PARTING PROCESSS

Gold parting
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Native gold on display in the Natural History Museum, London
Gold parting is the separating of gold from silver. Gold and silver are often extracted from the
same ores and are chemically similar and therefore hard to separate. Over the centuries special
means of separation have been invented.
The very earliest precious metals had mixes of gold and silver; gold and silver alloy is called
electrum. With the advent of coinage, methods had to be invented to remove impurities from the
gold so that gold of specific purities could be made. Cupellation was able to remove gold and
silver from mixtures containing lead and other metals, but silver could not be removed. Gold
parting as a process was specifically invented to remove the silver. The main ancient process of
gold parting was by salt cementation and there is archaeological evidence of that process from
the 6th century BC in Sardis, Lydia. In the post-medieval period parting using antimony,
sulphates and mineral acids was also used. In the modern period chlorination using the Miller
process, and electrolysis using the Wohlwill process are the most widely used methods of
refining gold by removing silver and platinum.
Contents
[hide]
1 History
o 1.1 Early history
o 1.2 Ancient and medieval world
o 1.3 Post medieval to Modern Period
2 Processes
o 2.1 Salt cementation
o 2.2 Sulphur and antimony processes
o 2.3 Acid parting
o 2.4 Miller process
o 2.5 Wohlwill process
o 2.6 Electroparting
3 See also
4 Footnotes
5 Bibliography
History[edit]
Early history[edit]
The very earliest attempts at refining gold can be shown by the surface enhancement of gold
rings. Gold quality was increased at the surface by 8095% gold compared to 6475% gold at
the interior found in Nahal Qanah Cave dated to the 4th millennium BC. Further evidence is
from three gold chisels from the 3rd Millennium BC royal cemetery at Ur that had a surface of
high gold (83%), low silver (9%) and copper (8%) compared with an interior of 45% gold, 10%
silver and 45% copper. The surface was compacted and heavily burnished and indicates early use
of depletion gilding.
Ancient and medieval world[edit]


Early 6th century BC Lydian gold coinage
Separation of gold from silver was not practised in antiquity prior to the Lydian Period (12th
century BC to 546BC).
[1]
Material from Sardis (in modern Turkey) is evidence of the earliest use
of gold and silver parting in the 6th century.
[2]
Literary sources and the lack of physical evidence
suggest that gold-silver parting was not practised before the mid first millennium BC. Gold
parting came with the invention of coinage and there is no evidence for the use of a true refining
processes before the introduction of coinage. As refining gold (as opposed to surface
enhancement) results in a noticeable loss in material, there would have been little reason to do
this before the advent of coinage and the need to have a standard grade of material.
The first possible literary reference to the salt cementation parting process is in the Arthasastra, a
4th-century BC treatise from India, that mentions heating of gold with Indus earth. Indus earth is
taken to mean soils high in salt, nitre and ammonium salts and therefore ideal for the
cementation parting process. A better known and more detailed early description is given by
Diodorus Siculus in the 1st century BC quoting an earlier lost book, On the Erythraean Sea from
the 2nd century BC by Agatharchides of Cnidus.
[3]
An experiment recreating the process as
described by Diodorus Siculus by heating a mixture of the gold and salt in a sealed pot for 5 days
was done by Notton and was found to be successful.
Pliny in this Naturalis Historia mentions the purification of gold a number of times and makes
reference to the salt cementation process of gold parting. He says that the gold is "roasted with a
double weight of salt and three times the weight of misy (ferric sulphates) and again with two
portions of salt and one of the stone which is called schiston." Here he is describing the heating
of gold with salt and iron sulphates which act to dissolve the copper and silver in the gold.
[4]

Parting vessels used for refining gold with the cementation process have been found in London,
Lincoln, York and Winchester. The London vessels, dating from the Flavian period (c.70
85AD), were sealed using luting clay; XRF analysis detected gold and silver, with highest
concentration around the sealed region showing possible escape of silver as the volatile silver
chloride.
[5]

