Banana peel: A green and economical sorbent for the selective removal of Cr(VI) from industrial wastewater

This study describes the use of banana peel, a commonly produced fruit waste, for the removal of Cr(VI) from industrial wastewater. The parameters pH, contact time, initial metal ion concentration, and temperature were investigated and the conditions resulting in rapid and efficient adsorption (95% within 10 min) were determined. The binding of metal ions was found to be pH dependent with the optimal sorption occurring at pH 2. The retained species were eluted with 5 mL of 2 M H₂SO₄. To elucidate the mechanism of the process, total amounts of chromium and Cr(VI) were analyzed using flame atomic absorption and ultraviolet–visible (UV–vis) spectroscopic techniques, respectively. The Langmuir and Dubinin–Radushkevich (D–R) isotherms were used to describe the partitioning behavior for the system at different temperatures. Kinetics and thermodynamics of Cr(VI) removal by banana peel were also studied. The influence of diverse ions on the sorption behavior revealed that only Fe(II) ions (of those tested) suppressed the sorption of Cr(VI) ions to some extent. The method was applied for the removal of Cr(VI) from industrial wastewater.     

Enrichment of Pb(II) ions using phthalic acid functionalized XAD-16 resin as a sorbent

A simple and reliable method has been developed using polymeric material containing phthalic acid as a chelating agent to concentrate ultratrace amounts of lead ions in aqueous solutions. After characterization by CHN, IR, and thermal studies, the static and dynamic sorption behavior of Pb(II) ions onto new synthetic resin has been investigated. The sorption has been optimized with respect to pH, shaking speed, and contact time between the two phases. Maximum sorption is achieved from solution of pH 5-8 after 10 min agitation time. The lowest concentration for quantitative recovery is 5.8 ng cm(-3) with a preconcentration factor of approximately 850. The kinetics of sorption follows the first-order rate equation with the rate constant k=0.58+/-0.04 min(-1). The variation of the equilibrium constant K(c) with temperature between 10 and 50 degrees C yields values of DeltaH, 52.4+/-1.65 kJmol(-1), DeltaS, 186+/-5.21 Jmol(-1)K(-1), and DeltaG(303K), -4.15+/-0.002 kJmol(-1). The sorption data of Pb(II) ions in the concentration range from 2.41x10(-6) to 1.44x10(-4) molL(-1) follows the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherms at all temperatures investigated. The sorption of Pb(II) ions onto synthesized resin in the presence of common anions and cations has also been measured. The possible sorption mechanism of Pb(II) ions onto phthalic acid modified XAD-16 is also discussed. The sorption procedure is utilized to preconcentrate Pb(II) ions prior to their determination in automobile exhaust particulates by atomic absorption spectrometry using direct and standard addition methods.     

Cr(III) and Cr(VI) Removal from Aqueous Solutions by Cheaply Available Fruit Waste and Algal Biomass

This study compared the effectiveness of different biosorbents, viz. materials commonly present in natural treatment systems (Scenedesmus quadricauda and reed) and commonly produced fruit wastes (orange and banana peel) to remove Cr(III) and Cr(VI) from a synthetic wastewater simulating tannery wastewater. The Cr(III) removal efficiency followed the order S. quadricauda?>?orange peel?>?banana peel?>?reed, whereas the Cr(VI) removal followed the order banana peel?>?S. quadricauda?>?reed?>?orange peel. The chromium biosorption kinetics were governed by the intraparticle diffusion mechanism. Isotherm data obtained using the different biosorbents were fitted to the Langmuir, Freundlich, and SIPS models, revealing that the experimental data followed most closely the monolayer sorption theory-based Langmuir model than the other models. The maximum Cr(III) sorption capacity, calculated using the Langmuir model, was found to be 12 and 9 mg/g for S. quadricauda and orange peel, respectively, and the maximum Cr(VI) sorption capacity calculated for banana peel was 3 mg/g. The influence of biosorbent size, pH, solid–liquid ratio, and competing ions were examined for Cr(III) biosorption by S. quadricauda and orange peel and for Cr(VI) sorption by banana peel. The solution pH was found to be the most influential parameter affecting the biosorption process: whereas pH 5 was found to be optimum for maximum removal of Cr(III), Cr(VI) was best removed at a pH as low as 3. Interference to chromium sorption by various ions revealed that Cr(III) binding onto orange peel occurs through electrostatic forces, whereas Cr(VI) binding onto banana peel through non-electrostatic forces.     

