Geosystem Eng.

, 3(1), 30-34, (March 2000)

Characteristics of Xanthates Related to Hydrocarbon Chain Length

Department of Environmental Science and Engineering, Ewha Womans University, Seoul 120-750, Korea 2) Korea Interfacial Science & Engineering Institute, Seoul, Korea (Received January 25, 2000 ; Accepted March 31, 2000)

ABSTRACT : Xanthate characteristics with relation to its hydrocarbon chain length has been considered. The free energy associated with one -CH2 group in homologous xanthates was calculated based on the standard redox potential of X2/X- couple and solubility products of transient metal xanthates. The estimated free energy using each method was found to be 690~920 cal and 799~824 cal, respectively, and was in good agreement with that for various homologues. Key words : xanthate, hydrocarbon chain length, free energy, standard redox potential, solubility product

the system potential and it is directly related with the free energy of xanthate ion. Therefore, it is important to estimate the free energy of homologous xanthate ion to plan and forecast the flotation process. In this study, free energy associated with one -CH2 group in homologous xanthates was estimated based on the standard redox potential of dixanthogen/xanthate couple and the solubility products of transient metal xanthates. This method is thought to be applicable to the case of calculation of free energy for other homologous organic compound.

XANTHATES AND HYDROCARBON CHAIN LENGTH

INTRODUCTION
Xanthate is a common name for the salts of alkyl dithiocarbonic acid, which has the structural formula:

R-O-C-S- M+

(1)

where R is non-polar alkyl group representing CnH2n+1 and M+ is usually alkali metal ion such as K+ or Na+ which forms salts. The name "Xanthate" was adopted from the Greek word "xanthos" meaning yellow, and refers to the color of the copper salt rather than that of alkali metal salts. Xanthate was discovered by Zeise in 1822, however, only after 1900 xanthate found its industrial applications in rubber polymerization and pesticides manufacturing as well as in synthetic textile manufacturing. The introduction of xanthate to mineral flotation industry was made by C. H. Keller in 1923, as disclosed in a U. S. patent, without any supporting theory for the application and it is most likely that he found the valuable collecting power of xanthate by blind trials. The general properties of xanthates and the related compounds were discussed extensively by Rao(1979). In this study, only xanthate characteristics related to the hydrocarbon chain length were considered. Various characteristics for other long-chain hydrocarbon compounds were studied by Fuerstenau, Healy and Somasundaran(1964a, 1964b). In the adsorption process of xanthate on various type of minerals, the adsorbed form of xanthate is determined by
30

(2) (3)

E = E + ( RT 2F ) ln ( A X2 A X - )

If concentration of xanthate ([X -]) is low enough, the activity of xanthate (AX-) can be taken as equal to [X -], and if the solution is saturated with dixanthogen at 25oC, Eqn. (3) can be simplified to
E = E 0.0591 log [ X ]
o

(4)

Eqn. (4) indicates that the redox potential of X2/X- couple is reduced by 59 mV for a ten fold increase in xanthate concentration. The standard redox potential (Eo) of xanthate-dixanthogen couple has been studied by many investigators; such as Kakovskii, et al(1959), Tolun and Kitchener(1964), Majima and Takeda(1968) and Winter and Woods(1973) all by potentiostatic methods and DuRietz(1957) by iodine

Characteristics of Xanthates Related to Hydrocarbon Chain Length

31

Fig. 1. Standard redox potential of X2/X- couple as a function of hydrocarbon chain length.

