Minerals Engineering 138 (2019) 60–64

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

Decomposition of flotation reagents in solutions containing metal ions. Part T

I: Gaseous compounds from xanthate decomposition
⁎
Yang Shena,b, , D.R. Nagarajc, Raymond Farinatoc, Ponisseril Somasundaranb, Shuiguang Tonga
a
Mechanical Engineering, Zhejiang University, Hangzhou 310027, China
b
Earth and Environmental Engineering, Columbia University, New York, NY 10027, USA
c
Technology Solutions, Cytec Solvay Group, Stamford, CT 06902, USA

A R T I C LE I N FO A B S T R A C T

Keywords: The mining industry faces increasing regulatory pressure from hazardous reagents used in mineral processing
Xanthate operations. Xanthates, a common class of collectors used in flotation, have come under scrutiny in recent years
Decomposition for their potential to present significant HSE (Health, Safety and Environmental) hazards resulting from their
Carbon disulfide propensity to generate toxic compounds (such as CS2) during transportation, storage, use and disposal.
Metal ions
Interactions between xanthate and metal ions are ubiquitous in flotation systems, and the products formed are
known to influence mineral separation efficiency and selectivity. The effect of such interactions (and the pro-
ducts formed) on the overall decomposition of xanthate is not well known. A method was developed to enable a
systematic and integrated analysis of compositional changes in gas, liquid and precipitate phases of a closed
system comprising xanthate solution and metal ions (Cu2+ or Fe3+). A study of compositional changes in the gas
phase indicated that Cu2+ suppresses decomposition of xanthate into CS2, and the magnitude of the effect
increases with an increase in temperature. Fe3+ ions, on the other hand, promote decomposition; however, the
effect of increasing temperature on decomposition is confounded by the oxidative effect of Fe3+ ions. How Cu2+
and Fe3+ ions affect decomposition in terms of the decomposition products is the focus of Part I and the me-
chanistic aspects of the effect of Cu2+ and Fe3+ ions are discussed in Part II.

1. Introduction
Xanthates, one commonly used classes of collectors for sulfide ore
beneficiation in froth flotation (Kirk-Othmer, 2004, Nagaraj and
Ravishankar, 2007, Pearse, 2005, Rao, 1971, Spottiswod and Kelly,
1982, Wills, 2006), are known to hydrolyze in the presence of moisture
and in aqueous solutions, and generate compounds such as CS2 (carbon
disulfide) and COS (carbonyl sulfide), which are hazardous compounds
of significant concern with respect to HSE (Health, Safety and En-
vironment) (Kirk-Othmer, 2004, Rao, 1971, Report, 2000). There have
been a certain amount of studies on xanthate decomposition in aqueous
solutions (Dunn et al., 1997, Finkelstein, 1967, Iwasaki and Cooke,
1958, Philip and Fichte, 1960, Rao and Patel, 1960a, Sun and Forsling,
1997, Von Halban and Hetcht, 1918); however, studies under the
conditions of relevance to flotation operations (e.g. in the presence of
minerals and/or metal ions typically present in process water) are
limited. Thus, it is necessary to understand xanthate decomposition
under these conditions to provide mining companies the mitigation
measures for any adverse effect.
Metal ions play a significant role in the interactions between mi-
nerals and xanthate (Buckley and Woods, 1997, Garrels and Christ,
1965, Somasundaran and Wang, 2006, Spottiswod and Kelly, 1982,
Vaughan and Craig, 1978, Woods, 1984, 1996). Through chemical or
electrochemical pathways, xanthates interact with various metal ions to
form a number of compounds, which affect mineral hydrophobicity and
the subsequent separation selectivity and efficiency by flotation
(Buckley and Woods, 1997, Woods, 1984, 1996). However, it is not
clear from the literature with respect to the effect of metal ions on
decomposition. In the limited literature, the effect is described as being
either “inhibitive” or “catalytic” (Rao, 1971). Nanjo et al found that the
metal xanthate formed from Pb, Cd or Zn is stable, so these ions are
“inhibitive” due to these metal xanthate compounds which inhibit de-
composition (Nanjo and Yamasaki, 1969). The “catalytic” feature of
metal ions quoted in the literature, as a matter of fact, is actually also
relevant to the transformation of xanthate to other compounds such as
metal xanthate or dixanthogen. For example, Cu2+ interacts with
xanthate to form cuprous xanthate and dixanthogen according to Eq.
(1) (Chang et al., 2003, Chang et al., 2007, Rao and Patel, 1961,

