응용 분야 및 기법
- 410000054-ATechnical Note: Method Development with NanoRam®-1064
Although the process of building, validating and using a method is well-defined through software, the robustness of the method is dependent on proper practice of sampling, validation, and method maintenance. In this document, we will detail the recommended practices for using the multivariate method with NanoRam-1064. These practices are recommended for end users who are in the pharmaceutical environment, and can expand to other industries as well. This document aims to serve as a general reference for NanoRam-1064 users who would like to build an SOP for method development, validation and implementation.
- 410000057-ATechnical Note: Spectral Preprocessing for Raman Quantitative Analysis
Raman spectroscopy’s use for process analytics in the pharmaceutical and chemical industries continues to grow due to its nondestructive measurements, fast analysis times, and ability to do both qualitative and quantitative analysis. Spectral preprocessing algorithms are routinely applied to quantitative spectroscopic data in order to enhance spectral features while minimizing variability unrelated to the analyte in question. In this technical note we discuss the main preprocessing options pertinent to Raman spectroscopy with real applications examples, and to review the algorithms available in B&W Tek and Metrohm software so that the reader becomes comfortable applying them to build Raman quantitative models.
- 410000059-BCharacterization of carbon materials with Raman spectroscopy
Raman spectroscopy is a valuable tool for the characterization of carbon nanomaterials due to its selectivity, speed, and ability to measure samples nondestructively. Carbon materials typically have simple Raman spectra, but they contain a wealth of information about internal microcrystalline structures in peak position, shape, and relative intensity.
- 8.000.6063Post-column chemistry for improved optical absorption detection
UV/VIS detection is one of the most sensitive detection techniques in trace-level chromatography. Sometimes, however, spectrophotometric detection lacks sensitivity, selectivity or reproducibility and chemical derivatizations are required. By using Metrohm`s rugged and versatile flow-through reactor, single- or multi-step derivatizations can be done fully automatically, in either pre- or post-column mode at any temperature between 25…120 °C. The variable reactor geometry allows to adjust the reactor residence time of the reactants according to derivatization kinetics. The flexibility of the reactor is demonstrated by optimizing four widespread post-column techniques: the relatively slow ninhydrin reaction with amino acids and the fast derivatizations of silicate, bromate and chromate(VI).
- 8.000.6071Trace-level determination of anions in the primary circuit of a PWR-type nuclear power plant using ion chromatography after inline sample preparation
The poster presents the ion chromatographic determination of organic degradation products such as glycolate, formate and acetate besides the standard anions fluoride, chloride, nitrate and sulfate.
- 8.000.6072Trace-level determination of cations in the secondary circuit of a PWR-type nuclear power plant using ion chromatography after inline sample preparation
The presented IC system with inline sample preparation allows the determination of traces of lithium and sodium (ppt) in the presence of ppm quantities of ammonium and ethanolamine.
- 8.000.6091Ion chromatographic determination of halogens and sulfur in solids using combustion as inline sample preparation
The Combustion IC system presented allows the automated determination of organic halogen and sulfur compounds in all flammable samples. Both combustion digestion, which is automatically controlled with a flame sensor, and the professional Liquid Handling guarantee highest precision and trueness. This poster describes the determination of the halogen and sulfur content in a certified polymer standard, a coal reference material as well as in latex and vinyl gloves.
- AB-066Potentiometric and thermometric determination of boric acid
Boric acid is used in many primary circuits of nuclear power plants, in nickel plating baths, and in the production of optical glasses. Furthermore, boron compounds are found in washing powders and fertilizers. This bulletin describes the potentiometric and thermometric determination of boric acid. The determination also covers further boron compounds, when acidic digestion is applied.
- AB-070Polarographic determination of nitrate in water samples, soil and plant extracts, vegetable juices, meat and sausages, fertilizers, liquid manure, etc.
The photometric determination of nitrate is limited by the fact that the respective methods (salicylic acid, brucine, 2,6-dimethyl phenol, Nesslers reagent after reduction of nitrate to ammonium) are subject to interferences. The direct potentiometric determination using an ion-selective nitrate electrode causes problems in the presence of fairly large amounts of chloride or organic compounds with carboxyl groups. The polarographic method, on the other hand, is not only more rapid, but also practically insensitive to chemical interference, thus ensuring more accurate results. The limit of quantification depends on the matrix of the sample and is approximately 1 mg/L.
- AB-199Determination of sulfide and sulfite by polarography
Sulfide and sulfite can be determined polarographically without any problems. For sulfide, polarography is performed in an alkaline solution, for sulfite in a slightly acidic primary solution. The method is suitable for the analysis of pharmaceuticals (infusion solutions), wastewater/flue gas water, photographic solutions, etc.
- AB-209Water in insulating oils, hydrocarbons, and their products – Accurate and reliable determination by Karl Fischer titration
Only coulometric Karl Fischer titration can determine low water contents with sufficient accuracy.This Application Bulletin describes the direct determination according to ASTM D6304, ASTM E1064, ASTM D1533, ASTM D3401, ASTM D4928, EN IEC 60814, EN ISO 12937, ISO 10337, DIN 51777, and GB/T 11146. The oven technique is described according to ASTM D6304, EN IEC 60814, and DIN 51777.
- AB-223Fully automated determination of uranium
This Bulletin describes the fully automated determination of uranium according to the method of Davies and Gray: Uranium(VI) is reduced in concentrated phosphoric acid solution with iron(II) to form Uranium(IV). With molybdenum as a catalyst, the excess iron(II) is oxidized with nitric acid. The nitrous acid that is formed is destroyed with sulfamic acid before uranium(IV) is titrated with a potassium dichromate solution in the presence of a vanadium catalyst.
- AB-266Determination of titanium by adsorptive stripping voltammetry
This Application Bulletin describes the determination of titanium by adsorptive stripping voltammetry (AdSV) using mandelic acid as complexing agent. The method is suitable for the analysis of ground, drinking, sea, surface and cooling waters, in which the concentration of titanium is of importance. The methods can, of course, also be used for the trace analysis in other matrices.The limit of detection is approx. 0.5 µg/L.
- AB-344Automated analysis of etch acid mixtures for silicon substrates with thermometric titration
This bulletin deals with the automated determination of mixtures of HNO3, HF and H2SiF6 in the range of approximately 200-600 g/L HNO3, 50-160 g/L HF, and 0-185 g/L H2SiF6 using thermometric titration.Etch acid mixtures containing HNO3, HF and H2SiF6 from the etching of silicon substrates can be analyzed in a sequence of two determinations using the 859 Titrotherm. The first determination involves a direct titration with standard c(NaOH) = 2 mol/L, followed by a back titration with c(HCl) = 2 mol/L. This determination yields the H2SiF6 content plus a value for the combined (HNO3+HF) contents. The second determination consists of a titration with c(Al3+) = 0.5 mol/L to determine the HF content. For freshly made up mixtures of HNO3 and HF containing no H2SiF6, a linked two-titration sequence is employed. Results from the two determinations are used by tiamoTM to yield individual results for HNO3, HF and H2SiF6.
- AB-434Water in lithium ion battery materials – Reliable and precise determination by Karl Fischer titration
Lithium-ion batteries must be completely free of water (concentration of H2O < 20 mg/kg), because water reacts with the conducting salt, e.g., LiPF6, to form hydrofluoric acid.The water content of several materials used in lithium ion batteries can be determined reliably and precisely by coulometric Karl-Fischer titration. In this Application Bulletin the determination for the following materials is described:raw materials for the manufacture of lithium-ion batteries (e.g., solvents for electrolytes, carbon black/graphite); electrode coating preparations (slurry) for anode and cathode coating; the coated anode and cathode foils as well as in separator foil and in the combined material; electrolytes for lithium-ion batteries;
- AN-BAT-001High voltage measurements: Characterization of NiMH batteries with Autolab PGSTAT302N in combination with voltage multiplier
A nickel metal hydride battery, abbreviated NiMH, is a type of rechargeable battery similar to a nickel-cadmium (NiCd) battery but, for the anode, instead of cadmium, it has a hydrogen absorbing alloy. Like in NiCd batteries, nickel is the cathode. The voltage output of such packs is directly proportional to the number of single cells in the pack. In some cases, the total voltage can exceed the maximum of 10 V that is measurable by the Autolab potentiostat/galvanostat. To apply and measure voltages greater than 10 V, we have developed a voltage multiplier that increases the voltage range of the Autolab.
- AN-BAT-002Galvanostatic charge-discharge of a Li-ion battery with Autolab
Lithium-ion (Li-ion) batteries are one of the most important energy storage devices in the market. A typical Li-ion battery is usually composed of one or more cells. Characterization of Li-ion cells and batteries usually involves the galvanostatic charge and discharge during various cycles.
- AN-BAT-003Galvanostatic intermittent titration technique (GITT) for Li-ion batteries
This Application Note outlines GITT, a key technique for studying Li-ion battery kinetics, OCV, and diffusion, using INTELLO for streamlined control and analysis.
- AN-BAT-004Potentiostatic intermittent titration technique (PITT)
During charge and discharge of a Li-ion battery, lithium ions are transported from one electrode through the electrolyte to the other electrode. Knowing the chemical diffusion coefficient of electrode materials is crucial. The potentiostatic intermittent titration technique (PITT) is one of the most used techniques to retrieve insights on the diffusion coefficient of the electrode active materials.
