Fusible and Slags

Tecsup Virtual

Lima - Peru
2008
Tecsup Virtu@l Topics on Gold Ore Smelting

INDEX

FUSIONS AND SLAGS

1. Introduction....................................................................................................1
2. Objectives .........................................................................................................1
3. Properties of fluxes....................................................................................1
3.1 Oxidizing fluxes ................................................................................. 2
3.2 Reducing agents................................................................................ 2
3.3 Neutral fluxes or regulators ............................................................... 3
3.4 Collector metals.................................................................................... 3
4. Description of the main fluxes ............................................................3
5. Reducing capacity of substances used in the quantification of gold and silver..6
5.1 Composition of a melting mixture......................................................... 6
5.2 Flux mixture for various concentrates
6. Main reactions during smelting.........................................................7
7. The slags .....................................................................................................8
8. Quantification of the process...............................................................................10
9. Practice of gold chemical analysis by fusion .............................................14
10. Summary........................................................................................................19
Tecsup Virtual Topics on Gold Ore Smelting

UNIT II

FUSIONS AND SLAG

1. INTRODUCTION

Before describing the casting processes, we invite the participants of

this virtual course to identify the fluxes used in the pyrometallurgy of gold and
the slags that are produced in the process.

While it is true that the separation of gold and silver contained in various
concentrates and minerals are preferably processed and satisfactorily
through fusion, based on empirical explanations that were not
sufficiently known. Currently, with the knowledge of the mechanisms
Physical and chemical properties can be easily determined and identified.
process variables.

Through the identification of the various oxidation chemical reactions and

reduction that occurs between the flux and the gangue during the smelting process,
It is possible to quantify an adequate load of fluxes in accordance with the
temperature and its rate of increase, to the characteristics of the materials and
reagents used, mainly based on the composition of the concentrate
to melt.

The product of the optimal mixture of fluxes, collector, and gold concentrate,
will allow to achieve; fundamentally, a fluid slag that, through which
precipitate towards the base of the crucible. The tiny molten metal globules
precious in its trajectory connects with other metal particles, all in its
set, at the base of the crucible they will give way to the formation of Doré.

2. OBJECTIVES

a) Identify and characterize the fluxes used in melting processes.

b) Differentiate and select the appropriate fluxes for a specific process.
c) Identify and characterize the slags produced in the melting processes.
d) Quantify the stoichiometric chemical reactions.

3. PROPERTIES OF THE FLUXES

This topic is extensively covered elsewhere in the virtual course, but it is necessary.
advance the following properties:

a) The melting temperature must be lower than that of the metals to be recovered.
b) The density in the molten state must be lower than that of the components of the
gold concentrate.

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c) It must be soluble in the metal for its chemical action to be effective.

d) The formed oxides must not be soluble in the metallic bath.
It should have a low vapor pressure and not release toxic gases.
f) In a molten state, it must have a strong affinity for base metal oxides and others.
impurities.

The purpose of the flux is to produce a slag with the following

properties:

• Low melting point

• Low viscosity
• Low density
• High solubility of basic metal oxides
• No solubility of precious metals
• Minimal action on refractories (corrosion / abrasion)
• Easy to break to be treated again (Glass-like and fragile)

CLASSIFICATION OF FLUXES

Prior to the development of pyrometallurgical processes, it is important

detenernos a revisar la aplicación de los reactivos fundentes.

The classification of fluxes is generally based on their action towards

the components of the material to be melted, they can be called fluxes
oxidizers, reducing fluxes, and neutral or regulating fluxes.

3.1 OXIDIZING FLUXES

These oxidizing fluxes or purifiers provide oxygen to convert

the base metals in oxides and slag it. Among them we have:

• Potassium nitrate
• Sodium nitrate
• Sodium chloride

The latter is generally used to purify high-grade gold. It scorifies the ...
silver, copper, zinc, and other metals.

3.2 REDUCING AGENTS

Reducing fluxes are those that remove oxygen or combine with it.
and they become slag. Transforming metal oxides into metals
properly.

In most cases, it is only required to transform the oxide of

lead to metallic lead, acting as a collector of gold and silver.