香蕉皮对重金属离子铅的吸附性能研究

建立了香蕉皮快速、高效对重金属离子铅吸附性能的方法。采用分光光度法测定重金属离子铅的浓度,分别研究了7种不同形态的吸附剂对废水中重金属离子铅的吸附性能。在优化的实验条件下,重金属离子铅浓度与吸光度的线性相关系数R=0.999 83,且方法相对标准偏差(RSD)低于3%。结果表明,香蕉皮对废水中的重金属离子铅有良好的吸附效果,吸附率达到91.3%。利用香蕉皮去除废水中的重金属离子,可以变废为宝,且方法吸附率高、准确可靠、精密度高,可用于吸附废水中重金属离子铅。     

Cadmium removal from single- and multi-metal (Cd + Pb + Zn + Cu) solutions by sorption on hydroxyapatite

Heavy metal contamination of waters and soils is particularly dangerous to the living organisms. Different studies have demonstrated that hydroxyapatite has a high removal capacity for divalent heavy metal ions in contaminated waters and soils. The removal of Cd from aqueous solutions by hydroxyapatite was investigated in batch conditions at 25+/-2 degrees C. Cadmium was applied both as single- or multi-metal (Cd + Pb + Zn + Cu) systems with initial concentrations from 0 to 8 mmol L(-1). The adsorption capacity of hydroxyapatite in single-metal system ranged from 0.058 to 1.681 mmol of Cd/g of hydroxyapatite. In the multi-metal system competitive metal sorption reduced the removal capacity by 63-83% compared to the single-metal system. The sorption of Cd by hydroxyapatite follows the Langmuir model. Cadmium immobilization occurs through a two-step mechanism: rapid surface complexation followed by partial dissolution of hydroxyapatite and ion exchange with Ca resulting in the formation of a cadmium-containing hydroxyapatite.     

Evaluation of the Sorptive Capacity of Sugarcane Bagasse and Its Coal for Heavy Metals in Solution

Recycling of sugarcane bagasse and its coal as metal sorbents to capture metal ions from wastewater is the aim of this study. Thus, stability of sugarcane bagasse and its coal, in addition to the solubilities of metal ions in synthetic solution, were determined in this study at different pH values. Also, sorption of Fe, Mn, Cd, and Pb ions with different concentrations (10‐100 mg L^?1) on different grain size fractions of sugarcane bagasse (< 150 > μm) and its coal (< 80 > μm) was carried out under different pH values (2, 4 and 6), dosage (2, 6, and 10 g L^?1), time intervals (15‐300 min.) and temperature (20‐50 °C). The results indicated that the sugarcane bagasse and its coal were more stable at pH 6, and the solubilities of metal ions in the synthetic solution exhibited high values at pH 2 more than pH 4 and 6, respectively. Generally, removal of metal ions using the sorbents increased with the decreasing of grain size fractions and with increasing of pH values (6 > 4 > 2), sorbent doses (10 > 6 > 2 g L^?1) and initial concentrations of metal ions (10‐100 mg L^?1). Coal of sugarcane bagasse was more effective than the sugarcane bagasse for removal of the metal ions from solution. Positive values of ΔH° suggest the endothermic nature of sorption in all cases. The negative Gibb's free energy values indicate the feasibility of the process and spontaneous nature of sorption (Fe‐bagasse coal system), while the positive value of ΔG° suggests the non‐spontaneous character of adsorption of all metals. The negative values of entropy change ΔS° (Pb‐bagasse system) indicate the highly ordered adsorption process in this case, while the positive values of ΔS° show the increased randomness at solid/solution interface during the sorption metal ion on bagasse. The results of activation energy values indicate the order of sorption feasibility is: Pb > Fe > Cd > Mn in the case of bagasse and Fe > Pb > Cd > Mn in the case of coal. Generally, the results of this study suggest that the sugarcane bagasse and its coal might provide an economical method for the removal of metal ions from wastewater.     

