Comparison of models for estimation of measurement uncertainties. Determination of BOD<Subscript>5</Subscript> in wastewaters using a manometric method

Biochemical oxygen demand after 5 days (BOD₅) is a bioassay frequently used to determine the polluting strength of wastewaters. It quantifies the mass concentration of dissolved O₂ consumed during an incubation period of 5 days at 20 °C, in the dark, by biological oxidation of organic and/or inorganic matter in wastewater. In this work, the BOD₅ measurand is reported as γ(O₂). Reporting analytical results with estimation of uncertainty is an ISO/IEC 17025:2005 requirement and allows results to be compared and their fitness for purpose to be demonstrated. The γ(O₂) uncertainty was estimated using two models: the individual components’ model (model 1) and the quality-control-criteria model in which the trueness component is calculated using the equation for recovery from CRMs (model 2.A) and the standard deviation of all recoveries (model 2.B). Model 1 provides a realistic strategy for estimation of γ(O₂) uncertainty and for assessment of performance. Models 2.A and 2.B are expeditious and simple procedures for the 100–800 mg L⁻¹ range. When γ(O₂) < 100 mg L⁻¹ model 1 must be used because with both Models 2 uncertainty was underestimated, more drastically close to the limit of quantification. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A simple chemiluminescence method for determination of chemical oxygen demand values in water

In this paper, a low cost chemiluminescence detector with a photodiode instead of photo-multiplier tube (PMT) was developed for environmental monitoring of water quality. Based on the chemiluminescent reaction of luminol-H₂O₂-Cr³⁺ system, light emission caused by luminol-H₂O₂-Cr³⁺ system was detected by the photodiode, and its intensity caused by the appearance of Cr³⁺ after samples digestion was proportional to the chemical oxygen demand (COD). Effects for COD determining such as pH, concentrations, interference, and digestion procedures were investigated. The experimental results show that this suggested method uses an instrument that is simpler and cheaper than the previous ones used for the same purpose. The data obtained by the present method were fairly in good agreement with those obtained by the standard reflux titrimetric method. It has been applied to determine real samples with satisfactory results.     

Study on Determination of Chemical Oxygen Demand in Water with Ion Chromatography

A new method for determining chemical oxygen demand （COD） value in water using ion chromatography coupled with nano TiO2-K2S2O8 co-existing system was described. The photocatalytic oxidation system and nano TiO2-K2S2O8 co-existing system could degrade the organic compounds in water. All sulfur-containing species in the reactive solution were eventually transformed to sulfate which could be determined by conductivity detector in ion chromatography. The change of conductivity of sulfate was proportional to COD value. The optimal experimental conditions and the mechanism of the detection were discussed. The application range was 10.0-300.0 mg·L^-1 and the lowest limit of detection was 3.5 mg·L^-1. It was considered that the value obtained could be reliably correlated with the COD value obtained using the conventional methods.     

Rules of electron correlation energies of van der Waals' complexes RgX (Rg = Ar,Kr, X = F,Cl, Br)

First, the intrapair and interpair correlation energies of the Rg atom, X atom, and the optimized RgX (Rg = Ar, Kr, X = F, Cl, Br) complexes are calculated by the MELD program at the 6‐311++g(d), 6‐311++g(3df, 3pd), and cc‐pvqz basis sets (denoted by basis sets a, b, and c, respectively). It is found that the relationship E_corr(RgX) ≈ E_corr(Rg) + E_corr(X) is correct for all the above systems but introducing an unsound absolute error for some RgX systems. Second, the same calculations are selectively carried out for ArF (the smallest system) and KrBr (the largest system) at their increasing interatomic distance. It was found that both the correlation energies of ArF and those of KrBr will decrease whenever the interatomic distance of them become larger. On the basis of our results, we provided an approach to quickly estimate the correlation energies of RgX complexes by which not only the absolute error becomes smaller but more computation work is saved than the direct calculation. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Single-shot measurement of solids and liquids T1 values by a small-angle flip-flop pulse sequence