Among the substances that act as reducers, we have:

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• The charcoal.
• Vegetable flours.
• Zinc.
• The iron.
• Sodium carbonate.
• Potassium carbonate.

3.3 NEUTRAL FUSING AGENTS OR REGULATORS

They are the ones that do not produce oxidation or reduction, they serve as a solvent for the
impurities produced by the action of oxidizing and reducing fluxes.

Its considerable presence is important to provide the

fluidity and solubility of impurities. This group includes:

• Borax.
• Silica.
• Ground glass.

3.4 COLLECTOR METALS

Among the metals that collect gold, we can mention in order of their
effectiveness; silver, lead, copper, and zinc. These metals are added
in powder form or as shavings, with the aim of achieving a large
dispersion in the mixture and collect all the gold present.

Lead is the metal commonly known for collecting gold, but not the
platinum group metals. Lead supplied as litharge is mixed
intimately with the gold-bearing material and the appropriate fluxes.

Silver is a better collector of gold than lead. For economic reasons.

it is usually used in combination with lead. This application of silver
should not be confused with its use for encumbrance in the partition process
or separation.

The advantages that copper provides as a collector reagent are also of interest;
primarily, it reduces environmental pollution (in comparison to
lead is null). The difficulty of use is easily overcome by a
suitable mixture of fluxes.

4. DESCRIPTION OF THE MAIN FUSING AGENTS

Below, in Table 1, the reagents that are used most frequently are listed.
in the process of extraction and/or recovery of precious metals contained in
the gold materials.

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Table 1: Fluxes used in the recovery of precious metals

Name Formula P. Molecular T. Fusion °C

Granulated borax Na2B4O7 201.2 742
Sodium carbonate NaCO3 106.0 852
Potassium nitrate KNO3 1001.1 339
Silica SiO2 60.0 1723
Carbon [Link] ----- -----

Table 1 has been extracted from the book by Vladimir Arias that is referenced in the
bibliography of the virtual text.

Based on the text by Vladimir Arias, we present the following

description of each flux reagent.

BORAX

Borax is sodium tetraborate, a strongly acidic reagent, it appears under the

form of transparent crystals or as white powder, its chemical formula is
Na2B4O7.10H2O, (contains 47% water).

When heated above 60°C, it starts to lose water up to 350°C,

when it is already free of water, its density increases to 2.37.

Its most important properties are:

• It is soluble in water.
• In solution, it dissolves the metal oxides.
• Density in crystallized state, 1.71
• In a molten state, it acts as a solvent for metal oxides and others. impurities.
• Melts at 878°C.
• When combined with metals, it facilitates their melting.
• It does not dissolve coal or graphite.

VEGETABLE CHARCOAL

This material is used in powder form, which helps to reduce metals or rather,
to convert metal oxides into metals proper.

Sodium carbonate

Sodium carbonate, a strongly basic reagent, is considered a deoxidizer.

and desulfurizer. Its chemical formula is Na2CO3it is presented in powder form
anhydrous, with a density of 2.53 and in crystalline state its formula is Na2CO3.10H2O.

Its most important properties are:

• Soluble in water.

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• Density in crystalline state, 1.45

• It is hygroscopic, meaning it absorbs water from the air.
• It melts at 850°C and partially dissociates at 950°C, releasing carbon dioxide.
carbon

Sodium Chloride

It is the known table salt or common salt, NaCl, which has a density of 2.17, it is found
in the form of colorless crystals.

Its main properties are:

• Soluble in water.
• Melting temperature 800°C
• It is hygroscopic.

It is generally used in the gold smelting to eliminate impurities in

form of chlorides.

POTASSIUM NITRATE

The best known as saltpeter, is a powerful oxidizing agent, it is found in

form of colorless crystals, with a density of 2.1.

Its main properties are:

• It is soluble in water.
• Melting temperature 339°C.
• It decomposes at around 400°C, releasing oxygen.
• The great disadvantage of its use is that it oxidizes silver and causes boiling.
bathroom.
• It is generally used to purify gold alloys.

SILICA

It is a reagent with acidic properties, supplied in the form of a white powder.

It produces a fluid slag. It easily combines with metal oxides.
especially with iron oxide. It protects the crucible from the corrosive action of
litharge and borax.

