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NIR spectroscopy: a 21 CFR Part 11 compliant tool for QC and product screening

NIR spectroscopy: a 21 CFR Part 11 compliant tool for QC and product screening

Pharmacology: a brief history

Our search for medicines is nearly as old as humanity itself. Medicinal ingredients from plant, mineral, and animal sources were used for healing purposes since the earliest of advanced civilizations. Herbal remedies from China date back to a couple of thousand years ago, while indigenous populations have been relying on environmental sources for healing for several millennia. Systematic descriptions of medicines have been handed down to us from the ancient Greeks and the Roman Empire, laying a foundation for contemporary pharmacology. It was not until the 16th century that the science began its departure from the models passed down from antiquity.

The path to developing synthetic drugs began with the emergence of organic chemistry at the beginning of the 19th century. Although drug therapies had been limited to naturally occurring substances and inorganic compounds up to that point, this changed with the targeted production of organic synthetic drugs based on substances isolated from medicinal plants. Within a very short period, this led to a vast number of synthesized active pharmaceutical ingredients (APIs). Researchers had finally come to understand the relationship linking the action of these substances to their chemical structures.

Pharmaceutical analysis provides information about the identity, purity, content, and stability of starting materials, excipients, and APIs. Medicinal products come in various forms (e.g., ointments, tinctures, pills, lotions, suppositories, infusions, sprays, etc.) and consist of the active substance and at least one pharmaceutical excipient. Impurities are mainly introduced during the synthesis of the active ingredients.
According to the World Health Organization (WHO), specifications and test methods for commonly used active ingredients and excipients are outlined in detail in monographs contained in the national pharmacopoeias of more than 38 countries. The pharmacopoeias are official compendia containing statutory requirements pertaining to identity, content, quality, purity, packaging, storage, and labeling of active pharmaceutical ingredients and other products used for therapeutic purposes. They are essential for anyone seeking to produce, test, or market medicinal products.

Near-infrared spectroscopy—a 21 CFR Part 11 compliant tool to assess the quality of pharmaceuticals

Near-infrared spectroscopy (NIRS) has been an established method for fast and reliable quality control within the petrochemical industry for more than 30 years. However, many companies still do not consistently consider the implementation of NIRS in their QA/QC labs. The reasons could be either limited experience regarding application possibilities or a general hesitation about implementing new methods.

However, the advantages of NIRS are numerous, such as the ability to measure multiple parameters in just 30 seconds with no sample preparation! The non-invasive light-matter interaction used by NIRS, influenced by physical as well as chemical sample properties, makes it an excellent method for the determination of both property types.

In the remainder of this post, we will indicate where NIRS technology can be used in the pharmaceutical production process and what parameters can be analyzed. Furthermore, we present proven applications developed according the NIRS implementation guidelines of ASTM E1655 (quantitative method development) and ASTM E1790 (qualitative method development).

For more detailed information about NIRS as a secondary technique and NIRS as a QC tool for pharmaceuticals, please read our previous blog posts.

NIRS compliance with international pharmacopoeias

As a secondary test method, NIRS is recommended in all the key pharmacopoeias – European (Ph. Eur. 2.2.40) as well as American (USP<856/1856>) and Japanese pharmacopoeias (Chapter 6, since 2007).

All Metrohm NIRS instruments are fully compliant with USP <856/1856> and all the other key pharmacopoeias. Furthermore, all Metrohm NIRS instruments meet the standards for wavelength precision, reproducibility, and photometric noise. Numerous reference standards and user-friendly software make it easy to check the instrument requirements specified in the pharmacopoeias. The pharmaceutical version of the Vision Air software is fully validated and compliant with 21 CFR Part 11.

Find out more about Metrohm NIRS instruments for laboratory and process analysis below.

Where can NIRS be used in pharmaceutical manufacturing processes and what parameters can be analyzed?

NIRS is an indispensable analysis technique that can be used along the entire production chain: from checking the incoming materials to the production line, even to the quality control of finished products. A typical pharmaceutical tablet production process is shown in Figure 1 with markers noting where NIRS can be implemented.

Figure 1. Illustration of a pharmaceutical tablet production plant with NIRS used all along the process.
Typical NIRS applications at the different stages of the pharmaceutical production process are outlined in Figure 2.
Figure 2. NIRS analysis can be used at several points in the pharmaceutical manufacturing process for many types of applications.
Relevant application notes can be found on the Metrohm website.

Applications and parameters for NIRS in pharmaceutical production

NIR spectroscopy is the fast solution for determining myriad parameters simultaneously in almost any sample matrix. In addition, this technique requires no sample preparation, and it is non-destructive. Table 1 contains a list of different administered forms of medications given with commonly measured parameters and related materials to download for more information.

Table 1. NIRS can be used to determine several parameters in many kinds of administered forms of pharmaceuticals.
Substance form Parameter Conventional method Related NIRS Application Notes
Powders or granulates API, Moisture HPLC / GC / KF titration AN-NIR-018

AN-NIR-014

Tablets and capsules API, Content uniformity, Moisture content, Dissolution profile HPLC / GC / KF titration AN-NIR-073

AN-NIR-066

AN-NIR-063

AN-NIR-017

Creams or gels API, Moisture content HPLC / GC / KF titration AN-NIR-020
Solutions or suspensions API HPLC / GC AN-NIR-088

AN-NIR-076

Injectables API HPLC / GC AN-NIR-042
Lyophilized products Moisture content KF titration AN-NIR-078
Following are a few examples of successfully implemented NIRS applications at numerous pharmaceutical companies worldwide.
Incoming (raw) material inspection

Raw material identification and qualification, shown in Figure 3, is one of the most mature applications in the pharmaceutical industry. Good manufacturing practice requirements demand that every single package unit that arrives in the warehouse needs to be checked.  Therefore, a rapid analytical technology as NIR spectroscopy is needed to measure many samples in a short period of time. NIRS is a general accepted alternative method by the USP.

Figure 3. Raw material inspection by NIR spectroscopy.
NIRS is an ideal analytical method for raw material inspection:

  • identify tests of APIs, excipients, packaging
  • quantitative control of materials (e.g., moisture)
  • GMP Requirement to test 100% of raw materials
  • quality control of materials (e.g., supplier, particle size, dyes)
Blending

Blending of APIs and excipients can be easily monitored without sample destruction by NIRS (Figure 4). This application focuses on the standard deviation between consecutive spectra. As the blending proceeds, the differences between consecutive spectra will become smaller and smaller, approaching unity. This parameter indicates when the blend is homogeneous. This information is important for operators to optimize the blending time and consequently increase the blending capacity of a facility.