⁎
Corresponding author.
E-mail address: ys2482@columbia.edu (Y. Shen).

https://doi.org/10.1016/j.mineng.2019.04.035
Received 25 September 2018; Received in revised form 19 February 2019; Accepted 25 April 2019
0892-6875/ © 2019 Elsevier Ltd. All rights reserved.
Y. Shen, et al.
Solozhenkin and Kopitsya, 1967, Sparrow et al., 1977).
2Cu2 + + 4X− → 2CuX2 → Cu2 X2 + X2 (1)
3+
Fe , on the other hand, promotes the reaction with xanthate via a
different pathway (Eq. (2)), resulting in the formation of ferric xan-
thate, dixanthogen and bicarbonate (Rao and Patel, 1960b, Sheikh,
1972, Sheikh and Leja, 1977).
O2,CO2
Fe3 + + X− → FeX3 → Fe3 + + X2 + HCO−3 (2)
Thus, both the “inhibitive” and “catalytic” effects by previous re-
searchers mean the transformation of xanthate to metal xanthate or
dixanthogen. With respect to their effect on the decomposition of the
xanthate molecule (which means the breakup of the xanthate mole-
cule), there has not been any research yet.
This paper (Part I) shows: (1) the experimental method and appa-
ratus developed to evaluate compositional changes in the gas phase;
and (2) the change of the compositional changes in the gas phase as a
function of time when xanthate decomposes in the presence of Cu2+ or
Fe3+ at 25 °C and 70 °C. The method to examine the interactions in the
liquid and precipitate phases and the correlation of the results to those
in Part I will be shown in Part II of the study.
2. Experimental
2.1. Materials
SIBX (Sodium iso-Butyl Xanthate, (CH3)2CHCH2OCS2Na, solid) of
≥95% purity was obtained from Cytec Industries Inc. (now Solvay).
Reagent Grade CS2 of ≥99.9% purity was purchased from Fisher
Scientific. CuSO4·5H2O and Fe2(SO4)3 were purchased from MP bio-
medicals, LLC.
Water used was triple distilled (EC = 1.5 μΩ−1). Fresh xanthate
solutions were prepared fresh before each experiment, and discarded
after two hours upon its first use. Standard solutions of CS2 at different
concentrations in distilled water were prepared to develop a calibration
curve for the estimation of the CS2 generated upon xanthate decom-
position. (The solubility of CS2 at 20 °C is 0.217 g/100 ml, and the
concentration prepared here were all below this value).
2.2. Method development
In all of our systematic investigations of xanthate decomposition
under various conditions, including those in aqueous solutions alone
(which is the control condition), in ore pulp under flotation conditions
(which is “real” condition that simulates plant conditions) or in solu-
tions containing metal ions (which is to understand the effect of one of
the most important factors on decomposition), a generic strategy has
been developed and is shown in Fig. 1. The reaction flask or vessel
where decomposition takes place is used to simulate the desired con-
ditions and accumulate the decomposition products for further analysis.
Effects of various factors can be examined by modifying the conditions
in the reaction flask or vessel. Decomposition products in the gas phase
can be either sent directly to analytical instrument for measurement, or
collected and sent for measurement afterwards. The instruments for
measuring the compositional changes in various phases include GC–MS
(Gas Chromatography-Mass Spectrometer), FTIR (Fourier Transformed
Infrared) spectrometer, UV–vis Spectrometer, and Raman Spectrometer.
Following this strategy, a simplified experimental configuration
shown in Fig. 2 (compared to the one developed previously to simulate
flotation conditions and collect decomposition products (Shen et al.,
2019)), was developed to study of the effect of metal ions on decom-
position. In a closed system where xanthate and metal ions are mixed in
solution, the three phases are being measured for compositional
changes: GC–MS is used to measure the decomposition products in the
gas phase; UV–vis is for the liquid phase of the solution without