CRUSHED GLASS

It is used in that way to facilitate contact with the oxides and to form a slag.
It performs functions very similar to silica, which is why in some places
preferably, silica is used.

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5. CAPACITY Reducer DE SUBSTANCES USED EN THE

QUANTIFICATION OF GOLD AND SILVER

This topic is important for understanding what happens in the fusion processes.
so we invite the participant of the virtual course to pause on this topic and not
continue until you understand it.

In the quantification of precious metals, the main substance that wants to be

reduced in order to fulfill its purpose, it is lead oxide (litharge); for that,
charcoal powder is generally used.

The substances that are often used as a substitute for charcoal (without producing
side effects), they have the following reduction capabilities.

Cassava starch.......................... 8 - 13
Bulk sugar........................... 10 - 14
Charcoal ............................ 20 - 28
Wheat flour............................ 11 - 15
Scrap metal....................... 3 - 6

5.1 COMPOSITION OF A FUSING MIXTURE

The composition of the flux mixture is determined based on the analysis.

chemical of the material to be melted, but this is generally not possible, due to the
cost that would be incurred, especially when recovering materials
coming from small workshops.

An understanding of the approximate percentage of the chemical constituents of

material will allow calculating the composition of the flux mixture. The
the composition of these mixtures may present significant differences,
depending on the type of waste.

Due to experience in the treatment of gold-bearing materials and metals, it can be

recommend using the following flux loads.

5.2 FUSING MIX FOR DIVERSE CONCENTRATES

a) Flux for zinc precipitates.

The obtained precipitate is melted with an appropriate amount of a

flux mixture, in order to achieve a rapid melting, with the consequent
fluidity of the slag and ensure its cleanliness.

For 10 kilos of precipitate, it is recommended to use:

• Granulated borax .. 3 kilos.

• Sodium carbonate 5 kilos.
• Potassium nitrate 1/2 kilos.

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• Silica powder .... 1.0 kilograms.

These reactants and the precipitate must be intimately mixed.

completely reducing any lump or clump, in this way
contribute to the efficiency of the process.

b) Flux for cutting and deformation products.

This material is generally covered with a mixture of borax and carbonate.

in such a quantity that it covers the molten metal and prevents oxidation.

For every 100 g of metal, it is recommended to use:

• Sodium carbonate 10 g.
• Borax 20 g.

c) Flux for the ash of the sandpapers.

For every 1000 gr. of ash, it is recommended to use:

• Sodium carbonate 800 g.

• Borax 500 g.
• Laziness 250 g.
• Silica 400 g.
• Charcoal 50 g.

This mixture of fluxes is also useful in some cases to melt the

red powder.

d) Flux for fine gold.

In this case, the fluxes serve to remove part of the impurities from the
almost pure gold. Gold refined by quartering usually has a title of 980 to
996 thousandths and yes, when melting it, the title improves by several thousandths.

For every 100 gr. of gold, it is recommended to use:

• Potassium nitrate 10 g.
• Borax 10 g.

6. MAIN REACTIONS DURING SMELTING

Based on the article by Vladimir Arias presented at the Mining Convention

from 1997, we present the chemical reactions that have been
identified during the casting process:

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Borax is a powerful acidic reagent with a strong affinity for oxides.

metallic. However, excess borax is harmful, it prevents the
formation of a fluid slag and the separation of the regulus.

3MO + Na2B4O7+ 2SiO2 Na2B2O4+ MB2O4+ 2MSiO3 (1)

3M2O3+ 3Na2B4O7+ 6SiO2 3Na2B2O4+ M2(B2O4)3+ 2M2(SiO3)3 (2)

3MSO4+ Na2B4O7+ 2SiO2 Na2B2O4+ MB2O4+ 2MSiO3+ 3SO3(3)

3Na2CO3+ Na2B4O7+ 2SiO2 2 Na2B2O4+ 2Na2SiO3+ 3CO2(4)

Sodium carbonate is a powerful basic flux that readily forms

alkali silicates and due to their chemical action are considered as a reagent
oxidizing and desulfurizing. In combination with litharge, it forms sulfates.