Figure 4. Blending of APIs and excipients is easier to monitor with NIRS.
NIRS is an ideal analytical method for blending processes:

  • determination of blend homogeneity
  • sample spectra statistically compared to library of well blended material
  • optimized blending for improved operation of next production steps
Learn more about the Metrohm NIRS DS2500 Analyzer here.
Lyophilized products

Moisture determination in lyophilized products is an ideal application for NIRS (Figure 5). Typical water content of lyophilizates is somewhere between 0.5% and 3.0%. For many pharmaceutical lyophilized products, this value must be lower than 2.0%. Water is a strong NIR absorber, so detection limits are low and the demands of the pharmaceutical industry can be easily met.

Primary methods like loss on drying (LOD) or Karl Fischer titration are typically time-consuming, especially compared to NIRS (data in seconds). These samples have a relatively high value combined with a low moisture content. NIRS analysis only illuminates the sample so the same sample can be used for compendial analysis without any damage. This application has a quick return on investment (ROI) due to the high sample frequency.

Figure 5. Moisture determination in lyophilized products with NIRS is fast and cost-effective compared to other techniques.
NIRS is an ideal analytical method for measuring moisture in lyophilized products:

  • samples can be easily altered to provide calibration sets with varying amounts of moisture
  • complete analysis takes less than one minute and is non-destructive
Tablet analysis

When analyzing intact tablets with a NIR spectrometer, it is important to measure them in diffuse transmission mode. This illuminates a larger sample big portion and investigates the inner composition of the tablet (Figure 6). Measuring the same tablet in reflectance mode will gather the information from the outside coating of the tablet due to the low penetration depth. Content uniformity parameters are measured within a minute, and the tablet trays allow unattended measurement of up to 30 tablets.

Figure 6. NIRS allows fast determination of API content in intact tablets.
Learn more about the differences in NIRS measurement modes in our previous blog post.

Summary

Near-infrared spectroscopy has long been one of the most important and versatile analytical techniques in the pharmaceutical industry. The biggest benefit of using NIRS is the possibility of obtaining reliable analysis results in just seconds without any sample preparation or reagents required.

The pharmaceutical version of Vision Air software from Metrohm is 21 CFR Part 11 compliant and compatible with third party method development software like Unscrambler.

For more information

About spectroscopy solutions provided by Metrohm, visit our website!

We offer NIRS for lab, NIRS for process, as well as Raman solutions

Post written by Wim Guns, International Sales Support Spectroscopy at Metrohm International Headquarters, Herisau, Switzerland.
Ion-selective electrodes: General tips – Part 1

Ion-selective electrodes: General tips – Part 1

Ions – we encounter these tiny charge carriers constantly. Depending on the concentration of certain anions (negative ions) and cations (positive ions), they can have a significant impact on humans and the environment. Thanks to ongoing quality control in several industries such as food and beverage, the metallurgical industry, and water management, defined limits are neither exceeded nor undercut.
So, how can these small, ubiquitous ions be determined? Mistakenly, I thought at first that ion measurement is only possible by means of more costly analytical methods such as ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP-OES), or atomic absorption spectroscopy (AAS). A promising cost-efficient alternative to these techniques is to use so-called ion-selective electrodes (ISE).

Types of ion-selective electrodes

If you want to determine, for example, the fluoride concentration in your toothpaste, the ammonium content of the water in your aquarium, or perhaps how much calcium is really in a fruit juice, then there are many suitable ion-selective electrodes for your application needs.

Membrane material

The very first ion-selective electrode was the pH electrode. However, this article will not discuss pH electrodes—you can find more information in our other posts pertaining to this special ISE.

Aside from the glass membrane used for pH electrodes, there are other membrane materials available for selective measurement of myriad ions. The most widely applied types are listed in Table 1.
Table 1. Various types of ion-selective electrodes.
Membrane material Description Ions Close-up view
Crystal membrane Crystal lattice containing defined gaps for the ion to be measured. Ag+, Cu2+, Pb2+, Br, Cl, CN, F, I, S2-
Polymer membrane Polymer membrane containing a molecule (ionophore) that only binds the ion to be measured. Ca2+, K+, Na+, surfactants, NO3
Glass membrane Framework of silicate glass with interstitial sites for H+ and Na+. Na+, H+
Gas permeable membrane Membrane acts as a permeable barrier through which only specific substances can move across. NH4+
The membrane material can limit the possible matrices in which the ISE can be used. For example, electrodes with a polymer membrane cannot be used to measure ions in organic solvents. For more information on the specific restrictions, check the user manual of your ISE.

Basic theory behind ISEs

Measuring range

Each electrode type has its own specific measuring range (see Table 2). Before beginning any ion measurement, first ensure that the ion-selective electrode is able to measure in the concentration range of the sample.

Table 2. Each ion-selective electrode has its specific measuring range. Note: The given measuring ranges only apply to ion-selective electrodes from Metrohm.
Cation of interest Measuring range
Ag+ 1×10–7 – 1 mol/L
Ca2+ 5×10–7 – 1 mol/L
Cd2+ 1×10–7 – 10–1 mol/L
Cu2+ 1×10–8 – 10–1 mol/L
H+ 1×10–14 – 1 mol/L
K+ 1×10–7 – 1 mol/L
Na+ (Polymer)

Na+ (Glass)

5×10–6 – 1 mol/L

1×10–5 – 1 mol/L

NH4+ 5×10–6 – 10–2 mol/L
Pb2+ 1×10–6 – 10-1 mol/L
Anion of interest Measuring range
Br 1×10–6 – 1 mol/L
Cl 1×10–5 – 1 mol/L
CN 8×10–6 – 10–2 mol/L
F 1×10–6 – sat. mol/L
I 5×10–8 – 1 mol/L
NO3 1×10–6 – 1 mol/L
S2- 1×10–7 – 1 mol/L
However, something more important than the measuring range is the linear range. Figure 1 illustrates a measuring range which also includes a linear range. Within this linear range the Nernst equation applies, and the signal is proportional to the analyte concentration. By performing an ion measurement within the linear range, the most precise and reproducible results will be obtained. Find out more about the Nernst equation in our previous blog post.
Figure 1. The measuring range of an electrode.
Outside of the linear range, the curve becomes flatter, and the potential difference becomes smaller, preventing a reliable measurement by standard addition. Even in this non-linear, flattened range, it is possible to determine the ion concentration by means of direct measurement – provided that your ion-selective electrode is also calibrated for this range.

If the concentration is too low or the sensor is saturated, this situation is considered outside of the measuring range. Potential changes can no longer be determined.