- AN-BAT-006Determination of the MacMullin number
The main components of a battery are the positive and negative electrodes, together with the electrolyte, which provides only the ionic conductivity. The most common electrolytes are in the liquid state. Therefore, a separator is needed to provide a physical separation between the electrodes. The separator is soaked with electrolyte. The MacMullin number is a parameter used to determine the quality of a separator, in terms of ionic conductivity, when soaked with an electrolyte. The MacMullin number can be calculated, using the results of data fitting of two EIS experiments and the geometric factors of the measurement cells. In this application note, a commercial electrolyte is employed, together with a porous filter, used as a separator.
- AN-BAT-007Simple CV and EIS test measurements carried out with electrochemical cells for air or moisture sensitive measurements
The TSC SW closed and TSC battery cells are compact systems designed for measurement of air or moisture sensitive materials, such as those materials used in rechargeable batteries. These cells offer well-controlled environment for the in-temperature measurement of solid and gel like materials in contact with metal electrodes in planar geometry. For example, battery active materials, ionically conductive solid-state electrolytes and battery separators can be tested using these cells. In this experiment, standard resistors of 100 Ω are used in both cells to understand the cell effects, if any, on the measurements.
- AN-BAT-008Metrohm Autolab DuoCoin Cell Holder with EIS measurements on a commercial battery
The DuoCoin Cell Holder is introduced. EIS measurements on a commercial coin cell battery are performed. Differences in impedance between the four-terminal configuration and two-terminal configuration is highlighted, putting in evidence the importance of having a direct four-terminal configuration, when low-impedance DUTs are investigated.
- AN-BAT-009Determination of the binary diffusion coefficient of a battery electrolyte
In this application note, we demonstrate how to determine the binary diffusion coefficient of a commercial liquid binary lithium ion battery electrolyte based on a galvanostatic pulse polarization method.
- AN-BAT-010Investigation of the Solid Electrolyte Interface Structure and Kinetics.
This application note presents the experimental details and an overview of the most important findings from the EIS and CV experiment to study the structure of a model solid electrolyte interface forming on a planar glassy carbon electrode in contact with a typical organic battery electrolyte.
- AN-BAT-011Determination of the Through-Plane Tortuosity of Battery Electrodes by EIS in a symmetric Lithium-iron-phosphate cell
In this application note, we demonstrate how to determine the through-plane tortuosity τ of a commercial lithium ion battery cathode material with known porosity and coating thickness, based on the electrochemical impedance spectroscopy (EIS) method.
- AN-BAT-012Determination of the Lithium Ion Transference Number of a Battery Electrolyte by VLF-EIS
In this application note, we demonstrate how to determine the lithium ion transference number of a commercial liquid binary lithium ion battery electrolyte, based on the very-low-frequency electrochemical impedance spectroscopy (VLF-EIS) method.
- AN-BAT-013Simultaneous EIS measurements of a Li-ion battery cathode and anode
In battery research, electrochemical impedance spectroscopy (EIS) is a necessary tool to investigate the processes occurring at the electrodes. With a common three-electrode battery, EIS can be performed sequentially first at one electrode and then at the other electrode.
- AN-BAT-014Constant current constant voltage (CCCV) cycling with INTELLO
This Application Note explains how researchers can determine the underlying chemistry and potential failure mechanisms from cycle testing batteries with INTELLO.
- AN-BAT-015Differential capacity analysis (DCA) for battery research with INTELLO
This Application Note discusses differential capacity analysis (DCA) and its impact on enhancing battery performance, with a focus on using the INTELLO platform.
- AN-BAT-016EIS at different states of charge with INTELLO
This application shows how EIS, combined with INTELLO and NOVA, tracks changes in internal battery resistance across SOC levels to study performance and aging mechanisms.
- AN-C-049Trace cations in power plant feed water stabilized with 7 ppm monoethanolamine (MEA)
Determination of zinc, lithium, cobalt, sodium, ammonium, potassium, manganese, magnesium, and calcium in power plant feed water stabilized with 7 ppm monoethanolamine using cation chromatography with direct conductivity detection.
- AN-C-060Magnesium, strontium, and barium in produced water (11 g/L sodium)
Determination of magnesium, strontium, and barium in produced water using cation chromatography with direct conductivity detection.
- AN-C-063Five cations in lithium bromide using post-column reaction
Determination of nickel, zinc, cobalt, iron(II), and manganese in lithium bromide using cation chromatography with UV/VIS detection (520 nm) after post-column reaction with PAR.
- AN-C-083Online monitoring of trace levels of cations in boiler feed water
Determination of trace levels of lithium, sodium, ammonium, potassium, magnesium, and calcium in boiler feed water using cation chromatography with direct conductivity detection.
- AN-C-090Traces of zinc and iron(II) in the presence of the standard cations
Determination of traces of zinc and iron(II) in the presence of lithium, sodium, ammonium, potassium, calcium, and magnesium in boiler water using cation chromatography with direct conductivity detection.
- AN-C-096Trace analysis of monovalent cations in an ethanolamine matrix (secondary cycle of a pressurized water reactor) using Metrohm Inline Sample Preparation with an 800 Dosino for liquid handling
Methylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) in methylpyrrolidone using Metrohm Inline Matrix Elimination.
- AN-C-126Methylamines and ethanolamines (Metrosep C 4 - 150/4.0)
Determination of monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) using cation chromatography with direct conductivity detection.
- AN-C-132Traces of lithium, sodium, and ammonium in the presence of ethanolamine (Metrosep C 4 - 250/4.0)
Determination of lithium, sodium, ammonium, and monoethanolamine (MEA) using cation chromatography with direct conductivity detection and Metrohm Inline Preconcentration and Inline Calibration.
- AN-C-137Copper, nickel, zinc, and common cations in the water-steam cycle of a boiling water reactor (BWR)
Water chemistry of the water-steam cycle is crucial for maintaining plant reliability and for ensuring optimal plant operational conditions. Impurities such as corrosion products in ionic, colloidal, or oxide forms are ubiquitous in feedwater, condensate, and reactor coolant. This application shows the determination of sub-ppb levels of Cu, Ni, Zn and standard cations (e.g., Na+, NH4+, Mg2+, Ca2+) in the water-steam cycle of a BWR.
- AN-C-138Zinc, nickel, calcium, and magnesium in borated water of a pressurized water reactor (PWR)
In pressurized water reactors (PWRs), light water is used as primary coolant. Boron (as boric acid) readily absorbs neutrons and is added to the coolant to control reactivity. Lithium hydroxide assures a pH value greater than 7 to prevent corrosion. This application allows to measure sub-ppb levels of zinc, nickel, calcium, and magnesium besides high boric acid and lithium hydroxide concentrations.
- AN-C-139Cations and amines in the water-steam cycle
Water in steel-based cooling systems requires a pH value slightly above 7 to prevent corrosion. Often ammonium or organic amines are applied for pH adjustement. This application shows the separation of typical amines besides inorganic cations. Sample preconcentration applies combined Inline Preconcentration and Matrix Elimination (MiPCT-ME).
- AN-C-140Lithium in borated water of a pressurized water reactor (PWR)
In pressurized water reactors (PWRs), light water is used as coolant in the primary side. Boron (as boric acid) is added to the coolant to absorb neutrons, thus controlling reactivity. Lithium hydroxide assures the alkaline pH value to prevent corrosion. This application allows to measure lithium content besides high boric acid concentrations. AN-C-138 shows the respective trace metal determination on the same system setup.
- AN-C-144Variable Inline Preconcentration including matrix elimination for trace cation determination (MiPCT-ME)
Metrohm Inline Preconcentration Technique with matrix elimination (MiPCT-ME) is a powerful method that combines preconcentration, matrix elimination, and multilevel calibration. In this Application Note, the methodology is applied to the determination of traces of sodium in addition to 2 mg/L ammonia. The Metrosep C 6 - 250/4.0 column is used for selectivity reasons.
- AN-C-170N-methyldiethanolamine, piper-azine and standard cations in scrubber solutions
N-methyldiethanolamine and piperazine are used in scrubber solutions, e.g., in the natural gas process. Testing this type of samples by ion chromatography requires a good resolution and the separation of amines from standard cations. The separation is achieved on a Metrosep C 4 - 150/4.0 column applying direct conductivity detection.
- AN-C-171N-methyldiethanolamine and piperazine in scrubber solution
Before the liquefaction process of the natural gas, carbonate and hydrogen sulfide need to be removed through a scrubber solution containing piperazine and N-methyl diethanolamine (MDEA). The concentration ratio of the two components is determined by ion chromatography on a Metrosep C 4 - 150/4.0 column applying direct conductivity detection.
- AN-C-189Cations in lithium ore
The exploration and processing of lithium ores is gaining importance with the growing demand for lithium hydroxide. Lithium hydroxide is a key component in the manufacturing of rechargeable batteries for use in various applications including electric vehicles, home storage systems, power tools and consumer electronics. To ensure the efficiency for advanced processing of high purity lithium hydroxide, a fast and reliable quantitative detection technique is required. This application has been developed to monitor the lithium, sodium, and calcium content in the lithium processing samples and mineral concentrates.