61
Minerals Engineering 138 (2019) 60–64
precipitate or other solids; and FTIR is used for tracking the formation
and compositional changes of the precipitate. With a combination of
the above techniques, the generation of decomposition products in the
gas phase could be correlated to the interactions in solution (both liquid
and precipitate).
The three instruments use different media to hold the sample, so it is
not possible to have one reactor that can be measured by all three in-
struments. Thus, the configuration shown in Fig. 2 is separately built on
each instrument. For GC–MS, the configuration can be realized easily
since this instrument extracts sample from the headspace of glass vial
which holds the test aliquot and can be sealed once the aliquot is in-
jected. Therefore, the glass vial was used as the reactor where xanthate
decomposition took place in the presence of metal ions in solution.
The GC–MS used was Agilent 6890GC/5973MS with an auto-sam-
pler HSS 86.50. The column was HP-PLOTQ (30 m length, 0.32 mm I.D.
and 0.20 µm film thickness). Key GC–MS parameters were: split ratio
5:1, injection port temperature 200 °C and flow rate constant 1 ml/min.
Carrier gas was helium. The glass vials used were 20 ml, and could be
crimped with aluminum caps lined with silicone septa. A Teflon film
covered the bottom of septum facing the vial.
2.3. Experimental program
Effects of metal ion type, metal ion/SIBX mole ratio and tempera-
ture were investigated. The general procedure was as follows: (1) pre-
pare the stock solutions of SIBX and metal salt (CuSO4·5H2O or
Fe2(SO4)3); (2) add measured amounts of the metal salt stock solution
and triple distilled water into the glass vial prior to injecting a mea-
sured amount of the SIBX stock solution, and then immediately seal the
vial; (3) measure the chromatograms as a function of time using
GC–MS. Only one GC–MS measurement was made per vial and a new
vial was prepared for each new measurement. The concentration of
SIBX used for GC–MS (which provided a satisfactory detection perfor-
mance) and the preparation details (such as the concentrations of the
stock solutions and the amounts that were added) are shown in Table 1.
Temperature was controlled at 25 °C.
Temperature was also elevated to 70 °C for some of the solutions
prepared as above to check the effect of temperature on xanthate de-
composition.
3. Results and discussion
The compositional changes in the gas phase due to SIBX decom-
position in the presence of metal ions examined by GC–MS are shown in
the following sections. The effects of metal ion type, metal ion/SIBX
mole ratio and temperature on SIBX decomposition were analyzed.
3.1. Decomposition products in the gas phase
At 25 °C, SIBX decomposition in the presence of Cu2+ or Fe3+ was
found to be similar to that under other conditions (e.g., in aqueous
solutions alone or in ore pulp under the flotation conditions); CS2 is the
major decomposition product that can be reliably detected in the gas
phase (Shen et al., 2016).
Using the calibration curve obtained from standard CS2 samples, the
mole of CS2 can be calculated from the peak area on GC–MS chroma-
tograms (Shen et al., 2016). The change of CS2 in the gas phase due to
SIBX decomposition at 25 °C in the presence of Cu2+ or Fe3+ is shown
in Figs. 3 and 4, respectively.
From Fig. 3, compared to SIBX decomposition in solution in the
absence of Cu2+ (Shen et al., 2016), the decomposition in the presence
of Cu2+ is generally lower. Moreover, the higher the ratio of Cu/SIBX,
the lower the CS2 found in the gas phase. From Fig. 4, SIBX decom-
position in the presence of Fe3+ is one of increasing the generation of
CS2. The higher the ratio of Fe/SIBX, the higher the CS2 in the gas
phase.
Y. Shen, et al. Minerals Engineering 138 (2019) 60–64

Fig. 1. General strategy for measuring decomposition products.