MS + 4PbO + Na2CO3 MO + 4Pb + Na2SO4+ CO2 (5)

2FeS2+ 14PbO + 4Na2CO3+ SiO2 14Pb + 4Na2SO4+ Fe2SiO4+ 4CO2(6)

10FeS2+ 28KNO + 6Na2CO3+ 5SiO2 14K2SO4+ 6Na2SO4+ 5Fe2SiO4+

14N2+ 6CO2 (7)

5M2S + 8KNO 5M2O + 4K2SO4+ SO3 (8)

4KNO3+ 2SiO2 2K20.2SiO3+ 2N2+ 4O2 (9)

2PbO + C 2Pb + CO2 (10)

Silicate is a very strong acidic reagent. In combination with litharge and

other metal oxides form highly stable silicates, participating in
fundamental of the slags and promoting their classification.

7. THE SLAGS

Based on the text by Vladimir Arias, a scoria can be defined as a

phase that contains useless substances of a mineral and that will inevitably be
in any pyrometallurgical process that involves molten systems.

Slags generally consist of requested mixtures, as follows for

different processes of smelting minerals or copper concentrates, and their
composition is managed in a way to obtain a material that is sufficiently fluid to
to allow for a good separation of the metallic phase.

Even though the major constituents are silica and iron oxides, it also
other such substances can be found, such as lime or alumina, but in lower percentages than
20% of the total. Is this the reason why the studies of thermodynamics of

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copper-related slag has typically been emitted into simple iron systems
silicates.

According to F. Habashi, all slags possess, to some extent,

refining properties and this property becomes increasingly important as
closer to pure metal is the extraction stage. In particular, in the case of the
color, these slags play a fundamental role during the pyrorefining, in the
dissolution of impurities from the metal phase.

In the smelting of precious metals, the slags are generally composed of

oxides, silicates and borates, can also contain sulfides, carbides and halides.

The slag collects all the undesirable components of the ore and due to its
great invisibility with molten metals, they separate from their components
undesirables.

Continuing with Habashi, whose text is referenced in the bibliography of this course
virtual, to provide the slag with the desired values of: melting point, viscosity,
density and chemical properties, a regulated charge of fluxes is added. The
common fluxes, most used in the quantification of gold and silver values,
son: silica, borax, sodium carbonate and potassium nitrate. Other reagents,
like the collector metal, they must contribute to obtaining the physical characteristics and
desired chemicals.

PROPERTIES OF SLAG

Based on the text by Vladimir Arias, common fluxes are characterized by

due to low melting temperatures, and this must be complemented by a
appropriate viscosity at the working temperature. For the so-called liquids
Newtonians, viscosity at constant temperature and composition does not depend on
the shear strain rate, but exclusively of the composition and
temperature.

The effect of temperature is very different between acid and basic slags. In
in the case of basic slags, the apparent viscosity increases only slightly when
decrease the temperature and then faster as they precipitate the
solid phases. In the case of high silica, the viscosity increases more gradually when
decrease the temperature.

The viscosity at temperatures around 1200°C increases with an increase in the

silica content and is counteracted by the presence of the so-called
basic oxides, which is attributed to the breaking of oxygen bridges in the structure
of silicate anions.

Density is a direct function of the composition of the slag and is determined by it.
the presence of metal oxides. Iron oxides significantly increase the
density of the slags.

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The surface tension of the liquid slags must be in the range of 300 to 400.
dinas/cm., and in general, decrease as the silica content and the oxides increase
of alkaline metals, while limestone and iron oxides increase the
surface tension of the slag. The surface tension decreases slightly when
increase the temperature.

In summary, the characteristics that the slag must possess in an operation

efficient pyrometallurgy

The slag must be completely liquid at the melting temperature.

of metal.

b. The slag must be easily manageable during the process, that is, it must
there is a trade-off between low viscosity and good flowability.

c. The slags that are to be discarded must contain minimal amounts of metal,
dissolved or in suspension.

The operational range of the slag must be such that it accommodates variations in both
in the composition of the slag as in the feed to the smelting furnace.

e. The slag must ensure good removal of the minor elements not
desired.

