IRRAS infrared spectroscopy

The three most commonly applied external reflectance techniques can be considered in terms of the means employed to overcome the sensitivity problem. Both electrically modulated infrared spectroscopy (EMIRS) and in situ FTIR use potential modulation while polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) takes advantage of the surface selection rule to enhance surface sensitivity. 

Electrochemical infrared spectroscopy can be used on all kinds of electrodes and for all substances that are IR active. It is particularly useful for the identification of reaction intermediates, and has been used extensively for the elucidation of the mechanisms of technologically important reactions. A case in point is the oxidation of methanol on platinum, where linearly bonded = C = O (i.e., CO bonded to one Pt atom) has been identified as an intermediate Figs. 15.7 and 15.8 show EMIRS [6c] and IRRAS [8] spectra of this species. Near 2070 cm-1 the EMIRS spectrum shows the typical form produced by a peak that shifts with potential. This shift can be followed in the IRRAS spectrum... 

Some characteristics of, and comparisons between, surface-enhanced Raman spectroscopy (SERS) and infrared reflection-absorption spectroscopy (IRRAS) for examining reactive as well as stable electrochemical adsorbates are illustrated by means of selected recent results from our laboratory. The differences in vibrational selection rules for surface Raman and infrared spectroscopy are discussed for the case of azide adsorbed on silver, and used to distinguish between "flat" and "end-on" surface orientations. Vibrational band intensity-coverage relationships are briefly considered for some other systems that are unlikely to involve coverage-induced reorientation. 

Ir spectra, of surface layers, 24 110. See also Infrared reflection-absorption spectroscopy (IRRAS) ir spectrometers, 23 132 Ir (infrared) spectroscopy, for analysis of MF resins, 15 790. See also Infrared technology Isanic acid, 5 34t... 

Most of the above membrane-oriented studies were carried out for peptides in multilayer systems that were collapsed or transferred onto a sample cell surface. An alternative and very interesting way to study membrane systems is by IRRAS (infrared reflection absorption spectroscopy) at the air-water interface. In this way, unilamellar systems can be studied as a function of surface pressure and under the influence of various membrane proteins and peptides added. Mendelsohn et al.[136] have studied a model series of peptides, [K2(LA) ] (n = 6, 8, 10, 12), in nonaqueous (solution), multilamellar (lipid), and unilamellar (peptide-IRRAS) conditions. In the multilamellar vesicles these peptides are predominantly helical in conformation, but as peptide only monolayers on a D20 subphase the conformation is (1-sheet like, at least initially. For different lengths, the peptides show variable surface pressure sensitivity to development of some helical component. These authors further use their IR data to hypothesize the existence of the less-usual parallel (i-sheet conformation in these peptides. A critical comparison is available for different secondary structures as detected using the IRRAS data for peptides on H20 and D20 subphasesJ137 ... 

IRAS = IRRAS infrared reflection-absorption spectroscopy 3.7c.i... 

A prerequisite for the development indicated above to occur, is a parallel development in instrumentation to facilitate both physical and chemical characterization. TEM and SPM based methods will continue to play a central role in this development, since they possess the required nanometer (and subnanometer) spatial resolution. Optical spectroscopy using reflection adsorption infrared spectroscopy (RAIRS), polarization modulation infrared adsorption reflection spectroscopy (PM-IRRAS), second harmonic generation (SFIG), sum frequency generation (SFG), various in situ X-ray absorption (XAFS) and X-ray diffraction spectroscopies (XRD), and maybe also surface enhanced Raman scattering (SERS), etc., will play an important role when characterizing adsorbates on catalyst surfaces under reaction conditions. Few other methods fulfill the requirements of being able to operate over a wide pressure gap (to several atmospheres) and to be nondestructive. 

Electronic Absorption and Emission Spectroscopy Visible Spectroscopy Ultraviolet Spectroscopy Luminescence Spectroscopy Electron Spectroscopy Atomic Identification and Analysis Infrared and Raman Spectroscopy Infrared Spectroscopy Infrared Sample Preparation Internal Reflection Spectroscopy (IRS, ATR) Reflection Absorption (RAIR or IRRAS)... 

Reflection Absorption (RAIR or IRRAS). A significant development in infrared spectroscopy during the 1960s has been reported in journals not commonly read by either polymer chemists or analytical chemists. It has developed in the fields of electrochemistry and catalysis and is called reflection-absorption spectroscopy. Papers by Greenler (115-118). Yates (119). and Hansen (120. 121) describe the theory and some experimental data, and Boerio and Gosselin report on its applications to polymers (122). 

In previous studies [3, 4], we had pointed out that the interphase formation mechanisms result from dissolution of the metallic surface layers, concomitantly with ion diffusion through the liquid prepolymer. In order to detect the dissolution phenomenon, pure amine (either DETA or IPDA) was previously applied to chemically etched metallic sheets (either A1 or Ti alloys were used, and had hydroxidic surfaces). After 3 h, the metallic surfaces were scraped with a PTFE spatula. The modified amine (i.e., the amine reacted with the metal) was analyzed. Whatever the natures of the amine and the metal were, metal ions were detected in the modified amines by ICP analysis and new peaks were detected by infrared spectroscopy [5]. To indicate hydroxide dissolution, a very thin layer of liquid amine was applied to chemically etched aluminum, and Infrared Reflection - Absorption Spectroscopy (IRRAS) spectra were recorded every 5 min (the hydroxide band intensity variation at ca. 3430 cm was followed). The OH group peak intensity decreased when the amine-metal contact time increased [5]. Conversely, if pure DGEBA monomer was apphed to the metal surfaces, even after 3 h in contact with the metallic surfaces, no metal ion was detected by ICP in the DGEBA recovered, and the infrared spectra remained identical before and after the contact with the metal. Finally, if pure amine monomer was applied to gold-coated substrates, no chemical reaction was observed (by either IGP or FTIR analyses). 

IR Infrared spectroscopy, see also EMIRS, IRRAS, LPSIRS... 

IRRAS Infrared reflection absorption spectroscopy, see also ... 

This technique is used to study thin (down to submonolayer) films adsorbed on reflective substrates such as metals. Experimentally it involves measuring the change in the reflectance spectrum of the substrate that accompanies thin film formation. Various acronyms for the technique are used infrared reflection—absorption spectroscopy (IRRAS, IRAS) and reflection—absorption infrared spectroscopy (RAIRS). The Basics of IRRAS spectra are described in Chapter 5.2. 

IRRAS Infrared Reflection-Absorption Spectroscopy, 33 IS Ionisation Spectroscopy ... 

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) Reflection-absorption infrared spectroscopy (RAIRS) (also known as infrared reflection absorption spectroscopy, IRAS or IRRAS) Multiple Internal reflection spectroscopy (MIR)... 

---