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3. Important Chemicals in Hydrometallurgy

Hydrometallurgy is about producing metals. However, many of the chemical reagents we use are not based on metals. The hydrometallurgist needs to be familiar with these, and with their typical uses. In this section some of the common, relevant industrial chemicals are listed. In addition, the common cations and anions are also listed. The chemical formulas and names need to be learned, particularly for those especially common in hydrometallurgy.

Acids

Table 3.1 - Acids
Chemical Formula Common Name Description
H2SO4 Sulfuric acid Most common acid: leaching, electrowinning.
HCl Hydrochloric acid Less commonly used: leaching, electrowinning (e.g. Ni).
HF Hydrofluoric acid Some specific applications: e.g. lead processing.
HNO3 Nitric acid Minor
H3PO4 Phosphoric acid Minor

For the purposes of hydrometallurgy acids are molecules or ions that ionize to form protons, H+, in aqueous solution. A fuller treatment of acids and bases is given in Part II of this review. Bases are species that accept protons, i.e. a base has some affinity to chemically combine with H+.

Bases

Table 3.2 - Bases
Chemical Formula Common Name Description
CaO Lime/hydrated lime Crucial: moderate strength/cheapest base
Ca(OH)2 Slaked lime Most commonly used base.
CaCO3 Calcium carbonate Weak, but cheap base. Natural mineral.
NaOH Sodium hydroxide Important: strong base, but expensive.
Na2CO3 Sodium carbonate Weaker base than NaOH; moderately priced
NH3 Ammonia Expensive, weak base. More important as a complexing agent (for Ni+2 and Co+2).

Oxidants

Redox reactions (electron transfer) are a very important class of chemical reactions. Note: An oxidizing agent is a species which accepts electrons. A reducing agent is one which donates electrons. In the process of electron transfer the oxidant (a reactant) gets reduced, or accepts electrons. The reductant (a reactant) gets oxidized, or donates electrons. It is very important to remember these distinctions.

Table 3.3 - Oxidates
Chemical Formula Common Name Description
O2 Oxygen Crucial for leaching; used as air (21% O2) or as purified O2 (moderately expensive).
Cl2 Chlorine Strong/expensive: Ni-sulfide leaching.
Fe2(SO4)3 • nH2O Ferric sulphate Crucial for leaching; may be generated in (n ≈ 5) situ (e.g. by oxidation of FeS2).
FeCl3 • 6H2O Ferric chloride Possible use in chloride leaching.
MnO2 Manganese dioxide Strong, insoluble oxidant: uranium leaching. Natural mineral.
NaOCl Sodium hypochlorite “Bleach.” Strong/expensive.
H2O2 Hydrogen peroxide Strong/Expensive: not commonly used.
CuCl2 • 2H2O Cupric chloride Comparable oxidant to FeCl3 in only concentrated chloride solution.

Reductants

Table 3.4 - Reductants
Chemical Formula Common Name Description
Zn Zinc metal Moderately strong: cementation (precipitation) to purify solutions and recover (precipitate) metal.
Fe Iron metal (scrap) Moderate: cementation; less common now.
SO2 Sulphur dioxide Some less common uses. Readily available by burning sulphur
Na2SO3 Sodium sulphite
H2 Hydrogen gas Important/expensive: for making metal powders, especially Ni, Co.
Cu Copper metal Moderately expensive: some cementation uses; some uses as a simple reductant.

The world is an oxidizing place, at least on the surface. Hence reductants are not commonly available, except where generated in: 1. anoxic (O2-free) environments (coal, natural gas, sour gas (H2S) and elemental sulfur), and 2. through photosynthesis, e.g. cellulose, starch). Consequently, reductants tend to be more expensive.

Complexing Agents

Complexing agents are molecules or ions that can bond with metals (atoms or ions). One ore more of the complexants may be bound to the metal. The chemical species formed is thought of as a complex of discrete ligands (the complexing agents) bound to a central metal. More on this later in this review.