Fig. 3. Cu/SIBX System: CS2 in the Gas Phase at 25 °C.

Fig. 2. Experimental configuration for studying decomposition in solutions

3.2. Effect of temperature on SIBX decomposition in solutions containing
containing metal ions.
metal ions

Note the scale difference between Figs. 3 and 4. Such results suggest
that Cu2+ has a suppressing effect while Fe3+ has a promoting effect on
SIBX decomposition. In both systems, CS2 generation increases with
time, but at reduced rates eventually reaching a plateau. This is dif-
ferent from SIBX decomposition in solutions without metal ions, for
which the generation of CS2 increases linearly with time.
The results of SIBX decomposition in the Cu/SIBX and Fe/SIBX
systems at 70 °C are shown in Figs. 5 and 6. The results are shown as the
decomposition products (CS2 or COS) in the presence of metal ion
normalized to that in the absence of metal ion at the same temperature.
It shows how much the metal ion depresses or promotes the generation
of a decomposition product upon the temperature change.
In the case of Cu2+, the normalized CS2 at 70 °C is still smaller than

Table 1
preparation details for GC–MS measurements.
Cu/SIBX Mole Ratio SIBX – Stock Solution CuSO4·5H2O – Stock Solution Triple Distilled Water

Conc (g/ml) Amount added to Vial (μl) Conc in Vial (ppm) Conc (g/ml) Amount added to Vial (ml) Amount added to Vial (ml)

1/2 0.1 22.2 222 0.00646 0.25 9.75

1/1 0.5 9.5
2/1 1 9

Fe/SIBX Mole Ratio SIBX – Stock Solution Fe2(SO4)3 – Stock Solution Triple Distilled Water

Conc (g/ml) Amount added to Vial (μl) Conc in Vial (ppm) Conc (g/ml) Amount added to Vial (ml) Amount added to Vial (ml)