We propose the small-angle flip-flop (SAFF) pulse sequence as an alternative procedure for the rapid measurement of the ¹H spin–lattice relaxation time in the laboratory frame (T₁) of solid and liquid substances, in a time-domain NMR experiment. Based on the original flip-flop pulse sequence, this technique allows the fast estimation of T₁ values of samples that require minutes to hours of acquisition time if traditional pulse sequences are employed. We have applied SAFF to different substances, with T₁ ranging from microseconds up to seconds, including natural clays, polymers, and organic and inorganic solvents. We also demonstrate the potential of the pulse sequence in the real-time monitoring of dynamic processes, such as the conformational changes of polymeric materials during heating. The results we obtained with SAFF are comparable with those acquired with the inversion-recovery pulse sequence, with the addition of several benefits. This pulse sequence obeys steady-state and magnetization-conserving principles, making it possible to dismiss the need for relaxation delay times of the order of 5T₁. SAFF has shown high sensitivity in the resolution of individual components of T₁ in multiexponential systems and can be easily integrated to well-established pulse sequences, such as Magic Sandwich Echo and Carr–Purcell–Meiboom–Gill, for the single-shot determination of T₁ and T₂ or T_2*.     

The coulometric determination of chemical oxygen demand

The chemical oxygen demand (COD) of solutions containing various organic compounds is calculated from the net faradaic charge (Q_net) estimated for the total electrolytic oxidation of Cr^III generated during oxidative degradation of the organic compounds in acidic media containing excess Cr^VI. Values of Q_net for conversion of Cr^III to Cr^VI are estimated from the linearized chronoamperometric data plotted as In {i_{tat, t}} vs. t. This procedure is preferred over determinations of Q_net from the total integrals of i_tot over the entire electrolysis period because of large errors that can result from uncertainty in the background current (i_bkg) for t → ∞. The proposed coulometric procedure offers the benefit that reagent solutions can be reused, thereby minimizing the need for disposal of wastes containing toxic Cr^VI. This procedure was applied in a single digest solution for consecutive determinations of COD. Average COD values for potassium acid phthalate and glucose were 103.8% (s - 6.0, N - 10) and 100.2% (s - 4.2, N - 11), respectively, based on the theoretical degradation to CO₂. In comparison for these same samples, an EPA approved method, based on colorimetric determination of Cr^III, gave COD values of 101.4% (S - 1.4, N - 5) and 100.1% (s - 1.4, N - 5) of the theoretical. Statistical tests indicate no significant difference in the COD values determined for these compounds using the coulometric and EPA methods.     

纳米TiO2膜用于光催化氧化测定化学需氧量的研究

A photocatalytic oxidation method for determination of chemical oxygen demand （COD） using nano-TiO2 film, based on the use of a nano-TiO2-Ce（SO4）2 system and electrochemical detection, was proposed. The technique was originated from the direct determination of the Ce（Ⅲ） concentration change resulting from photocatalytic oxidation of organic compounds. Ce（Ⅲ）, which was produced by photocatalytic reduction of Ce（SO4）2, could be measured at a multi-walled carbon nanotubes （MWNT） chemically modified electrode （CME）. The COD values by this method were calculated from the differential pulse voltammetry （DPV） current of Ce（Ⅲ） at the CME. Under the optimal operation conditions, the detection limit of 0.5 mg·L^-1 COD with the linear range of 1-600 mg·L^-1 was achieved. This method was also applied to determination of various COD of ground water and wastewater samples. The resuits were in good agreement with those from the conventional COD methods, i.e., permanganate and dichromate ones.     

