Applications

In this article portable Raman spectroscopy as an effective tool for at-line characterization of carbon black is presented. Raman spectroscopic analysis can be an effective test to characterize carbon black material, including the structural order.

Raman spectroscopy is used for material characterization by analyzing molecular or crystal symmetrical vibrations and rotations that are excited by a laser, and exhibit vibrations specific to the molecular bonds and crystal arrangements in the molecules. Raman technology is a valuable tool in distinguishing different polymorphs. Examples of portable Raman spectroscopy for identification of polymorphs and in monitoring the polymorphic transiton of citric acid and its hydrated form are presented.

Portable Raman spectroscopy is an invaluable tool in the study of archaeological sites, allowing for in situ analysis which minimizes the impact of such studies on important cultural sites. The flexibility of the use of a fiber optic probe and tripod-mounted video microscope with a light weight instrument reduces the need for sampling, and increases the ability to make representative measurements over what can be very large sample areas. The information content of Raman spectroscopy aids in the understanding of the materials used in the construction and restoration of important archaeological sites, and in understanding the degradation that is occurring which should aid in preservation and restoration work.

For SERS developers and end users of SERS for specific applications to investigate low concetation levels of compounds, the centerpiece of their technological platform must be a Raman setup that provides reliable lab grade performance and is affordable and portable, allowing them to tackle real world problems. The portable i-Raman Plus system coupled with a BAC151 video microscope sampling accessory provides an ideal setup. With the performance and flexibility of use with different laser spot size and power for SERS research.

Raman spectroscopy is an advantageous analytical tool that allows for the measurement of molecular structure and identifying chemical composition of materials based on the rotational and vibrational modes of a molecule. With advanced technology and an optimized optical design, the B&W Tek BAC102 series E-grade probe can access lower frequency modes down to 65 cm-1, providing key information for applications in protein characterization, polymorph detection, and identification, along with material phase and structure determination.

The NanoRam is able to test material through multiple layers of transparent plastic bags. Postive identification of material on PE bags from 1 to 9 layers were obtained, demonstrating minimum interference from the PE bags on the material identification result.

Portable Raman is used to quantify trigonelline, an alkaloid that contributes to the health benefits of some foods. A simple method to quantify the presence of diluted trigonelline in solutions using surface enhanced Raman spectroscopy is described. Portable Raman is a tool that could be used in quality control of food items such as coffee and quinoa.

This article demonstrates the utility of portable Raman spectroscopy as a versatile tool for process analytical technology (PAT) for raw material identification, in-situ monitoring of reactions in developing active pharmaceutical ingredients (APIs), and for real-time process monitoring. Raw material identification is done for verification of starting materials as required by PIC/S and cGMP, and can be readily done with handheld Raman. Portable Raman systems allow users to make measurements to bring process understanding and also provide proof of concept for the Raman measurements to be implemented in pilot plants or large-scale production sites. For known reactions which are repetitively performed or for continuous online process monitoring of reactions, Raman provides a convenient solution for process understanding and the basis for process control.

Urea in widely employed as a nitrogen-release fertilizer with more than 90 % of urea production destined for agricultural applications. Urea is also known to form complexes with fatty acids, which have been employed for separation of complex mixtures and purification processes. In this application note, we present the quantification of the concentration of urea in ethanol by Raman Spectroscopy and show how this method can be employed for determining the percentage of urea in a solid inclusion compound with stearic acid.

A new Raman system design is presented that expands the applicability of Raman to See Through diffusely scattering media such as opaque packaging materials, as well as to measure the Raman spectrum and identify thermolabile, photolabile, or heterogeneous samples.

Edible oils are not only a major source of nutrition but also a key basic material in the food industry. Vegetable oils are increasingly important because of their high content in mono- and polyunsaturated fatty acids in comparison with animal fats. In this application note, the main ingredients of olive oil, camellia oil, arachis oil, sunflower seed oil, and colza oil are analyzed using a portable Raman spectrometer combined with chemometrics software.