Interfering ions

Compared to a pH electrode with a linear range over 14 decades, the sensitivity of ISEs is limited since interfering ions reduce the linear and measuring ranges (see Figure 1).

There are two different types of interfering ions, both outlined in Table 3.

Table 3. Types of interfering ions and their impact on measurement with ISEs.
Interfering ion Description Impact
Irreversible
  • Binds to the membrane material and reacts with it or
  • Forms complexes and precipitates with the measuring ion
Destruction of the ISE since the irreversible interfering ion reacts with the membrane and is unavailable for further analysis.
Reversible
  • Exhibits cross-sensitivities
Erroneous results since the reversible interfering ion binds to the membrane material and contribute to the signal.
Nowadays, the most important interfering ions for an ISE are known, and information about them is provided by the sensor manufacturer. For the measurement, the impact of interfering ions is considered in a so-called selectivity coefficient, which in turn is used in the Nikolsky equation—an expanded version of the Nernst equation.
Table 4. Each ion to be measured has at least one interfering ion that must be considered when setting up an experiment.
Measuring cation Interfering ion(s)
Ag+ Hg2+, proteins
Ca2+ Na+, Pb2+, Fe2+, Zn2+, Cu2+, Mg2+
Cu2+ Ag+, Hg2+, S2-, Cl, Br, I, Fe3+, Cd2+
K+ Na+, NH4+, Cs+, Li+, H+
Na+ (Polymer)

Na+ (Glass)

SCN, acetate

H+, Li+, K+, Ag+

Pb2+ Ag+, Hg2+, Cu2+, Fe3+, Cd2+
Measuring anion Interfering ion(s)
Br Hg2+, I, S2-, CN, NH4+, S2O32-
Cl Hg2+, Br, I, S2-, CN, NH4+, S2O32-
CN S2-, Ag+ complexing substances, I, Cl, Br
F OH
I Hg2+, S2-, CN, Cl, Br, S2O32-
NO3 Br, NO2, Cl, acetate
S2- Hg2+, proteins
Some examples for the most important interfering ions of ISEs are listed in Table 4. For more information on the theoretical background of pH as well as ion-selective electrodes, download our free monograph below.

Ionic strength adjustment

The measurement depends on the activity of the measuring ion in solution, which in turn depends on the ionic strength. For this reason, ion-selective measurements are always carried out in solutions with approximately the same ionic strength. By addition of ionic strength adjuster (ISA) or total ionic strength adjustment buffers (TISAB), a constant ionic background can be achieved.

ISA and TISAB are chemically inert respective to the measurement, and they contain a relatively high concentration of salt so that the ionic strength of the sample solution can be neglected. Some examples can be found in Table 5. Check the user manual of your ISE to find its ideal ISA or TISAB solution.

Table 5. Recommended ISA and TISAB solutions for ion-selective electrodes and further information about each procedure.
Ion to be measured ISA / TISAB Further information about procedure
Fluoride (F) NaCl / glacial acetic acid / CDTA Application Bulletin AB-082
Potassium (K+) c(NaCl) = 0.1–1 mol/L Application Bulletin AB-134
Sodium (Na+), glass membrane c(Tris(hydroxymethyl)aminoethane) = 1 mol/L Application Bulletin AB-083
Sodium (Na+), polymer membrane c(CaCl2) = 1 mol/L
Ammonium (NH4+) c(NaOH) = 10 mol/L Application Bulletin AB-133

Electrode maintenance and lifetime

Cleaning the ISE
DO:
  • After each measurement or titration, the ISE has to be rinsed thoroughly with distilled water.
DON’T:
  • Never use organic solvents for cleaning. They may attack or irreversibly destroy the polymer membrane ISE or reduce the lifetime of your crystal membrane ISE.
Conditioning the ISE

Conditioning steps must be performed before the first use as well as in between measurements. This step activates the measuring membrane and provides a stable equilibrium of the measuring ion in the membrane. By doing so, an accurate ion measurement is possible. An ion standard solution with a concentration of c(ion) = 0.01 mol/L is recommended as the conditioning solution.

Storing the ISE

An overview of proper storage instructions for your ion-selective electrode is shown in Table 6. For more detailed information, check the ISE manual.

Table 6. Recommended storage conditions for different ISE types.
Membrane material Short storage period Long storage period
Crystal membrane In c(ion) = 0.1 mol/L Dry, with protective cap
Polymer membrane Dry Dry
Polymer membrane, combined In c(ion) = 0.01–0.1 mol/L Dry, with some residual moisture
Glass membrane In c(ion) = 0.1 mol/L In deionized water
Lifetime of an ISE

The lifetime of an ion-selective electrode depends on several influencing parameters including membrane type, sample matrix, and electrode maintenance. Don’t forget to regularly exchange the electrolyte of your combined ISE or – in case of a separate ISE – your reference electrode. Furthermore, never touch the membrane with bare fingers.

In general, the following can be said:

  • Polymer membrane electrodes: Limited lifetime of about half a year since the membrane ages, resulting in a loss of performance.
  • Crystal membrane electrodes: Lifetime of several years – the membrane can be regenerated by polishing using an appropriate polishing material. Watch the video below for more details.

Summary

  • If you decide to perform an ion measurement using an ion-selective electrode, you must consider the measuring range and any interfering ions that may be present in advance.
  • In addition to the membrane type and the sample matrix, the cleaning, storage, and conditioning all have an influence on the lifetime of your ion-selective electrode.
Hungry for more information regarding direct measurement and standard addition? Check out Part 2 (coming soon!) where we will discuss the different determination methods.

Can’t wait? Download our free White Paper: «Overcoming difficulties in ion measurement: Tips for standard addition and direct measurement».

Free White Paper:

Overcoming difficulties in ion measurement: Tips for standard addition and direct measurement
Post written by Doris Hoffmann, Product Manager Titration at Metrohm International Headquarters, Herisau, Switzerland.
Five myths about online dispersive NIR spectroscopy, FT-NIR, and FT-IR – Part 1

Five myths about online dispersive NIR spectroscopy, FT-NIR, and FT-IR – Part 1

Spectroscopy is not just spectroscopy—or is it?

When talking with our project partners and customers, the topic of near-infrared (NIR) spectroscopy is often automatically associated with FT-NIR spectroscopy. So, why isn’t it just called NIR? What is the difference between IR and NIR? Some of you might even wonder: “Can I replace an old IR analyzer with NIR hardware?” And additionally: “Why should I replace the IR with a NIR process analyzer?”

This two-part series aims to explain the differences between these techniques and dispel some myths.