The removal efficiency of chestnut shells for selected pesticides from aqueous solutions

The removal of selected pesticides such as carbofuran (CF) and methyl parathion (MP) using low-cost abundant sorbent chestnut shells from aqueous solutions has been investigated in the present study. The sorption parameters, i.e., contact time, pH, initial pesticide solution concentration and temperature have been studied. Maximum percent sorption (99+/-1%) was achieved for (0.38-3.80) x10(-4) and (0.45-4.5) x10(-4) mol dm(-3) of MP and CF pesticide solutions respectively, using 0.4 g of sorbent in 100 ml of solution for 30 min agitation time at pH 6. The Freundlich, Langmuir and Dubinin-Radushkevich (D-R) models have been applied, and their constants for methyl parathion and carbofuran, sorption intensity 1/n (0.55+/-0.02 and 0.54+/-0.04), multilayer sorption capacity C(m) (28.3+/-0.5 and 16.4+/-0.7) x10(-3) mol l(1-1/n)dm(3/n)g(-1), monolayer sorption capacity Q (22.5+/-0.5 and 10.8+/-0.3) x10(-6) mo lg(-1), binding energy, b (2.9+/-0.2 and 5.2+/-0.5) x10(4) dm(3)mol(-1), and sorption energy E (11.2+/-0.1 and 11.5+/-0.2 kJ mol(-1)) have been evaluated respectively. Lagergren, Morris-Weber and Reichenberg equations were employed to study kinetics of sorption process. Thermodynamic parameters DeltaH (-5.09+/-0.1 and 22.8+/-0.4 kJ mol(-1)), DeltaS (-4.33+/-0.0003 and 0.09+/-0.001 kJ mol(-1)K(-1)) and DeltaG((303K)) (-2.9 and -3.8 kJ mol(-1)) have been calculated for methyl parathion and carbofuran, respectively. The developed sorption procedure has been employed to environmental samples.     

Amperometric biosensor based on denatured DNA for the study of heavy metals complexing with DNA and their determination in biological, water and food samples

Amperometric biosensor (BS) has been elaborated based on the stationary mercury-film electrode (SMFE) with silver support and cellulose nitrate (CN) membrane containing immobilized single-stranded DNA (ssIDNA). The sorption isotherms and ssDNA-heavy metal binding constants have been obtained with the BS. According to these data, the chosen heavy metals form the following series of binding strength with ssIDNA: Pb(II)>Fe(III)>Cd(II). It has been found that upon the competitive adsorption, there exists practically simultaneous sorption of different ions at ssIDNA containing membrane. The method of the determination of heavy metals based on preconcentration of metal ions on the BS followed by the destruction of DNA-metal complexes with ethylenediamine tetraacetate (EDTA) and voltammogram recording has been proposed. The lower limits of detectable contents are 1.0x10(-10), 1.0x10(-9) and 1.0x10(-7) mol l(-1) for Pb(II), Cd(II) and Fe(III), respectively. Heavy metals have been assayed in natural and drinking water, milk and blood serum samples even under simultaneous presence with a selectivity factor of 1:10. The effect of matrix components has been estimated.     

Synthesis, characterization and applications of pyrocatechol modified amberlite XAD-2 resin for preconcentration and determination of metal ions in water samples by flame atomic absorption spectrometry (FAAS)

A new chelating resin is prepared by coupling Amberlite XAD-2 with pyrocatechol through an azo spacer, characterized (by elemental analysis, IR and TGA) and studied for preconcentrating Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The sorption is quantitative in the pH range 3.0-6.5, whereas quantitative desorption occurs instantaneously with 2 M HCl or HNO(3) The sorption capacity has been found to be in the range 0.023-0.092 mmol g(-1) of resin. The loading half time (t(1/2)) is 1.4, 4.8, 1.6, 3.2, 2.3 and 1.8 min, respectively for Cd, Co, Cu, Fe, Ni and Zn. The tolerance limits of electrolytes NaCl, NaBr, NaNO(3), Na(2)SO(4) and Na(3)PO(4) in the sorption of all the six metal ions (0.2 mug ml(-1)) are reported. The Mg(II) and Ca(II) are tolerable with each of them (0.2 mug ml(-1)) up to a concentration level of 0.01-1.0 M. The enrichment factor has been found to be 200 except for Fe and Cu for which the values are 80 and 100, respectively. The lowest concentration of metal ion for quantitative recovery is 5, 10, 20, 25, 10 and 10 mug l(-1) for Cd, Co, Cu, Fe, Ni and Zn, respectively. The simultaneous determination of all these metal ions is possible and the method has been applied to determine all the six metal ions in tap and river water samples (RSD相似文献   

Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd²⁺, Cu²⁺ and Pb²⁺, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm⁻¹ after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.     

