Kinetics of asphaltene thermal cracking and catalytic hydrocracking

A pentane-insoluble asphaltene was processed by thermal cracking and catalytic hydrocracking over NiMo/γ-Al₂O₃ in a microbatch reactor at 430 °C. Kinetic analysis shows that the first-order kinetics fits the data of conversion in reaction times ≤ 30 min approximately, but deviates from the data of times over 30 min significantly; whereas the second-order kinetics fits the data of the reaction times up to 60 min adequately, to give the apparent rate constants of 1.704 × 10⁻² and 9.360 × 10⁻² wt frac⁻¹min⁻¹ for the two cracking processes. Furthermore, a three-lump kinetic model is proposed to include parallel reactions of asphaltenes to produce liquid oil (k₁) and gas + coke (k₃), and consecutive reaction from liquid to gas + coke (k₂). The evaluated value of k₁ is 1.697 × 10⁻² and 9.355 × 10⁻² wt frac⁻¹min⁻¹, k₂ is 3.605 × 10⁻² and 6.347 × 10⁻³ min⁻¹ , and k₃ is 6.934 × 10⁻⁵ and 4.803 × 10⁻⁵ wt frac⁻¹min⁻¹ for asphaltenes thermal cracking and catalytic hydrocracking, respectively. Selectivity analysis shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.     

Kinetics and selectivity of asphaltene hydrocracking

Thermal hydrocracking and catalytic hydrocracking over NiMo/γ-Al₂O₃ of a pentane-insoluble asphaltene were conducted in a microbatch reactor at 430 °C. The experimental data of asphaltene conversion fit second-order kinetics adequately, to give the apparent rate constants of 2.435 × 10⁻² and 9.360 × 10⁻² wt frac⁻¹ min⁻¹ for the two processes respectively. A three-lump kinetic model is proposed to evaluate rate constants of parallel reactions from asphaltenes to liquid oil (k₁) and to gas + coke (k₃), and consecutive reaction from liquid to gas + coke (k₂). The evaluated k₁ is 2.430 × 10⁻² and 9.355 × 10⁻² wt frac⁻¹ min⁻¹, k₂ is 2.426 × 10⁻² and 6.347 × 10⁻³ min⁻¹, and k₃ is 5.416 × 10⁻⁵ and 4.803 × 10⁻⁵ wt frac⁻¹ min⁻¹ for asphaltenes hydrocracking in the presence or absence of the catalyst, respectively. Analysis of selectivity shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.     

Electrochemical behavior and adsorptive stripping voltammetric determination of quercetin at multi-wall carbon nanotubes-modified paraffin-impregnated graphite disk electrode

Multi-wall carbon nanotubes-modified paraffin-impregnated graphite disk was fabricated by using choline bond and catalyzer (MWCNT/Ch/WGE), and the properties were, respectively, investigated by field emission scanning electron microscope (FE-SEM) and X-ray photoelectron spectroscopy (XPS). Electrochemical behavior of quercetin was studied in detail by FE-SEM, UV-spectroelectrochemical and various electrochemical methods, which related with the two catechol hydroxyl groups and the other three hydroxyl groups, the former is electron-donating group with a two electron two proton reversible reaction, and is pH dependent. A highly sensitive adsorptive stripping voltammetric measurement (AdSV) for quercetin was also shown at this electrode. On the optimum conditions, the adsorptive stripping response of the peak (E = 0.15 V, 3 min accumulation) was proportional to the concentration in a range of 9.0 × 10⁻⁹ to 4.0 × 10⁻⁵ M. A detection limit of 4.8 × 10⁻⁹ M was obtained with a signal-to-noise ratio (s/n) of 3 and a good precision (R.S.D.: 2.1%, n: 9). Such attractive ability of MWCNT/Ch/WGE suggests a great promise for a quercetin amperometric sensor.     