Fig. 2. Free energy of reaction (Gor) for X2/X- couple and free energy of formation (Gof) for various homologous hydrocarbons vs number of hydrocarbon atoms (n).

titration method. Those results are presented in Fig. 1. As can be seen in Fig. 1, only the most recent two investigations agree with each other in their standard redox potential of xanthate-dixanthogen redox couple. The average of the five reported standard redox potentials of potassium ethyl xanthate-dixanthogen couple is -0.057 volt which agrees with Winter and Woods' result(1973). Therefore, the standard redox potential of potassium ethyl xanthate system can be taken to be -0.057 volt as a good approximation. Tolun and Kitchener(1964), Majima and Takeda(1968) and Winter and Woods(1973) agree that the redox couple of X2/X- is reversible and the standard redox potential of X2/X- couple is decreased by 59 mV with one order of magnitude increase in xanthate concentration as indicated by Eqn. (4). Linear regression analysis of the standard redox potential of X2/X- couple indicated that data given by Majima and Takeda(1968) and Winter and Woods(1973) became more negative by 40 mV per one additional -CH2 group in hydrocarbon chain, while Kakovskii, et al's(1959) data gave the slope of -30 mV per one additional -CH2 group. Gibbs free energy of reaction(Gor) calculated from the standard redox potential of X2/X- couple is shown in Fig. 2. In Fig. 2, free energy of formation (from Weast(1972)) of alkenes, alkynes and alkyl benzenes has been plotted as a function of the length of hydrocarbon chain for comparison. It can be seen that the free energy of reaction for various homologs of X-/X2 system increases with increasing number of ethylene groups, following general trends of free energy of formation for various homologous compounds. Solubility Products of Transient Metal Xanthates Kakovskii(1957) and Pilipenko and Varchanko's(1957) solubility products for various transient metal xanthates have been replotted as a function of hydrocarbon chain

Fig. 3. Solubility product (Ksp) of metal xanthates as a function of hydrocarbon chain length (n).

length in Fig. 3. The slope for the logarithm of solubility of metal xanthates vs number of hydrocarbons in the homologues was about -0.5854 for monovalent metal xanthates and -1.2077 for divalent metal xanthate, indicating that the slope of -0.5854 was a characteristic of monoxanthate system. Dissociation Constant of Xanthic Acids Dissociation constant of homologous xanthic acids has been taken from Majima(1961) and replotted in Fig. 4 as a function of hydrocarbon chain length. Dissociation constant of homologous xanthic acid decreased progressively with increasing chain length. Since the plus inductive

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Dong Su Kim et al.

stenau, Healy and Somasundaran(1964a, 1964b) found that the van der Walls cohesive free energy per -CH2 group responsible for hemi-micelle formation was about 600 cal. Langmuir(Adamson, 1967) obtained 640 cal for the work to bring one -CH2 group from the body of the solution into the surface region based on the Traube's finding that the concentration of organic homologues required to give a certain surface tension was reduced by a factor of 3 for each additional -CH2 group.

CONCLUSIONS
In this study, it has been made clear that hydrocarbon chain length plays a significant role in determining their characteristics. The free energy associated with one -CH2 group in xanthate homologs was estimated by the methods using the standard redox potential of dixanthogen/ xanthate couple and the solubility of transient metal xanthates and found to be 700~900 cal which is in good agreement with that for various homologues.

Fig. 4. Dissociation constant (Kd) of homologous xanthic acid as a function of hydrocarbon chain length (n).

effect of the electrophobic hydrocarbon groups intensified the negative charge at the functional group to make the acid weaker for longer chain xanthic acids, dissociation constant was lower for longer chain xanthates than for shorter chain xanthates. Recovery and Selectivity of Sulphide Flotation The process of xanthate adsorption on sulphide minerals from aqueous solution and the change in the surface activity can be considered as the opposite process to dissolution of metal xanthate. Therefore, with an increase in hydrocarbon chain length, the surface activity should be increased. Usually longer chain xanthates are more effective in flotation of sulphide minerals and thus less collector is needed to achieve the same recovery of sulphides. However, xanthates with very long hydrocarbon chains are poorly soluble in water so that their effectiveness is sharply reduced. Therefore, there exists an optimum chain length of xanthates for a particular flotation system. In alkaline solution, selectivity will be lowered due to the increased activity of longer chain xanthate. In acidic solution, however, the selectivity will be improved with an increase in the length of hydrocarbon chain due to a decrease in the concentration of collector ions in the pulp as a result of the decrease in the dissociation of xanthates (Klassen and Mokrousov, 1963). Free Energy Associated with One -CH2 Group The free energy required to add one -CH2 group to the xanthate homologs is estimated to be 690~920 cal from standard redox potential of X2/X- couple and 799~824 cal from solubility products of transient metal xanthates(see Appendix) For homologues of alkyl ammonium acetate, Fuer-