Cadmium ion-selective electrode based on tetrathia-12-crown-4

A new polyvinylchloride membrane sensor for Cd(2+) ions based on tetrathia-12-crown-4 as an ionophore was prepared. The sensor exhibits a Nernstian response for cadmium ions over a wide concentration range (4.0 x 10(-7) to 1.0 x 10(-1) M) with a slope of 29+/-1 mV decade(-1). The limit of detection is 1.0 x 10(-7) M (0.01 ppm). It has a fast response time of <10 s and can be used for at least 6 weeks without any divergence in potential. The electrode can be used in the pH range from 2.5 to 8.5. The proposed sensor shows fairly good discriminating ability towards Cd(2+) ion in comparison with some alkali, alkaline earth, transition and heavy metal ions. It was successfully applied for the direct determination of Cd(2+) in solution and, as an indicator electrode, in potentiometric titration of cadmium ions.     

Removal of heavy metals by using adsorption on alumina or chitosan

The removal of heavy metals from wastewater by using activated alumina or chitosan as adsorbers was evaluated. Cd(II) and Cr(III) were employed as models of the behaviour of divalent and trivalent metal ions. The adsorption of Cd(II) and Cr(III) onto the adsorbers evaluated was studied as a function of pH, time, amount of adsorber, concentration of metal ions and sample volume. A 0.4-g portion of activated alumina can retain 0.6 mg Cr(III) and 0.2 mg Cd(II) from 20 mL sample adjusted at pH 4 and stirred for 30 min. It is therefore possible to totally decontaminate 500 mL of a waste containing 5 mg L(-1) Cd(II) and Cr(III) with 10 g alumina. On the other hand, 0.4 g chitosan can totally decontaminate 20 mL of a pH 5 solution containing up to 50 mg L(-1) Cd(II) and Cr(III). A 99.2+/-0.1% retention of Cd(II) and 83+/-1% retention of Cr(III) was obtained from 500 mL of a laboratory waste. The aforementioned strategies were applied for the minimization of analytical chemistry teaching laboratories and atomic spectrometry laboratory wastes. On comparing both adsorbers it can be concluded that chitosan is more preferable than alumina due to the reduced price of chitosan and the absence of side-pollution effects.     

Copper(II)-selective electrode using 2,2'-dithiodianiline as neutral carrier

Poly(vinyl chloride) membrane electrode, that is highly selective and sensitive to Cu(II) ions, was developed by using 2,2'-dithiodianiline and dibutyl phthalate as carrier and plasticizer, respectively. The electrode exhibits good potentiometric response for Cu(II) over a wide concentration range (5.0x10(-2)-7.0x10(-7) mol l(-1)) with Nernstian slope of 30+/-1 mV per decade. The response time of the electrode is 10 s and it has been used for a period of one month and exhibits good selectivity towards Cu(2+) in comparison to alkali, alkaline earth, transition and heavy metal ions, with no interference caused by Pb(2+), Cd(2+) and Fe(+2) which are known to interfere with many other copper electrodes.     

Coated-wire silver ion-selective electrode based on silver complex of cyclam.

A coated-wire ion-selective electrode (ISE) based on cyclam (1,4,8,11-tetraazacyclotetradecane) as a neutral carrier in a polyvinyl chloride (PVC) matrix was fabricated for the determination of Ag(I) ions. The coated-wire ISE exhibited a linear Nernstian response over the range 1 x 10(-1) to 1 x 10(-7) M with a slope of 59 +/- 2 mV per decade change and a detection limit of 5 x 10(-8) M. The ISE shows a greater preference for Ag over other cations with good precision. The electrode was selective towards Ag(I) ions in the presence of 13 different metal ions tested. The selectivity coefficients (K(ij)) were determined for Na(I), K(I), Mg(II), Ca(II), Ba(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Hg(II). The selectivity coefficients of these cations are in the range of 10(-4) to 10(-2). This ISE was used for the determination of free silver and total silver in electroplating bath solutions, additives and brighteners.     