- AN-C-193Alkyl amines in scrubber solutions
Harmful industrial flue gases like H2S and CO2 cause corrosion of pipes and damage the environment. Adding the correct amount of amines in scrubber solutions, e.g. ethanolamines and methylamines, will neutralize these gases («gas sweetening»). Non-suppressed cation analysis with direct conductivity detection is a straightforward and robust technique for the quantification of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) via ion chromatography. Thanks to the high capacity of the Metrosep C 6 column, large volumes can be injected without compromising the peak shapes. The analytical technique can be used at laboratory scale but also for process analysis.
- AN-CIC-011Analysis of an ion exchanger using Metrohm Combustion IC
The manufacture of ultrapure water for the pharmaceuticals industry or the semiconductor industry requires high-quality ion exchangers. Metrohm Combustion Ion Chromatography is an indispensable tool in this connection for testing the purity of anion exchange material. The output sample was wet and had to be dried at 105 °C in a special oven with waste air evacuation.Keyword: pyrohydrolysis
- AN-CIC-016Halogen traces in coal with the Metrohm Combustion IC
The burning of coal contaminates the atmosphere with halogens. Fluorine and chlorine are natural components of coal, whereas the bromide that is found therein is often adulterated as calcium bromide in order to reduce mercury emissions. This Application Note shows the results of combustion digestion with Combustion IC for three coal samples, each with a different bromide content.Keyword: pyrohydrolysis
- AN-CIC-020Fluorine in coal sample applying Metrohm Combustion IC
Coal contains a certain amount of fluorine, chlorine, and sulfur compounds. During combustion of the coal, these components release corrosive acids (e.g., fluorine compounds form hydrofluoric acid). Thermal power plants therefore request low-fluorine coal to avoid massive hydrofluoric acid production. In this application note, fluorine content in coal is determined by ion chromatography after pyrohydrolysis.
- AN-CIC-031Sulfur determination in ammonia gas applying Combustion IC
Sulfur species are critical contaminants in ammonia gas. They can cause high-temperature sulfidation of metals, form aggressive complexes with other elements, or react subsequently in processes where the ammonia gas is used. The concentration of such impurities tends to be very low, but they may not exceed critical levels of 0.5 mg/L. Although this level is very close to the system blank of the Combustion IC system, the setup can be used to prove that such critical limits are not exceeded.
- AN-COR-010Electrochemical Corrosion Studies of Various Metals
Corrosion of metals is a problem seriously affecting not only many industrial sectors, but also private life, resulting in enormous costs. In this application note, the results gained during electrochemical corrosion studies on different metals are compared to literature data.
- AN-COR-011ASTM G100: Cyclic Galvanostaircase Polarization
The ASTM standard G100 is an electrochemical method to test localized corrosion of aluminum 3003-H14 and other alloys. A cyclic galvanostatic staircase polarization (galvanostaircase) is composed of an upward and a downward scan. The potential values at the end of each step are collected and linearly fitted, and the potential values at zero current are found.
- AN-COR-012ASTM G5: Potentiodynamic anodic polarization measurements
This Application Note evaluates corrosion in Type 430 stainless steel according to ASTM G5 with VIONIC powered by INTELLO and an ASTM-compliant corrosion cell setup.
- AN-COR-014Corrosion Inhibitor Efficiency Measurement in Turbulent Flow Conditions with the Autolab Rotating Cylinder Electrode (RCE), According to ASTM G185
The rotating cylinder electrode (RCE) is a technique used in corrosion research to simulate in a laboratory environment the turbulent flow which usually occurs when liquids are transported through pipelines. The RCE is used to generate a turbulent flow at the surface of a sample, simulating the pipe flow conditions. Experiments that involve an RCE are regulated by the ASTM G185 standard. In this application note, The RCE with a 1018 carbon steel cylinder sample was used with the linear polarization (LP) measurement technique.
- AN-COR-015Corrosion Rates Measurements in Quiescent and Turbulent Flow conditions by using Rotating Cylinder Electrode (RCE)
The rotating cylinder electrode (RCE) is successfully used in a laboratory environment to generate a turbulent flow at the surface of a sample, simulating realistic pipe flow conditions. In this application note, the corrosion rate is measured and compared between quiescent and turbulent flow conditions, while keeping all the other experimental conditions unchanged. The linear polarization (LP) technique was used together with the RCE (with and without rotation).
- AN-COR-016ASTM G61: Standard test method for conducting cyclic potentiodynamic polarization
This Application Note details ASTM G61-compliant corrosion measurements performed with VIONIC powered by INTELLO using Metrohm’s ASTM-compliant corrosion cells.
- AN-COR-017Coulometric Reduction as per ASTM B825
The ASTM B825 is used to determine the corrosion and tarnish film on metal surfaces. This is achieved by using the so-called cathodic reduction method. With the help of a Metrohm Autolab PGSTAT302N and a Metrohm Autolab 1 L corrosion cell, a procedure to replicate the ASTM B825 is shown.
- AN-CS-010Traces of lithium and sodium besides monoethanolamine in water-steam circuits of thermal power plants
Boiler feed water is a working medium in thermal power plant. To keep corrosion low, the pH value should be in the slightly alkali range, which is why amines are added to the feed water. This addition must be monitored regularly. Also important is the monitoring of the sodium concentration, because an increase of this indicates that cooling water is seeping into the condenser. Ion chromatography with conductivity detection following sequential suppression is the optimum system for monitoring, particularly in combination with intelligent Sample Preconcentration and Matrix Elimination.
- AN-CS-011Cation traces in lithium hexafluorophosphate
Lithium hexafluorophosphate (LiPF6) is used as an electrolyte in rechargeable batteries. Its high solubility in non-polar solvents and its non-coordinating character in particular make lithium hexafluorophosphate the ideal salt for use in lithium-ion cells. This Application describes the determination of cation traces in LiPF6 with conductivity detection following sequential suppression.
- AN-CS-016Metrosep C Supp 2 - 150/4.0: Amines applying suppressed cation chromatography
The Metrosep C Supp 2 column family is polystyrene/divinylbenzene based and therefore sequential cation suppression may be applied. This AN shows the separation and detection of different amines on the 150 mm version of the column with subsequent conductivity detection after sequential cation suppression.
- AN-EC-002Reference electrodes and their usage
A reference electrode has a stable and well-defined electrochemical potential (at constant temperature), against which the applied or measured potentials in an electrochemical cell are referred. A good reference electrode is therefore stable and non-polarizable. In other words, the potential of such an electrode will remain stable in the used environment and also upon the passage of a small current. This application note lists the most used reference electrodes, together with their range of use.
- AN-EC-003Ohmic Drop Part 1 – Basic Principles
This application explains ohmic iR drop in electrochemical cells, its causes, and strategies to minimize its impact for accurate and reliable potential measurements.
- AN-EC-010In-temperature ionic conductivity measurements with the Autolab Microcell HC setup
To improve the performance of electrochemical energy storage devices like batteries and supercapacitors, one can focus on enhancing the ion conductivity (ƠDC) of the electrolyte. It is a common method for obtaining ƠDC values of different electrolyte systems, to carry out electrochemical impedance spectroscopy (EIS) experiments, at different temperatures, in a 2-electrode setup.
- AN-EC-013The importance of using four-terminal sensing for EIS measurements on low-impedance systems
In this application note, electrochemical impedance spectroscopy (EIS) is used to test a commercial battery connected in two different ways. In the first EIS measurement, the battery is connected in a two-terminal sensing configuration. In the second EIS measurement, the battery is connected in a four-terminal sensing (Kelvin sensing) configuration. The difference in how the leads are connected results in different measured impedance values for the battery.
- AN-EC-014Oxygen Reduction Reaction with the Rotating Ring Disk Electrode
The oxygen reduction reaction (ORR) is important to the functional readiness of a fuel cell. Rotating ring disk electrode (RRDE) experiments allow the reaction to be studied in hydrodynamic conditions to determine kinetic properties via the Levich and Koutecký-Levich equations. Mechanistic information is simultaneously obtained from the reaction of intermediates at the secondary (ring) electrode. This application note describes how the RRDE from Metrohm Autolab can be used to study the ORR.
- AN-EC-017Cyclic Voltammetry and Electrochemical Impedance Spectroscopy measurements carried out with the Microcell HCsetup – the TSC SW Closed and the TSC Battery cells
The TSC SW Closed and TSC Battery cells are compact systems designed for measurements on air or moisture-sensitive materials, such as those used in batteries. In this document, two testing procedures are explained. The first procedure is withpotentiostatic cyclic voltammetry (CV), while the second is via electrochemical impedance spectroscopy (EIS).
- AN-EC-018Electrochemical Impedance Spectroscopy of a Commercial Battery with different Types of Connections
The way low-impedance devices, like fuel cells and battery, are connected to a load influences their performances. In this document, a comparison of EIS results on a commercial Li-ion battery is shown. Different EIS measurements have been performed, changing the way the battery has been connected to the potentiostat.