1/6 0.1 22.2 222 0.00172 0.25 9.75

1/3 0.5 9.5
2/3 1 9

62
Y. Shen, et al.
Fig. 4. Fe/SIBX System: CS2 in the Gas Phase at 25 °C.
Fig. 5. Cu/SIBX System: Comparison of Decomposition at 25 and 70 °C.
2+
1, meaning that Cu suppresses decomposition. Moreover, all the
curves at different Cu/SIBX ratios at 70 °C exhibit decreasing amounts
of CS2 with time and these values are lower than those at 25 °C,
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Minerals Engineering 138 (2019) 60–64
Fig. 6. Fe/SIBX System: Comparison of Decomposition at 25 and 70 °C.
suggesting a more pronounced suppression of CS2 generation at 70 °C
relative to 25 °C. At 25 °C, generation of COS as a product of SIBX de-
composition in the presence of Cu2+ is too low to be detected; however,
at 70 °C COS generation becomes detectable. From Fig. 5, it can be seen
that at 70 °C the normalized COS is higher than 1 and increases with the
Y. Shen, et al.
Cu/SIBX ratio, meaning that COS generation is slightly promoted by
Cu2+.
In the case of Fe3+, although the normalized CS2 at 70 °C is much
lower than that at 25 °C, they are still all higher than 1, meaning that
Fe3+ still promotes SIBX decomposition at 70 °C. On the other hand,
normalized COS at 70 °C is much higher than 1 and increases with the
Fe/SIBX ratio, suggesting the promoting effect of Fe3+ on COS gen-
eration. More interestingly, there is also a third compound, SO2, formed
at 70 °C. SO2 does not appear as immediately as CS2 and COS. The
higher the Fe/SIBX ratio, the earlier SO2 is detected: 20 min at Fe/
SIBX = 1/6; 11 min at Fe/SIBX = 1/3; and 8 min at Fe/SIBX = 2/3. In
Fig. 6(c) SO2 is normalized by the amount of SO2 generated at Fe/
SIBX = 1/6 and 20 min. It can be seen that SO2 increases with the Fe/
SIBX ratio, implying that Fe3+ has a promoting effect on the generation
of SO2. The generation of SO2 might come from the disappearance of
CS2 and/or COS, due to the strong oxidizing power of Fe3+ at 70 °C.
In summary, increase of temperature from 25 °C to 70 °C enhances
the suppression effect of Cu2+ on the CS2 generation. However, the
effect of Fe3+ on xanthate decomposition is far more complex and
confounded involving generation of CS2, COS and SO2, as a result of
oxidation of species by Fe3+. The major difference between Cu and Fe
could be related to the stability and lability of the corresponding xan-
thate complexes: Cu xanthate complex is more favorable and stable and
resistant to further changes, while Fe xanthate complex is less favored
and is expected to be more decomposable.
4. Conclusions
Cu2+ suppresses while Fe3+ promotes the SIBX decomposition into
CS2. As temperature increases, the suppressing effect of Cu2+ on SIBX
decomposition is enhanced, while the promoting effect of Fe3+ be-
comes complicated due to competing oxidation of species by Fe3+
which leads to the oxidation of the decomposition products (such as
CS2) into others (such as SO2). CS2 generation kinetics in the presence
of either Cu2+ or Fe3+ does not follow a first order rate law, which is in
contrast to that of SIBX decomposition alone in aqueous solutions.
Decomposition kinetics in the presence of the metal ions are complex,
suggesting that compounds other than SIBX are contributing to the
overall decomposition behavior as well. Thus, it is necessary to study
the interactions occurring in solution.
Acknowledgements
The authors are grateful to NSF I/UCR CPaSS (Center for Particulate
and Surfactant Systems) for supporting this research under the Grant
#IIP-0749461, with special thanks to the industrial sponsors of Barrick,
Cytec Solvay Group, Freeport McMoRan, Newmont and Vale.
References
Buckley, A.N., Woods, R., 1997. Chemisorption – the thermodynamically favoured
64
Minerals Engineering 138 (2019) 60–64
process in the interaction of thiol collectors with sulphide minerals. Int. J. Miner.
Process. 51 (1–4), 15–26.