Click below to jump directly to a section:

A brief historical overview

Wavelengths

The NIR wavelength range has a long history. As early as the 1880s, organic components were investigated in the NIR range and the strong –OH band relating to the presence of water was discovered as a very important piece of information. Shortly after, measurement of oils from the agricultural industry and investigations into various polymers followed. Some of the first industrial applications of dispersive NIR spectrometers were in the food and agricultural industries. In such applications, parameters including moisture, protein content, and fat content were analyzed quantitatively.

On the other hand, some strong advantages came from using the infrared (IR) wavelength range—high structural sensitivity and specificity—making it possible to obtain precise fingerprints for structural identification.

Figure 1. Historical punch card for assigning various spectral features to acetyl chloride in the infrared wavelength region [1]. (Click to enlarge image)
For more information about the differences between IR and NIR spectroscopy, read our previous blog posts.
Hardware

The hardware for NIR and IR analysis was fundamentally different. At that time, even though the evaluation of NIR spectra seemed to be too difficult and ambiguous due to the broad overlapping peaks, there was one major advantage: robust and cheap materials could be used for NIRS (e.g., PbS detectors, tungsten lamps, and simple glass materials for the optics). Since the NIR-bands were broad and overlapped, users were limited to only the essential information and therefore did not need higher resolution, so simple dispersive gratings (monochromator gratings) were sufficient.

For IR, Fourier transform infrared spectrometers (FT-IR) were used which operated based on Michelson interferometers. This was necessary to obtain the spectral resolution needed for structural interpretation (e.g., distinguishing the isomers 1-propanol and 2-propanol at about 2700 nm for the first time). These spectrometers were introduced to the market in the 1960s. Due to the high costs for interferometers, special optics, and lasers, they were mainly used for research purposes.

Software

Significant progress has been made in the field of spectroscopy due to the development of more powerful computers in the 1980s and 1990s in combination with chemometrics. While IR spectroscopy, due to its high data point density, was still far behind in the application of computer-based chemometric methods, NIR spectrometers were already able to benefit from fast evaluation methods.

Chemometric tools combined with the hardware benefits of NIR technology led many manufacturers to transfer their existing FT-IR measurement technology to the NIR range. And other companies? They just used and improved their already existing measurement technology to achieve perfect synergy between spectrometer and chemometrics.

Now that some of the background has been laid out, it’s time to answer some myths about NIR, FT-NIR, and FT-IR spectroscopy.

Myth 1: NIR spectroscopy always means FT-NIR

This is a persistent myth that you could easily miss unless you look closely. What exactly does the «FT» mean and why doesn’t everyone use it to describe NIR spectroscopy?

When using a FT-NIR spectrometer, first an interferogram is generated—not a spectrum in that sense. The conversion of the interferogram into a spectrum is done by applying a mathematical operation, the Fourier transform (FT). This transforms the path-dependent information (e.g., relative mirror position of two mirrors in the spectrometer) into a frequency-dependent function. This means FT-NIR is nothing more than the methodology of generating the spectrum in the NIR wavelength range.

As before, it is NIR spectroscopy that provides the same information as dispersive NIR spectroscopy or diode array spectroscopy. FT-NIR uses the interferences produced by an interferometer to extract single wavelengths from white light (halogen lamp), while dispersive spectrometers use gratings. Gratings are produced by very modern lithographic techniques and offer the highest precision (of wavelength accuracy).

Table 1. Comparison of FT-NIR and dispersive NIR spectroscopy

Parameter FT-NIR NIR
Wavelength splitting Mathematical calculation (Fourier transformation) from the phase shift of two incident light beams (interferogram) Diffraction or dispersion, movement by a digital encoder
Resolution depends on… Setting the maximum offset of the moving mirror Number of lines of the monochromator grid, slit width, encoder quality
Moving elements Yes (motor of the interference mirror) Yes (motor of the grid)
Wavelength range 12500 cm-1–4000 cm-1

(800–2500 nm)

800–2500 nm

(expandable to 400 nm)

Noise Depending on the resolution, higher than dispersive NIR with comparable setup Depending on the resolution, lower than FT-NIR with comparable setup
Method transferability (i.e., to other spectrometers) Yes Yes (due to the Metrohm calibration concept)

 

Consumables Laser source, halogen lamp, and desiccant Halogen lamp
Compared to a dispersive analyzer, a FT-NIR spectrometer uses a laser to control the position of the interferometer mirror. This laser must be changed periodically, however this task is generally not done by the end-user themselves compared to halogen lamp, which is easily replaceable.

Looking a little bit deeper into the details of Table 1, it is clear that dispersive spectroscopic instruments are more suitable for industrial process applications. Why? A low acquisition time is critical for real-time measurements with the least time loss. Compared to a FT-NIR instrument, the acquisition time is lower for a dispersive analyzer (leading to faster results) at the same resolution.

If you have ever wondered why you might need to calculate a Fourier transform, you will know after the next myth is answered.

Myth 2: Method transfer is only possible with FT-NIR spectrometers and not with dispersive spectrometers

Where does this myth originate?

Visualize the internal structure of an interferometer. A He-Ne laser is used as the reference measurement for the precise determination of the mirror position and thus also obtains an exact spectrum with high wavelength reproducibility at the same spatial coordinate by the Fourier transformation.

What is different about the dispersive spectrum?

In this case, the spectrum is not calculated in a mathematically complex way but is recorded directly via the dispersing element (the monochromator) on the detector. Here, a high-resolution state of the art grating and an accurate digital encoder that is precisely matched with the detector play an important role. NIRS XDS Process Analyzers from Metrohm Process Analytics (Figure 2) use wavelength standards to achieve both high wavelength precision and reproducibility and to ensure the transferability of the developed method.

Figure 2. The NIRS XDS Process Analyzer from Metrohm Process Analytics. 
Wavelength Precision <0.015 nm Valid
975.880 nm 0.0012 nm Yes
1221.342 nm 0.0005 nm Yes
1678.040 nm 0.0012 nm Yes
Figure 3. Results of the wavelength reproducibility test of a NIRS XDS Process Analyzer during a performance test. The precision meets the very narrowly defined testing specifications.
By using a wavelength and reference standard built into the spectrometer, additional diagnostics can be carried out at routine intervals (either as part of maintenance or automated within regular process operation) to check the wavelength accuracy and precision.

Due to the standardization concept with reference standards and wavelength standards, methods can be transferred without much effort even when changing or adjusting accessories (e.g., longer optical fibers, partially changed probes).

To summarize: a good standardization concept with NIST certified reference and wavelength standards as well as internally installed standards allow robust method transfers to other spectrometers and excellent long-term stability in the production process.