APPENDIX
Estimation of the energy required to add one -CH2 group to xanthate homologs has been conducted by the following methods. (A) Methods using the standard redox potential of X2/Xcouple. If we assume the following hypothetical reactions for the homologous xanthates: K1 (CH3(CH2)nOCS2)2 2e- 2CH3(CH2)nOCS2K2 2CH3(CH2)nOCS2- 2CH3OCS2- 2n

(A1) (A2)

 CH

Then the equilibrium constants, K1 and K2 become; K1=[CH3(CH2)nOCS2-]2 / {[(CH3(CH2)nOCS2)2] [e-]2} (A3) In dixanthogen saturated solutions, K1 = [CH3(CH2)nOCS2-] 2 / [e-]2 K2 ={[CH3OCS ]
- 2 2

[CH ]
2

(A4)
- 2

2n

}/[CH3(CH2)nOCS2 ]

(A5)

From Equations (A4) and (A5),

K1 ={[CH3OCS2-]2 [CH2]2n}/{[e-]2 K2}

(A6)

Since the standard reduction potential of X2/X- couple at 25oC can be expressed in terms of K1, Eo =(0.0591/2)

logK

(A7)

Characteristics of Xanthates Related to Hydrocarbon Chain Length

33

Substitution of Eqn. (A6) to Eqn. (A7) gives, Eo = (0.0591/2) log{[CH3OCS2-]2/([e]2 K2)} {0.0591 log[CH2]} n

(A8)

From this slope of {0.0591 log[CH2]} and the measured slope in Fig. 1, log[CH2] can be calculated and hence the free energy associated with a group of -CH2. Using Majima and Takeda's(1968) slope of -0.04V per -CH2 group (from Fig. 1): 0.0591 log[CH2] = -0.04 log[CH2] = -0.676 Go = -1.3643 log[CH2] ; (at 25oC) = 0.92 (Kcal/g mole of [CH2])

For AgX, log[CH2] = -0.5854 Go = -1.3643 log[CH2] ; (at 25oC) = 0.799 (Kcal/g mole of [CH2])

REFERENCES
Adamson, A. W., 1967, Physical Chemistry of Surfaces, 2nd Ed., Interscience Publishers, New York, p.102. DuRietz, C., 1957, Xanthate Analysis by Means of Potentiometric Titration: Some Chemical Properties of Xanthates, Svensk Kem. Tidskr., 69, pp. 310-327. Fuerstenau, D. W., Healy, T. W. and Somasundaran, P., 1964, The Role of Hydrocarbon Chain of Alkyl Collectors in Flotation, Trans. SME/AIME, 229, pp. 321-325. Kakovskii, I. A., 1957, Proc. of 2nd International Cong. on Surface Activity, Vol. 4, edit. by Schulman, J. H., Butterworth, London, pp. 225-238. Kakovskii, I. A., Serebrajakova, N. V. and Stephanov, B. A., 1959, Oxidation Reduction Potential of Xanthates, Nauch. Dokl. Vysshei. Shkoly, Khim. Khim. Technol., 2, pp. 277280. Klassen, V. I. and Mokrousov, V. A., 1963, An Introduction to the Theory of Flotation, Trans. by Leja, J. and Poling, G. W., Butterworths, London, pp. 179-195. Majima, H., 1961, Dissociation and Decomposition of Xanthic Acids, Sci. Rept. Res. Inst. Tohoku Univ. Ser. A, 13, pp. 183-197. Majima, H. and Takeda, M., 1968, Electrochemical Studies of the Xanthate-Dixanthogen System on Pyrite, Trans. SME/AIME, 241, pp.431-436. Pilipenko, A. T. and Varchanko, T. P., 1957, Zh. Analit. Khim., 12, pp. 457-461. Rao, S. R., 1979, Xanthates and Related Compounds, Marcel Dekker, Inc., New York, pp. 52-53, pp. 260-292. Shaw, D. J., 1980, Introduction to Colloid and Surface Chemistry, Butterworth, London, pp. 73-78. Somasundaran, P., Healy, T. W. and Fuerstenau, D. W., 1964, Surfactant Adsorption at the Solid-Liquid Interface; Dependence of Mechanism on Chain Length, J. of Phy. Chem., 68, pp. 3562-3566. Tolun, R. and Kitchener, J. A., 1964, Electrochemical Study of the Galena-Xanthate-Oxygen Flotation System, Trans. IMM, 73, pp. 313-322. Weast, R. C., 1972, Handbook of Chemistry and Physics, 53rd. Ed., The Chemical Rubber Co., Cleveland, Ohio, B232, D-44. Winter, G. and Woods, R., 1973, The Relation of Collector Redox Potential to Flotation Efficiency: Monothiocarbonates, Sep. Sci., 8, pp. 261-267.