Greener photocatalysts: Hydroxyapatite derived from waste mussel shells for the photocatalytic degradation of a model azo dye wastewater

This paper demonstrates for the first time the feasibility of utilising waste mussel shells for the synthesis of hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂ (denoted as HAP) to be used as a greener, renewable photocatalyst for recalcitrant wastewater remediation. HAP was synthesised from Perna canaliculus (green-lipped mussel) shells using a novel pyrolysis–wet slurry precipitation process. The physicochemical properties of the HAP were characterised using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The HAP produced was of comparable quality to commercial (Sulzer Metco) HAP. The synthesised HAP had good photocatalytic activity, whereby methylene blue (a model textile wastewater compound) and its azo dye breakdown products were degraded with an initial rate of 2.5 × 10⁻⁸ mol L⁻¹ min⁻¹. The overall azo dye degradation was nearly 54% within 6 h and 62% within 24 h in an oxygen saturated feed in a batch reactor using a HAP concentration of 2.0 g/L, methylene blue concentration of 5 mg L⁻¹, UV irradiation wavelength of 254 nm and a stirring speed of 300 rpm. The kinetics were well described by three first order reactions in series, reflecting the reaction pathway from methylene blue to azo dye intermediates, then to smaller more highly oxidised intermediates and finally degradation of the recalcitrants. The final two steps of the reaction had significantly slower rates than the initial step (rates constants of 6.2 × 10⁻³ min⁻¹, 1.2 × 10⁻³ min⁻¹ and approximately (due to limited data points) 1.6 × 10⁻⁴ min⁻¹ for the first, second and third step respectively), which tie in with this mechanism, however it could also indicate that the reaction is either product inhibited and/or affected by catalyst deactivation. FTIR analysis of the post-reaction HAP revealed surface PO₄³⁻ group loss. Since there is good photocatalytic activity with oxygen in limited and excess supply during the photoreaction, this indicates the possibility of lattice oxygen participation in the photocatalytic reaction, which needs to be characterised more fully. However, overall, these results indicate that the HAP derived from the mussel shells is a promising greener, renewable photocatalyst for the photocatalytic degradation of wastewater components.     

Assisted electrochemical conversion of nitrogen heterocompounds using active hydrogen passing through a Pd membrane. A non conventional diesel and VGO hydrotreating option

The conversion of pyridine (PY), quinoline (QUI) and meso-tetraphenylporphyrin (TPP) using active hydrogen passing through a Pd membrane under mild conditions (25 °C and ambient pressure) by applying −1.92 mA cm⁻² is reported. Moreover, some results regarding VGO and diesel hydrotreating, under similar conditions, are shown. Relative kinetic conversion constants (k′), calculated for each tested molecules, support the following reactivity order: PY (k′ = 87 × 10⁻⁴ min⁻¹) > QUI (k′ = 5 × 10⁻⁴ min⁻¹) > TPP (k′ = 1 × 10⁻⁴ min⁻¹). Based on the reduction and increasing factors found for aromatic and saturated fractions respectively, it can be established that diesel is easier to transform than VGO. Nevertheless, hydrodenitrogenation seems to be more notable for VGO than for diesel.     

Termination rate coefficients for acrylamide in the aqueous phase at low conversion

The kinetics of acrylamide (AAm) free radical polymerization at low conversion of monomer to polymer in the aqueous phase was investigated at 50 °C using γ-radiolysis relaxation, which is sensitive to radical-loss processes. The values of the termination rate coefficients for AAm ranged from 8×10⁶ to 3×10⁷ M⁻¹ s⁻¹ as the weight fraction of polymer ranged from 0.002 to 0.0035, which is significantly lower than the low-conversion values for monomers such as styrene (2×10⁸ M⁻¹ s⁻¹) and methyl methacrylate (4×10⁷ M⁻¹ s⁻¹) in organic media. These can be quantitatively explained by applying a chain-length-dependent model of free-radical polymerization kinetics [Russell GT, Gilbert RG, Napper DH. Macromolecules 1992;25:2459. [19]] in which termination kinetics are expressed in terms of a diffusion-controlled encounter of radicals which ultimately yields an expression for the chain-length-averaged termination rate coefficient, 〈k_t〉. The lower 〈k_t〉 for AAm arises due to a combination of the high k_p value, promoting rapid formation of slower terminating long chains, and the slow diffusion of short propagating chains, relative to other common monomers. The chain transfer to monomer constant for AAm in water at 50 °C, C_M, was estimated using the chain-length-distribution method with correction for band-broadening [Castro JV, van Berkel KY, Russell GT, Gilbert RG. Aust J Chem 2005;58:178. [21]] and found to be 1.2×10⁻⁴ (±10%). The diffusion characteristics for AAm were adapted from those obtained for a similar aqueous system (hydroxyethyl methacrylate) together with a 0.5 exponent for the power law dependence on penetrant degree of polymerization at zero weight fraction polymer. This provides an adequate fit to the 〈k_t〉 data. This is the first application of the chain-length-dependent model to describe experimental termination rate coefficients for an aqueous system at low conversion to polymer. The result that the experimental termination rate coefficients can be reproduced with an a priori model with physically reasonable parameters supports the physical assumptions underlying that model.     