Myth 3: Many applications cannot be measured with dispersive NIRS, but require well-resolved FT-NIR spectroscopy

The Michelson interferometer and the monochromator grating were both developed in the 1800s. Both of these technologies have been used industrially since the advancement of computer technology and utilize the same light sources, detectors, optical fibers, and probes.

Monochromator gratings now consist of, e.g., a holographic concave diffraction grating with an optimized image plane to avoid aberrations and stray light. Holographic gratings are created by etching interference lines via laser into a photoresist layer. An advantage of this is very high spectral resolution, which together with a detailed adjustable encoder (and other components of the monochromator), provides very good resolution with the NIR spectrometer. For example, the NIRS XDS Process Analyzer (Figure 2) has a real resolution of 8.75 nm.

In comparison, higher resolutions can be achieved with interferometers, but this can also decrease the signal-to-noise (S/N) ratio. Usually, resolutions of approximately 8 cm-1 or 16 cm-1 are used, which corresponds to 10–25 nm at 2500 nm.

Parameter FT-NIR Dispersive NIR (Metrohm)
Wavelength range (nm) 800–2200

(12,500–4545 cm-1)

800–2200

400–2200 (optional)

Wavelength precision (nm) ~0.01 ~0.005
Wavelength accuracy (nm) ~0.05–0.2 ~0.05
Figure 4. Noise spectra recorded with a Metrohm dispersive NIRS analyzer and a typical FT-NIR spectrometer.
Higher resolutions are usually not required for the majority of applications since harmonics/overtones and combination bands of pure substances in the NIR wavelength range have a broad bandwidth. The absorption peak with the smallest bandwidth currently known in the NIR region is talc at slightly more than 10 nm.

Very similar overlapping information (e.g., –OH bands or –COOH bands) are separated by using chemometric methods and are evaluated individually and specifically.

Another example that shows how powerful dispersive NIR spectroscopy is compared to FT techniques and IR spectroscopy can be seen in the separation of xylene isomers in a mixture of several aromatics/hydrocarbons (Figure 5).

Figure 5. Xylene isomers present in a mixture of aromatics and other hydrocarbons. (L) Raw spectra of all components from 800–2200 nm. (R) Raw spectra of xylene isomers show significant molecular vibration variations in the –CH region from 1700–1850 nm.
Figure 5 shows that the three xylene isomers can be clearly distinguished spectroscopically. Applying chemometrics elaborates the information even more and ultimately all six components can be determined individually and quantitatively. In a production process, the real-time reaction monitoring can be performed for all six components (Figure 6).
Figure 6. Graph showing real-time monitoring during a feed separation process of a mixture including three xylene isomers.
The application shown in Figures 5 and 6 has often been implemented with IR photometers in the past. We have now shown that the application can not only be transferred to the NIR wavelength range, but that even minimal structural differences between the functional groups of molecules can be detected by dispersive NIR spectroscopy.

To summarize: dispersive spectrometers have very good spectral resolution—in some cases better than FT-NIR spectrometers—and can even distinguish between different isomers in complex mixtures, or between very similar components like –OH and –COOH functional groups.

Summary

In the first part of this series, we went more into detail about the practical differences between FT-NIR and dispersive NIR spectroscopy. Three myths were discussed: that NIR spectroscopy always means FT-NIR—False, method transfer is only possible with FT-NIR spectrometers and not with dispersive spectrometers—False, and many applications cannot be measured with dispersive NIRS, but require well-resolved FT-NIR spectroscopy—False.

Some myths should no longer be kept alive because they are not facts!

We have also compared FT-NIR spectrometers to dispersive spectrometers when used in a process environment. Some critical points to remember: the dispersive analyzer is less sensitive to vibrations; less maintenance is necessary, and the grating is post-dispersive and therefore less prone to pollution due to lower ambient light.

To prove those arguments, Part 2 will show that, contrary to some expectations, it is possible to replace IR measurement techniques in industrial processes with easy-to-implement NIR measurement techniques. We will dispel some more myths and go into detail of an extremely low water content measurement in a process with the support of our primary analysis methods.

Reference

[1] Baker, A. W.; Wright, N.; Opler, A. Automatic Infrared Punched Card Identification of Mixtures. Anal. Chem. 1953, 25 (10), 1457–1460. doi:10.1021/ac60082a011

Find your process application

Our Applications Book contains hundreds of sold process applications from our more than 10,000 installed analyzers over several industries!

Post written by Sabrina Hakelberg, Product Manager NIRS Process Analyzers, Deutsche Metrohm Prozessanalytik (Germany).

NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 5

NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 5

History of ASTM International

The American Society for Testing and Materials (ASTM) is an organization that currently provides over 12,500 international standards. Its roots date back to 1898, when ASTM was formed by a group of scientists and engineers to address the frequent rail breaks affecting the fast-growing railroad industry. The group developed a standard for the steel used to fabricate rails.

Originally, this organization was called the «American Society for Testing Materials» (1902) and was changed to the «American Society for Testing and Materials» in 1961. In 2001, ASTM officially changed its name to «ASTM International» and added the tagline «Standards Worldwide». This tagline was modified in 2014 to «Helping our world work better». Now, aside from the US, ASTM International also has offices in Belgium, Canada, China, and Peru.

ASTM International aims to ensure that quality and standard requirements are met when using materials for engineering projects. Therefore, they had to agree upon a single language for engineers and technicians to enhance compatibility, and ultimately developed a system grouped according to industries in the form of letters A–G. Currently, there are over 12,500 ASTM standards used by about 150 countries. This has increased trade in different markets by instilling and strengthening consumer confidence.

ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants

Formed in 1904, ASTM Committee D02 currently meets twice per year for five days of technical meetings, attended by approximately 1000 members (out of around 2500). D02 has jurisdiction over 814 standards with a prominent role in all aspects relating to the standardization of petroleum products and lubricants, which are published in the Annual Book of ASTM Standards (Volumes 05.01 through 05.06).

Near-infrared spectroscopy—an ASTM compliant tool to assess the quality of petrochemical products

Near-infrared spectroscopy (NIRS) has been an established method for fast and reliable quality control within the petrochemical industry for more than 30 years. However, many companies still do not consistently consider the implementation of NIRS in their QA/QC labs. The reasons could be either limited experience regarding application possibilities or a general hesitation about implementing NIRS as an alternative technology.

Many companies are not aware that now there are many ASTM standards about how to implement NIR spectroscopy as an alternative to conventional methods. Several NIRS-related ASTM guidelines are shown in Figure 1.

ASTM E1655 (method development quantitative NIR analysis) and ASTM E1790 (method development qualitative NIR analysis) are applicable for all industries (e.g., polymer, chemical, petrochemical, etc.).