8. QUANTIFICATION OF THE PROCESS

At the Mining Convention of 1997, Vladimir Arias presented a technical paper on

the mass balance in the pyrometallurgy of gold, from which we extract some of its
parts.

The knowledge of the chemical composition of the mineral to be tested is of utmost importance.
importance. Frequently, in the laboratories where the analysis is to be conducted
for precious metals, it is almost impossible to determine the chemical composition of the
components of the sample, but it is possible to have approximate percentages
In what are the main constituents present, either
in elemental form or as mineral species.

The percentage composition will allow the following calculations to be made:

requirement of each of the fluxing agents and collector. Making use of
The previously mentioned reactions are used to calculate those requirements.

To facilitate the calculation of flux load, it is advisable to classify the minerals.

in two fundamental types, which are: Minerals with deficient reducing power and
excessively reducing minerals, which will necessarily require a
reducing reagent (carbon) and a powerful oxidizing reagent (nitric)
respectively.

Example of flux calculation for a gold-bearing mineral as follows

composition

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Table 2.- Main components of a gold-bearing mineral

COMPONENT Percentage Molecular weight

FeS2 55.0 119,8
Cu2S 5.0 159.0
ZnS 2.0 97,4
Iron(II) oxide 3.0 71.8
SiO2 35.0 60.0

The requirements for each fluxing agent are made based on the
previously posed reactions.

Amount of litharge and carbonate required for the oxidation of pyrite.

According to equation 3:

30 x (7 x 223.2) / 119.8 = 390.6 grams of PbO

30 x (2 x 106.0) / 119.8 = 53.6 grams of Na2CO3

Base oxide produced, FeO: 30 x 71.8/120 = 17.95 gr

Produced sulfate, Na2SO4: 30 x (2 x 142)/ 120 = 71,0 gr.

Amount of KNO3required to oxidize 25% of pyrite. According to equation 8:

25 x (10 x 101,1)/(4 x 119,8) = 14,98 gramos de KNO3

Base oxide produced, FeO: 25 x 71.8/119.8 = 14.98 g

Produced sulfate, K2SO4: 25 x (5 x 174,2)/ (4 x 119,8) = 45,4 gr

Amount of borax and silica required to react with the base metal. Equation 1:

FeO total = 3.0 + 17, 95 + 14,98 = 35,91 gr

35,91 x 201,2/(3 x 71,8) = 33,54 gr de bórax

35.91 x (2 x 60)/(3 x 71.8) = 20.0 g of Silica

Amount of litharge and carbonate required to oxidize ZnO. Making use of

from equation 5:

2.0 x (4 x 223.2)/97.4 = 28.33 g of litharge

2.0 x 106.0/97.4 = 2.18 g of sodium carbonate

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Base oxide produced, ZnO: 2 x 81, 4/97.4 = 1.67 gr

Produced sulfate, Na2SO42 x 142.0/97.4 = 2.92 g

Amount of borax and silica required to react with the base metal, ZnO.
By equation 1.

1.67 x 201.2 / (3 x 81.4) = 1.38 g of borax

1.67 x (2 x 60)/(3 x 81.4) = 0.82 g of silica

Amount of KNO3required for the oxidation of Cu2S. Equation 8:

5 x (8 x 101.1)/(5 x 159.0) = 5.09 grams of potassium nitrate

Base oxide produced, Cu2O: 5 x 143.0/159.0 = 4.5 g.

Sulfate produced, K2SO4 : 5 x (4 x 174.2)/(5 x 159.0) = 4.38 g.

Amount of borax and silica required to react with Cu2O Equation 1:

4.50 x 201.2/(3 x 143) = 2.11 grs. de bórax

4.50 x (2 x 60)/(3 x 143) = 1.26 grams of silica

Amount of borax and silica required to react with sodium sulfate

produced. Equation 3:

Na2SO4 total: 71.0 + 2.92 = 74.0 g. Equation 4

74.0 x 201.2/(3 x 142) = 34.95 grs. de bórax

74.0 x (2 x 60)/(3 x 142) = 20.85 grams of silicon

Amount of borax and silica required to react with potassium sulfate

produced.

