Ratio measure

Lasers can be used in either pulsed or continuous mode to desorb material from a sample, which can then be examined as such or mixed or dissolved in a matrix. The desorbed (ablated) material contains few or sometimes even no ions, and a second ionization step is frequently needed to improve the yield of ions. The most common methods of providing the second ionization use MALDI to give protonated molecular ions or a plasma torch to give atomic ions for isotope ratio measurement. By adjusting the laser s focus and power, laser desorption can be used for either depth or surface profiling. 

Gases and vapors of volatile liquids can be introduced directly into a plasma flame for elemental analysis or for isotope ratio measurements. Some elements can be examined by first converting them chemically into volatile forms, as with the formation of hydrides of arsenic and tellurium. It is important that not too much analyte pass into the flame, as the extra material introduced into the plasma can cause it to become unstable or even to go out altogether, thereby compromising accuracy or continuity of measurement. 

Since detailed chemical structure information is not usually required from isotope ratio measurements, it is possible to vaporize samples by simply pyrolyzing them. For this purpose, the sample can be placed on a tungsten, rhenium, or platinum wire and heated strongly in vacuum by passing an electric current through the wire. This is thermal or surface ionization (TI). Alternatively, a small electric furnace can be used when removal of solvent from a dilute solution is desirable before vaporization of residual solute. Again, a wide variety of mass analyzers can be used to measure m/z values of atomic ions and their relative abundances. 

The use of accurate isotope ratio measurement is exemplified here by a method used to determine the temperature of the Mediterranean Sea 10,000 years ago. It is known that the relative solubility of the two isotopic forms of carbon dioxide COj) in sea water depends on temperature... 

Because variations in accurate isotope ratio measurements typically concern only a few parts per 1000 by mass and there are no universal absolute ratios, it is necessary to define some standards. For this purpose, samples of standard substances are produced and made available at two major centers IAEA (International Atomic Energy Authority, U.K.) and NIST (National Institute for Standards and Technology, U.S.). Standards from other sources are also available. These primary standards can be used as such, or alternative standards can be employed if the primary ones are not available. However, any alternative standards need to be related accurately to the primary ones (see formulae below). For example, the material PDB (PeeDee belemnite), used particularly as a standard for the ratio of isotopes, is no longer readily available, and a new standard, VPDB,... 

For example, if a carbonaceous sample (S) is examined mass spectrometrically, the ratio of abundances for the carbon isotopes C, in the sample is Rg. This ratio by itself is of little significance and needs to be related to a reference standard of some sort. The same isotope ratio measured for a reference sample is then R. The reference ratio also serves to check the performance of the mass spectrometer. If two ratios are measured, it is natural to assess them against each other as, for example, the sample versus the reference material. This assessment is defined by another ratio, a (the fractionation factor Figure 48.2). 

From a series of isotope ratio measurements, the precision of measurement can be assessed statistically, as shown here. Precision reveals the reproducibility of the measurement method, but it does not provide information on the accuracy of the measurement (see also Figures 48.8 and 48.9). 

Suppose that a true value for the ratio measured by the series in Figure 7,6 is 64.5. In the first series (Figure 7), the mean value was found to be 56.3 12.4 and this certainly encompasses the true result. 

Almost any type of analyzer could be used to separate isotopes, so their ratios of abundances can be measured. In practice, the type of analyzer employed will depend on the resolution needed to differentiate among a range of isotopes. When the isotopes are locked into multielement ions, it becomes difficult to separate all of the possible isotopes. For example, an ion of composition CgHijOj will actually consist of many compositions if all of the isotopes ( C, C, H, H, 0, O, and 0) are considered. To resolve all of these isotopic compositions before measurement of their abundances is difficult. For low-molecular-mass ions (HjO, COj) or for atomic ions (Ca, Cl), the problems are not so severe. Therefore, most accurate isotope ratio measurements are made on low-molecular-mass species, and resolution of these even with simple analyzers is not difficult. The most widely used analyzers are based on magnets, quadrupoles, ion traps, and time-of-flight instruments. 

Almost any kind of ion source could be used, but, again, in practice only a few types are used routinely and are often associated with the method used for sample introduction. Thus, a plasma torch is used most frequently for materials that can be vaporized (see Chapters 14-17 and 19). Chapter 7, Thermal Ionization, should be consulted for another popular method in accurate isotope ratio measurement. 

Accurate, precise isotope ratio measurements are important in a wide variety of applications, including dating, examination of environmental samples, and studies on drug metabolism. The degree of accuracy and precision required necessitates the use of special isotope mass spectrometers, which mostly use thermal ionization or inductively coupled plasma ionization, often together with multiple ion collectors. 

This is the basic process in an inductively coupled plasma discharge (ICP). The excited ions can be examined by observing the emitted light or by mass spectrometry. Since the molecules have been broken down into their constituent atoms (as ions) including isotopes, these can be identified and quantified by mass spectrometry, as happens with isotope ratio measurements. 

Thermal or surface emission of ions is one of the oldest ionization techniques used for isotope ratio measurements. 