See through Raman Spectroscopy (STRaman®) is a newly developed technology that expands the capability of Raman spectroscopy to measure samples beneath diffusely scattering packaging material. The STRaman technology features a much larger sampling area than the confocal approach. This design enhances the relative intensity of the signal from the deeper layers, thereby increasing the effective sampling depth, allowing the measurement of material inside visually opaque containers. The larger sampling area has the additional advantage of preventing sample damage by reducing the power density, as well as improving measurement accuracy by eliminating heterogeneous effect.

Ternary mixtures of aqueous sugar solutions are measured and multivariate models of the concentration of analytes developed using BWIQ software.

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.

In this case study, a suspected counterfeit Adderall pill was measured directly with a TacticID Mobile using a point-and-shoot adapter. The spectra of the suspected couterfeit pill was found to contain cellulose and caffeine, but not the active ingredient. The TacticiD Mobile with 1064-nm laser excitation provides fluorescence suppression, giving those on the front lines a tool in the fight against dangerous counterfeit drugs.

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.

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.

The simultaneous ion chromatographic determination of trace-levels of lanthanides (or lanthanoides) was achieved by using either direct non-suppressed conductivity detection or UV/VIS detection after post-column reaction (PCR) with arsenazo III at 655 nm. Conductivity detection under isocratic conditions resulted in an overall analysis time of approx. 70 minutes. In contrast, the determination of the lanthanides via gradient elution and subsequent spectrophotometric detection of the arsenazo III-lanthanide(III) complexes was performed within 22 minutes. Besides the outstanding analysis time, UV/VIS detection excelled by its enhanced selectivity and sensitivity and did not suffer from interferences by ubiquitous non-lanthanide impurities such as iron(III) or other transition metals. For both conductivity and spectrophotometric detection, the inclusion of sample preconcentration steps lowered the limit of detection (LOD) to the sub-ppb range.

Compared to the classical Epton titration, potentiometrically indicated two-phase titrations using organic-solvent-resistant Surfactrodes can be easily automated and require no toxic and environmentally hazardous chloroform. Even challenging matrices such as fats and oils in bath oils and hair conditioners or strong oxidizing agents in washing powder and industrial cleaners do not interfere with the titration of the ionic surfactants. Results obtained show excellent agreement to those of the Epton titration. Irrespective of the matrix, relative standard deviations of threefold determinations are all below 2.1%. While the Surfactrode Resistant is mainly used for oil-containing formulations, the Surfactrode Refill is ideal for washing powders and soaps. Both electrodes excel by their ruggedness and allow the rapid and precise determination of anionic and cationic surfactants.

In modern days, a new breed of energetic (explosive) materials is emerging. Traditional aromatic nitrates are still in use, but there is dire need of analytical techniques for energetic materials in the chemical class of peroxides, azo etc. This presentation will demonstrate the use of a modern HPLC system with traditional detector (DAD) and also coupled with mass spectrometry for the analysis of abovementioned various classes of energetic materials.

Three different suppressor systems are compared in terms of sensitivity. Additionally, binary gradient elution was applied to analyze phosphates in the presence of mono- and divalent ions.

Thermometric titration can solve application problems that potentiometry cannot solve at all, or at least not satisfactorily.

This poster describes a method for automated and precise dosing of liquid samples into the Karl Fischer titration cell using Metrohm Dosino liquid handling technology. First, the titer was automatically determined with ultrapure water. The same dosing procedure proved valuable for the automated water determination in highly viscous water-glycol fluids and low-boiling organic solvents such as n-pentane. Lastly, the method copes with the labor-intensive and human error-prone suitability test stipulated in chapter 2.5.12 in the European Pharmacopoeia.

The poster shows the use of Vis-NIR spectroscopy for the simultaneous quantification of cobalt content, solids content, relative density and viscosity in paint driers as an outstanding alternative to conventional wet chemical laboratory methods. The advantages of the expanded wavelength range over the visible range become clear in this application: the visible range (400 – 780 nm) correlates directly with the cobalt content; the NIR range (780 – 2500 nm) is used for determining the chemical and physical parameters.