Studies on the electrochemical behavior of 3-nitrobenzaldehyde thiosemicarbazone at glass carbon electrode modified with nano-γ-Al2O3

Nano-γ-Al₂O₃ is dispersed onto the glass carbon electrode (GCE) by polishing. This nanostructured modified GCE exhibits a great enhancement to the redox responses of 3-nitrobenzaldehyde thiosemicarbazone (3-NBT). In comparison with bare GCE, 3-NBT gives a more sensitive voltammetric response because of the nanoparticle’s unique properties. The lowest detectable concentration (3σ) of 3-NBT is estimated to be 1.18 × 10⁻⁶ M (accumulation for 4 min). The linear relationship between peak current and concentration of 3-NBT holds in the range 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁴ M (r = 0.9981). The electrochemical properties of 3-NBT on this modified electrode have been investigated with various electrochemical methods. The results indicate that the transference of one electron and one proton involves electrode radical reaction processes I and II, respectively. The coverage value (Γ) of 1.62 × 10⁻⁹ mol cm⁻² was calculated and the electrochemical parameters, diffusion coefficient D (2.54 × 10⁻³ cm² s⁻¹, 2.03 × 10⁻³ cm² s⁻¹) and reaction rate constant k_s (5.9573 s⁻¹, 7.15 × 10⁻² cm s⁻¹) were obtained for quasi-reversible system I and irreversible system II, respectively.     

Kinetics of catalytic steam gasification of bitumen coke

The catalytic steam gasification of coke from Athabasca bitumen was investigated by thermogravimetric analysis using K₂CO₃ and Na₂CO₃ as catalysts, both of which reduced the activation energy of the reaction considerably to 1.2 × 10⁵ J mol⁻¹ and 1.3 × 10⁵ J mol⁻¹, respectively, down from 2.1 × 10⁵ J mol⁻¹ for the uncatalyzed reaction. The reaction rates varied with the partial pressure of steam between 60 kPa and 85 kPa consistent with a Langmuir-Hinshelwood model, but a first order equation was also sufficient given the low partial pressures. The initial rate of gasification of the coke particles correlated linearly with the estimated external surface area of the particles, as expected from a surface reaction involving a non-porous solid. The initial reaction rate increased with increasing the catalyst loading up to 2.4 (mol potassium)/kg. A portion of the catalyst penetrated into the coke, as confirmed by secondary ion mass spectroscopy analysis, where it could not promote the reaction with steam. This result was consistent with a small increase observed in the reaction rate at low catalyst loading. The shrinking core model was successful in predicting the rates at higher conversions from the initial rate data, despite increases in BET surface area with conversion.     

Kinetic study of hydrogen sulfide absorption in aqueous chlorine solution

Hydrogen sulfide (H₂S) is currently removed from gaseous effluents by chemical scrubbing using water. Chlorine is a top-grade oxidant, reacting with H₂S with a fast kinetic rate and enhancing its mass transfer rate. To design, optimize and scale-up scrubbers, knowledge of the reaction kinetics and mechanism is requested. This study investigates the H₂S oxidation rate by reactive absorption in a mechanically agitated gas–liquid reactor. Mass transfer (gas and liquid sides mass transfer coefficients) and hydrodynamic (interfacial area) performances of the gas–liquid reactor were measured using appropriated physical or chemical absorption methods. The accuracy of these parameters was checked by modeling the H₂S absorption in water without oxidant. A sensitivity analysis confirmed the robustness of the model. Finally, reactive absorption of H₂S in chlorine solution for acidic or circumneutral pH allowed to investigate the kinetics of reaction. The overall oxidation mechanism could be described assuming that H₂S is oxidized irreversibly by both hypochlorite anion ClO⁻ (k = 6.75 × 10⁶ L mol⁻¹ s⁻¹) and hypochlorous acid ClOH (k = 1.62 × 10⁵ L mol⁻¹ s⁻¹).     

