WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

Compiled by: L.S Mogashoa Designation: Graduate Metallurgist PF Number: Z4330558 Place: Beatrix No.2 Plant Date: July 2011

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

Table of Contents
1. Literature study ......................................................................................................... 4 2. Plant practice ............................................................................................................ 5 3. Cynoprobe at Beatrix No.2 Plant .............................................................................. 6 4. Reference ................................................................................................................. 8

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

Executive Summary
This paper outlines briefly the literature of WAD cyanide in terms of what it is, how it is formed and the dangers associated with it. The cyanide addition and control procedure at Beatrix No.2 plant is also discussed in brief. The aperometric technique employed by the Mintek Cynoprobe devices is clearly highlighted in this paper.

Keywords: WAD; Cyanide;

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

1. Literature study
Cyanide is used extensively in the gold processing industry as a lixiviant. It forms complexes with base metals such as copper (Cu), zinc (Zn), cadmium (Cd), mercury (Hg), nickel (Ni), iron (Fe) and silver (Ag). These complexes can be classified into three different groups namely free cyanide, weak acid dissociable (WAD) and strong acid dissociable (SAD). The WAD and SAD can be differentiated by employing the concept of log K whereby for log k 30 then the complex is a WAD while for log k > 30 then the complex is a SAD. The stability constants of complexes of Au, Ag, Fe, Cu, Ni and Zn are shown in Table 1. Table 1: Stability constants for metal-cyanide specie. Species Au(CN)2Ag (CN)2Cu(CN)2Cu(CN)32Cu(CN)43Fe(CN)64Fe(CN)63Ni(CN)42Zn(CN)42Stability (log ) 39.3 20.48 16.26 21.66 23.1 35.4 43.6 30.22 19.62

There are two most common types in which cyanide can be analyzed quantitatively and these are the total cyanide and the weak acid dissociable cyanide. Total cyanide is a combination of both WAD cyanide and strong metal-cyanide complexes while WAD cyanide is made up of free cyanide (i.e. CN- and HCN) and the weak metal-cyanide complexes of Ag, Cd, Cu, Hg, Ni and Zn. Figure 1 below is a representation of the classification of cyanide compounds.

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

Strong Metal-Cyanide Complexes of Fe Weak and Moderately Strong Metal-Cyanide Complexes of Ag, Cd, Cu, Hg, Ni and Zn Free Cyanide CNHCN

Total Cyanide

WAD Cyanide

Figure 1: Classification of cyanide compounds.

2. Plant practice
At Beatrix No.2 plant single stage cyanide dosing is employed. The addition of cyanide takes place directly into the leach feed sump unlike at Kloof were a double stage dosing technique is employed. Due to strict standards stipulated by the ICMI code Gold Fields has decided to install an online analyzer that monitors WAD cyanide on the plant exit stream. This online analyzer is supplied by Mintek and it is call a WAD Cynoprobe. The sample point for this instrument is located at the residue transfer sump. The ICMI code stipulated that the WAD cyanide concentration at the plant exit section should at most be 50ppm which automatically forces the free cyanide concentration to be well below 50ppm in order to adhere with this code. Gold Fields is one of the signatories of the ICMI and therefore all its operations including Beatrix must adhere to the code. The control procedure employed at Beatrix No.2 plant is such that when the WAD cyanide concentration is well above the set-point then the main residue pumps trips. This is a very strict control mechanism because if the WAD cyanide concentration can become more than the set-point and the residue pumps trips then production stops. This is a good mechanism because it forces the plant to make sure that their exit cyanide in the residue is always right in order to meet the production targets.

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

3. Cynoprobe at Beatrix No.2 Plant

This device uses the amperometry principle whereby the steady-state current is measured in the electrolytic cell and this current is as a result of the oxidation and/or reduction reactions of the species in the analyte. The working silver electrode (anode) and the free cyanide ion react to produce this current according to the following equation: +2 ( ) +

It is very significant to note that the mass transfer of the cyanide ions to the electrode surface is the rate determining step and this mass transfer rate is controlled by a set of environmental factors such as solution temperature, cyanide ions concentration, electrode surface area and agitation. The effect of all these factors is directly proportional to the current produced in the electrolytic cell. Due to the use of the amperometry principle used by the Cynoprobe, all factors are kept constant but cyanide ion concentration which then allows the following straight line mathematical interpretation: = [ ]

In this equation m is the slope/gradient of a plot of current as a function of free cyanide concentration. According to the Cynoprobe setup, the cyanide ions in solution induces a measureable current on the working electrode and because the setup is inclusive of a resistor therefore the combination of the induced current and the installed resistor in the circuit

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

results in a measureable voltage. This voltage is translated into the signal for the PLC and this signal is further translated by the PLC and produces a count value between 0 and 32768. This becomes easy to deal with since the counts value is related to the cyanide concentration by the following equation: = [ ]+

In this case m is as outlined above and c is a constant but the value for c = 0 should be used. The above information vividly explains how the Mintek Cynoprobe measure the free cyanide concentration from a given solution but the big question is how it measures WAD cyanide which is the combination of both free cyanide and the weakly bound cyanide by base metals in particular Ag, Cd, Cu, Hg, Ni and Zn. Well the answer to it is quite simple; the WAD cyanide analysis is based upon simple chemistry which is the ligand exchange principle. Cynoprobe utilizes a ligand exchange reagent that simply liberates the WAD cyanide bound to base metals and this ligand is called LEX. The reaction governing the ligand exchange reaction is as follows: ( ) + ( ) +

The reaction above releases the free cyanide ions that were previously bound to the metal and with the free cyanide measuring principle conducted by the Cynoprobe it becomes then easy to measure for WAD cyanide if combined with the ligand exchange principle. The Cynoprobe device at Beatrix No.2 plant reports both free cyanide and WAD cyanide. It does this by analyzing the free cyanide in the filtrate before addition of LEX, this will give the free cyanide reading and it then performs the second analysis after addition of LEX to obtain the total free cyanide which is equivalent to WAD cyanide.

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WAD cyanide analysis by Mintek WAD Cynoprobe presented by: Lesibana Solomon Mogashoa

4. Reference
Smith, G.C and van der Merve, W (2006) WAD Cynoprobe User Manual, Mintek, South Africa, PP. 6-13

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