Chang, Y.K., Chang, J.E., Chiang, L.C., 2003. Leaching behavior and chemical stability of
copper butyl xanthate complex under acidic conditions. Chemosphere 52 (6),
1089–1094.
Chang, Y.K., Leu, M.H., Chang, J.E., Lin, T.F., Chian, L.C., Shih, P.H., Chen, T.C., 2007.
Combined two-stage xanthate processes for the treatment of copper-containing
wastewater. Eng. Life Sci. 7 (1), 75–80.
Dunn, J.G., Chamberlain, A.C., Fisher, N.G., Avraamides, J., 1997. The influence of ac-
tivated carbon on the thermal decomposition of sodium ethyl xanthate. J. Therm.
Anal. 49 (3), 1399–1408.
Finkelstein, N.P., 1967. kinetic and thermodynamic aspects of the interaction between
potassium ethyl xanthate and oxygen in aqueous solution. Trans. Instn. Min.
Metall. 76.
Garrels, R.M., Christ, C.L., 1965. Solutions Minerals and Equilibria. Jones amd Bartlett,
Boston.
Iwasaki, I., Cooke, S.R.B., 1958. The decomposition of xanthate in acid solution. J. Am.
Chem. Soc. 80 (2), 285–288.
Kirk-Othmer, 2004. Kirk-Othmer Encyclopedia of Chemical Technology. Wiley Online
Library.
Nagaraj, D.R., Ravishankar, S.A., 2007. Froth flotation: a century of innovation. Society
for Mining, Metallurgy, and Exploration, Inc. (SME), pp. 375424.
Nanjo, M., Yamasaki, T., 1969. Acid decomposition of metal xanthate complexes and their
stability constants. Bull. Chem. Soc. Jpn. 42 (4), 972.
Pearse, M.J., 2005. An overview of the use of chemical reagents in mineral processing.
Miner. Eng. 18 (2), 139–149.
Philip, B., Fichte, C., 1960. Kinetic studies on the decomposition of xanthate. Faserforsch,
Textiltech, pp. 11.
Rao, S.R., 1971. Xanthates and Related Compounds. Marcel Dekker, Inc., New York.
Rao, S.R., Patel, C.C., 1960a. Kinetics of decomposition of xanthates. J. Mines, Metals
Fuels 8 (7), 9–14.
Rao, S.R., Patel, C.C., 1960b. Kinetics of decomposition of xanthates in the presence of
ferric salts. J. Mines, Metals Fuels 8 (7), 15–17.
Rao, S.R., Patel, C.C., 1961. Kinetics of decomposition of xanthates in the presence of
copper salts. J. Sci. Ind. Res (India) 20 (D), 299–303.
Report, 2000. Sodium Ehtyl Xanthate Priority Existing Chemical No. 5, NICNAS (National
Industrial Chemicals Notification and Assessment Scheme), Austrilia.
Sheikh, N., 1972. The Chemical Stability of Heavy Metal Xanthates. The University of
British Columbia.
Sheikh, N., Leja, J., 1977. Mossbauer-spectroscopy of Fe xanthates. Separat. Sci. 12 (5),
529–540.
Shen, Y., Nagaraj, D.R., Farinato, R., Somasundaran, P., 2016. Study of xanthate de-
composition in aqueous solutions. Miner. Eng. 93, 10–15.
Shen, Y., Nagaraj, D.R., Farinato, R., Somasundaran, P., 2019. Xanthate decomposition in
ore pulp under flotation conditions: method development of effects of minerals on
decomposition. Miner. Eng. 131, 198–205.
Solozhenkin, P.M., Kopitsya, N.I., 1967. Electron paramagnetic resonance in solutions of
divalent copper xanthates. Zhurnal Strukturnoi Khimii 8 (3), 534–535.
Somasundaran, P., Wang, D., 2006. Solution Chemistry: Minerals and Reagents. Elsevier.
Sparrow, G., Pomianowski, A., Leja, J., 1977. Soluble copper xanthate complexes.
Separat. Sci. 12 (1), 87–102.
Spottiswod, D.J., Kelly, E.G., 1982. Mineral Processing: An Introduction to the Principles.
John Wiley Sons Inc.
Sun, Z., Forsling, W., 1997. The degradation kinectis of ethyl xanthate as a function of pH
in aqueous solution. Mineral Eng. 10 (4).
Vaughan, D.J., Craig, J.R., 1978. Mineral Chemistry of Metal Sulfides. Cambridge
University Press.
Von Halban, H., Hetcht, W., 1918. Stability of xanthic acids in aqueous solutions. Z.
Elektrochem. 24.
Wills, B.A., 2006. Wills' Mineral Processing Technology. Butterworth-Heinemann.
Woods, R., 1984. In: Jones, M.H., Woodcock, J.T. (Eds.), Principles of Mineral Flotation.
Australia Institute of Mining and Metallurgy, Parkville, Victoria, Australia, pp.
91–115.
Woods, R., 1996. In: Bockris, J.O., Conway, B.E., White, R.E. (Eds.), Modern Aspects of
Electrochemistry. Plenum Press, New York, pp. 401–453.