Electrochemistry of Enargite:

Reactivity in Alkaline Solutions

R. Nick Gow
Montana Tech / University of Montana
(E) robert.gow@flsmidth.com

 Introduction to Enargite
Project Objectives
Thermodynamic Database
Raman Spectroscopy
Cyclic Voltammetry
Updated EH - pH Diagram
Conclusions
Further Work

Cu-As Sulfosalts

CuAsS
Cu3AsS4
Cu3AsS4
Cu6As4S9
Cu12As4S13

Lautite
Luzonite (tetragonal)
Enargite (orthorhombic)
Sinnerite
Tennantite

Usually some Sb substitution

(will see in the sample MLA scans)

Environmental/Processing Issues
Smelter limitations 0.5% As with future
consideration to be lowered to 0.3%
One of the more refractory copper sulfides
Higher reagent consumption for gold processes
Copper competes for cyanide
Arsenic competes for oxygen

Potential Processing Methods

Reductive Pre Roast

Selective Flotation
Sulfuric Acid Bake

Galvanox Pyrite Catalyzed Leach

Acidic Pressure Leach
Nitrogen Species Catalyzed

Bioreduction of Sulfur
Bioleach of Copper

Hypochlorite
Sunshine -Alkaline Sulfide

Albion -Ultrafine Grind

PROJECT OBJECTIVES

Task 1 Compile a thermodynamic database for Cu-As-S system

Comparison of Cu-As-S Mass Balanced and Line Plot Diagrams
(Oxidation to Sulfate vs Oxidation to Sulfide)

Task 2 Modification and Validation of Thermodynamic Models using a

combination of Raman Spectroscopy and Cyclic Voltammetry
Reactivity in Alkaline Solutions (Selective As Leach)
Reactivity in Acidic Solutions (Co-dissolution of As and Cu)
Addition of HS- as a lixiviant

Task 3

Determine Viability of Arsenic Adsorption using a

Nanographene Material

Novel nano-graphene material as an arsenic adsorbent

Task 1

Compile a thermodynamic database for Cu-As-S system

Comparison of Cu-As-S Mass Balanced and Line Plot Diagrams

(Oxidation to Sulfate vs Oxidation to Sulfide)

Task 2

Modification and Validation of Thermodynamic Models using a

combination of Raman Spectroscopy and Cyclic Voltammetry

Reactivity in Alkaline Solutions

Reactivity in Acidic Solutions (Co-dissolution of As and Cu)
Addition of HS- as a lixiviant

Task 3

Determine Viability of Arsenic Adsorption using a Nanographene Material

Novel nano-graphene material as an arsenic adsorbent

THERMODYNAMIC DATABASE

 Over 100 Cu-As-S Species compiled from several

sources
Minteq (primary database)
USGS
Several other species taken from individual authors

Species

G (kcal)

Species

G (kcal)

Cu3AsS4 Enargite

-49.808

Cu(AsO2)2

-169.2

Cu12As4S13 Tennantite

-180.908

Cu3As - Domeykite

-3.184

Cu6As4S9 Sinnerite

-110.256

H3AsSO2

-103.412

StabCal
Thermodynamic Stability Program (Huang, 2013)
Mass balanced EH pH diagrams (@ 25C) at the following
molecular ratios (Cu:As:S)

0.66
0.75
0.92
1

0.44
0.25
0.77
1

1
1
1
1

(Sinnerite)
(Enargite)
(Tennanite)
(Lautite)

Sulfur vs Sulfate Oxidation States

Previous Cu-As-S Stability Diagram

Activity of soluble species 0.1, 25C

CuO + HAsO42- vs
Cu2AsO4OH

Cu + AsH3

Padilla et al, 2008.

vs

Cu3As

Cu-As-S Stability Diagrams:

Oxidation to Sulfate

Cu-As-S Stability Diagrams:

Oxidation to Sulfur only

RAMAN SPECTROSCOPY

Mineral phase determination in conjunction with RRUFF database

(Downs, 2006)

Raman Spectroscopy

n
n

Renishaw Raman 100 InVia

100 mW He-Ne laser (632.8 nm)

n
n
n

Pt counter electrode
Ag/AgCl Sat. KCl ref. electrode
Mineral working electrode

MLA - Butte

MLA - Peru

Characteristic Raman of Enargite

Covellite (CuS) pH 9, 300 mV, 60 min

Chalcocite (Cu2 S) pH 12, -600 mV, 10 min

Enargite Surface Progression - pH 9, -1000 mV vs SHE, 60 min

Enargite Surface Progression - pH 9, 0 mV vs SHE, 60 min

Possible Olivenite

Arsenate

Enargite Surface Progression - pH 9, 500 mV vs SHE

Hydroxyl

(Frost et al, 2002)

CYCLIC VOLTAMMETRY
Multifile Raman program to frequently scan the surface as the potential
cycled

Voltammetry Profile
Scan direction Negative or Positive
Scan speed 5 mV/s
Upper Potential 800 mV vs Ag/AgCl saturated KCl
Lower Potential -1200 mV
Start Potential -200 mV
Number of cycles 3
Not stirred
Raman Spectra 5 sec per scan
100% Laser power

pH 8 CV Scan

pH 8 CV Scan
Cycle

1
2
3

C3

C2

C1

C1
C4

C2

C3

Cu3AsS4 Cu12As4S13 Cu2S + As Cu0

C4

CuS CuxS Cu2S

pH 8 CV Scan

Cycle
A3
A2

A1

A2

Cu(OH)2

Cu0 Cu2S CuS

A1

A3

Cu2AsO4OH

(A4)

As HAsO43-

(A5)

(A4)

1
2
3

(A5)

Cu3AsS4 Cu2AsO4OH

MODIFICATIONS TO THE EH PH
DIAGRAMS
Oxidation to sulfur only database.

Based on Raman results - removed CuO, Cu2O, and Cu3As.

Region of elemental sulfur formation included

The dotted line indicates the regions of water stability, copper-only transitions are indicated by
the dashed line, and area above the bolded line indicates stability of elemental sulfur.

Updated EH-pH Diagram for the Cu-As-S system overlaid with CV Inflection Points

Nonstoichiometric transition between CuS and Cu2S

Potential operating region: ~ -300 mV, pH >12

CONCLUSIONS & FINDINGS

Potential identification of olivenite
Arsenic depletion layer (CuxS/S) causes sulfur
formation above -200 mV
Cu3AsS4 AsO43- + CuxS/Cu(OH)2 + 3 S0

Non-stoichiometric metastable copper sulfides may explain

some of the CV transitions
Operating region corresponds to the expected region
for alkaline sulfide

Acknowledgements

Co-authors
H. Huang and C. Young Montana Tech
G. Hope Griffith University

QUESTIONS?