K2SO4total: 45.44 + 4.38 = 49.82

49.82 x 201.2/(3 x 174.2) = 19.18 g de bórax

49.82 x 120/(3 x 174.2) = 11.44 grs. de sílice

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Amount of borax and carbonate required to react with silica of the

mineral (35% of the total).

Table 3: Summary of the calculation of reagents

Mineral Founders (gr.)

Species % Weight Na2CO3 Na2B4O7 Lead(II) oxideSiO2 Carbon

FeS2 8 8.3 112.16 201.6 28.34 .......

CuFeS2 5 6.2 3.8 ....... 22.26 .......
ZnS 2 ....... 1.7 8.33 ....... .......
Iron(II) oxide 3 ....... ....... ....... ....... .......
SiO2 82 178.3 ....... ....... -82 4.3
Subtotal 100 192.8 117.66 209.93 ....... 4.3
Total 100g 524.69

the anhydrous representation of borax.

The amount of potassium nitrate is replaced by another reagent with oxidizing characteristics.
should be present at no more than 5%; this way, effervescence and others are avoided.
harmful effects.

Silica consumed by base metals: 20.0 + 0.82 + 1.26 + 20.85 + 11.44 =

54.37 grams.

Addition of silica: 54.37 – 35.0 = 19.37 grams

Following V. Arias, we present the summary of the

the results obtained appear in Table 3, while in Table 4
presents the calculation of reagents for the mineral with a predominance of quartz.

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Table 4: Summary of the calculation of reagents for a mineral with

predominance of quartz

Mineral founders (gr.)

(1)
Species % Weight Na2CO3Na2B4O7 Lead(II) oxide
SiO2 KNO3

FeS2 55 53 80.76 390.6 48.77 52.74(2)

Cu2S 5 ....... 3.8 ....... 2.26 5.09
ZnS 2 2.18 3.8 18.33 1.67 .......
FeO 3 ....... 2.8 ....... 1.67 .......
SiO2 35 ....... ....... ....... -35 .......
Subtotal 100 55.18 91.16 408.93 19.37 7.83
Total 100 632.47

9. PRACTICE OF CHEMICAL ANALYSIS OF GOLD BY SMELTING

Based on the text by Vladimir Arias, we present the analysis of

gold and silver by fire assays is a quantitative chemical analysis, which is
based on the use of high temperatures and the presence of lead oxide,
that with the action of reducing agents in the smelting stage allows the
lead formation which collects precious metals such as gold, silver,
platinum and some impurities.

This alloy is oxidized in another stage of the analysis in order to oxidize the lead and
obtain a gold button called Doré (sweating), this button is attacked by
acids (aqua regia). To separate the metal we are interested in according to its
proportion (partition) is finally analyzed by classical means (weight) or by
instrumentation (Atomic Absorption Equipment)

Classical analysis is a common method anywhere in the world; that

they can apparently be displaced by advancements in instrumentation, but what
making these advances is nothing more than giving reliability and validation to the method
classic route.

It should be noted, finally, that it is the men and not the methods or the instruments.
Even the most sophisticated ones that influence the quality of the outcome due to
Such is the indispensability of capacity and experience for each of the stages and
obtain a satisfactory final result.

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a) ACTION OF THE REAGENTS

ANHYDROUS SODIUM CARBONATE

It combines with the silica from the mineral to form sodium silicate, with
detachment of CO2according to the following equation:

Na2CO3 + SiO2+ CO2 (1)

It also combines with alumina producing fusible aluminates and acts

as a sulfurating agent for example: (acting together with Litharge).

Example: 4Na2CO3+ 2FeS2+ 15PbO→4Na2SO4+ 15PbO + 4CO

Sodium Bicarbonate

It behaves like anhydrous sodium carbonate, since due to the action

the heat unfolds with the following equation:

2 Sodium Bicarbonate3Æ Na2CO3+ CO2+ H2O (2)

Na2CO3+ SiO2Æ No2SiO3+ CO2 (3)

The action of baking soda produces large amounts of gas, because

for which the flux mixture tends to rise, projecting particles of the
molten metal over the walls of the crucible or outside of it. It must be operated with
care to avoid these projections that mean losses. They are avoided
adding common salt in the melting itself.