- AN-EC-020Calculation of Cell Constants using the Autolab Microcell HC TSC70 and TSC1600
In order to calculate the conductivity of an electrolyte, the cell constant of the cell must be known. The combination of the Metrohm Autolab PGSTAT204 equipped with the FRA32M module in combination with the Autolab Microcell HC setup was used for the determination of the conductivity cell constants of TSC1600 temperature controlled electrochemical cell.
- AN-EC-023Determination of the T-dependent conductivity of a solid proton conductor
The proton conductivity of membranes made of a proton conductive material is an essential quantity to be determined. In this application note, we present the results of an exemplary study of σDC(T) determined by impedance spectroscopy for a novel solid proton conductor in its dry state.
- AN-EC-026Comparison between linear and staircase cyclic voltammetry on a commercial capacitor
Capacitors are electronic components necessary for the success of the electronics industry. They have also become essential components of both electric and hybrid vehicles. Electrochemical tests, such as potentiostatic cyclic voltammetry, are used to check the performance of capacitors. VIONIC powered by INTELLO can perform both staircase and linear cyclic voltammetries (CV). This Application Note gives a comparison between the linear and the staircase potentiostatic cyclic voltammetries and highlights the necessity of using the linear CV to best study the performance of capacitors.
- AN-EC-027Measuring the potential at the counter electrode with VIONIC powered by INTELLO
Many different configurations are made possible when using two-, three-, or four-electrode cell setups in research. Depending on the experimental requirements, one setup may be preferred over another. Therefore, the proper electrode arrangements for these three situations are defined in this Application Note. As an example, the potential at the counter electrode is measured during the platinum oxidation in acidic media, with the second sense (S2) of VIONIC powered by INTELLO. Since dissolved Pt in solution could bias the results, it is important to be able to monitor the potential of the counter electrode.
- AN-EC-036Ohmic iR drop Part 3 – Measurement with EIS
This Application Note explains manual and automated iR drop correction with electrochemical impedance spectroscopy and cautions against using less accurate methods.
- AN-EC-037Differential electrochemical mass spectrometry
Differential electrochemical mass spectrometry (DEMS) is used to monitor gaseous and volatile species during electrochemical reactions in situ.
- AN-EC-038Measuring ionic conductivity using screen-printing technology
Using disposable 11COND screen printed electrodes and electrochemical impedance spectroscopy, conductivity in drinking water can be measured using only 100 µL samples.
- AN-EC-041Studying nickel deposition with EQCM-D and EC-Raman
This application note demonstrates EQCM D for simultaneous mass and dissipation analysis of Ni(OH)₂ electrodeposition.
- AN-EIS-001Electrochemical impedance Spectroscopy (EIS) Part 1 – Basic Principles
Electrochemical impedance spectroscopy (EIS) is a widely used multidisciplinary technique for characterizing the behavior of complex electrochemical systems. EIS is employed in the study of a range of complex systems including batteries, catalysis, and corrosion processes. This Application Note focuses on the basic principles of EIS measurements.
- AN-EIS-002Electrochemical Impedance Spectroscopy (EIS) Part 2 – Experimental Setup
A typical electrochemical impedance spectroscopy (EIS) experimental setup consists of an electrochemical cell, a potentiostat/galvanostat, and a frequency response analyzer (FRA). This Application Note introduces common EIS experimental setups as well as details of the main experimental parameters.
- AN-EIS-003Electrochemical Impedance Spectroscopy (EIS) Part 3 – Data Analysis
Here, the most common circuit elements for EIS are introduced which may be assembled in different configurations to obtain equivalent circuits used for data analysis.
- AN-EIS-004Electrochemical Impedance Spectroscopy (EIS) Part 4 – Equivalent Circuit Models
Explore how to construct simple and complex equivalent circuit models for fitting EIS data in this Application Note. Nyquist plots are shown for each example.
- AN-EIS-005Electrochemical Impedance Spectroscopy (EIS) Part 5 – Parameter Estimation
In the application note AN-EIS-004 on equivalent circuit models, an overview of the different circuit elements that are used to build an equivalent circuit model was given. After identifying a suitable model for the system under investigation, the next step in the data analysis is estimation of the model parameters. This is done by the non-linear regression of the model to the data. Most impedance systems come with a data-fitting program. In this application note, the way NOVA is uses to fit the data is shown.
- AN-EIS-006Electrochemical Impedance Spectroscopy (EIS) Part 6 – Measuring raw signals in EIS
In this application note, the advantage of recording the raw time domain data for each individual frequency during an electrochemical impedance measurement is described.
- AN-EIS-007EIS Data fitting – How to obtain good starting values of equivalent circuit elements
Electrochemical impedance spectroscopy (EIS) is a powerful technique which provides information about the processes occurring at the electrode-electrolyte interface. The data collected with EIS are modeled with a suitable electrical equivalent circuit. The fitting procedure will change the values of the parameters until the mathematical function matches the experimental data within a certain margin of error. In this Application Note, some suggestions are given in order to get acceptable initial parameters and to perform an accurate fitting.
- AN-EIS-009Mott-Schottky Analysis
This Application Note presents the Mott-Schottky measurement, an extension of electrochemical impedance spectroscopy (EIS), on a popular semiconducting material.
- AN-FC-001Fuel cells part 1 – what is a fuel cell?
A fuel cell is an electrochemical energy conversion device that produces electricity and heat by electrochemically combining a fuel (typically hydrogen) and an oxidant (typically oxygen). The higher efficiency also results in much lower carbon dioxide emissions and negligible amounts of SOx and NOx (when reformed fuel is used) compared with fossil fuel-based technologies for the same power output.
- AN-FC-002Fuel cells part 2 – types of fuel cells
To overcome the various technical problems, many different fuel cell types have been developed. In this Application Note, proton exchange membrane, direct methanol and solid oxide fuel cells are discussed in more detail.
- AN-FC-003Fuel cells part 3 – characterization using EIS
In this Application Note the use of Electrochemical Impedance Spectroscopy (EIS) for the characterisation of PEM fuel will be demonstrated. It will be shown that EIS is a powerful diagnostic tool for the determination of the following factors that can influence the performance of a PEM fuel cell.
- AN-FC-004Impedance Measurements on Fuel Cells and Fuel Cell Stacks at High Currents: Part 1 – Autolab in combination with an electronic load
In this application note, a combination of PGSTAT and electronic load is use to perform electrochemical impedance spectroscopy in a fuel cell operating at high currents.
- AN-FC-005Impedance measurements on fuel cells and fuel cell stacks at high currents: Part 2 – Autolab in combination with an electronic load
The use of impedance measurements on fuel cells under load makes it possible to study the influence of the different fuel cell elements on the behavior and (if detectable) on the ageing of the fuel cell. To perform high current density measurements, the Autolab systems can be connected to a third party electronic load. This extends the measurable range of the instrument by several current decades.
- AN-FC-006i/V characterization of a fuel cell stack, DC measurements at high current densities
The operational behavior of a fuel cell stack is usually evaluated by determining the polarization and power density curves of the cell. These curves provide a quick characterization of the stack performance and an assessment of its optimal operating conditions (temperature, humidity, electrocatalyst, ion-exchange membrane).
- AN-H-012Determination of ferrous ion content of heat exchanger wash solutions
Determination of ferrous ions in heat exchanger and vessel acid wash solutions, for measuring the effectiveness of acid inhibitors used in the solutions. Depending on the condition of the sample, the lower practical limit for the determination will vary from approximately 20-100mg/Kg Fe2+. Samples with high silicic acid contents require relatively large amounts of dilution water to render them mobile, and this limits the aliquot size and hence the amount of Fe2+ which can be analyzed.
- AN-H-079Determination of free acid in heat exchanger cleaning acid
Determination of free acid in sulfuric acid («acid shot») solutions employed in the removal of silicate scale in heat exchangers. This method is suitable for acid shot solutions where the silicic acid content is so high that the solutions have gelled.
- AN-H-089Automated analysis of hexafluorosilicic acid
Automated determination of the H2SiF6 and HF contents of industrial grade hexafluorosilicic acid.
- AN-H-092Analysis of zirconium acetate
Automated determination of the zirconium content of zirconium acetate, as well as other zirconium compounds which can be rendered soluble as zirconium acetate.
- AN-H-098Determination of hydrofluoric acid in silicon etch solutions
This Application Note describes the determination of fluoride in silicon etch solutions with thermometric titration.
- AN-H-100Determination of total acids in highly acidic etch solutions
Determination of the total acids concentration in mixtures of nitric-hydrofluoric acid intended for etching silicon substrates.
- AN-H-114Determination of sulfuric acid, nitric acid, and hydrofluoric acid in etch solutions
Two separate titration sequences are required to analyze the mixture:- titration of the HF content with Al(NO3)3 (the «elpasolite» reaction)- titration of the H2SO4 with BaCl2 followed by titration with NaOH to determine the «total acids» contentThe HF, H2SO4, and «total acids» contents are converted to a HNO3 equivalent, with the HNO3 content found by subtracting the HF and H2SO4 from the «total acids» content.
- AN-H-139Determination of nitric acid, hydrofluoric acid and hexafluorosilic acid in simulated etching baths using thermometric titration
Following the addition of caustic soda, hexafluorosilic acid can be determined through back titration of excess hydroxide with hydrochloric acid. Hydrofluoric acid (hydrogen fluoride) is determined by precipitation with aluminum in the presence of sodium and potassium ions. Nitric acid is determined by subtracting the equivalence concentrations of hexafluorosilic acid and hydrofluoric acid from the total acid concentration.