Diffusional mass transfer model for the adsorption of food dyes on chitosan films

The adsorption kinetics of erythrosine B and indigo carmine on chitosan films was studied by a diffusional mass transfer model. The experimental curves were obtained in batch system under different conditions of stirring rate (80–200 rpm) and initial dye concentration (20–100 mg L⁻¹). For the model development, external mass transfer and intraparticle diffusion steps were considered and the specific simplifications were based on the system characteristics. The proposed diffusional mass transfer model agreed very well with the experimental curves, indicating that the surface diffusion was the rate limiting step. The external mass transfer coefficient (k_f) was dependent of the operating conditions and ranged from 1.32 × 10⁻⁴ to 2.17 × 10⁻⁴ m s⁻¹. The values of surface diffusion coefficient (D_s) increased with the initial dye concentration and were in the range from 0.41 × 10⁻¹⁴ to 22.90 × 10⁻¹⁴ m² s⁻¹. The Biot number ranged from 17.0 to 478.5, confirming that the intraparticle diffusion due to surface diffusion was the rate limiting step in the adsorption of erythrosine B and indigo carmine on chitosan films.     

Thermally reversible cross-linked polyamides and thermo-responsive gels by means of Diels-Alder reaction

Cross-linked polyamides and polyamide gels were prepared from maleimide-containing polyamides and a tri-functional furan compound and showed thermal reversibility in cross-linking behavior and in gel formation through Diels-Alder (DA) and retro-DA reactions. The rate constant k of the DA cross-linking reaction were 1.25-4.83×10⁻⁵ dm³ mol⁻¹ s⁻¹ in the temperature range of 20-60 °C with an activation energy of 32.1 kJ mol⁻¹. The cross-linking densities, thermal properties, and thermal reversibility of the polyamides/furan polymers were adjustable with the contents of maleimide groups in polyamides.     

Electrochemical determination of bromide at a multiwall carbon nanotubes-chitosan modified electrode

A multiwall carbon nanotubes (MWNTs)-chitosan modified glassy carbon electrode (GCE) exhibits attractive ability for highly sensitive cathodic stripping voltammetric measurements of bromide (Br⁻). In pH 1.8 H₂SO₄ solution, a substantial increase in the stripping peak current of Br⁻ (compared to bare GCE and chitosan modified GCE) is observed using MWNTs-chitosan modified electrode. Operational parameters were optimized and the electrochemical behaviors of Br⁻ were studied by different electrochemical methods. The kinetics parameters were measured, the number of electron transfer (n) was 1 and the transfer coefficient (α) is 0.17. A wide linear calibration range (3.6 × 10⁻⁷-1.4 × 10⁻⁵ g mL⁻¹) was achieved, with a detection limit of 9.6 × 10⁻⁸ g mL⁻¹. The mechanism of electrode reaction was fully discussed.     

Catalytic effects of NaOH and ZrO2 for partial oxidative gasification of n-hexadecane and lignin in supercritical water☆

Partial oxidative gasification of n-hexadecane (n-C₁₆) and organosolv-lignin (lignin) was studied by use of a batch type reactor in supercritical water: 673 K, 0.52 cm⁻³ of water density (40 MPa of water pressure at 673 K), and 0.3 of O/C ratio for the n-C₁₆ experiments; 673 K, 0.35 cm⁻³ of water density (30 MPa of water pressure at 673 K), and 1.0 of O/C ratio for the lignin experiments. The experiments without O₂ were also conducted for lignin (lignin decomposition). For all the cases (n-C₁₆ partial oxidation, lignin decomposition, lignin partial oxidation), NaOH or zirconia (ZrO₂) was added in the system as catalysts. Through n-C₁₆ studies, the catalytic effect of NaOH and ZrO₂ on partial oxidation in supercritical water were examined. In the case of lignin partial oxidation, we studied the possibility of partial oxidation in supercritical water for gasification technique of wastes. The yield of H₂ from n-C₁₆ and lignin with zirconia was twice as same as that without catalyst at the same condition. The H₂ yield with NaOH was 4 times higher than that without catalyst. Thus, a base catalyst has a positive effect on partial oxidation of n-C₁₆ and lignin to produce H₂. The catalytic effect of NaOH and ZrO₂ was found to be enhancement of decomposition of intermediate (aldehyde and ketone) into CO, through n-C₁₆ studies. In the case of lignin studies, the enhancement of decomposition of the carbonyl compounds by catalytic effect of NaOH and ZrO₂ inhibit char formation and promotes CO and thus H₂ formation.     