ANHYDROUS BORAX

Molten borax dissolves a large number of metal oxides, such as by

example: FeO, Al2O3, Cr2O8etc., and also dissolve large amounts of
silica. In the presence of oxide for example:

Na2B4O7+ 2SO2+ 3 CuO2Æ No2B2O4+ CuB2O4CuSO4

The power of dissolution is explained if the formula of borax is examined.

consists of two molecules of metaborate and one boric anhydride.

Na2B4O7Æ 2 NaBO2+ B2O3 (4)

LITURGY

It is the most important reagent in laboratory smelting. One part

litharge (PbO) is reduced to metallic lead using starch or
any other reducer.

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This lead plays the role of collector of the gold and silver contained in the
mineral. The rest of the litharge acts partly by oxidizing the metallic impurities
or it becomes part of the slag in the state of lead silicate, or it is also,
It is very possible, it can form plumbates with metal oxides.

2PbO + C(starch)Æ CO2+ 2Pb

(Collector reaction of precious metals)

Litargyrite residue acts by oxidizing impurities:

PbO + SiO2Æ Lead(II) oxide.silica2

FeS2+ 7PbOÆ 7Pb + FeO + 2SO3

SILICA

Silica acts primarily as a flux for iron.

SiO2+ FeSiO3 (5)

It also reacts with PbO; Na2CO3; etc.

SiO2+ PbÆ Lead Silicon Oxide3 (6)

SiO2+ Na2CO3Æ Na2SiO3+ CO2 (7)

Sodium Chloride

It is used as a casting cover because it is very fluid and does not decompose when
state of fusion.

POTASSIUM NITRATE

It is used as an oxidizing agent in pyrite minerals (sulfide samples).

always prefers potassium nitrate over sodium nitrate for not being
hygroscopic.

METALLIC SILVER

Metallic silver, pure in granules, is used for quartering in the analyses of the
gold in order to obtain an alloy of gold and silver with an excess of the latter
last metal, in order to properly separate the gold from the silver that it contains
mineral.

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It is important to remember that silver is a metal that always accompanies gold.

in the minerals, in greater or lesser proportion.

b) FOUNDRY

Process of greater importance in which some of the

Possible reactions.

- Reacción de Reducción.

The sulfides, such as pyrite (FeS2the ferrotita (Fe7S3arsenopyrite

(FeAsS); chalcopyrite (CuFe2chalcocite (Cu)2S) the stibnite (Sb2S3) the
galena (PbS); blende (ZnS) and others reduce litharge to lead
metallic.

The different reduction reactions experience certain variations.

depending on the casting flow used, as we can observe
considering pyrite, as an example:

a) In the presence of litharge and Na2CO3:

2FeS2+ 15PbOÆ Fe2O3+ 4SO3+ 15Pb (8)

4SO3+ 4Na2CO3Æ 4Na2SO4+ 4CO2 (9)

b) In the presence of a smaller amount of litharge and a smaller amount of

Na2CO3it has:

FeS2+ 7PbOÆ FeO + 2SO3+ 7Pb (10)

2SO3+ 2Na2CO3Æ 2Na2SO4+ 2CO (11)

c) In the presence of litharge and absence of sodium carbonate, it does not

sulfate form. The following equation is given:

FeS2+ 5PbOÆ 2SO2+ 5Pb + FeO (12)

In the presence of litharge and sodium carbonate, the different sulfides

they reduce litharge to metallic lead in the proportions
adequate.

Potassium tartrate and starch also reduce the litharge to

metallic lead

10PbO + 2KHC4H4O6Æ 10Pb + 5H2O + K2O + 8CO2(13)

Through the reduction reactions that take place in the

foundry, many of the metallic impurities are reduced to metal and

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they proceed to impurify the lead gold-silver button to the state

elemental, as observed in the following equation:

Cu + PbOÆ Cu + Pb (14)

But the copper oxide in contact with molten lead is reduced to

With elemental:

CuO + PbÆ PbO + Cu.

Oxidation Reaction

The oxidation of impurities is essential for the formation of slag.

with the smelting reagents and do not pass to the lead button.