Sorption behavior of Zn(II) ions on synthesized hydroxyapatites

Calcium hydroxyapatite (CaHAP) and barium hydroxyapatite (BaHAP) have been prepared by a wet method from aqueous solutions with cation/P molar ratio of 1.67. The prepared particles were characterized using XRD, IR, TG-DTA and BET-N(2) adsorption measurements. The potential of the synthesized hydroxyapatites to remove Zn(II) from aqueous solutions was investigated in batch reactor under different experimental conditions. Both hydroxyapatites remove Zn(II) from aqueous solutions with an efficiency higher than 98% at initial pH around 6-8. The data reveal that the initial uptake was rapid and equilibrium was established in 20 and 60 min for CaHAP and BaHAP. The sorption process follows the pseudo-first-order kinetic with a rate constant (k(ads)) equals to 1.06x10(-2) and 1.91x10(-2) min(-1) for CaHAP and BaHAP, respectively. Zn(II) removal was quantitatively evaluated using Langmuir isotherm model and the monolayer sorption capacity (Q(max)) shows the values 102.04 and 36.62 mg g(-1) for CaHAP and BaHAP clarifying the high affinity of these novel sorbents for Zn(II) ions. Kinetically, the prepared apatites are feasible sorbents retain Zn(II) ions through a favorable and spontaneous sorption process. The possibility of metal recovery and regeneration of hydroxyapatites were investigated using several eluting agents include hydrochloric acids, double distilled water, calcium chloride, barium hydroxide, and copper chloride. Different desorption levels were obtained with the different adsorbents and the maximum recovery yield was achieved with copper chloride.     

Single, binary and multi-component adsorption of copper and cadmium from aqueous solutions on Kraft lignin--a biosorbent

A new biosorbent for removing toxic metal ions from water/industrial wastewater has been investigated using by-product lignin from paper production. Lignin was extracted from black liquor waste, characterized and utilized for the removal of copper and cadmium from aqueous solutions in single, binary and multi-component systems. Adsorption studies were conducted at different temperatures, lignin particle sizes, pHs and solid to liquid ratios. All the studies were conducted by a batch method to determine equilibrium and kinetic parameters. The Langmuir and Freundlich isotherm models were applied. The Langmuir model fits best the equilibrium isotherm data. The maximum lignin adsorption capacities at 25 degrees C were 87.05 mg/g (1.37 mmol/g) and 137.14 mg/g (1.22 mmol/g) for Cu(II) and Cd(II), respectively. Adsorption of Cu2+ (68.63 mg/g at 10 degrees C and 94.68 mg/g at 40 degrees C) and Cd2+ (59.58 mg/g at 10 degrees C and 175.36 mg/g at 40 degrees C) increased with an increase in temperature. Copper and cadmium adsorption followed pseudo-second order rate kinetics. From kinetic studies, various rate and thermodynamic parameters such as effective diffusion coefficients, activation energy, and activation entropy were evaluated. Adsorption occurs through a particle diffusion mechanism at temperatures 10 and 25 degrees C while at 40 degrees C it occurs through a film diffusion mechanism. The sorption capacity of black liquor lignin is higher than many other adsorbents/carbons/biosorbents utilized for the removal of Cu(II) and Cd(II) from water/wastewater in single and multi-component systems.     

Adsorption of cadmium ions from aqueous solutions using nano-montmorillonite: kinetics,isotherm and mechanism evaluations

With increasing industrial development, heavy metal pollution, e.g., cadmium (Cd) pollution, is increasingly serious in soil and water environments. This study investigated the sorption performance of nano-montmorillonite (NMMT) for Cd ions. Adsorption experiments were carried out to examine the effects of the initial metal ion concentration (22.4–224 mg/L), pH (2.5–7.5), contact time (2–180 min) and temperature (15–40 °C). A simulated acid rain solution was prepared to study the desorption of Cd adsorbed on NMMT. After the adsorption or desorption process, the supernatant was analyzed using a flame atomic absorption spectrometry method. The Cd removal rate increased as the pH and contact time increased but decreased as the initial metal ion concentration increased. The maximum adsorption capacity was estimated to be 17.61 mg/g at a Cd²⁺ concentration of 22.4 mg/L. The sorption process can be described by both the Langmuir and Freundlich models, and the kinetic studies revealed that the pseudo-second-order model fit the experimental data. The Cd desorption rate when exposed to simulated acid rain was less than 1%. NMMT possesses a good adsorption capacity for Cd ions. Additionally, ion exchange was the main adsorption mechanism, but some precipitation or surface adsorption also occurred.     