Gold parting had been well used throughout the ancient times but only in the Medieval period
were clear and detailed descriptions of the processes written. All the archaeological finds of
Roman and early medieval parting point to a solid state process using common salt as the active
ingredient.
[6]
The only large group of medieval parting vessels so far discovered were found at
Coppergate and Picadilly sites in York.
[7]
The pinkish-purple discolouration of the vessels
showed them to have been used with the salt cementation process which removes iron from the
clay as ferric chloride. Other vessel fragments are known from Carlisle and Winchester.
[8]

Theophilus was a 12th-century German monk and in his book De Diversus Artibus
[9]
gives the
clearest description of the salt cementation process.
break into tiny pieces a tile or piece of burnt and reddened furnace-clay and when it is
powdered, divide it into two equal parts by weight and add to it a third part of salt of the same
weight. It should then be likely sprinkled with urine and mixed so that it does not stick together
but is just moistened.
Theophilus,
[10]

This mixture is then added to an earthenware pot and layered with thin sheets of gold fold. The
pot is then sealed and heated in a furnace.
Then put the fire and wood below and see that a plentiful fire is not lacking for the space of a
day and a night. In the morning, however, take out the gold and melt it again, hammer it, and put
it into the furnace as before. After another day and night take it out again, mix a little red copper
with it, melt as before, and put it back into the furnace. And when you have taken it out a third
time, wash it and carefully dry it. Weigh it, when dried, and see how much has been lost, then
fold it up and keep it.
Theophilus,
[11]

It was during the medieval period that distillation was discovered and the first description of
nitric acid production was given by Pseudo-Geber in the Summa perfectionis, 1330. Nitric acid is
able to dissolve silver. The addition of sal ammoniac to nitric acid creates Aqua regia and this
acid is able to dissolve gold. Both acids are used in the acid method of parting but the acids were
expensive so were not used until the post medieval period.
[12]

Post medieval to Modern Period[edit]


Distillation using an alembic


Title page of the 1556 edition of Argicola's De Re Metallica
Comprehensive accounts of the salt cementation processes is given by; Biringuccio in his The
Method of cementing gold and of Bringing it to its Ultimate Fineness.; in the Probierbuchlein
Little Books on Assaying; by Georgius Agricola in book 10 of De Re Metallica; and by Ercker in
his Treatise on ores and assaying. This was a period where new techniques began to be explored.
Granulation of the gold instead of gold foil increased surface area and therefore the efficiency of
the reaction. Salt cementation continued to be the main method of parting until the 16th century
but in later Middle Ages processes using sulphur, antimony and mineral acids began to be used.
There are archaeological finds at sites in London of distillation vessels for making acids in
Britain from the 15th century which include fragments of ceramic cucurbits (vessels for heating
reacting chemicals) which were used with alembics for distillation.
[13]
By the 18th century
cementation was rarely used and had been replaced by acid treatment. Into modern times the acid
parting method continued to be used but other methods were discovered. In 1860's Australia the
Miller process was developed, this removed silver by bubbling chlorine gas through the molten
gold mixture. Soon after, in the 1870s, Electrolytic refining of gold was developed, the Wohlwill
process, to deal with the problem of removing platinum from the gold. This technique is the most
commonly used today.
[14]

Processes[edit]
Salt cementation[edit]
This process was used from Lydian to post medieval times. It is a solid state process relying on
common salt as the active ingredient but it is possible to use a mixture of saltpetre (KNO
3
) and
green vitriol (FeSO
4
). The basic process involved the mixing of argentiferous gold foil (in later
periods granules were used), common salt and brick dust or burnt clay in a closed and sealed
container. Theophilus mentions the addition of urine to the mix. With heating, the silver reacts
with the salt to form silver chloride which is removed leaving a purified gold behind. Conditions
needed for this process are below 1000C as the gold should not melt. Silver can be recovered by
smelting the debris.
[15]
Heating can take 24 hours. Hoover and Hoover
[16]
explains the process
thus: under heating salt (sodium chloride, NaCl) decomposes in the presence of silica and
alumina (from the brick dust or clay) to produce hydrochloric acid and also some chlorine. This
reacts with the silver to produce silver chloride (AgCl). The urine is acidic and aids
decomposition. Silver chloride is volatile and would be removed from the metal. And the
container is sealed to stop the escape of the silver which can be recovered later. Notton in
experiments found that with one heating the gold content could be taken from 37.5% to 93%
[17]