Modeling and design of transdermal drug delivery patches containing an external heating device

Process modeling and design concepts were implemented to aid in the manufacturing of heat-enhanced transdermal drug-delivery systems. The simulated prototype consists of a corticosterone-loaded polymer patch applied to the skin and connected to a heating device in which an exothermic reaction occurs. To achieve a desired transdermal flux of 1.2 × 10⁻⁵ mg/cm² h, this contribution focuses on the influences of the (1) initial reaction rate (−r_A0), (2) mass of filler material in the device (m), (3) initial concentration (C₀) of medicament in the patch and (4) overall heat transfer coefficient (U). A regression technique yielded the following results: −r_A0 = 3.000 × 10⁻² kg/m³ s, m = 1.251 × 10⁻⁸ kg, U = 6.124 × 10 J/m² K s and C₀ = 1.966 × 10⁻¹ kg/m³. When m was fixed at 12.5 g, the optimum design required the following specifications: r_A0 = 2.765 × 10⁻² kg/m³ s, U = 1.402 × 10³ J/m² K s and C₀ = 1.941 × 10⁻¹ kg/m³. The priority (S_i) of the input factors (i) in reaching the target delivery rate is: SC₀>S−rA0>Sm>SU.     

Electroanalytical determination of TBHQ, a synthetic antioxidant, in soybean biodiesel samples

This paper reports an electroanalytical method developed for tert-butylhydroquinone (TBHQ) determination in biodiesel in the presence of surfactant Triton X-100 (T-100). T-100 was shown to improve the electroanalytical signal and its use was decisive for direct analysis of TBHQ in biodiesel, only requiring previous dilution of biodiesel samples in methanol. Several parameters were studied and optimized for the development of this methodology. Under optimal conditions, oxidation peak current was proportional to TBHQ concentration in the range of 1.05-10.10 × 10⁻⁶ mol L⁻¹, with limits of detection and quantification of 3.43 × 10⁻⁸ mol L⁻¹ and 1.14 × 10⁻⁷ mol L⁻¹, respectively, by square wave voltammetry (SWV). The results achieved with the proposed method were satisfactory, relative to those obtained using high-performance liquid chromatography (HPLC).     

Catalytic adsorptive stripping voltammetric determination of Cr(VI) in EDTA extracts from solid samples

A catalytic adsorptive stripping voltammetric procedure which allows for Cr(VI) determination in EDTA extracts is presented. EDTA used for extraction can be exploited as a masking agent for Cr(III). The calibration graph for Cr(VI) for an accumulation time of 60 s was linear in the range from 2 × 10⁻¹⁰ to 3 × 10⁻⁸ mol L⁻¹. The relative standard deviation for a Cr(VI) concentration of 2 × 10⁻⁹ mol L⁻¹ was 5.1% (n = 5). The detection limit estimated from three times the standard deviation of low Cr(VI) concentration and accumulation time of 60 s was about 7 × 10⁻¹¹ mol L⁻¹. The influence of foreign ions commonly present in extracts from solid samples is presented. The proposed voltammetric procedure was applied to determine Cr(VI) in EDTA extractable chromium from soil certified reference materials CRM 483 and CRM 041. The performance of the method was also verified by studying the recovery of Cr(VI) from spiked river water.     