A method for the potentiometric determination of CaCO3 in cement raw meal is described, in which the accurately weighed-out sample is treated with HCl, heated to boiling and the excess HCl is then back-titrated with NaOH.

A potentiometric, nonaqueous method is described for analyzing nitrating acid using cyclohexylamine as titrant. Both sulfuric and nitric acid can be determined quantitatively.

The potentiometric titration of Kjeldahl nitrogen is one of the most common analytic procedures. It is referenced in numerous standards, ranging from the food and animal feed industries through sewage and waste analysis and all the way to the fertilizer industry. As a rule, the samples are digested with concentrated sulfuric acid with the addition of a catalyst. The ammonium sulfate that is formed is distilled as ammonia in alkali solution, collected in an absorption solution and titrated there.This Bulletin provides a detailed description of potentiometric nitrogen determination following distillation of the digestion solution, followed by a discussion of the possibilities of coulometric titration (without distillation).

As much as the many types of cement may differ from one another, the characteristic that all of them have in common is the presence of the elements calcium, magnesium, iron, aluminum and silicon.Calcium, magnesium, iron and aluminum can be determined using various indicators following digestion of the cement sample using photometric titration with the Optrode at 610 nm. The determination of silicon, on the other hand, is gravimetric.

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.

Halides interfere with most determinations of mercury or silver. However, if mercury or silver is titrated with sulfide ions, extremely insoluble sulfides are formed.A simple method is described that allows the direct titration of mercury(II) or silver(I) compounds in the presence of halides. The potentiometric titration takes place under alkaline conditions using thioacetamide as the titrant after formation of the EDTA complex.Organic compounds that are insoluble in alkaline EDTA can also be titrated after a Schoeniger digestion.

This Application Bulletin gives an overview of the volumetric water content determination according to Karl Fischer. Amongst others, it describes the handling of electrodes, samples, and water standards. The described procedures and parameters comply with the ASTM E203.

The potassium (or ammonium) ion is precipitated with sodium tetraphenyl borate, and the excess of this reagent back-titrated against the thallous(I) ion, using biamperometric endpoint detection. Ammonium can either be titrated together in an acid solution, or driven off by previous boiling in an alkaline solution. Methods are given for determining potassium in the presence of large excesses of sodium, ammonium, calcium, and magnesium.

This Bulletin describes the complexometric potentiometric titration of metal ions. An ion-selective copper electrode is used to indicate the endpoint of the titration. Since this electrode does not respond directly to complexing agents, the corresponding Cu complex is added to the solution. With the described electrode, it is possible to determine water hardness and to analyze metal concentrations in electroplating baths, metal salts, minerals, and ores. The following metal ions have been determined: Al3+, Ba2+, Bi3+, Ca2+, Co2+, Fe3+, Mg2+, Ni2+, Pb2+, Sr2+, and Zn2+.

It has been known for years that consuming too much nitrates from foodstuffs can result in cyanosis, particularly for small children and susceptible adults. According to the WHO standard, the hazard level lies at a mass concentration c(NO3-) ≥ 50 mg/L. However, more recent studies have shown that when nitrate concentrations in the human body are too high, they can (via nitrite) result in the formation of carcinogenic and even more hazardous nitrosamines.Known photometric methods for the determination of the nitrate anion are time-consuming and prone to a wide range of interferences. With nitrate analysis continually increasing in importance, the demand for a selective, rapid, and relatively accurate method has also increased. Such a method is described in this Application Bulletin. The Appendix contains a cselection of application examples where nitrate concentrations have been determined in water samples, soil extracts, fertilizers, vegetables, and beverages.