A Series Piezoelectric Quartz Crystal Microbial Sensing Technique Used for Biochemical Oxygen Demand Assay in Environmental Monitoring

A new method for biochemical oxygen demand (BOD) determination, which combines the series piezoelectric quartz crystal (SPQC) technique with the growth of a microorganism is presented in this paper. This method needs no immobilization of bacteria and is simple and convenient. When a calibration technique was used for BOD analysis, the detection time was 2.5 h at 37°C. There was a good linear relationship between the frequency shift and BOD value in the range 2.2–11 mg/L and the regression equation was ΔF = 64.10 + 11.23[BOD]. The proposed method was compared with the conventional BOD₅ method. This method was more rapid than the BOD₅ method and the results obtained by the former were in good agreement with those obtained by the latter. The experimental conditions are also discussed in detail.     

Ti/TiO2 Electrode Preparation Using Laser Anneal and Its Application to Determination of Chemical Oxygen Demand

A method for Ti/TiO₂ photoelectrode preparation using laser calcination instead of oven calcination process was introduced. The prepared TiO₂ film was investigated by X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and amperometry, and it was found that the prepared electrode mainly consisted of anatase TiO₂ nanoparticles on its surface and exhibited a superior photocatalytic activity. The electrode was employed as a sensor to measure chemical oxygen demand (COD) of the wastewater. The measuring principle was based on the photocurrent responses of the electrode which were proportional to the COD values. Under the optimized experimental conditions, the linear range was 50–2000 mg L⁻¹, and the detection limit was 16 mg L⁻¹ (S/N=3). This method was characterized by short analysis time, simplicity, low environmental impact and long lifetime of the sensor. Additionally, the COD values obtained from the proposed and conventional methods agreed well as demonstrated by the high significant correlation between the two sets of COD values (R=0.9895, n=25).     

Chemiluminescence system for automatic determination of chemical oxygen demand using flow injection analysis

A novel chemiluminescence (CL) system for automatic determination of chemical oxygen demand (COD) combined with flow injection analysis is proposed in this paper. In this system, potassium permanganate is reduced to Mn²⁺ which is first adsorbed on a strongly acid cation-exchange resin mini-column to be concentrated during chemical oxidation of the organic compounds at room temperature, while the excessive MnO₄⁻ passes through the mini-column to be waste, then the concentrated Mn²⁺ is eluted reversely and measured by the luminol-H₂O₂ CL system. The calibration graph is linear in the range of 4-4000 mg l⁻¹ and the detection limit is 2 mg l⁻¹. A complete analysis could be performed in 1.5 min including washing and sampling, giving a throughout of about 40 h⁻¹. The relative standard deviation was 4.4% for 10 mg l⁻¹ COD (n=11), 4.8% for 100 mg l⁻¹ COD (n=11). This CL flow system for determination of COD is very simple, rapid and suitable for automatic and continuous analysis. The presented system has been applied successfully to the determination of COD of water samples.     

Native biofilm cultured under controllable condition and used in mediated method for BOD measurement

In this article, we developed a native biofilm (NBF) bioreactor used for biochemical oxygen demand mediated method (BOD_Med). There were two innovations differed from previous BOD_Med assay. Firstly, the immobilization of microorganisms was adopted in BOD_Med. Secondly, the NBF was introduced for BOD measurement. The NBF bioreactor has been characterized by optical microscopy. A culture condition of NBF with 24 h, 35 °C and pH 7 was optimized. Furthermore, a measuring condition with 35 °C, pH 7 and 55 mM ferricyanide in 1 h incubation were optimized. Based on the optimized condition, the real wastewater samples from local sewage treatment plant had been measured. Performances of the NBFs proposed at different culture conditions were recorded for 110 d, and the results indicated that long-term storage stability was obtained. With the proposed method, an uncontaminated native microbial source solution can be obtained from a wastewater treatment plant. In this way, we can ensure that the microbial species of all in the NBF are same as that in the target to be measured.     