Sulphur and antimony processes[edit]


Separation of gold and silver by sulfur, De Re Metallica 1556
This is similar to the salt cementation process but creates sulphides instead of chlorides. Finely
divided impure gold and elemental sulphur are reacted together under moderate heat in a sealed
crucible. The impurities form metal sulphides and the gold is left unreacted. The gaseous
sulphide condenses on the crucible fabric. The antimony process is the same but uses stibnite
(Sb
2
S
3
) instead of sulphur because stibnite is stable at a higher temperature than sulphur. This is
much quicker than the salt process and gave a purer gold, but it could dissolve some of the gold
as well. This process is first described in the Probierbuchlein.
[18]

Acid parting[edit]


Pure gold precipitate produced by the aqua regia refining process
The distillation was used in the 12th century Europe after its introduction from the East
[19]
and
after that period more powerful acids could be created. Nitric acid (aqua valens) could be made
by the distillation of saltpetre (KNO
3
) with alum (KAl(SO
4
)
2
) or vitriol (FeSO
4
) with water.
[14][13]

2KNO
3
+ H
2
O + FeSO
4
FeO + K
2
SO
4
+ 2HNO
3

Nitric acid, after distillation to increase the acid strength, was capable of dissolving the silver
from a finely divided mixture of silver and gold, leaving the gold. Aqua regia was also used for
parting. It was made by adding sal ammoniac to nitric acid which produced a mixture of
hydrochloric acid and nitric acid. This acid dissolved the gold to a soluble chloride and the silver
was attacked and precipitated as an insoluble chloride. Silver was removed by filtering and gold
was then recovered by evaporating the liquid and heating the residue. Nitric acid was suitable for
separating small quantities of gold from silver and Aqua regia used to separate small quantities
of silver from gold. Aqua regia acid process is used by refiners of scrap gold used in jewelry
manufacturing. This process is also well suited to recycling consumers used or broken jewelry
directly back onto the global market 24kt inventory.
[12]

Miller process[edit]
Main article: Miller process
The Miller process was invented by Francis Bowyer Miller in 1860's Australia. It is able to refine
gold up to 99.5% purity. The process involves blowing a stream of chlorine gas over and through
a crucible filled with molten impure gold. Impurities in the gold form chlorides before the gold
does and these insoluble salts are removed from the melt by skimming the surface.
[20][21]

Wohlwill process[edit]
Main article: Wohlwill process
Invented by Emil Wohlwill in 1874 this produces the highest purity gold (99.999%). It is an
electrolytic process using pure gold for the cathode (or titanium as a starter cathode) and
chloroauric acid (gold chloride-hydrochloric acid) as the electrolyte; this is made by dissolving
gold with chlorine gas in the presence of hydrochloric acid. Gold is dissolved at the anode, and
pure gold, traveling through the acid by ion transfer, is plated onto the cathode. Silver forms an
insoluble chloride slime and copper and platinum form soluble chlorides that are removed. This
procedure is used on a very large industrial scale and has a large set up cost due to the amount of
gold that needs to be permanently dissolved in the electrolyte.
[20][21]

Electroparting[edit]
Main article: Electroparting process
Electroparting is recent gold refining procedure where gold is separated from other metals in
electrolytic cell in a way that dissolves all metals except gold and platinum. This procedure
refines gold directly, producing up to 99.5% purity gold powder in a single step.