After acid digestion, the sample solution is neutralized with sodium hydroxide to form sodium dihydrogen phosphate. An excess of lanthanum nitrate is added and the released nitric acid is then titrated with sodium hydroxide solution.NaH2PO4 + La(NO3)3 → LaPO4 + 2 HNO3 + NaNO3This determination method is suitable for higher phosphate concentrations.

Potentiometric titration is an accurate method for determining chloride content. For detailed instructions and troubleshooting tips, download our Application Bulletin.

Although the known photometric methods for the determination of ammonia/ammonium are accurate, they require a considerable amount of time (Nessler method 30 min, indophenol method 90 min reaction time). A further disadvantage of these methods is that only clear solutions can be measured. Opaque solutions must first be clarified by time-consuming procedures. These problems do not exist with the ion-selective ammonia electrode. Measurements can be easily performed in waste water, liquid fertilizer, and urine as well as in soil extracts. Especially for fresh water and waste water samples several standards, such as ISO 6778, EPA 350.2, EPA 305.3 and ASTM D1426, describe the analysis of ammonium by ion measurement. In this Application Bulletin, the determination according to these standards is described besides the determination of other samples as well as some general tips and tricks on how to handle the ammonia ion selective electrode. Determination of ammonia in ammonium salts, of the nitric acid content in nitrates, and of the nitrogen content of organic compounds with the ion-selective ammonia electrode is based on the principle that the ammonium ion is released as ammonia gas upon addition of excess caustic soda:NH4+ + OH- = NH3 + H2OThe outer membrane of the electrode allows the ammonia to diffuse through. The change in the pH value of the inner electrolyte solution is monitored by a combined glass electrode. If the substance to be measured is not present in the form of an ammonium salt, it must first be converted into one. Organic nitrogen compounds, especially amino compounds are digested according to Kjeldahl by heating with concentrated sulfuric acid. The carbon is oxidized to carbon dioxide in the process while the organic nitrogen is transformed quantitatively into ammonium sulfate.

This Application Bulletin gives an overview of the coulometric water content determination according to Karl Fischer.Amongst others, it describes the handling of electrodes, samples, and water standards. The described procedures and parameters comply with the ASTM E1064.

This Bulletin describes three potentiometric, one photometric, one thermometric and one conductometric titration method for sulfate determination. The question of which indication method is the most suitable depends primarily on the sample matrix.Method 1: Precipitation as barium sulfate and back titration of the Ba2+ surplus with EGTA. Use of the ion-selective calcium electrode as indicator electrode.Method 2: As with Method 1, although with the electrode combination tungsten/platinum.Method 3: Precipitation titration in semi-aqueous solution with lead nitrate in accordance with the European Pharmacopoeia using the ion-selective lead electrode as indicator electrode.Method 4: Photometric titration with lead nitrate, dithizone indicator and the Optrode 610 nm, particularly suitable for low concentrations (up to 5 mg SO42- in the sample solution).Method 5: Thermometric precipitation titration with Ba2+ in aqueous solution, particularly suitable for fertilizers.Method 6: Conductometric titration with barium acetate in accordance with DIN 53127

Application Bulletin AB-076 contains a description of the polarographic determination of low concentrations (1–100 mg/L) of NTA and EDTA in bodies of water. NTA, EDTA and citrate have gained in importance as complexing agents and builders due to the fact that the laws of some countries have made it necessary to find a substitute for phosphates in detergents.This Bulletin describes the determination of larger quantities of complexing agents in detergents using potentiometric titration. The ion-selective copper electrode (Cu-ISE) is used here as the indicator electrode. The determination of complexing agents is not disturbed by the other constituents often present in detergents.

The bromine number and bromine index are important quality control parameters for the determination of aliphatic C=Cdouble bonds in petroleum products. Both indices provide information on the content of substances that react withbromine. The difference between the two indices is that the bromine number indicates the consumption of bromine in gfor 100 g sample and the bromine index in mg for 100 g sample.This Application Bulletin describes the determination of the bromine number according to ASTM D1159, ISO 3839, BS2000-130, IP 130, GB/T 11135 and DIN-51774-1. The bromine index determination for aliphatic hydrocarbons is described according to ASTM D2710, IP 299, GB/T 11136 and DIN 51774-2. For aromatic hydrocarbons the determination of the bromine index is described according to ASTM D5776 and SH/T 1767. UOP 304 is not recommended for the determination of the bromine number or bromine index because its titration solvent contains mercuric chloride.