Kinetics of nitroxide-controlled radical polymerization during the non-stationary state

The activation-deactivation equilibrium of nitroxide-controlled radical polymerization of styrene at 123 °C was investigated. For this purpose the reaction solution was examined time dependently during the initial phase of the polymerization by using an SEC column combination providing a very good separation of the low-molecular weight species. By time-dependent measurement of the alkoxyamine concentration the activation rate of the alkoxyamines PhEt-TIPNO (N-tert-butyl-N-(2-methyl-1-phenyl-propyl)-O-(1-phenyl-ethyl)-hydroxylamine) k_act = 3.2 × 10⁻³ s⁻¹ and PhEt-BIPNO (N-tert-butyl-N-(1-isopropyl-2-methyl-propyl)-O-(1-phenyl-ethyl)-hydroxylamine) k_act = 6.4 × 10⁻³ s⁻¹ can be determined directly.Considering the Persistent Radical Effect theory, the measurement of the free nitroxide concentration allows to determine the pseudo-equilibrium constant of dissociation/combination between dormant and active species for polystyryl-TIPNO and polystyryl-BIPNO, K = 7.5 × 10⁻⁹ mol/L and 1.08 × 10⁻⁸ mol/L, respectively.     

Self-assembled monolayers-based immunosensor for detection of Escherichia coli using electrochemical impedance spectroscopy

An electrochemical impedance immunosensor for the detection of Escherichia coli was developed by immobilizing anti-E. coli antibodies at an Au electrode. The immobilization of antibodies at the Au electrode was carried out through a stable acyl amino ester intermediate generated by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydrosuccinimide (NHS), which could condense antibodies reproducibly and densely on the self-assembled monolayer (SAM). The surface characteristics of the immunosensor before and after the binding reaction of antibodies with E. coli were characterized by atomic force microscopy (AFM). The immobilization of antibodies and the binding of E. coli cells to the electrode could increase the electro-transfer resistance, which was directly detected by electrochemical impedance spectroscopy (EIS) in the presence of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ as a redox probe. A linear relationship between the electron-transfer resistance and the logarithmic value of E. coli concentration was found in the range of E. coli cells from 3.0 × 10³ to 3.0 × 10⁷ cfu mL⁻¹ with the detection limit of 1.0 × 10³ cfu mL⁻¹. With preconcentration and pre-enrichment steps, it was possible to detect E. coli concentration as low as 50 cfu/mL in river water samples.     

Degradation of the antimicrobial triclocarban (TCC) with ozone

Triclocarban (TCC) has been used as an antimicrobial compound for many decades due to its sanitising properties. Recent studies showed that TCC is toxic and causes disruption to the endocrine system. In this work, ozone oxidation of TCC was studied in 70% acetonitrile:30% water solutions. Ozone degraded TCC effectively and the reaction rates increased substantially with ozone gas concentration, pH and temperature. Second-order-reaction kinetics was suitable to describe the chemical reaction. The effect of temperature was described by the Arrhenius equation and the activation energy was found equal to 31.0 kJ/mol. The stoichiometry of the reaction was one and the value of the rate constant at pH 7 was 5 × 10³ M⁻¹ s⁻¹.     

High sensitive simultaneous determination of catechol and hydroquinone at mesoporous carbon CMK-3 electrode in comparison with multi-walled carbon nanotubes and Vulcan XC-72 carbon electrodes

The simultaneous voltammetric determination of catechol (CC) and hydroquinone (HQ) has been achieved at a mesoporous carbon CMK-3 modified electrode in phosphate buffer solution (pH 7.0). At the electrode both CC and HQ can cause a pair of quasi-reversible and well-defined redox peaks and their peak potential difference increases. In comparison with multi-walled carbon nanotubes (MWCNTs) and Vulcan XC-72 carbon modified electrodes the CMK-3 modified electrode shows larger peak currents and higher adsorbed amounts for the two dihydroxybenzene isomers. This is related to the higher specific surface area of CMK-3. Under the optimized conditions, the linear concentration ranges for CC and HQ are 5 × 10⁻⁷ to 3.5 × 10⁻⁵ M and 1 × 10⁻⁶ to 3 × 10⁻⁵ M, respectively. In the presence of 5 μM isomer, the linear concentration range of CC (or HQ) is 5 × 10⁻⁷ to 2.5 × 10⁻⁵ M (or 5 × 10⁻⁷ to 2.0 × 10⁻⁵ M). The sensitivity for CC or HQ is 41 A M⁻¹ cm⁻² or 52 A M⁻¹ cm⁻², which is close to that without isomer. The detection limits (S/N = 3) for CC and HQ are 1 × 10⁻⁷ M after preconcentration on open circuit for 240 s.