ASTM D6122 (method validation), ASTM D8321 (development and validation of multivariate analysis), and ASTM D8340 (performance qualification) are dedicated for the petrochemical industry. These three standards were released recently in 2020, and ASTM D8340 was updated at the end of 2021.

Figure 1. Overview of NIRS-related ASTM guidelines.

Method development

ASTM E1655: Standard Practices for Infrared Multivariate Quantitative Analysis

«These practices cover a guide for the multivariate calibration of infrared spectrometers used in determining the physical or chemical characteristics of materials. These practices are applicable to analyses conducted in the near infrared (NIR) spectral region (roughly 780 to 2500 nm).»

ASTM E1790: Standard Practice for Near Infrared Qualitative Analysis

«This practice covers the use of near-infrared (NIR) spectroscopy for the qualitative analysis of liquids and solids. The practice is written under the assumption that most NIR qualitative analyses will be performed with instruments designed specifically for this purpose and equipped with computerized data handling algorithms.»

Method validation

ASTM D6122: Standard Practice for Validation of the Performance of Multivariate Online, At-Line, Field and Laboratory Infrared Spectrophotometer, and Raman Spectrometer Based Analyzer Systems

«This practice covers requirements for the validation of measurements made by laboratory, field, or process (online or at-line) infrared (near- or mid-infrared analyzers, or both), and Raman analyzers, used in the calculation of physical, chemical, or quality parameters (that is, properties) of liquid petroleum products and fuels.»

These requirements include the following topics:

  • Analyzer calibration
  • Correlation of NIRS vs. lab method (treated and untreated samples)
  • Probationary validation
  • General & Continual validation

Results validation

ASTM D8321: Standard Practice for Development and Validation of Multivariate Analyses for Use in Predicting Properties of Petroleum Products, Liquid Fuels, and Lubricants based on Spectroscopic Measurements

«This practice covers a guide for the multivariate calibration of infrared (IR) spectrophotometers and Raman spectrometers used in determining the physical, chemical, and performance properties of petroleum products, liquid fuels including biofuels, and lubricants. This practice is applicable to analyses conducted in the near infrared (NIR) spectral region (roughly 780 nm to 2500 nm).»

The main purpose for this standard is to establish the validity of test results during calibration.

ASTM D8340: Standard Practice for Performance-Based Qualification of Spectroscopic Analyzer Systems

«This practice covers requirements for establishing performance-based qualification of vibrational spectroscopic analyzer systems intended to be used to predict the test result of a material that would be produced by a Primary Test Method (PTM) if the same material is tested by the PTM.»

Furthermore, it includes the prescriptive requirements regarding multivariate models, including Multi Linear Regression (MLR), Partial Least Square (PLS), Principal Component Regression (PCR), Cross validation, and Outlier statistics, as well as instrument considerations.

Regarding the required accuracy of the NIRS method the expected agreement and user requirements is that the Standard Error of Prediction for the NIRS value should be equal to or smaller than the laboratory method reproducibility.

ASTM D8340 compliance with the NIRS DS2500 Petro Analyzer and Vision Air

Temperature stability, section 5.4:

There are prescriptive requirements included in this norm regarding temperature stability of the NIRS Analyzer. Section 5.4 requires sample temperature to be carefully controlled in the analyzer system hardware or that effects of temperature change be compensated in the modeling or software. Metrohm’s solution to this issue for the NIRS DS2500 Petro Analyzer is shown in Figure 2.

Figure 2. Temperature stability for the NIRS DS2500 Petro Analyzer.
Learn more about the possibilities of petrochemical analysis with Metrohm NIRS DS2500 Petro Analyzers in our free brochure.
Analyzer wavelength accuracy and precision, section 6.3:

Section 6.3 requires that the analyzer shall include a means of demonstrating that it is operating within the vendor’s specification. Therefore, the analyzer shall incorporate instrument performance tests to demonstrate that it is operating within historically expected limits. Furthermore, the analyzer shall have a means of validating wavelength/frequency precision and accuracy. Also, the wavelength precision must be sufficient to allow spectra to be collected and used in creating a multivariate model that meets or exceeds user’s specifications. The wavelength precision of the analyzer used for calibration and the analyzer-to-analyzer wavelength accuracy and reproducibility must be sufficient to allow analyzers to be validated by Practice D6122. Metrohm’s solution to this is the Vision Air software shown in Figure 3.

Figure 3. Analyzer wavelength accuracy and precision for ASTM D8340 section 6.3 (click to enlarge image).
Vendor created global multivariate model, section 8.2.2:

The multivariate model can be that of a standardized test method, a user/vendor-created global multivariate model, or a user-created site-specific multivariate model. A global multivariate model is one developed by use of samples and data that may represent materials produced at multiple facilities or locations. Some locations may start with a global model and add site-specific sample to it. Metrohm offers several pre-calibrations for the NIRS DS2500 Petro Analyzer, listed in Figure 4.

Figure 4. Available NIRS pre-calibrations for the petrochemical industry.
Discover our selection of NIRS pre-calibrations available for the petrochemical industry in our free brochure.
Outlier statistics, sections 9.3, 9.4, and 9.5:

The requirements of outlier handling are described in these sections. Identification and handling of outliers is important to the success of meeting this performance-based practice. It is permissible for the identification and handling of outliers to be performed by the same or separate software used for generating predictions from spectra. For analysis of a sample for the purposes of determining property values, the software shall indicate whether the spectrum is identified as an outlier, based on the criteria set by the user. The sample analysis may indicate that expected performance is not reached for a sample identified as an outlier.

Vision Air is Metrohm’s universal software for Vis-NIR spectroscopy. Vision Air accounts for the unique needs of each type of instrument user. It offers specific interfaces optimized for the most common tasks – simplifying routine measurement, method development, outlier handling, and both data and instrument management. Vision Air is also compatible with third-party software like Unscrambler (Figure 5).

Figure 5Vision Air—Metrohm’s universal software for lab Vis-NIR spectroscopy.

Summary

In the petrochemical industry, typical requirements from management are usually that quality control should be quick, operating costs should be low, feedback should be fast, and operation should be safe.

Typical requirements from the user are that the analysis should be accurate and precise, and the instrumentation should be easy to use, fast, and safe.

NIR spectroscopy is compliant with all of these requirements, and as shown in this blog series, the technology is supported by several ASTM guidelines for method development, method validation, and results validation.

By utilizing NIRS in the petrochemical industry, manufacturers not only improve the efficiency of screening and quality control of petrochemical products, but also fully adhere to internationally accepted standards.

For more information

About spectroscopy solutions provided by Metrohm, visit our website!