Revisiting the design of experiments for copolymer reactivity ratio estimation

Tidwell and Mortimer used the D-optimal criterion to design terminal model reactivity ratio estimation experiments. In this paper, two problems are investigated which were not addressed by Tidwell and Mortimer. The first problem is the design of reactivity ratio estimation experiments subject to composition constraints. It is shown that all the key information contained in the D-optimal criterion can be summarized in two equations: one which is a function of r?₁, and one which in a function of r?₂. These two equations can be used to design reactivity ratio estimation experiments under composition constraints which are within 3 mol % of the D-optimal feed compositions. The second problem is the design of penultimate reactivity ratio estimation experiments. The D-optimal criterion for the penultimate model was derived and optimized for two existing systems as well as a large number of hypothetical systems. The D-optimal criterion for the penultimate model was found to be much more complicated than the terminal model criterion. For this reason, the optimal penultimate reactivity ratio estimation experiments can not be approximated by simple equations. Anyone interested in designing such experiments must derive and optimize the D-optimal criterion. © 1993 John Wiley & Sons, Inc.     

Chemical Intergrowth of Dimeric and Trimeric Clusters in Reduced Tin Oxomolybdates: A study by high-resolution electron microscopy

By high-resolution electron microscopy, chemical intergrowth was studied of dimeric Mo₁₀O₁₆ and trimeric Mo₁₄O₂₂ clusters in reduced tin oxomolybdates within the Sn_xMo₁₀O₁₆? Sn_yMo₁₄O₂₂ system. The variety of observed intergrowth patterns includes polysynthetically twinned structures as well as a number of different superstructures. For an orthorhombic superstructure formed by alternating layers of dimeric and trimeric clusters, the lattice parameters and the Sn content were determined. The chemical reason for the amazing abundance of structures in the considered system is discussed.     

Predictive correlations based on large experimental datasets: Critical constants for pure compounds

A framework for development of estimation methods is demonstrated using prediction of critical constants for pure compounds as an example. The dataset of critical temperature T_c and critical pressure p_c for over 850 compounds used in the present work was extracted from the TRC SOURCE data archival system and is based exclusively on experimental values taken from the literature. Experimental T_c and p_c values were critically evaluated using the methods of robust regression and their uncertainties were assigned in a rigorous manner. The correlations for critical constants were developed based on Quantitative Structure–Property Relationships (QSPR) methodology combined with the Support Vector Machines (SVM) regression. The propagation of the experimental uncertainties into the predictions produced by the correlations was also assessed using a procedure based on stochastic sampling. The new method is shown to perform significantly better than a number of commonly used estimation methods.     

Density,speed of sound,refractive index and derivatives properties of the binary mixture n-hexane + n-heptane (or n-octane or n-nonane), T = 288.15 – 313.15 K

This article reports experimental values of refractive index n_D , density ρ, speed of sound u, isentropic compressibility κ_s, excess molar volume of mixing V _E, deviations of refractive index δn_D and isentropic compressibility δκ_s of the binary mixture n-hexane + n-alkane from T = (288.15 to 323.15) K and atmospheric condition. The corresponding excess derived property was computed from the experimental data. Parameters of analytical expressions which represent the composition dependences of the derived property are reported. Values of physical properties were compared with the results obtained by different prediction methods.     

Reductive Activation of O2 and Monooxygenation of Hydrocarbons by Eu Catalyst

Europium catalysis for reductive activation of O₂ and monooxygenation of hydrocarbons are discussed in this review. Two Eu-systems, the Eu(III)-O₂-Zn system and the Eu(III)-Ti(IV)-Pt-O₂-H₂ system, are described. A whole scheme of the Eu-system is proposed from various kinetic studies for the oxidation of cyclohexane, the epoxidation of 1-hexene, and the hydroxylation of benzene. The reactivities of the active oxygen species for various hydrocarbons (methane, ethane, propane, hexane, adamantane, cy-C₅H₁₀+cy-C₆H₁₂, cy-C₆D₁₂+cy-C₆H₁₂, cis- and trans-1,2-dimethylcyclohexane, propylene, cis- and trans-2-hexene, benzene, toluene) are summarized and compared with well-known oxidation systems. Oxidation state of Eu species was studied by cyclic voltammogram and UV-visible absorption techniques. On the basis of experimental results, the models of reaction mechanism is proposed.     