Oxidation can be verified in the casting itself, by adding nitrate of

potassium, or by strongly calcining the mineral as mentioned in the paragraph
corresponding to 'complex minerals'. In oxidation, through the
potassium nitrate is present:

7Pb + 6KNO3 Æ 7 PbO + 3k2O + 3N2+ 402 (16)

5C + 4KNO3 Æ 2K2O + 5CO2+ 2N2 (17)

2FeS2+ 6KNO3Æ Fe2O3+ SO3+ 3K2SO4+ 3N2

SO3+ Na2CO3 Æ No2SO4+ CO2 (18)

c) Culpability

The process of cupellation aims at the oxidation of lead and other metals.
existing metallic impurities, which mixed with greater or lesser amounts of
PbO is absorbed by the cupel, the rest volatilizes. It remains as residue.
a shiny little button, made of non-corrosive metals, such as gold,
silver and platinum.

The metallic impurities that accompany the lead gold-silver button

they can be oxidized directly by the oxygen in the air, for which purpose, to
to begin the copulation, the door of the muffler is slightly opened, or they are
oxidized through PbO as can be seen in the following equation:

SAs + 3OÆ AsS2O3 (in the first case)

Cu + PbOÆ CuO + Pb (in the second case)

Some impurities like Cu, Fe, Cd, etc. are completely eliminated by
absorption in the cupel, as long as it is found in amounts that do not
prevent the process of piling up. Instead, others, like the

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Bi, As, Zn, etc. are partially removed by absorption in the cupel and partially
by volatilization the state of oxide.

Depending on the metallic impurities, some properties vary.

immediately recognized, such as: hardness, malleability, etc.

By placing the lead button in order to eliminate the adhered slag, it is possible to
observe:

a) Brittle button: Indicates that it contains zinc, arsenic, antimony, sulfur.

PbO (by low-temperature fusion). Or that contains more than 30%
of gold or silver.

b) Hard button: Indicates a significant amount of Fe, etc.

Summarizing this process, we can express it with the following

equation:

Lead Button PbO + metallic oxides that are

Gold + Silver + Impurities + O2Æ (Au+Ag) + absorbed by the cup or
metallic Metallics volatilize

10. SUMMARY

Before concluding Unit II, it is important to summarize the aspects

more notable than the virtual course participant must retain. The
the most important properties of fluxes are:

a) The melting temperature must be lower than that of the metals to be recovered.
b) The density in the molten state must be less than that of the components
of the gold concentrate.
c) It must be soluble in the metal for its chemical action to be effective.
d) The formed oxides must not be soluble in the metallic bath.
e) It must have a low vapor pressure and not emit toxic gases.
In a molten state, it should have a great affinity for base metal oxides and
other impurities.

The oxidizing fluxes or purifiers provide oxygen to convert the

base metals in oxides and slag it. Among them we have: Potassium nitrate,
sodium nitrate and sodium chloride.

Reducing fluxes are those that eliminate oxygen, or combine with it.
They turn into slag. Transforming metallic oxides into proper metals.
Among them we have: charcoal, vegetable flours, zinc, iron, carbonate.
sodium and potassium carbonate.

Neutral fluxes are those that do not cause oxidation or reduction; they serve as
solvent of the impurities produced by the action of oxidizing fluxes and
reducers. Among them we have: Borax, silica, and ground glass.

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The composition of the flux mixture is determined based on the analysis.

chemical of the material to be melted. A knowledge of the approximate percentage of the
chemical constituents of the material will allow calculating the composition of the mixture
flux.

The most important properties of slags are:

a) Low melting point.

b) Low viscosity.
c) Low density.
d) High solubility of basic metal oxides.
e) No solubility of precious metals.
f) Easy to break to be treated again (glassy and fragile).

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BIBLIOGRAPHIC REFERENCES

• Fathi Habashi
Extractive Metallurgy Fundamentals
Text Book Course
Canada, 1990.

• Vladimir Arias Arce

Precious Metal Refining Technology
Lima, 1997

• Velasco, Carlos
Pyrometallurgy of Gold
International Symposium on Gold Metallurgy
Pontifical Catholic University of Peru
Lima, 1999

END OF THE UNIT

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