- AN-K-010Water in coal dust
The water content of coal dust is determined according to Karl Fischer. Because of the low water content of the voluminous sample, the oven method (nitrogen, 270 °C) and coulometric titration have to be used.
- AN-M-007Determination of urea in ultrapure water using IC-MS
Urea is not a typical analyte for ion chromatography. In combination with MS, however, IC is the method of choice for the trace analysis of urea in ultrapure water. This Application Note shows the determination of urea concentrations in the ppb range using the Metrosep C 6 - 250/4.0 column.
- AN-N-005Traces of silica (SiO2) in water (e.g., boiler water) after preconcentration
Determination of silica (as silicate) in pure water with preconcentration using anion chromatography with direct conductivity detection (without any post-column reaction).
- AN-N-037Perchlorate in process water
Determination of perchlorate in process water using anion chromatography with direct conductivity detection.
- AN-N-058LOD and LOQ for silicate and borate determination according to EPA (MDL procedure)
Determination of silicate and borate and their limits of determination (LOD) and quantification (LOQ) according to the EPA procedure for method detection limit (MDL) using anion chromatography with direct conductivity detection and Metrohm Inline Calibration.
- AN-N-065Borate in borate effluent
Determination of borate in a borate effluent using anion chromatography with direct conductivity detection.
- AN-NIR-117Analysis of moisture, ash, carbon, and volatile content in coal by NIRS
Conventional methods used to analyze moisture, ash, fixed carbon, and volatile content in coal samples, are time consuming and costly. Near-infrared (NIR) spectroscopy is excellently suited to determine all parameters simultaneously in less than one minute without any sample preparation.
- AN-O-018Boric acid and acetic acid in process water
Determination of boric acid and acetic acid in process water using ion-exclusion chromatography with conductivity detection after chemical suppression.
- AN-P-058Amines in gas scrubber solutions using IC and pulsed amperometric detection
Scrubber solutions for scrubbing flue gas often contain amines for absorbing acid gases, e.g., sulfur dioxide (SO2). 1-(2-hydroxyethyl)piperazine and 1,4- Bis(2-hydroxyethyl)piperazine from gas scrubber solutions are separated in the Metrosep Carb 2 - 150/4.0 column and then determined using pulsed amperometric detection.
- AN-PAN-1003Online analysis of amines concentration in carbon capture plants
Carbon capture systems strip carbon dioxide from flue gases. Online analysis of amines and carbon dioxide enhances amine usage efficiency and reduces operational costs.
- AN-PAN-1013Online analysis of boric acid in the cooling water of pressurized water reactors
Boric acid requires precise monitoring in the primary circuit to control nuclear reactor reactivity. The 2060 TI Process Analyzer monitors boric acid online in near-real time.
- AN-PAN-1015Calcium and sulfate in flue-gas desulfuration
This Process Application Note deals with the online monitoring of calcium and sulfate in flue gas scrubbing solutions using titration. Other contaminants that can be measured are sulfite, chloride, and chlorine. Low concentrations of heavy metals such as cadmium, zinc, copper, and lead can be measured in the ppb/ppm range with the ADI 2045VA Process Analyzer using voltammetry.
- AN-PAN-1016Online analysis of silica in boiler feed water of power plants
Excessive silica concentrations in the boiler feed water can lead to deposits on turbine blades and must therefore be avoided. Silica analysis is carried out via differential photometry using a leading-edge technology thermostatic cuvette module for non-sample contact at the detector. Typical concentration ranges for silica are 0–50 ppb and 0–1 ppm or higher.
- AN-PAN-1032Monitoring corrosion in power plants with online process analysis
Corrosion in the water-steam circuit of power plants leads to shorter lifetimes of most metal components and potentially dangerous situations. Flow Accelerated Corrosion (FAC) is a specific case, leading to thinned pipes and elevated Fe concentrations in the circuit. Additionally, metal transport issues such as with Cu from copper heat exchangers can lead to deposition on the high pressure turbine blades, decreasing their efficiency. Current methods can monitor but not prevent these issues, and analysis times are extremely long (up to three weeks). In combination with the power plant’s Distributed Control System (DCS), online monitoring of Fe and Cu with the 2060 Process Analyzer from Metrohm Process Analytics ensures that corrosion can be controlled before it affects the power plant efficiency, ultimately decreasing downtime and lowering maintenance costs. Results are offered within 20 minutes, allowing fast adjustments to the water-steam circuit to protect company assets.
- AN-PAN-1038Power generation: Analysis of the m value (Alkalinity) in cooling water
One way to maximize heat transfer efficiency and reduce costs in a power plant is by controlling the water chemistry in the cooling circuit. This cooling water is kept alkaline to maintain the protective oxide layer on the metal piping throughout the water circuit. However alkalinity above the recommended range increases the probability of scale formation (deposition), so it is buffered with carbonate (CO32-) and bicarbonate ions (HCO3-). Titration of the cooling water to pH 4.5 gives the so-called "M-Alkalinity" (methyl orange alkalinity), a measure of total alkalinity. Below this pH, there is no more alkalinity present, only free acid (H+), carbonic acid (H2CO3), and CO2.
- AN-PAN-1040Ammonia in cooling water of thermal power plants
Thermal power plants require enormous amounts of water, using high purity steam at high pressure to rotate turbines. A separate cooling water circuit is implemented, which helps to form a vacuum when the steam condenses after the turbines. Maintaining this vacuum with optimal condensation parameters is critical for the power plant efficiency. The copper condensers are susceptible to corrosion by ammonia, leading to an upper limit of 2 mg/L NH3 set by EPRI in cooling water. Small cracks in the condenser combined with the large pressure differential between the steam circuit and the cooling water circuit will contaminate the high purity water in the boiler, causing major problems and necessitating a shutdown for plant maintenance. Monitoring NH3 online in cooling water with a process analyzer can signal early problems in a plant before significant intermediation is necessary.
- AN-PAN-1042Online trace analysis of anions in the primary circuit of nuclear power plants
Measures to monitor or prevent corrosion are crucial in nuclear power plants, where significant risks to health and safety can occur if corrosion is left unchecked. Anions corrode metals under high temperature and pressure, therefore their concentrations must be monitored at all times. The analytical challenge in the primary circuit is detection of anions in the μg/L range alongside gram quantities of boric acid and lithium hydroxide. Precise, reliable trace analysis requires the method to be automated as much as possible. The 2060 IC Process Analyzer from Metrohm Process Analytics can measure several anions from a single injection, with combined Inline Preconcentration and Inline Matrix Elimination to measure low anion concentrations precisely and reliably time after time.
- AN-PAN-1043Online trace analysis of cations in the primary circuit of nuclear power plants
In power plants, corrosion is the primary factor leading to costly and critical downtimes. In a nuclear power plant, a separate water circuit known as the Pressurized Water Reactor (PWR) ensures radioactive material stays contained while still transferring heat and energy to the other circuits. Boric acid and lithium hydroxide are added specially to the PWR circuit in amounts which can complicate other analytical measurements. Lithium prevents corrosion and must be monitored, along with other cations such as zinc, nickel, and ammonium. In order to measure these cations online at sub-µg/L range in a single analysis, the 2060 IC Process Analyzer is offered with combined Inline Preconcentration and Inline Matrix Elimination. Several cations can be analyzed in a single injection, with automated sample preparation making precise and reliable measurements easier.
- AN-PAN-1044Online trace analysis of amines in the alkaline water-steam circuit of power plants
Neutralizing amines are added to adjust pH levels within the water-steam circuit of power plants to avoid corrosion-inducing conditions. This preventive maintenance can reduce costly and critical downtimes due to corrosion, however frequent monitoring of the amine chemistry is necessary to ensure conditions stay optimal. The 2060 IC Process Analyzer featuring the Metrohm intelligent Partial Loop Technique (MiPT) option is ideal for this application, with the ability to measure trace amounts of the analytes precisely and reliably through an automated method. The benefit of using IC is that multiple analytes can be monitored simultaneously, and here the ability to measure the presence of sodium next to the high ammonium or amine concentrations could indicate that cooling water is seeping into the circuit, indicating a problem upstream.
- AN-PAN-1045Online monitoring of copper corrosion inhibitors in cooling water
Copper is used widely in industrial cooling water systems for its heat transfer properties, although it is susceptible to corrosion. Corrosion can cause a loss of efficiency and eventually a failure of equipment, leading to costly maintenance, replacement, and downtime. Corrosion inhibitors (triazoles) can be added to the water chemistry, which form sparingly soluble protective layers on the surface of the metal. Triazole concentrations must be maintained to protect the copper, which necessitates regular concentration determinations in cooling water. The 2060 IC Process Analyzer with UV/VIS detection is well-suited for this application, able to precisely and reliably measure multiple ionic and UV-active compounds simultaneously in cooling water.
