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Minerals Engineering 105 (2017) 1921

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Technical note

Free cyanide analysis by silver nitrate titration with sulfide ion as


interference
Omero Alonso-Gonzlez a,, Csar Jimnez-Velasco b, Fabiola Nava-Alonso b, Fransico Alvarado-Hernndez a,
Juan Antonio Gonzlez-Anaya a
a
Universidad Autnoma de Zacatecas Francisco Garca Salinas, Unidad Acadmica de Ingeniera I, Av. Lpez Velarde 801, Zacatecas 98040, Mexico
b
CINVESTAV Unidad Saltillo, Av. Industria Metalrgica 1062, Parque Industrial Saltillo-Ramos Arizpe, Ramos Arizpe, Coahuila 25900, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: In cyanidation process, the free cyanide concentration is the main variable that controls the efficiency of
Received 29 November 2016 the process, and the plant operators determine it by silver nitrate titration. If sulfide ion is present in the
Revised 20 December 2016 solution the free cyanide concentration cannot be determined by titration as the silver added in the titra-
Accepted 3 January 2017
tion reacts with the sulfide ion to form a black solid (silver sulfide) that hinders the visual detection of the
titration endpoint. This work proposes the potentiometric detection of the endpoint of the titration and
demonstrates, thermodynamically and with analyses performed in synthetic solutions, that it is possible
Keywords:
to determine both, sulfide and cyanide in the solution, even if the endpoint of the titration cannot be
Free cyanide
Cyanide chemical analysis
visually detected.
Sulfide titration 2017 Elsevier Ltd. All rights reserved.

1. Introduction the potentiometric determination of the endpoint. The present


study proposes the use of the potentiometric determination of
The most used method for the determination of free cyanide in the endpoint in the analysis of free cyanide concentration by titra-
the industry is the titration with silver nitrate. Once all free cya- tion with silver nitrate in solutions containing sulfide. By doing
nide has reacted with silver, if no indicator is present, the silver this, the interference caused by sulfide ions is eliminated and free
added reacts with the argentocyanide ion to form a white silver cyanide and sulfide concentrations can thus be determined.
cyanide solid AgCN (Breuer et al., 2011; Breuer and Rumball,
2007; Singh et al., 1986; Breuer and Henderson, 2010). 3. Thermodynamic aspects
This indicates the endpoint of the titration, and the volume of
silver nitrate consumed can be directly related to the free cyanide The reactions involved in the titration of sulfide and free cya-
concentration in the analyzed solution. nide with silver are presented in Table 1, as well as their Standard
The presence of sulfide ions is the main interference for the Gibbs Free Energy. It is important to consider that the silver added
titrimetric determination of free cyanide. When sulfide ion is pre- as titrant will react with both, the free cyanide and the sulfide ion if
sent, the titration with silver nitrate cannot be used to determine they are present in the solution. With the aid of this thermody-
the free cyanide concentration because the ionic silver added to a namic data it will be possible to understand the experimental
solution reacts with the sulfide ions to instantly form a black solid results obtained, and to validate the possibility of analyzing cya-
(silver sulfide Ag2S), hindering the visual detection of the endpoint nide in presence of sulfide. The possibility of thiocyanate formation
of the titration. in the evaluated solutions was discarded the colorimetric
technique to determine thiocyanate (Clesceri, 1998, Method
2. Background 4500-CN-M) confirmed the absence of thiocyanate.

Breuer and Henderson (2010) proposed a method to determine 4. Materials and methodology
the free cyanide concentration by silver nitrate titration when cop-
per cyanide complexes are present in the solution by making use of Six synthetic solutions were titrated in order to evaluate the
feasibility of analyzing cyanide in presence of sulfide their compo-
Corresponding author. sitions are presented in Table 1. All solutions were prepared from
E-mail address: omeroag@hotmail.com (O. Alonso-Gonzlez). analytical grade reagents (sodium sulfide nonahydrate, potassium

http://dx.doi.org/10.1016/j.mineng.2017.01.001
0892-6875/ 2017 Elsevier Ltd. All rights reserved.
20 O. Alonso-Gonzlez et al. / Minerals Engineering 105 (2017) 1921

Table 1
Shows the Standard Gibbs Free Energy at 25 C (HSC Chemistry database v6.12) and the results of titrations with potentiometric endpoint detection.

Eq. Reaction DG (J/mol)


+ 2
3 2Ag + S = AgS(s) 280.58
4 Ag+ + 2CN = Ag(CN)
2 115.9
5 Ag+ + I = AgI(s) 91.433

6 Ag+ + Ag(CN)2 = 2AgCN(s) 68.877
Volumetric determination of sulfide and free cyanide by silver nitrate
Molar ratio CN S2 Peak 1 Peak 2a Sulfide conc. CN conc.
Sol. CN/S2 mg/L mg/L mL mL mg/L % error mg/L % error
A 1/0 100 3 94 6
B 0/1 11 123 12.9 103 16
C 1/1 100 123 14.6 4 117 5 105 4
D 2/1 200 123 14.3 7.7 115 7 200 0
E 3/1 300 123 14.2 11.8 114 8 307 2
F 4/1 400 123 14.5 15.7 116 6 408 2
a
Peak 2 is the volume of the second peak menus the volume of the first peak.