Adsorption of heavy metal ions onto dithizone-anchored poly (EGDMA-HEMA) microbeads

The dithizone-anchored poly (EGDMA-HEMA) microbeads were prepared for the removal of heavy metal ions (i.e. cadmium, mercury, chromium and lead) from aqueous media containing different amounts of these ions (25-500 ppm) and at different pH values (2.0-8.0). The maximum adsorptions of heavy metal ions onto the dithizone-anchored microbeads from their solutions was 18.3, Cd(II); 43.1, Hg(II); 62.2, Cr(III) and 155.2 mg g(-1) for Pb(II). Competition between heavy metal ions (in the case of adsorption from mixture) yielded adsorption capacities of 9.7, Cd(II); 28.7, Hg(II); 17.6, Cr(III) and 38.3 mg g(-1) for Pb(II). The same affinity order was observed under non-competitive and competitive adsorption, i.e. Cr(III)>Pb(II)>Hg(II)>Cd(II). The adsorption of heavy metal ions increased with increasing pH and reached a plateaue value at around pH 5.0. Heavy metal ion adsorption from artificial wastewater was also studied. The adsorption capacities are 4.3, Cd(II); 13.2, Hg(II); 7.2, Cr(III) and 16.4 mg g(-1) for Pb(II). Desorption of heavy metal ions was achieved using 0.1 M HNO(3). The dithizone-anchored microbeads are suitable for repeated use (for more than five cycles) without noticeable loss of capacity.     

Dye-ligand immobilized IPNs membrane for removal heavy metal ions

We have developed a novel approach to obtain high metal sorption capacity utilizing a membrane containing chitosan and an immobilized reactive dye (i.e. Reactive Yellow-2). The composite membrane was characterized by SEM, FT-IR, swelling test, and elemental analysis. The membrane has uniform small pores distribution and the pore dimensions are between 5 and 10 μm, and the HEMA:chitosan ratio was 50:1. The reactive dye immobilized composite membrane was used in the removal of heavy metal ions [i.e., Pb(II), Hg(II) and Cd(II)] from aqueous medium containing different amounts of these ions (5-600 mg l⁻¹) and at different pH values (2.0-7.0). The maximum adsorption capacities of heavy metal ions onto the composite membrane under non-competitive conditions were 64.3 mmol m⁻² for Pb(II), 52.7 mmol m⁻² for Hg(II), 39.6 mmol m⁻² for Cd(II) and the affinity order was Pb(II) > Hg(II)>Cd(II).     

Kinetics of the reactions of Cl*(2P(1/2)) and Cl(2P(3/2)) atoms with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH at 295 K

The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques. The two spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), were detected using LIF at 135.2 and 134.7 nm, respectively. Measured reaction rate constants were as follows (units of cm3 molecule(-1) s(-1)): k(Cl(2P(3/2))+CH3OH) = (5.35 +/- 0.24) x 10(-11), k(Cl(2P(3/2))+C2H5OH) = (9.50 +/- 0.85) x 10(-11), k(Cl(2P(3/2))+n-C3H7OH) = (1.71 +/- 0.11) x 10(-10), and k(Cl(2P(3/2))+i-C3H7OH) = (9.11 +/- 0.60) x 10(-11). Measured rate constants for total removal of Cl*(2P(1/2)) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 +/- 0.13) x 10(-10), (2.48 +/- 0.18) x 10(-10), (3.13 +/- 0.18) x 10(-10), and (2.84 +/- 0.16) x 10(-10), respectively; quoted errors are two-standard deviations. Although spin-orbit excited Cl*(2P(1/2)) atoms have 2.52 kcal/mol more energy than Cl(2P(3/2)), the rates of chemical reaction of Cl*(2P(1/2)) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH are only 60-90% of the corresponding Cl(2P(3/2)) atom reactions. Under ambient conditions spin-orbit excited Cl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Cl atoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.