling slows down - the curve gets less steep.

However, the graph doesn't go horizontal yet. Although

energy is being given off as the lead turns to a solid, there
isn't anything similar happening to the tin. That means that
there isn't enough energy released to keep the temperature
constant.

The temperature does stop falling at 183C. Now both tin

and lead are freezing. Once everything has solidified, the
temperature continues to fall.

Changing the proportions of tin and lead

If you had less tin in the mixture, the overall shape of the curve
stays much the same, but the point at which the lead first starts to
freeze changes.
The less tin there is, the smaller the drop in the freezing point of the
lead.

For a mixture containing only 20% of tin, the freezing point of the
lead is about 275C. That's where the graph would suddenly
become less steep.

BUT . . . you will still get the graph going horizontal (showing the
freezing of both the tin and lead) at exactly the same temperature:
183C.

As you increase the proportion of tin, the first signs of solid lead
appear at lower and lower temperatures, but the final freezing of
the whole mixture still happens at 183C.

That continues until you have added enough tin that the mixture
contains 62% tin and 38% lead. At that point, the graph changes.

This particular mixture of lead and tin has a cooling curve which
looks exactly like that of a pure substance rather than a mixture.
There is just the single horizontal part of the graph where
everything is freezing.

However, it is still a mixture. If you use a microscope to look at the

solid formed after freezing, you can see the individual crystals of tin
and lead.

This particular mixture is known as a eutectic mixture. The word

"eutectic" comes from Greek and means "easily melted".

The eutectic mixture has the lowest melting point (which is, of
course, the same as the freezing point) of any mixture of lead and
tin. The temperature at which the eutectic mixture freezes or melts
is known as the eutectic temperature.

What happens if there is more than 62% of tin in the mixture?

You can trace it through in exactly the same way, by imagining

starting with pure tin and then adding lead to it.

The cooling curve for pure liquid tin looks like this:

It's just like the pure lead cooling curve except that tin's freezing
point is lower.

If you add small amounts of lead to the tin, so that you have
perhaps 80% tin and 20% lead, you will get a curve like this:
Notice the lowered freezing point of the tin. Notice also the final
freezing of the whole mixture again takes place at 183C.

As you increase the amount of lead (or decrease the amount of tin -
same thing!) until there is 62% of tin and 38% of lead, you will
again get the eutectic mixture with the curve we've already looked
at.

The phase diagram

Constructing the phase diagram

You start from data obtained from the cooling curves. You draw a
graph of the temperature at which freezing first starts against the
proportion of tin and lead in the mixture. The only unusual thing is
that you draw the temperature scale at each end of the diagram
instead of only at the left-hand side.

Notice that at the left-hand side and right-hand sides of the curves
you have the freezing points (melting points) of the pure lead and
tin.

Note: The two lines meeting at the eutectic point have been
simplified slightly so that they are drawn as straight lines rather than
slight curves. It doesn't affect the argument in any way. I haven't
been able to find the actual data to plot them accurately, so the
simplification is to avoid giving the impression that I actually
know exactly what the curves look like!

To finish off the phase diagram, all you have to do is draw a single
horizontal line across at the eutectic temperature. Then you label
each area of the diagram with what you would find under the
various different conditions.
 Important: This is a simplified version of the real tin-lead phase
diagram. In particular, it ignores the formation of solid solutions of tin
and lead. You will find the correct diagram onthis NIST web page.
Beware that on that page, the tin-lead axis is reversed from the one I
have drawn above - in other words 100% lead is on the right rather
than the left.

If you are just using this page as an introduction to this sort of phase
diagram, you don't need to worry about this.

Using the phase diagram

Important: One of the problems with the various sorts of phase

diagrams is that they are all interpreted slightly differently. You can't
assume that because you know how to use one sort of phase
diagram that you can treat others exactly the same. If you already
know about other phase diagrams, look at this one completely
afresh.