cyanide, silver nitrate, potassium iodide and deionized water). same manner, but with the assistance of a silver rod electrode
Titrations were performed in a beaker with 10 mL of sample at and a saturated calomel electrode as reference, both immersed in
pH of 12 using NaOH. The titrant solution was silver nitrate the solution and connected to a potentiometer (Orion EA940).
0.005 M, and potassium iodide solution (5% wt/v) was used as The potentiometric determination of the endpoint is achieved by
the visual indicator for the endpoint determination. The objective detecting volume corresponding to the peak in the Potential
of titrating these solutions is to differentiate, by means of the Change curve (Eq. (1)). The Potential Change variable, is the ratio
potentiometric detection of the endpoint, the silver reacting with of the change in potential to the change in volume of titrant added
the sulfide from the silver reacting with the free cyanide, and to (mVmL1). If this new variable (Potential Change) is graphed
validate, with the aid of thermodynamics, the consecutive determi- against the average volume of titrant corresponding to the two
nation of both species. potential values considered, the graph will show a peak that
The conventional free cyanide determination was performed as indicates the endpoint of the titration.
indicated in the Standard Methods (Clesceri, 1998, Method
Potential 2  Potential1
4500-CN-D). The potentiometric titration was performed in the Potential Chante 1
Volume 2  Volume1

Fig. 1. Titration of 10 mL of solutions C, D, E and F with 0.005 M silver nitrate at different CN/S2 molar ratios (1 mL titrant = 26 mg/L free cyanide and 1 mL titrant = 8 mg/L
sulfide ion).
O. Alonso-Gonzlez et al. / Minerals Engineering 105 (2017) 1921 21

5. Results and discussion and hinders the visual determination of the endpoint. However,
if the endpoint is determined by the peaks of the Potential Change
The results obtained for the potentiometric endpoint determi- curve, it is possible to determine consecutively both species:
nations are presented in Table 1 and Fig. 1. For the first solution sulfide and free cyanide. The sulfide ion will be determined by the
(A), when only 100 mg/L cyanide is present in the solution, the free rise of a first peak, as indicated by the thermodynamics, followed
cyanide titrated is 93.66 mg/L (as indicated by the stoichiometry of by a second peak corresponding to the free cyanide concentration.
Reaction 4). In this case the endpoint can also be visually deter- When the solution contains only sulfide ion it is also possible to
mined, with the same result. For the titration of solution B, the determine its concentration by titration with silver nitrate if the
visual determination is not possible, and the potentiometric endpoint is detected by the Potential Change peak, as it was
determination of the endpoint indicates a sulfide concentration demonstrated with synthetic solutions.
of 103 mg/L, as indicated by Reaction 3.
Solutions C, D, E and F contain both species: free cyanide and Acknowledgments
sulfide. According to the thermodynamics data presented in
Table 1, when silver is added to the solution, the chemical reaction The authors thank CONACYT for the financial support received
that will occur in first place will be the reaction with the Gibbs free through the project CB-2013-C01-222922 and the collaboration
energy more negative value, i.e. the reaction of silver with sulfide of Ing. Rosario Beln Juyo Salazar and M.Sc. Judith Osiris Martnez
ion, followed by the reaction of silver with free cyanide. The first Mrquez.
reaction produces a black solid (Ag2S) that hinders the visual deter-
mination of endpoint; however, the Potential Change curve shows References
two peaks, as it can be observed in Fig. 1. The first peak would cor-
Breuer, P.L., Henderson, P., 2010. Online cyanide measurement and control for
respond to the titration of sulfide ion, and the second peak would
complex ores. ALTA, Gold Symp., Perth, Australia, May 2010, ALTA Metallurgical
correspond to the reaction of silver with free cyanide. The concen- Services, Melbourne, Australia. pp. 112.
trations obtained, reported in Table 1, are very similar to the Breuer, P.L., Rumball, J.A., 2007. Cyanide measurement and control for complex ores
theoretical ones, and indicate that the consecutive titration of and concentrates. In9th Mill Operators Conf., Carlton, Victoria, Australia,
AusIMM, pp. 249254.
sulfide and free cyanide by the silver nitrate is possible if the end- Breuer, P.L., Sutcliffe, C.A., Meakin, R.L., 2011. Cyanide measurement by silver
points are determined by the Potential Change curve. nitrate titrationcomparison of rhodanine and potentiometric endpoint.
Hydrometallurgy 106 (34), 135140.
Clesceri, L.S., 1998. Free cyanide analysis by titration (4500-CN-D), and Thiocyanate
6. Conclusions (4500-CN-M). In: Clesceri, L.S., Greenberg, A.E., Trussell, R.R. (Eds.), Standard
Methods for the Examinations of Waste and Wastewater. 20th ed. American
Public Heath Association, Washington, USA.
The analysis of free cyanide by titration with silver nitrate when
Singh, H.B., Wasi, N., Mehra, M.C., 1986. Detection and determination of cyanide. A
sulfide ion is present in the solution is not possible because the review. Int. J. Environ. Anal. Chem. 26, 115136.
silver added reacts with the sulfide to form a black solid (Ag2S)