1. ACTIVATED CARBON OPEN CIRCUIT POTENTIAL SHIFTS IN AQUEOUS SOLUTIONS ABSTRACT Interaction of certain organic compounds with activated carbon and its effect on the carbon open circuit potentials were studied. It was shown that shifts in open circuit potentials depended on the filling of the activated carbon surface. Whereas adsorption of the investigated compounds on the carbon led to positive potential shifts, their elimination (desorption) from carbon surface led to shifts in the opposite direction. It was also observed that the time dependence of potential shifts is similar for different carbon brands. The magnitude of shifts depended on adsorption activity and porometric characteristics of the carbon adsorbent, as well as the nature of the adsorbate. BACKGROUND Open circuit potential shifts in the course of interaction of electrodes with inorganic compounds were first observed by Frumkin, et al. on platinum (1) and were studied in detail on catalytically active metals of the platinum group. This phenomenon was attributed to changes in composition of surface platinum oxides, formation of adatoms, and other interactions of platinum electrode with inorganic ions, as well as adsorption of organic substances on platinum and other metal electrodes. However, it has not been studied sufficiently on porous carbon electrodes, and the nature of the shifts is still unclear. According to the electrochemical theory of adsorption on activated carbons (1), activated carbon immersed in water adsorbs dissolved oxygen from water, in the form of C + …O −, thereby becoming an oxygen electrode. Frumkin’s general theory of adsorption of ions and organic molecules on electrodes (1,8), made clear the necessity of taking into account the electrochemical properties of adsorption processes on activated carbons. The competing chemical theory of adsorption and ion-exchange properties of activated carbons attributes the interaction of organic or inorganic substances with carbons to their composition and properties of substances on their surface. It is likely that only a combination of electrochemical, chemical, hydrophobic-hydrophilic properties of surface compounds, as well as structural parameters of activated carbons, would yield a more complete understanding of the phenomena occurring at the interface between activated carbon and solution. In spite of the perennial interest in adsorption on porous carbon materials and the development of a theoretical electrochemical conception of the process, open circuit potential shifts of activated carbon due to adsorption or other interactions with substances have not yet attracted researchers’ attention. Mikhail M. Goldin a, Gary J. Blanchard a, Alexander G. Volkov b, Mogely Sh. Khubutiya c, Vladimir A. Kolesnikov c, Anatoly K. Evseev c, Mark M. Goldin c a Department of Chemistry, Michigan State University, East Lansing, MI 48824-1322, USA b Department of Chemistry, Oakwood College, 7000, Adventist Blvd., Huntsville, AL 35896, USA c N.V. Sklifosovsky Research Institute for Emergency Medicine, Moscow 129010, Russia GOALS To measure open circuit potentials of activated carbon during the interaction of aqueous solutions of certain inorganic and organic compounds with granulated activated carbon of different types (brands); To elucidate the mechanism of this phenomenon. It is supposed that activated carbon open circuit potential shifts are a reflection of above mechanism. Therefore such simple measurements could be used to study the complex phenomena and processes involved. METHODS Figure 1. Column for granulated carbon potential measurement The total quantities of Fe 2+ and Fe 3+, Cr VI and Cr 3+ were determined by flame absorption spectrometry (20) using a Buck Scientific 210-VGP Flame Atomic Absorption Spectrometer. Qualitative tests for ferrous and ferric iron complexes, as well as for chromium(III) ions and for sulfate ions in the presence of sulfite ions, were used. To detect the presence of the hexacyanoferrate(II) ion, a solution of Fe(NO 3 ) 3 was used: 4 Fe 3+ (aq) + 3 Fe(CN) 6 4− (aq)  Fe 4 [Fe(CN) 6 ] 3 (s)[1] Likewise, for the hexacyanoferrate(III) ion, a solution of FeSO 4 was used 3 Fe 2+ (aq) + 2 Fe(CN) 6 3− (aq)  Fe 3 [Fe(CN) 6 ] 2 (s)[2] To detect the presence of sulfates in solutions containing sulfites and the presence of sulfites in solutions containing sulfates, solutions of BaCl 2 and I 2 were used: [3] [4] Chromium(III) ions in the presence of potassium dichromate were determined by boiling a sample of the solution being tested with 2M KOH and a 3% solution of H 2 O 2 Acetone and 2-propanol were determined by gas chromatography on a Carbowax 20M phase using the Shimadzu GC17 chromatograph. Sodium barbital (Medinal) was determined spectrophotometrically (22), using the Shimadzu UV 2401 PC spectrophotometer. RESULTS Table 1. Measured initial potentials of various activated carbon brands CONCLUSIONS Activated carbon open circuit potential shifts occur in systems of activated carbon/aqueous solution of inorganic or organic substances. Positive and negative potential shifts of varying magnitudes were observed. Activated carbon open circuit potential shifts in aqueous solutions can be caused by reduction/oxidation, as well as by adsorption activity of inorganic or organic substances towards activated carbon. Magnitudes of activated carbon open circuit potential shifts depended on the degree of coverage of the activated carbon surface by the adsorbate. The phenomenon of activated carbon open circuit potential shifts could be used to ascertain whether a given organic or inorganic substance interacts with the surface of activated carbon and to elucidate the mechanisms of such interactions. Table 2. Directions of potential shifts on various carbons  Table 1. Measured initial potentials of various activated carbon brands Substance E(V) for Various Carbons SKT-6AAG-3AR-3AVSKAKU K 4 [Fe(CN) 6 ]0.2420.3730.0880.064-0.036 K 3 [Fe(CN) 6 ]0.3150.3740.1970.040-0.030 Na 2 SO 3 0.2800.0800.2700.026-0.042 Na 2 SO 4 0.3100.4550.1110.075-0.030 NaNO 2 0.2700.3600.100-0.015-0.032 NaNO 3 0.2900.3600.067-0.016-0.034 ZnSO 4 0.3560.4070.0750.057-0.020 CuSO 4 0.3410.4170.1610.0810.045 K 2 Cr 2 O 7 0.3410.3600.1200.035 – 0.092-0.060 – 0.000 Average0.3050.3600.1320.071-0.021 Carbon Substance SKT-6AAG-3AR-3AVSKAKU K 4 [Fe(CN) 6 ]+−−++ K 3 [Fe(CN) 6 ]+++++ Na 2 SO 3 −−−−− Na 2 SO 4 +−+−+ NaNO 2 ++−−+ NaNO 3 +−−−− ZnSO 4 +++++ CuSO 4 +++++ K 2 Cr 2 O 7 +++++ Table 3. Values of potential shifts of investigated substances on various carbons  E (mV) Carbon Substance SKT-6AAG-3AR-3AVSKAKU K 4 [Fe(CN) 6 ]18.0−85.0−24.07.977.7 K 3 [Fe(CN) 6 ]74.197.0252.0168.6227.5 Na 2 SO 3 −306−380−294−200.5−142 Na 2 SO 4 11.0−20.019.0−12.524.3 NaNO 2 6.211−31.4−10.95.2 NaNO 3 3.0−19−3.6−19-2.1 ZnSO 4 50.022.5101.030.8103.0 CuSO 4 86.080.0180.089.096.0 K 2 Cr 2 O 7 144.2163269.0142.3202.0 Figure 2. Open circuit potentials of SIT-1 (1) and SKT-6A (2) vs. time for Medinal adsorption Table 4. Adsorption of organic compounds on SIT-1 activated carbon (120 min). AdsorbateC i (M)A m, (M/g)A calc, (M/g) (%)  E (mV) Acetone8.8 × 10 -1 7.7 × 10 -3 9.1 × 10 -3 85145 2-Propanol6.7 × 10 -2 8.3 × 10 -4 5.9 × 10 -3 1420 Sodium barbital2.4 × 10 -2 3.6 × 10 -4 5.2 × 10 -4 75101 Albumin5.0 × 10 -6 3.0 × 10- 8 3.6 × 10 -5 10 -2 0 Figure 3. Potential shifts of SKT-6A carbon for acetone and isopropanol solutions Figure 4. Albumin adsorption on SKT-6A carbon