formed from some pure compounds containing sulfur, we now plan to examine the effect of other gases on the surface species and then to investigate their reactions. Literature Cited
American Chemical Society, “Cleaning Our EnvironmentThe Chemical Basis for Action,” Washington, D. C., 1969. Bell, J. V., Heisler, J., Tannenbaum, H., Goldenson, J., Anal. Chem. 25,1720 (1953). Blyholder, G., J. Chem. Phys. 36,2036 (1962). Blyholder, G., Bowen, D. O., J . Phys. Chem. 66,1288 (1956). Blyholder, G.,Neff, L. D., J . Phys. Chem. 70,893 (1966a). Blyholder, G., Neff, L. D., ibid., 1738 (1966b). Blyholder, G., Neff, L. D., J. Cataly. 2, 138 (1963). Blyholder, G., Richardson, E. A., J. Phys. Chem. 66, 2597 (1962). Eyring, E. M., Wadsworth, M. E., Mining Eng. N. Y. 5, 531 (1956). Garland, C. W.,J. Phys. Chem. 63,1423 (1954). Guertin, D . L., Wiberley, S. E., Bauer, W. H., Goldenson, J.,J. Phys. Chem. 60,1018 (1956).
Herzberg, G., “Infrared and Raman Spectra of Polyatomic Molecules,” Van Nostrand, New York, 1945, (a) p. 285, (b) p. 178. Kriegsmann, V. H., Licht, K., 2. Elektrochem. 62, 1163 (1958). Nakamoto, K., “Infrared Spectra of Inorganic and Coordination Compounds,” Wiley, New York, 1963, (a) p. 107, (b) p.164. Sheppard, N., Trans. Faraday SOC.51,1465 (1955). Stern, A. C., Ed., “Air Pollution,” Vols. 1 and 2, Academic Press, New York, 1962. Thompson, H. W., Skerrett, N. P., Trans. Faraday Soc. 36,812 (1940). Wilhoit, R . C., Burton, J. R., Kuo, F., Huang, S., Viguesnel, A., J . Inorg. Nucl. Chem. 24, 851 (1962). Wilson, E. B., Jr., Decius, J. C., Cross, P. C., “Molecular Vibrations,” McGraw-Hill, New York, 1955, p. 74. Receiued .for review December 15, 1969. Accepted May 13, 1970. This incestigation was supported in part by PHS Research Grant No. AP 00818-01 Jrorn the National Air Pollution Control Administration and in part by a grant from the National Science Foundation for an Undergraduate Research Participation Program.
COM M U N I CAT IONS
Continuous Extraction of Organic Materials from Water’ Marvin C. Goldberg and Lewis DeLong U S . Geological Survey, Denver Federal Center, Denver, Colo. 80225
Lloyd Kahn Federal Water Quality Administration, Edison, N.J. 08817
A continuous liquid solvent extractor, designed to utilize organic solvents that are heavier than water, is described. The extractor is capable of handling input rates up to 2 liters per hour and has a 500-ml. extractant capacity. Extraction efficiency is dependent upon the p-value, the two solvent ratios, rate of flow of the aqueous phase, and rate of reflux of the organic phase. Extractors can be serially coupled to increase extraction efficiency and, when coupled with a lighter-thanwater extractor, the system will allow the use of any immiscible solvent.
degrading organic solutes. Many solvents are available which can retard biodegradation and inhibit most chemical reactions. Careful sample handling will prevent photochemical or thermal activation. Solvent extraction from an immiscible phase can be made as complete as desired, depending on the p-value (defined in Equation 1) for the reaction. Solvent p-values for pesticides, for example, can be calculated from the data given by Beroza and Bowman (1965). Equation 1 (Laitinen, 1960) shows that at any given p-value, n extractions will result in any specified extraction efficiency. fn =
N
aturally occurring organic solutes and organic colloids in environmental surface and groundwaters are present in low concentrations. These quantities are usually less than 100 mg. per liter in freshwater supplies. Detailed laboratory examination of these materials, however, is facilitated by having sample weights in the order of 100 mg. To obtain this sample weight, the original organic load must be concentrated. One good method of concentration is liquidliquid, solvent extraction. When dealing with naturally occurring organic materials, a first consideration of the analyst is maintaining the sample in its original form, from the time of collection to the final analysis. Solvent extraction allows the analyst to deactivate the organic molecules through choice of the proper extraction solvent and thus prevent biological or physical degradation. It is a gentle technique and one that is rarely implicated in Publication authorized by the director of the U.S. Geological Survey.