Oxidation of diazo compounds by triphenyl phosphite ozonide. Quenching of singlet oxygen by diazo compounds

The reaction of triphenyl phosphite ozonide with various types of diazo compounds results in their oxidation, which is accomplished by singlet oxygen (¹O₂) evolved during thermal decomposition of the ozonide. A decrease in the ionization potential of the substrate results in an increase in the overall rate constant of quenching of¹O₂. In the case of 9-diazofluorene, the main channel of¹O₂ quenching is physical quenching.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1567–1571, September, 1994.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-5231).     

丙烯酸生产外排废水化学需氧量与总有机碳相关性研究

化学需氧量（COD_Cr）与总有机碳（TOC）指标均可用来表征废水的有机物污染程度.不过,以COD_Cr表征有机物污染程度一般只能反映水中部分有机物的量,而TOC能更全面地反映废水中有机物的含量.以丙烯酸生产外排废水为研究对象,分析结果表明：在一定范围内,废水中COD_Cr与TOC满足关系式y=1.147 4x+74.75（R²=0.955 26）,回收率范围98%~115%,TOC测定结果的精密度高、可靠、准确,在一定条件下,可使用TOC来间接换算COD_Cr.     

Substituenteneffekte auf die C–C-Bindungsstärke, 8. Standardbildungsenthalpien und Spannungsenthalpien von 1,1,2,2-Tetraethylethylenglykol-dimethylether und D,L-1,2-Dimethyl-1,2-diphenylethylenglykol-dimethylether

Effects of Substituents on the Strength of C - C Bonds, 8¹. - Heats of Formation and Strain of 1,1,2,2-Tetraethylethylene Glycol Dimethyl Ether and D,L .-1,2-Dimethyl-l,2-diphenylethylene Glycol Dimethyl Ether The heats of combustion of the title compounds 1 and 2 were measured calorimetrically with the result (kcal mol ^-1, s. d. in parentheses) ΔH°_c = − 1880.1 (± 0.6) and − 2373.3 (± 1.4). The heat of vaporisation of 1 ΔH^v = 14.3 (± 0.3) and the heat of sublimation of 2 ΔH^sub = 27.2 (± 0.5) were derived from their temperature dependance of the vapor pressure. The latter were determined between 30 and 80°C using a flow method. The resulting standard heats of formation ΔH°_t(g) = −122.4 (± 0.7) and −43.8 (±1.5) for 1 and 2 correspond to a strain enthalpy (_s) of 15.9 and 8.0 kcal mol^-1, respectively. The steric strain of the dimethoxyethanes 1 and 2 is about one fourth lower than the strain of the corresponding dimethylethanes 3 and 4 bearing the same substituents. Thus, a methoxy group causes less steric stress than a methyl group.     

A surface-fluorinated-TiO2-KMnO4 photocatalytic system for determination of chemical oxygen demand

A new method for chemical oxygen demand (COD) determination has been developed, based on photocatalytic oxidative degradation by using a fluorinated-TiO₂-KMnO₄ system. In such a system, a linear correlation is observed between the amount of oxidizable dissolved organic matter and the amount of MnO₄⁻ consumed by the coupled reduction process. Thus, the COD determination is transformed to a simple and direct determination of the deletion of MnO₄⁻. The surface fluorination of TiO₂ nanoparticles can enhance the rate of photocatalytic oxidation of organic matter and the rate of coupled photocatalytic reduction of MnO₄⁻. This makes the method be rapid, environment friendly and easy for operation. Under optimized conditions, this method can respond linearly to COD of potassium hydrogen phthalate (KHP) in the range of 0.1-280 mg L⁻¹, with a detection limit of 0.02 mg L⁻¹ COD. The COD in samples of tap water, lake water and paper industry sewage has been determined satisfactorily by using this method.