Table 3.5 - Complexing Agents
Chemical Formula Common Name Description
Compound (ligand, if different):
NaCN (CN-) Sodium cyanide Crucial for gold. Expensive.
NaCl (Cl-) Sodium chloride Chloride leaching. Less common.
MgCl2 (Cl-) Magnesium chloride
NH3 Ammonia Leaching, especially for Ni, Co. Moderately expensive.
M2S2O3 (S2O32-); M = Na+, NH4+ Ammonium or sodium thiosulfate Possible alternative for gold/silver leaching?
CO Carbon monoxide Used in separation of nickel as Ni(CO)4. Extremely toxic!
Organics Many As specific extractants for metal ions, into organic solutions. Solution purification. Expensive.

Note: cations in salts are typically not involved in the complexes, other than as counterions.

Precipitating Agents

Many anions form quite insoluble compounds with many cations. Precipitation can be used to recover a metal ion (wanted or unwanted) from aqueous solutions.

Table 3.7 - Other Organic Chemicals
Chemical Formula Common Name Description
Hydrocarbons e.g. Kerosene Crucial: solvents for solvent extraction.
Activated carbon C Crucial: adsorbent for gold cyanide complex. Used in gold extraction.

Other Organic Chemicals

Table 3.7 - Other Organic Chemicals
Chemical Formula Common Name Description
Hydrocarbons e.g. Kerosene Crucial: solvents for solvent extraction.
Activated carbon C Crucial: adsorbent for gold cyanide complex. Used in gold extraction.

Numerous organic chemicals and mixtures are used as process additives. Organic reagents will be described and discussed as needed.

Common Simple Anions

The common simple anions are listed below. Note: Some O2- does not exist in aqueous solution! It occurs in many solid metal oxides (e.g. CaO), but O2- itself is such a strong base that it reacts completely with water:

\[\ce{O_2^- + H_2O -> 2OH^-}\tag {117}\]
The prefix “bi” indicates that a proton is added to an anion, e.g. S2- is sulfide; HS is bisulfide.

Table 3.8 - Common Simple Anions
Chemical Formula Common Name
S2- sulphide
Se2- selenide
F– fluoride
Cl– chloride
Br– bromide
I- iodide
OH- hydroxide
HS- bisulphide / hydrosulphide
SO42- sulphate
HSO4 bisulfate
SO32 sulfite
HSO3 bisulfite
S2O32 thiosulfate
Sx2 polysulfides (x = 2-9)
S2O82 peroxodisulfate
HSO5 hydrogen peroxosulfate
CN cyanide
SCN thiocyanate
OCN cyanate
CO32 carbonate
HCO3 bicarbonate
NO3 nitrate
NO2 nitrite
PO43 phosphate
HPO42 hydrogen phosphate
H2PO4 dihydrogen phosphate
AsO43 arsenate
MnO4 permanganate
CrO42 chromate
Cr2O72 dichromate
MoO42 molybdate
WO42 tungstate
VO43 vanadate
ClO4 perchlorate
ClO3 chlorate
OCl hypochlorite
BrO3 bromate
IO3 iodate
CH3CO2 acetate
C2O42 oxalate
BF4 tetrafluoroborate
PF6 hexafluorophosphate

Common Simple Cations

The common simple cations are listed below. In water they form aquo complexes (water as the ligand). It is important to be able to write the formulas and recognize the names. More on coordination chemistry later in this review.

  • H+ (or H3O+; the proton is strongly hydrated in water)
  • NH4+ ammonium
  • Li+
  • Na+
  • K+
  • Rb+ (low natural abundance)
  • Cs+ (low natural abundance)
  • Mg+2
  • Ca+2
  • Sr+2 (low natural abundance)
  • Ba+2 (low natural abundance)
  • Cr+3
  • Mn+2
  • Fe+2 ferrous
  • Fe+3 ferric
  • Co+2
  • Ni+2
  • Cu+ cuprous (unstable in water)
  • Cu+2 cupric
  • Ag+
  • Zn+2
  • Cd+2
  • Hg+2 mercuric
  • Hg2+2 mercurous
  • Al+3
  • Tl+ thallous
  • Tl+3 thallic
  • Pb+2
  • VO+2 vanadyl
  • VO2+
  • UO2+2 unranyl
  • BiO+
  • La+3 (also many other lanthanide +3 cations)

Cations and anions of course occur in combination with each other as electrically neutral salts, with varying degrees of solubility in water and other solvents.

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Aqueous Pathways (DRAFT) Copyright © by Bé Wassink and Amir M. Dehkoda is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, except where otherwise noted.

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