- AN-PAN-1056Online monitoring of sodium in industrial power plants
In power plants, corrosion is the greatest enemy. If corrosive impurities are present in the circuit streams (e.g., chlorides and hydroxides), deposition of an insulating layer of scale on the heat transfer surfaces occurs, resulting in costly and critical downtimes. To ensure high throughput of power plants, online analysis of critical parameters such as sodium is highly advantageous for safety, protection, and process optimization. With the 2035 Process Analyzer from Metrohm Process Analytics, operators gain the information they need to accurately identify trends, reduce downtimes, and address operational issues before costly problems arise.
- AN-PAN-1058Online determination of lithium in brine streams with ion chromatography
Lithium is a soft alkali metal that is typically obtained from salt lake brines. Lithium is used for many applications, but especially for production of lithium-ion batteries in electric cars, mobile phones, and more. This Process Application Note presents a method to monitor lithium as well as other cations in brines by online process ion chromatography (IC), a multiparameter analytical technique that can measure ionic analytes in a wide range of concentrations.
- AN-PAN-1064Monitoring complexing agents in galvanic baths inline with Raman spectroscopy
Accurate analysis of complexing agents in galvanic baths is possible with inline Raman spectroscopy. This Application Note shows an example using a 2060 Raman Analyzer.
- AN-PAN-1066Online analysis of cadmium in incineration plant wet gas scrubbers
Incineration flue gas requires treatment such as wet scrubbing. The 2060 VA Process Analyzer monitors heavy metals in the scrubbing water, ensuring compliance.
- AN-PV-001Dye-Sensitized Solar Cells – i-V and Power Plots with the Autolab Optical Bench
A solar cell or photovoltaic cell is a device that converts light energy into electrical energy. Dye-sensitized solar cells (DSC) are currently the subject of intense research in the context of renewable energies as a low-cost photovoltaic (PV) device. Electricity generated from a PV produces zero emissions, is modular, and can produce energy anywhere the sun shines. The standard characterization technique of a PV device consists in the determination of the DC current-voltage curves under different incident light intensities.
- AN-PV-002Photovoltaics part 2 – dye sensitized solar cells, impedance measurements
DC techniques do not provide any information about the internal dynamics of the PV device. Therefore, additional information can be obtained using time-dependent and frequency-dependent measurements. Electrochemical impedance spectroscopy in particular, offers the possibility to investigate the behavior of the device in the frequency domain under operating conditions, at various light intensities.
- AN-PV-003Dye-sensitized solar cells, IMVS and IMPS measurements
Dye-sensitized solar cells (DSC) are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic (PV) device. To characterize photovoltaic devices, two additional frequency domain methods can be used, based on the modulation of the light intensity. These two methods are Intensity modulated photovoltage spectroscopy (IMVS): measurement of the transfer function between the modulated light intensity and the generated AC voltage, and Intensity modulated photocurrent spectroscopy (IMPS): measurement of the transfer function between the modulated light intensity and the generated AC current.This Application Note illustrates the use of the Metrohm Autolab PGSTAT302N equipped with a FRA32M module, in combination with the Autolab Optical Bench kit to perform IMVS and IMPS characterization of photovoltaic devices.
- AN-PV-004Charge Extraction Method to Study Dye-Sensitized Solar Cells
This application note shows how it is possible with Metrohm Autolab PGSTATs and the Metrohm Autolab Optical Bench, to retrieve information about the mechanism and the kinetics of the back reaction, a side reaction which limits the performances of dye-sensitized solar cells.
- AN-PV-005LED Lights Calibration – Monochromatic LEDs
In this document, a procedure to calibrate the LED light of the Metrohm Autolab Optical Bench is presented. The procedure can be applied to the single-wavelength LED lights. Calibration is performed in order to relate the LED light intensity to the LED driver current. In this way, it is possible to correct the light intensity values when the distance between the solar cell under test and the LED light is changed. Additonally, the calibration allows the user to perform measurements on solar cells while specifying the light intensity values, instead of the LED driver current.
- AN-PV-006Using the Autolab Spectrophotometer for Calibration of the White LED Lights
This Application Note presents the procedure to determine the responsitivity value for calibrating the white lights of the Metrohm Autolab Optical Bench.
- AN-Q-003Online monitoring of trace levels of anions in boiler feed water
Determination of trace levels of chloride, nitrate, phosphate, and sulfate in boiler feed water using anion chromatography with conductivity detection after chemical suppression.
- AN-Q-004Online analysis of trace cations in power plant water matrices
A setup that allows online sampling is crucial for immediate and contamination-free analysis of power plant water samples. This application recommends a setup that facilitates simultaneous anion/cation determinations. Automated inline sample preparation combines variable preconcentration (MiPCT) and calibration with a single multi-ion standard. AN-Q-005 shows the respective anion results.
- AN-Q-005Online analysis of trace anions in power plant water matrices
A setup that allows online sampling is crucial for immediate and contamination-free analysis of power plant water samples. This application recommends a setup that facilitates simultaneous anion/cation determinations. Automated inline sample preparation combines variable preconcentration (MiPCT) and calibration with a single multi-ion standard. AN-Q-004 displays the respective cation results.
- AN-Q-006Online analysis of trace anions in borated water of a pressurized water reactor (PWR)
Water of the primary cycle of pressurized water reactors (PWR) contains boron for neutron absorption. The high borate content interferes with the direct analysis of trace anions. Inline Neutralization combined with variable preconcentration and Inline Matrix Elimination (MiPCT-ME) allows to remove boron as boric acid before injection.
- AN-Q-007Online analysis of chloride and sulfate in supercritical water-steam cycles
A combination of the 850 Professional IC and the 872 Extension Module Liquid Handling opens the field of Metrohm’s online monitoring by IC. In this application, Inline Preconcentration is coupled to Matrix Elimination (MiPCT-ME). By removing excess matrix components, corrosive anions can be sensitively determined. Additionally, this technique allows automated calibration using a single multi-ion standard solution. Online trace analysis for chloride and sulfate is possible for several different sample lines.
- AN-RA-002The carbon battle characterization of screen-printed carbon electrodes with SPELEC RAMAN
Carbon materials are a remarkable choice as electrode surfaces. They are not only cost-effective and chemically inert, but also have a low background current and a wide potential window. Physical and chemical properties of new carbon nanomaterials depend mainly on their structure, so their characterization is essential to choose the right material for different applications.Raman spectroscopy is a very attractive technique for this purpose, effortlessly distinguishing information about the bond structure of carbon materials, and, therefore, about their possible properties. DropSens screen-printed electrodes (SPEs) are low-cost, disposable devices, available with working electrodes fabricated in several carbon materials. This Application Note describes how their properties can be studied by Raman spectroscopy.
- AN-RA-009Comparison of SPELEC RAMAN and standard Raman microscopes
This Application Note compares SPELEC RAMAN and a standard Raman instrument by analyzing their performance in measuring single-walled carbon nanotubes (SWCNT).
- AN-RS-042Revealing battery secrets with EC-Raman solutions
Electrochemical Raman (EC-Raman) spectroscopy enhances comprehension of energy storage devices by tracking physicochemical changes. This note details EC-Raman findings during nickel-metal hydride (NiMH) battery charge and discharge simulations.
- AN-S-005Six anions in cooling water
Determination of fluoride, chloride, nitrite, nitrate, phosphate, and sulfate in cooling water using anion chromatography with conductivity detection after chemical suppression.
- AN-S-032ppt analysis (ng/L) in ion chromatography
Determination of chloride, nitrate, and sulfate in ultrapure water after sample preconcentration using anion chromatography with conductivity detection after chemical suppression.
- AN-S-048Traces of chloride in a technical product containing benzotriazole and sulfuric acid
Determination of traces of chloride in a technical product using anion chromatography with conductivity detection after chemical suppression.
- AN-S-157Trace anions in boiler feed water containing 10 mg/L ammonia
Determination of traces of fluoride, chloride, bromide, nitrate, and sulfate in a boiler feed water containing 10 mg/L ammonia using anion chromatography with conductivity detection after chemical suppression and inline sample preparation by cation exchange.
- AN-S-206Online monitoring of trace anions in boiler feed water
Determination of trace levels of chloride, nitrate, phosphate, and sulfate in a boiler feed water using anion chromatography with conductivity detection after chemical suppression.
- AN-S-218Common anions in a closed cooling water system
Determination of fluoride, chloride, nitrite, nitrate, and sulfate in a closed cooling water system using anion chromatography with conductivity detection after chemical suppression.
- AN-S-222Anions in borate effluent
Determination of fluoride, chloride, nitrate, phosphate, and sulfate in a borate effluent using anion chromatography with conductivity detection after chemical suppression.
- AN-S-228Anions in perfluorocarbon
Determination of fluoride, chloride, nitrate, sulfate, and oxalate in a perfluorocarbon material using anion chromatography with conductivity detection after chemical suppression.
- AN-S-237Phosphor species in process water
Determination of hypophosphite, phosphite, and phosphate in the presence of fluoride, chloride, and sulfate in process water using anion chromatography with suppressed conductivity detection.
- AN-S-242Trace analysis of anions in the primary cycle of a nuclear power plant (PWR) using Metrohm Inline Sample Preparation
Determination of fluoride, glycolate, acetate, formate, chloride, nitrite, nitrate, and sulfate in the primary cycle water of a pressurized water reactor (PWR) using anion chromatography with conductivity detection after chemical suppression calibrated with Metrohm Inline Calibration.