(+ 1
P-:)-n
(1)
where J’ = fraction remaining unextracted; n = number of successive extractions; p = X o / X w ;X = mole fraction; V = volume; X , = organic mole fraction; and X , = aqueous mole fraction. There are some inherent suppositions to the application of Equation 1 to this extractor: The volume of water in the extractor is constant. The volume of solvent in the extractor is constant. At any given time, an equilibrium condition exists for the organic solute distribution between V , and V,. It is assumed that the flow rate of the aqueous phase is slow enough to approximate the equilibrium condition. Two limiting factors in solvent extraction are the solvent saturation capacity and the volume of liquid available for extraction. Both limitations have been partially removed from the extractor de’scribed in this text. In addition to continuous rather than batch operation, this extractor makes available an almost-pure solvent as the extraction agent during the entire time of operation. It is also portable, inexpensive to Volume 5, Number 2, February 1971 161
fabricate and operate, and it allows selective extraction of dissolved solutes. The extractor apparatus is similar to that described by Kahn and Wayman (1964), but it is designed to operate with heavierthan-water solvents. When this extractor is coupled with a lighter-than-water solvent extractor, the total system can use any immiscible solvent as the extracting agent. Apparatus The extractor (Figure 1) consists of a 1000-ml. Erlenmeyer flask (4) containing a side arm flask (6) with a reflux condenser (1) mounted on top. The side arm flask penetrates the side of the Erlenmeyer flask and has a n opening at the bottom which contacts the organic solvent. Inside the side arm flask is a funnel (5) held in position by glass struts at the top of the funnel. An adapter (7) with ground joints on both ends enters a 500-ml. round-bottomed flask (8), which rests in a heating mantle (9). The Erlenmeyer flask has two glass tubes (2 and 3) which extend into the flask. At the bottom of this flask (4) is a glass-lined magnetic stirring bar (10). Operation
The extractor combines two cyclical systems, each immiscible in the other. The first system is an aqueous system and
‘.IO
Figure 1. Continuous organic heavier-than-water solvent extractor
1, reflux condenser; 2, water inlet; 3, water outlet; 4, extraction flask; 5, dropping funnel; 6, reflux side arm; 7, adapter; 8, 500-ml. roundbottomed boiling flask; 9, heating mantle; 10 glass-lined stirring bar 162 Environmental Science & Technology
contains the material to be extracted. The second system is a nonaqueous system and acts as the extractant. Since the aqueous system is passive, it needs only t o circulate through the extractor. The aqueous solvent enters tube (2) under a constant pressure and is conducted to the bottom of the Erlenmeyer flask, where it mixes with the organic solvent to form a n emulsion. By properly regulating the stirring rate, the emulsion can be formed by relatively large water bubbles in the organic solvent. These bubbles rise to the surface of the solvent to add to the aqueous solution. A carefully regulated siphoning action will pull the aqueous layer out of flask (4), exiting through tube (3). While the aqueous solution contacts the organic solvent, the extraction process takes place. Variation in contact time is regulated by aqueous pumping rate and stirring rate. A typical pumping rate is 2 liters per hour. The second system is the organic system composed of the organic solvent at the bottom half of flask (4) and half of the round-bottomed boiling flask (8). The usual charge in the flask (8) is 500 ml. The organic solvent is represented by heavy shading in Figure 1. Nonaqueous solvent cycling is done by heating the solvent in flask (8) with heating mantle (9) to the boiling point. Vapor rises into adapter (7) through the side arm (8) and around the funnel into the reflux condenser (1). After condensation, it is conducted by a lip at the end of the reflux condenser into the funnel (5) and back into the organic solvent reservoir in flask (4). The condensate, being pure solvent, replenishes the extraction agent. Solvent already stored in flask (4) undergoes hydraulic lift, overflows side arm (6), and returns to boiling flask (8), completing the cycle. A second important variable, in addition to p-value, is residence time of the aqueous solution in the extraction flask (4). This variable is controlled through regulation of the flow rate into the influent tube (2) along with pressure-head adjustment, at the output (3) of the last extractor in the series. For optimum utilization, these procedures should be followed: Where use of multiple extractors is desired, a connection between extractors is best effected by the use of ground-glass ball joints; the influent into the first extractor should be stored in a reservoir that can be elevated above the extractor in such a way that any desired static hydraulic head may be maintained. Even though the solvents are immiscible, a small volume of influent water will be collected with the extraction solvent. This solution will accumulate in the boiler (8). For aqueous organic systems, the volume of the aqueous portion will usually be less than 10% of the total extractant volume collected in flask (8). This small aqueous volume can easily be separated by passing the extractant through a separatory funnel, then treating with anhydrous sodium sulphate. Once the influent water has been extracted, the organic solvent can be stripped from the solute. First, the organic extractant is concentrated in a Kuderna-Danish concentrator t o bring the solvent volume t o a few milliliters (the original solvent volume is usually 500 ml. and the final solvent concentrate volume is below 5 ml.); second, a preparative gas chromatograph is used t o strip off the organic solvent. Literature Cited Beroza, M., Bowman, M. C., Anal. Chem. 31,291 and 2 (1965). Kahn, L., Wayman, C. H., Anal. Chem. 36,1340-3 (1964). Laitinen, H. A., “Chemical Analysis,” McGraw-Hill Book Co., Inc., New York, 1960, p. 483-5. Receioed,for reoiew March 4, 1970. Accepted August 14, 1970.