We offer NIRS for lab, NIRS for process, as well as Raman solutions

Post written by Wim Guns, International Sales Support Spectroscopy at Metrohm International Headquarters, Herisau, Switzerland.
USP  – simple automated analysis of ultrapure water

USP <645> – simple automated analysis of ultrapure water

H2O – two simple elements, oxygen (O) and hydrogen (H), fuse together to form one of the most important molecules in the world: water. Water is everywhere on Earth and it is vital for our health and survival. It often contains other ions like calcium, magnesium, and chloride which are essential for the human body to function. However, in specific situations, ultrapure water (UPW) is needed to prepare e.g., injections or other solutions used in hospitals. How is the quality of UPW ensured so that it is always suitable for such medical purposes? The answer to this comes from USP <645>. This standard explains how the water quality can be determined and how this analysis must be performed.

Instruments

For this analysis, a measuring device capable of measuring the conductivity and the pH value is required. If a combined device is not available, then using two separate ones is also fine. Then, a pH electrode that is especially suitable for the determination of the pH value of water and a conductivity cell for measurement of low conductivities is necessary. In this case, the Aquatrode plus and the stainless steel conductivity cell are recommended.

The Aquatrode plus responds very quickly in ion-deficient matrices (such as ultrapure water) and thanks to its double junction system, the bridge electrolyte can be chosen freely.
The stainless steel conductivity cell has been specially designed for measurements in samples with low conductivity. With a cell constant of c = 0.1 cm-1, it is ideal for conductivities ranging from 0–300 µS/cm. The built-in temperature sensor makes handling even easier as no additional sensor is needed for the temperature measurement.

USP <645> procedure

Now that the necessary instrumentation has been introduced, it’s time to take a look at the standard procedure itself. At first glance this looks a bit difficult as it is a three-step analysis, or actually a four-step analysis if you count the calibration as well.

Step 1: First, calibrate the pH electrode and the stainless steel conductivity cell (sensor). The pH electrode is calibrated with pH 4 and 7 solutions, whereas the stainless steel sensor is calibrated with a 100 µS/cm standard.

Find the standard solutions you need here:

Step 2: After calibrating the sensors, both the temperature of the water and the conductivity are measured without temperature compensation. If the measured conductivity is lower than the value mentioned in the table of USP <645>, then the requirement for the conductivity is met and the water can be used for medical purposes. If this is not the case, then step 3 must be performed.

Step 3: 100 mL water is transferred to an external titration vessel where its temperature is adjusted to 25 ± 1 °C. The water is stirred vigorously to incorporate carbon dioxide present in the air. If the conductivity does not change by more than 0.1 µS/cm per 5 minutes, the value is noted for further evaluation. If this value is below 2.1 µS/cm, then the water is usable for medical purposes. If not, then proceed with step 4.

Step 4: The solution is tempered to 25 ± 1 °C. Once the temperature is stable, 0.3 mL of saturated KCl solution is added and the pH of the water is measured. The pH value must lie between pH 5 and 7. If this is not the case, the water does not meet the requirements and must be discarded. If the pH is measured between 5 and 7, then the conductivity must additionally be lower as mentioned in the USP <645> table. If this is the case, the analysis passes and the water can be used for medical purposes.

Automation of USP <645>

The analysis can be quite time-consuming and therefore Metrohm has provided a solution to make this process much easier. Our system combines all of these steps into one method, allowing you to perform walk-away automation and focus on more important tasks.

To expand the capabilities of the measuring system, the 856/867 modules can be exchanged with a modular OMNIS Titrator which can also be used for other standard potentiometric titrations.

Take a closer look at our automated analysis solution

Proper electrode immersion depth
  • Aquatrode plus for accurate pH measurement in ion-deficient matrices
  • Stainless steel conductivity cell for low conducting samples
  • Special holder for performing step 2 of the standard procedure
  • Thermostated vessel (for step 2)
  • DIS-Cover lid to prevent the sample from CO2 uptake (before step 3)
  • Rod stirrer to saturate the solution with carbon dioxide (for step 3)

Conclusion

With this complete system, standard analysis of UPW quality according to USP <645> is performed in a fully automatic and reliable manner. At the end of each analysis a clear message is received if the deionized water (UPW) has passed the test or not. Handling is very easy and allows users to check if an analysis passes or not with just a glance.

Download our Application Bulletin

Automatic conductometry in water samples with low electrical conductivity in accordance with USP<645>
Post written by Iris Kalkman (Product Specialist Titration) and Heike Risse (Product Manager Titration – Automation), Metrohm International Headquarters, Herisau, Switzerland.
NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 4

NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 4

What is a lubricant?

A lubricant is defined as a petroleum-derived product used to control and reduce the friction and wear of moving machinery parts (e.g., in engines and turbines). The main purpose of lubricants  is to help protect and prolong the lifetime of the equipment.

Machinery and lubricants go hand in hand, as shown here.
These goals are accomplished in the following ways:

Lubrication by reducing friction and wear. The lubricant forms a film between the mechanical moving parts of the equipment. In this way the metal-to-metal contact and, thus, the wear is reduced.

Cooling by acting as a heat sink. This causes the heat to dissipate away from critical parts of the equipment so that deformation due to increased temperature is prevented.

Protection by building a film. This film is unaffected by oxygen or corrosive substances and therefore prevents metal damage and oxidation (rust) and therefore also prevents wear.

Types of lubricants

For the most part, lubricants consist of oils to which additives and other chemical substances are added. There are two common types of lubricants which are based on the origin of the oil:

1. Lubricants based on mineral oils (Figure 1a) are the most commonly used type. They are comprised of petroleum products (base stock) to which synthetic additives are added. These types of lubricants are used in applications where there are no high temperature requirements. Typical areas where mineral oil-based lubricants are used include: engines, hydraulics, gears, and bearings.
2. Lubricants based on synthetic oils (Figure 1b) are artificially developed substitutes for mineral oils. They are less common and more expensive. Synthetic oils are specifically developed to create lubricants with superior properties to mineral oils. For example, heat-resistant synthetic oils are used in high performance machinery operating at high temperatures.
a)
b)
Figure 1. Difference in the molecular structure found in lubricants: a) mineral oil and b) synthetic oil.
In the following table, different lubricant types with sub-classes are listed.
Table 1. Different lubricating oil types.

Lubricant type

Sub-classes

Automotive oil Engine oil

Gear oil

Transmission fluids

Industrial oil Hydraulic oil

Turbine oil

Greases
Metal working fluids Forming fluids

Cutting fluids

The physical properties of a lubricant (such as viscosity and density) mostly depend on the oil base stock, whereas the additives fine-tune the chemical properties, e.g., the acid number or base number. For each application, the oil is typically formulated to meet the physical and chemical properties required by the customer. Therefore, various types of oil exist (Table 1).