Using Kakovskii, et al's(1959) slope of -0.03V per -CH2 group (from Fig. 1); 0.0591 log[CH2] = -0.03 log[CH2] = -0.507 Go = -1.3643 log[CH2] ; (at 25oC) = 0.69 (Kcal/g mole of [CH2])

Thus, the free energy required to add one -CH2 group to xanthate homologues at 25oC is estimated as 0.6~0.92 Kcal using standard redox potential of X2/X- couple. (B) Methods using the solubility of transient metal xanthates. If one assumes the following reaction: Ksp Zn(CH3(CH2)nOCS2)2 Zn2+ + 2CH3(CH2)nOCS2Ksp=[Zn2+][CH3(CH2)nOCS2-]2 K' 2CH3(CH2)nOCS2- 2CH3OCS2- + 2n CH2 K' = {[CH3OCS2-]2 [CH2]2n} / [CH3(CH2)nOCS2-]2 From Eqn. (A10) and (A12):

(A9) (A10)

(A11) (A12)

Ksp = [Zn2+] [CH3OCS2-]2 [CH2]2n / K'

logKsp = log{[Zn2+] [CH3OCS2-]2/K'}+{2 log[CH2]} n (A14) From the slope of {2 log[CH2]} and the measured slope of -1.2077 for ZnX2 in Fig. 3: 2 log[CH2] = -1.2077 log[CH2] = -0.60385 Go = -1.3643 log[CH2] ; (at 25oC) = 0.824 (Kcal/g mole of [CH2])

(A13)

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Dong Su Kim et al.

Dong-su Kim is an assistant professor of the division of architecture and environmental system engineering at Ewha Womans University, Korea. He holds BS and MS degrees from Seoul National University and Ph.D. degree from Virginia Polytechnic Institute and State University. His research interests are wastewater treatment, industrial waste treatment, resources recycling, and environmental chemistry. Sung-Eun Kuh is a graduate student in the department of environmental science and engineering, at Ewha Womans University, Korea. She holds BS degree in environmental Science and engineering from Ewha Womans University. Her research activities are focused on wastewater treatment espe-

cially by physicochemical method, materials recycling and reuse, and solid-liquid separation by filtration. Kwang Soon Moon is a President of Korea Interfacial Science and Engineering Institute Korea. He holds BS degree from Seoul National University and MS degree from Univ. of British Columbia and Ph. D. degree from Univ. of California at Berkeley, U.S.A.. His research interests are interfacial Science, Surface Physical Chemistry, Materials Mineral Processing, Environmental Sciences, Colloid Chemistry, Surface Crystal Chemistry, Aquatic Chemistry, Desulphurization of Coal, Fossil Energy, Resources Recycling, Corrosion., Prevention.

Dong-su Kim

Sung-Eun Kuh

Kwang Soon Moon