- AN-S-295Anions in boiler water including sulfur speciation (sulfite and sulfate)
Boiler water analysis is an important task in power plant applications. Under the given conditions, the "Metrosep A Supp 10 - 100/4.0" column separates sulfite and sulfate without any organic modifier in the eluent. Even without any stabilizer, sulfite can be determined with a high reproducibility.
- AN-S-306Trace anions including chromate in water-steam cycle of a boiling water reactor (BWR)
Water of the water-steam cycle of boiling water reactors (BWR) needs to be free of corrosive anions. Analyzing these trace anions allows the parallel determination of chromate, which is a potential corrosion product. Automated sample preparation includes variable Inline Preconcentration (MiPCT) and automatic calibration with a single multi-ion calibration standard.
- AN-S-310Short-chain organic acid anions in addition to standard anions applying a Dose-in Gradient and MiPuT
Formate, acetate, propionate, and butyrate in addition to standard anions are determined in a coal extract. To improve the separation of the early eluting organic acid anions, a Dose-in Gradient is applied. Due to the limited sample volume available, Metrohm intelligent Pick-up Technique (MiPuT) is also utilized.
- AN-S-329Anions in FDG gypsum in accordance with VGB-M 701e (consultative document of European Technical Association for the Generation of Electricity and Heat)
FDG gypsum originates from flue gas desulfurization systems in power plants. VGB-M 701 E (2008) describes aqueous extraction methods for determining chloride in FDG gypsum using ion chromatography. The sample preparation described in the VGB permits the determination of other anions besides chloride.
- AN-S-372Analysis of Li-ion battery electrolytes with ion chromatography
Lithium-ion (Li-ion) battery electrolyte quality is essential for performance, stability, and safety reasons. Ion chromatography is an accurate method for electrolyte analysis.
- AN-S-403Anions in lithium-ion battery solvents
N-Methylpyrrolidone (NMP) is crucial for lithium-ion battery production. Metrohm’s intelligent Preconcentration Technique with Matrix Elimination enables µg/L-level anion analysis in NMP.
- AN-SC-001Supercapacitors: Principles and characterization using Autolab
Supercapacitors (also known as ultracapacitors, electrochemical capacitors, or double-layer capacitors) are electrochemical devices that have the ability to store and release charge and deliver high power densities over short periods of time. Their ability to store electrical energy efficiently and release electrical energy very quickly make them ideally suited for applications where short time backup power and peak power needs are critical.
- AN-SEC-004Spectroelectrochemical analysis of electrochromic materials
Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most promising ICPs due to its high conductivity, electrochemical stability, catalytic properties, high insolubility in almost all common solvents and interesting electrochromic properties (transparent in the doped state and colored in the neutral state). In this Application Note, PEDOT film is evaluated by spectroelectrochemical techniques.
- AN-T-027Alkalinity of amine-containing gas washing solutions
Determination of the alkalinity of gas washing solutions containing alkanolamines by potentiometric titration with sulfuric acid using the combined glass electrode.
- AN-T-092Acid number in insulating, transformer and turbine oils – Use of a photometric sensor increases precision and reliability for the determination according to ASTM D974
The acid number (AN) of insulating, transformer, and turbine oils is crucial to ensure safe operation, operating equipment control, and corrosion prevention. These oils generally have low AN specifications and their AN determination by manual color-indicator titration is difficult, especially when analyzing colored samples.Using a Titrator with a photometric sensor to detect the end point ensures that the titrations are always carried out under the same conditions. This greatly increases the precision and reliability of the results, which in turn results in improved monitoring for your operations.
- AN-T-181Lithium in brine
Lithium is a soft metal which is used for many applications, such as production of high-temperature lubricants or heat-resistant glass. Furthermore, lithium is used in large quantities in for battery production. It is obtained from brines and high-grade lithium ores. Depending on the lithium concentration, extraction may or may not be economically viable.This Application Note demonstrates a method to determine the lithium concentration in brines by potentiometric titration. Lithium and fluoride precipitate in ethanol as insoluble lithium fluoride. Using ammonium fluoride as the titrant and a fluoride ion-selective electrode (ISE), determination via potentiometric titration is possible. This method is more reliable, faster, and less expensive than the determination of lithium in brine by other more sophisticated techniques such as atomic absorption spectroscopy (AAS).
- AN-T-201pH value of engine coolants or antirust
Corrosion of metallic components is an inherent problem for engines, because metals naturally tend to oxidize in the presence of water and/or acids. Increased acid content is indicated by a low pH value, and could lead to a variety of problems like a shorter storage life (stability) or a reduced buffer capacity of the used engine coolant or antirust.In this Application Note, engine coolants or antirust samples are dissolved in water, and the pH measurement using the Profitrode is carried out according to ASTM D1287.
- AN-T-202Reserve alkalinity of engine coolants
Corrosion of metallic components is an inherent problem for engines, because metals naturally tend to oxidize in the presence of water and/or low pH value. The reserve alkalinity of engine coolants and antirusts is a measure of the buffering ability to absorb acidity. The reserve alkalinity is frequently used for quality control during production and often listed in the specifications of the coolants. A fast and accurate determination is therefore important.This Application Note describes the straightforward determination of reserve alkalinity according to ASTM D1121. Using a fully automated system allows an accurate and reliable determination due to the reduction of human errors. Furthermore, the operator is free to carry out other tasks increasing the efficiency of the laboratory.
- AN-T-212FOS/TAC in fermentation substrate – Reliable determination for the monitoring of biogas plants
The FOS/TAC value, sometimes referred to as VFA/TA, is a meaningful parameter for assessing both the current condition and the development of anaerobic digestion processes in a digester of a biogas plant. Knowledge of this value can help decrease the risk of acidification problems, which can result in a costly crash of the entire digestion process. Therefore, an accurate and reliable determination of the FOS/TAC value is important for both efficient and cost-effective production operations. This value is determined by an acid-base titration. Using the Eco Titrator from Metrohm equipped with an Ecotrode plus electrode, a reproducible and accurate determination of the FOS/TAC value is possible.
- AN-T-215Assay of lithium hydroxide and lithium carbonate
Lithium salts (e.g., lithium carbonate and lithium hydroxide) are used in myriad applications. Lithium hydroxide is used for the production of lithium stearate, an important engine lubricant. In addition, it is utilized as an air purifier due to its ability to bind carbon dioxide. While the majority of lithium carbonate is used for aluminum production, it is also used for the glass and ceramic industry. It lowers the melting point of these materials, lowering the associated electricity costs and making it cheaper to produce them.For all of these applications, it is important to know the quality of the pure lithium salts used in the various production processes. This Application Note presents an easy method for the assay of lithium hydroxide and lithium carbonate on an automated OMNIS system.
- AN-T-216Assay of lithium nitrate
Lithium nitrate is an oxidizing agent used in the manufacture of red-colored fireworks and flares. In addition, the lithium nitrate trihydrate compound absorbs heat well and can be used for thermal energy storage. Since lithium nitrate is a hygroscopic substance, its purity must first be verified before it is used for synthesis or other applications. The purity assay is done by a fully automated precipitation titration between lithium and fluoride in an ethanolic solution. The benefit of titration is that the lithium nitrate does not need to be diluted after dissolving in ethanol as with other techniques such as ICP-MS.
- AN-T-218Analysis of Li-ion battery cathode materials made from Co, Ni, and Mn
The lithium-ion battery market is continuously growing due to the tremendous demand for battery powered consumer products. So-called «NCMs», a mixture of nickel, cobalt, and manganese oxides, have been gathering interest as cathode materials, replacing traditional compounds like cobalt oxides.Quality analysis of the post-sintered materials or recycled batteries can be performed by titration, as demonstrated in this Application Note. A fully automated analysis of the corresponding metals can be performed with OMNIS and its pipetting equipment.
- AN-T-226Determination of functional groups in graphite and graphene oxide
Boehm titration is a quantitative analysis of functional groups on the surface of carbon materials based on their reactions with basic solutions of NaHCO3 (pKa = 6.4), Na2CO3 (pKa = 10.3), and NaOH (pKa = 15.7). This is a cost-efficient method that gives absolute values with high precision of the accessible, mainly oxygen-containing functional groups on the surface. Originally, Boehm titration was developed for carbon materials like conductive carbon black (CCB), activated carbon, porous carbon, and graphite. Modern carbon-based materials like graphene, graphene oxide (GO), or carbon nanotubes can also be analyzed this way.
- AN-T-235Determination of pH in carbon black
The pH value in carbon black, an essential additive in modern lithium-ion batteries, is accurately and reliably analyzed in this Application Note by using the 913 pH Meter equipped with a Unitrode easyClean according to ASTM D1512 as well as ISO 787-9 and GB/T 1717-1986.
- AN-U-013HEDPA, PBTC, and NTP
Determination of HEDPA, PBTC, and NTP using anion chromatography with UV/VIS detection after post column reaction (PCR).
- AN-U-046Aluminum in an acid extract using UV/VIS detection after post-column reaction with Tiron
Determination of aluminum in an acidic extract containing metals (e.g., alkali, alkaline earth, iron, chromium, molybdenum, etc.) using cation chromatography with UV detection after post-column reaction with Tiron.