Suppose you have a mixture of 67% lead and 33% tin. That's the
mixture from the first cooling curve plotted above. Suppose it is at a
temperature of 300C.
That corresponds to a set of conditions in the area of the phase
diagram labelled as molten tin and lead.

Now consider what happens if you cool that mixture. Eventually the
temperature will drop to a point where it crosses the line into the
next region of the diagram.

At that point, the mixture will start to produce some solid lead - in
other words, the lead (but not the tin) starts to freeze. That happens
at a temperature of about 250C.
Now there is a bit of a problem, because you might come across
two different ways of explaining what happens next. We'll look at
both.

Thinking about changes in the composition of the liquid

When the first of the lead freezes, the composition of the remaining
liquid changes. It obviously becomes proportionally richer in tin.
That lowers the freezing point of the lead a bit more, and so the
next bit of lead freezes at a slightly lower temperature - leaving a
liquid still richer in tin.

This process goes on. The liquid gets richer and richer in tin, and
the temperature needed to freeze the next lot of lead continues to
fall. The set of conditions of temperature and composition of the
liquid essentially moves down the curve - until it reaches the
eutectic point.
Once it has reached the eutectic point, if the temperature continues
to fall, you obviously just move into the region of a mixture of solid
lead and solid tin - in other words, all the remaining liquid freezes.

If you haven't come across this way of looking at it before, then

please don't bother to learn it now! The second way is more in line
with how we look at other phase diagrams, and actually needs less
thinking about.

Thinking about the composition of the system as a whole

We've seen that as the liquid gradually freezes, its composition

changes. But if you look at the system as a whole, obviously the
proportions of lead and tin remain constant - you aren't taking
anything away or adding anything. All that is happening is that
things are changing from liquids to solids.

So suppose we continue the cooling beyond the temperature that

the first solid lead appears and the temperature drops to the point
shown in the next diagram - a point clearly in the "solid lead and
molten mixture" area.
What would you see in the mixture? To find out, you draw a
horizontal tie line through that point, and then look at the ends of it.

At the left-hand end, you have 100% lead. That represents the solid
lead that has frozen from the mixture. At the right-hand end, you
have the composition of the liquid mixture. This is now much richer
in tin than the whole system is - because obviously a fair bit of solid
lead has separated out.

As the temperature continues to fall, the composition of the liquid

mixture (as shown by the right-hand end of the tie line) will get
closer and closer to the eutectic mixture.

It will finally reach the eutectic composition when the temperature

drops to the eutectic temperature - and the whole lot then freezes.

At a temperature lower than the eutectic temperature, you are

obviously in the solid lead plus solid tin region. That's fairly obvious!

If you cooled a liquid mixture on the right-hand side of the phase

diagram (to the right of the eutectic mixture), everything would work
exactly the same except that solid tin would be formed instead of
solid lead. If you have understood what has gone before, it isn't at
all difficult to work out what happens.

Finally . . . what happens if you cool a liquid mixture which has

exactly the eutectic composition?
It simply stays as a liquid mixture until the temperature falls enough
that it all solidifies. You never get into the awkward areas of the
phase diagram.

Tin-lead mixtures as solder

Traditionally, tin-lead mixtures have been used as solder, but these

are being phased out because of health concerns over the lead.
This is especially the case where the solder is used to join water
pipes where the water is used for drinking. New non-lead solders
have been developed as safer replacements.

Typical old-fashioned solders include:

60% tin and 40% lead. This is close to the eutectic

composition (62% tin and 38% lead), giving a low melting
point. It will also melt and freeze cleanly over a very limited
temperature range. This is useful for electrical work.

50% tin and 50% lead. This will melt and freeze over a wider
range of temperatures. When it is molten it will start to freeze
at about 220C and finally solidify at the eutectic
temperature of 183C. That means that it stays workable for
a useful amount of time. That's helpful if it is being used for
plumbing joints.