Near-infrared spectroscopy—an ASTM compliant tool to assess the quality of lubricants

Near-infrared spectroscopy (NIRS) has been an established method for fast and reliable quality control within the petrochemical industry for more than 30 years. However, many companies still do not consistently consider the implementation of NIRS in their QA/QC labs. The reasons could be either limited experience regarding application possibilities or a general hesitation about implementing new methods.

There are several advantages of using NIRS over other conventional analytical technologies. For one, NIRS is able to measure multiple parameters in just 30 seconds without any sample preparation! The non-invasive light matter interaction used by NIRS, influenced by physical as well as chemical sample properties, makes it an excellent method for the determination of both property types.

In the remainder of this post, available solutions for lubricants are discussed which have been developed according the NIRS implementation guidelines of ASTM E1655 (method development), ASTM D6122 (method validation), and ASTM D8340 (results validation).

Did you miss the first parts in this series about NIRS as a QC tool for the petrochemical industry? Find them all below!

Read our previous blog posts to learn more about NIRS as a secondary technique.

Applications and parameters for lubricant analysis with NIRS

The main NIRS application for lubricants is to easily monitor the oil condition, i.e., checking if the oil is still of suitable quality for proper lubrication of the equipment. Reducing unnecessary oil changes means significant cost savings. On the other hand, changing the oil too infrequently can result in possible damage of the equipment, leading to costly repairs. Therefore optimizing the usage of the lubricating oil is very important.

The following parameters can be correlated between NIRS and the values from a primary method: kinematic viscosity, viscosity index, color, density, water content, TAN (total acid number), and TBN (total base number). A large set of samples provided by several different companies was used to develop working NIRS models of these parameters, including hydraulic oil, gear oil, and others. In some cases, it was not clear for what application the lubricant was used, so the exact identity of the oil was unknown.

The most relevant application notes for NIRS analysis of lubricants are listed below in Table 2.

Table 2. Metrohm’s NIRS solutions for lubricants including application details and benefits.
Parameter Reference method Norm NIRS Application Notes NIRS benefits
Acid number Titration ASTM D664 AN-NIR-071

AN-NIR-041

All parameters are measured simultaneously within a minute, without requiring any sample preparation or chemical reagents.
Kinematic viscosity at 40 °C Viscosimeter ASTM D445
Kinematic viscosity at 100 °C Viscosimeter ASTM D445
Viscosity index Calculation ASTM D2270
Color number Colorimeter ASTM D1500
Moisture content Karl Fischer titration ASTM D6304
Base number Titration ASTM D2896
Density Density meter ASTM D4052

 

Solutions by means of starter models—expedite and simplify quality control of lubricants

Lubricants keep our modern lives running smoothly. During use, the oil needs to be monitored to check if it still of good enough quality or whether it needs to be exchanged.

The data obtained here indicate that lubricants vary per application and per supplier. This means that there is still not sufficient information for each oil type and subtype to prepare a model robust enough to transform into a pre-calibration. However, if a partner provides the samples, a feasibility study can quickly indicate if the NIR spectra are able to be correlated to the primary method values.

Typically, several key parameters such as the acid and base numbers (AN and BN), viscosity, moisture content, color, and density are determined in the laboratory by various chemical and physical methods. These methods not only incur high running costs, they are also quite time consuming to perform.

NIRS on the other hand requires neither chemicals nor sample preparation, and provides results in less than a minute. This spectroscopic technique is also easy enough to be used by non-chemists. Furthermore, multiple chemical and physical parameters can be determined simultaneously. The combined benefits of this technology make NIRS the ideal solution for many daily QA/QC measurements or ad-hoc atline analysis.

Application example: starter model for lubricants with the NIRS DS2500 Liquid Analyzer

For lubricant analysis, determination of the acid number (ASTM D664), viscosity (ASTM D445), moisture content (ASTM D6304), and color number (ASTM D1500) require the use of multiple analytical technologies and, in part, large volumes of chemicals. The time to result can therefore be quite a long and costly process.

In this example, different lubricant samples were measured with a Metrohm NIRS DS2500 Liquid Analyzer in transmission mode over the full wavelength range (400–2500 nm). The built-in temperature controlled sample chamber was set to 40 °C to provide a stable sample environment. For convenience reasons, disposable vials with a pathlength of 8 mm were used, which made a cleaning procedure obsolete.

Learn more about the possibilities of petrochemical analysis with Metrohm NIRS DS2500 Analyzers in our free brochure.
Figure 2. Quality control of lubricants as performed by the Metrohm NIRS DS2500 Liquid Analyzer.
The obtained Vis-NIR spectra (Figure 2) were used to create prediction models for the determination of key lubricant parameters (such as those in Table 2). The quality of the prediction models was evaluated using correlation diagrams, which display the correlation between the Vis-NIR prediction and primary method values. The respective figures of merit (FOM) display the expected precision of a prediction during routine analysis (Figure 3).
Figure 3. Correlation plots and figures of merit (FOM) for different parameters measured in lubricants.
This solution demonstrates that NIR spectroscopy is excellently suited for the analysis of multiple parameters in lubricants in less than one minute without sample preparation or using any chemical reagents.

In case a large series of samples must be analyzed, there is also the possibility to measure lubricant samples in a fully automated way, as detailed in our free Application Note below.

Here, the samples were measured in transmission mode over the full wavelength range (400–2500 nm) using a NIRS XDS RapidLiquid Analyzer in combination with an 815 Robotic USB Sample Processor, which can carry a total of 141 samples (Figure 4).
Figure 4. Metrohm NIRS XDS RapidLiquid Analyzer equipped with a with 5.0 mm flow cell (left) and the 815 Sample Processor (right).

Summary

Near-infrared spectroscopy is very well suited for lubricant analysis. Available starter models are developed and validated in accordance with the ASTM guidelines. Positive aspects of using NIRS as an alternative technology to primary methods are the short time to result (less than one minute), no chemicals or other expensive equipment needed, and ease of handling so that even shift workers and non-chemists can perform these analyses in a safe manner.

Future installments in this series

This blog article was dedicated to the topic of lubricants and how NIR spectroscopy can be used as the ideal QC tool for the petrochemical / refinery industry. The final installment will be dedicated to:

 

For more information

About spectroscopy solutions provided by Metrohm, visit our website!

We offer NIRS for lab, NIRS for process, as well as Raman solutions

Post written by Wim Guns, International Sales Support Spectroscopy at Metrohm International Headquarters, Herisau, Switzerland.