- AN-U-048Silicate and hexafluorosilicate
Determination of silicate and hexafluorosilicate (calculated) using anion chromatography with conductivity detection after chemical suppression (see AN S-277) and subsequent UV/VIS detection with post-column reaction. Hexafluorosilicate is hydrolyzed into fluoride and silicate. Both anion concentrations may be used for the calculation of the SiF62- concentration.
- AN-U-059Transition metals in feedwater using post-column reaction and subsequent UV/VIS detection
Feedwater for steam generation in boiling water reactors (BWR) needs to be analyzed for corrosion products. Presence of transition metals, mainly nickel and iron, indicates corrosion problems. Traces of these ions are determined using Inline Preconcentration (MiPCT). After separation, post-column reaction with 4-(2-pyridylazo)resorcinol (PAR) allows VIS detection at 510 nm.
- AN-U-060Corrosion inhibitors in cooling water
In industrial cooling water systems, copper and its alloys are widely used because of their superior heat transfer properties. These materials are, however, susceptible to corrosion. Azoles are commonly used to protect copper and its alloys from corrosion. These corrosion inhibitors are quantified by ion chromatography with UV/VIS detection.
- AN-V-022Antimony and bismuth in an alkaline zinc oxide solution in one run
Simultaneous determination of Sb and Bi in an alkaline ZnO solution.
- AN-V-023Aluminum in an alkaline zinc oxide solution
Determination of Al in alkaline ZnO solution with Eriochrome Blue Black R at 60 °C.
- AN-V-061Iron speciation in water with the Multi-Mode Electrode pro
Accurate determination of Fe(II) and Fe(III) in water is crucial for many industries. Cathodic sweeping voltammetry (CSV) offers a robust, cost-effective solution.
- AN-V-179Iron in boiler feed water
The iron concentration in boiler feed water has to be monitored to ensure reliable and safe operation of the water-steam circuit. Various guidelines set limits for the maximum iron content.The concentration of total iron in boiler feed water can be determined with high sensitivity using adsorptive stripping voltammetry (AdSV) using 2,3- dihydroxynaphthalene (DHN) as complexing agent. Voltammetry is a viable, less sophisticated alternative to atomic absorption spectroscopy (AAS) or inductive couple plasma (ICP) for the determination of iron with only a moderate investment in hardware required and low running costs.
- AN-V-203Determination of copper in electrolyte solutions for production of CIGS solar cells
This Application Note describes the polarograhic determination of copper in electroplating baths used in the production of thin-film copper indium gallium diselenide solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on a molybdenum-coated substrate.Copper analysis is carried out after dilution of the sample with sulfuric acid as supporting electrolyte.
- AN-V-204Determination of indium in electrolyte solutions for production of CIGS solar cells
This Application Note describes the polarographic determination of indium in electroplating baths used in the production of copper indium gallium diselenide thin-film solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on the molybdenum-coated substrate. Indium analysis is carried out after dilution of the bath sample with sulfuric acid as supporting electrolyte.
- AN-V-205Determination of gallium in electrolyte solutions for production of CIGS solar cells
This Application Note describes the determination of gallium in electroplating baths used in the production of copper indium gallium diselenide thin-film solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on a molybdenum-coated substrate. Gallium analysis using anodic stripping voltammetry (ASV) is carried out after dilution of the sample with sulfuric acid as supporting electrolyte.
- AN-V-206Determination of selenite in electrolyte solutions for production of CIGS solar cells
This Application Note describes the polarographic determination of selenite in electroplating baths used in the production of copper indium gallium diselenide thin-film solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on a molybdenum-coated substrate. Selenite analysis is carried out after dilution of the sample with sulfuric acid as supporting electrolyte.
- AN-V-207Determination of cadmium in electrolyte solutions for production of CIS and CIGS solar cells
This Application Note describes the polarographic determination of cadmium in electroplating baths used in the production of copper indium gallium diselenide (CIGS) or copper indium diselenide thin-film solar cells (CIS). Cadmium sulfide (CdS) from the electrolyte solution is deposited as a thin film on the CIS or CIGS absorber layer via chemical bath deposition (CBD).
- AN-V-208Determination of thiourea in electrolytes for production of CIS and CIGS solar cells
This Application Note describes the polarographic determination of thiourea in electroplating baths used in the production of copper indium gallium diselenide (CIGS) or copper indium diselenide thin-film solar cells (CIS). Cadmium sulfide (CdS) from the electrolyte solution is deposited as a thin film on the CIS or CIGS absorber layer via chemical bath deposition (CBD).
- AN-V-239Iron speciation in LiFePO4 batteries
Lithium iron phosphate batteries offer users safety and durability. Polarographic speciation evaluates Fe(II) and Fe(III) in cathode material, useful for several tests.
- TA-019Simultaneous determination of mineral acids, fluoride and silicate in etching baths.
This article describes an ion chromatography method for the simultaneous determination of HF, HNO3, H2SO4, short-chain organic acids, and of H2SiF6 in acid texturing baths.
- TA-020IC-MS and IC-ICP/MS analysis in the environment
This article describes the coupling of ion chromatography with mass spectrometry (IC-MS) and plasma mass spectrometry (IC-ICP/MS) for the trace analysis of potentially hazardous compounds in the environment.
- WP-046Overcoming the aqueous limitation at NIR Spectroelectrochemistry
NIR spectroscopy has been traditionally limited due to the water absorption in this spectral range. In this way, the well-known water restriction has limited the development of new applications for NIR spectroelectrochemistry. In this work, several interesting alternatives are proposed in order to minimize or even to remove the aqueous contribution in this spectral range.
- WP-052A Guide to Li-ion Battery Research and Development
The commercialization of Li-ion batteries in 1991 was the culmination of in-depth R&D conducted by scientists and engineers around the globe over the preceding few decades. Further development of Li-ion batteries and alternative rechargeable batteries has continued until today. As the world is rapidly moving towards a new era defined by green technologies, more practical and accurate R&D is required in order to meet the increasing demands for energy storage systems, specifically from the automotive industry. This white paper presents the basics of the Li-ion battery technology and guides the reader through the relevant techniques and terminologies in Li-ion battery research.
- WP-057FOS/TAC Quotient for the optimization of methane production from biomass
The FOS/TAC value is an important characteristic to assess the status of the fermenter before costly problems arise. The new Eco Titrator from Metrohm allows the determination of this quotient in a fast, cost-efficient, and precise way.
- WP-071Improving the corn to ethanol fermentation process with near-infrared spectroscopy (NIRS)
The fermentation of corn starch to produce ethanol is a complex biochemical process that requires monitoring of many different parameters (e.g., solids, pH, sugar profile, glycerol, lactic and acetic acid, and water and ethanol content). Traditional laboratory analysis using primary methods (e.g. Karl Fischer titration) takes about an hour to complete and is a limiting step for increasing plant capacity and efficiency. As a fast and non-destructive analytical technique, near-infrared spectroscopy (NIRS) can replace routine laboratory analysis, decreasing operating costs and increasing plant efficiency and capacity. This White Paper describes the capabilities of the modern analytical method near-infrared (NIR) spectroscopy for monitoring and improving the fermentation process of corn to ethanol.
- WP-079How to characterize a catalyst? Cyclic voltammetry in action
This White Paper introduces the principles of cyclic voltammetry (CV) and the various ways it can be used for catalyst investigation. A case study and helpful glossary are provided to support your understanding.
- WP-083Hyphenated electrochemical-Raman spectroscopy: Another dimension for your research
White paper about Raman spectroscopy and electrochemistry and their combination (electrochemical Raman).
- WP-084Quality control of analytical parameters in battery production
Lithium-ion batteries (LIBs) are the most common rechargeable options available today. Production of LIBs needs to follow stringent quality standards.
- WP-085Improved antioxidant monitoring of in-service industrial lubricants
Voltammetry (VA) is a fast and established method for testing the remaining antioxidant content in industrial lubricants. The flexible and modular Metrohm VA system setup discussed in this White Paper delivers more repeatable and more reproducible results which fulfill all ASTM requirements. Additionally, users can automate the complete analysis process which makes it possible to run series of samples completely unattended.
- WP-087Green alternative methods for voltammetric analysis in different water matrices
This White Paper presents four different «green» sensors: the scTRACE Gold, screen-printed electrodes, the glassy carbon electrode, and the Bi drop electrode from Metrohm that can be used to determine low concentrations of heavy metals in different sample matrices, such as boiler feed water, drinking water, and sea water.
- WP-089Water content determination in ketones using Hydranal™ NEXTGEN FA reagents
With Hydranal™ NEXTGEN FA reagents, the water content in ketones can be determined quickly and reliably. Compared to other existing KF reagents for ketones on the market, the side reactions are measurably better suppressed.
- WP-095The future of manufacturing and commercializing green ammonia with electrochemistry
Free White Paper outlines the fundamental principles of the nitrogen reduction reaction. It then delves into the technical barriers hindering the industrialization of green ammonia production, their impact on final yield and selectivity, and potential strategies or research gaps to overcome these issues.
- WP-097Why switch to OMNIS Client/Server (C/S)?
OMNIS Client/Server boosts business performance with scalable server management, cutting costs by reducing hardware, energy use, and maintenance across locations.