Formaldehyde can be determined reductively at the DME. Depending on the sample composition it may be possible to determine the formaldehyde directly in the sample. If interferences occur then sample preparation may be necessary, e.g. absorption, extraction, or distillation.Two methods are described. In the first method formaldehyde is reduced directly in alkaline solution. Higher concentrations of alkaline or alkaline earth metals interfere. In such cases the second method can be applied. Formaldehyde is derivatized with hydrazine forming the hydrazone, which can be measured polarographically in acidic solution.

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.

Anionic surfactants can be titrated with cationic surfactants and vice-versa. The Bulletin describes a multitude of substances that can be determined in this fashion and specifies the respective working conditions and parameters. In contrast to the classic two-phase titration in accordance with Epton, the titration with the anionic and cationic surfactants electrodes can be performed without chloroform. Furthermore, the equivalence point of the titration is difficult to determine in some cases with the Epton method and the titration cannot be automated.In many cases, a surfactant ISE is a remedy that is both environmentally friendly and suitable here. It was developed specially for application with potentiometrically indicated surfactant determinations.

The two potentiometric titration methods described here allow the determination of the content of commercial betaine solutions. Neither method is suitable for determining the betaine content of formulations. The possibilities and limits of both methods are described and distinctive features and possible sources of interference are mentioned. The Bulletin explains the most important theoretical principles and is intended to help users to develop their own product-specific titration methods.

The present Bulletin offers an overview of the multitude of surfactants and pharmaceuticals that can be determined with potentiometric titration. Metrohm provides five different surfactant electrodes for indicating the titration endpoint: the Ionic Surfactant, the High Sense, the Surfactrode Resistant, the Surfactrode Refill and the NIO Surfactant electrode. The manufacture of the respective titrants and their titer determination are described in detail. In addition to this, the Bulletin contains a tabular overview of more than 170 proven applications from the area of surfactant and pharmaceutical analysis. This guideline leads you reliably to your destination: At a glance you can see from the table which surfactant electrode and which titrant are optimally suitable for your product.

On the basis of a multitude of practical examples, this Bulletin describes the potentiometric two-phase titration of ionic surfactants in raw materials and many other formulations.Two surfactant electrodes – the Surfactrode Resistant and the Surfactrode Refill – make it possible to perform this type of surfactant titration, analogous to the classic "Epton titration", with a high degree of automation. The achieved results correlate very well with those of Epton titration. The toxic, carcinogenic and environmentally hazardous chloroform can be replaced by other solvents such as methyl iosbutyl ketone or n-hexane.

Two-phase titration with potentiometric indication is a universal method for the determination of ionic surfactants in detergents. The results obtained are comparable to those with the classic two-phase titration in accordance with Epton (mixed indicator system disulfine blue / dimidium bromide). The present Bulletin addresses various parameters that could have an influence on potentiometric surfactant titration. The information provided makes it possible for the user to determine precisely the anionic surfactant content in practically all formulations.

Sulfate can be rapidly and easily titrated thermometrically using a standard solution of Ba2+ as titrant. In industry, the widespread procedure is applied to the determination of sulfate in wet-process phosphoric acid. This bulletin deals with the determination of sulfate in granular fertilizers such as MAP (monoammonium phosphate), DAP (diammonium phosphate) and TSP (triple superphosphate). Results are reported as percentage of elemental sulfur, %S.

Sulfate can be rapidly and easily titrated thermometrically using a standard solution of Ba2+ as titrant. In industry, the widespread procedure is applied to the determination of sulfate in wet-process phosphoric acid.