With such mass spectrometers, plasma torches and thermal ionization are the most widely used means for ionizing samples for ratio measurements. 

Accurate, precise isotope ratio measurements are used in a variety of applications including dating of artifacts or rocks, studies on drug metabolism, and investigations of environmental issues. Special mass spectrometers are needed for such accuracy and precision. 

The vapor pressure ratio measures the intrinsic tendency of component 1 to enter the vapor phase relative to component 2. Likewise, ri measures the tendency of Mi to add to Mi - relative to M2 adding to Mi-. In this sense there is a certain parallel, but it is based on Mi - as a reference radical and hence appears to be less general than the vapor pressure ratio. Note, however, that ri = l/r2 means kn/ki2 = k2i/k22- In this case the ratio of rate constants for monomer 1 relative to monomer 2 is the same regardless of the reference radical examined. This shows the parallelism to be exact. 

Signal-to-noise ratio measured at conditions wavelength (A) = 800 nm, carrier frequency (/) = 1 MHz, linear velocity of the disk (t ) = 5 m/s, bandwidth (BW) = 30 kHz, unless otherwise noted. 

The rate constant k iv for solvolysis is assumed to reflect the stability and reactivity of (i.e., faster solvolysis gives a more stable cation, which, therefore, reacts more slowly with nucleophiles). The ratio measured by product distribution... 

Ratio measurement, polarity check and phase relationship ... 

FIGURE 6.19 Use of the clextral displacement produced by an insurmountable antagonist to estimate dose ratios and subsequent pA2 values. Response according to model for orthosteric noncompetitive blockade (Equation 6.31 with Emax = 1, t = 3, Ka = 0.3 pM, Kb = 1 pM) for 1 pM and 3 pM antagonist. Dose ratios measured at response = 0.24 for 1 pM antagonist and response = 0.15 for 3pM antagonist. Resulting pA2 values are close estimates of the true pKB (6.0) as modified by the [A]/Ka term (see Equation 6.37). 

FIGURE 12.13 Calculation of a pA2 value for an insurmountable antagonist, (a) Conner ation-response curve for control (filled circles) and in the presence of 2 jiM antagonist (open circles), (b) Data points fit to logistic functions. Dose ratio measured at response value 0.3 (dotted line). In this case, the DR = (200nM/50nM = 4). 

One final point should be made. The observation of significant solvent effects on kp in homopolymerization and on reactivity ratios in copolymerization (Section 8.3.1) calls into question the methods for reactivity ratio measurement which rely on evaluation of the polymer composition for various monomer feed ratios (Section 7.3.2). If solvent effects arc significant, it would seem to follow that reactivity ratios in bulk copolymerization should be a function of the feed composition.138 Moreover, since the reaction medium alters with conversion, the reactivity ratios may also vary with conversion. Thus the two most common sources of data used in reactivity ratio determination (i.e. low conversion composition measurements and composition conversion measurements) are potentially flawed. A corollary of this statement also provides one explanation for any failure of reactivity ratios to predict copolymer composition at high conversion. The effect of solvents on radical copolymerization remains an area in need of further research. 

M diethyltriaminepentraacetate (DTPA), and 0.50 M NH4OH. Distribution ratios measured by ICP/AES analysis were estimated to have a standard deviation of 20%. 

TABLE IV. Distribution Ratios (Measured by ICP/AES) from Synthetic HLLW. 50°C... 

Major limitations in fission product decontamination will require tests with mixer-settlers. However, we anticipate from the distribution ratio measurements that Tc, Ru, and Pd will limit the overall decontamination from beta activity (other than from lanthanides). ... 

If the wavelength of maximum absorption of the analyte (Xmax) is known, it can be monitored and the detector may be considered to be selective for that analyte(s). Since UV absorptions are, however, generally broad, this form of detection is rarely sufficiently selective. If a diode-array instrument is available, more than one wavelength may be monitored and the ratio of absorbances measured. Agreement of the ratio measured from the unknown with that measured in a reference sample provides greater confidence that the analyte of interest is being measured, although it still does not provide absolute certainty. 

Coplen, T.B. (2011). Guidelines and recommended terms for expression of stableisotope-ratio and gas-ratio measurement results. Rapid Gommunications in Mass Spectrometry, 25, 2538-2560. DOl 10.1002/rcm.5129 Cormie, A.B., Luz, B., Schwarcz, H.P. (1994a). Relationship between the hydrogen and oxygen isotopes of deer bone and their use in the estimation of relative humidity. Geochimica et Cosmochimica Acta, 58, pp. 3439-49. 

Figure 36 shows the contact ratios measured for different types of lubricant, at the speed ranging from 0.13 to 62... 

The Mo/Al ratio measured by XPS always decreased upon sulfiding. Bulk analysis showed no change in molybdenum concentration upon sulfiding, indicating that no molybdenum was lost during sulfiding. 

In addition to obtaining Information about the size, relative mass, and structure of the platinum crystallites, the STEM can provide a qualitative evaluation of the metal distribution from support particle to support particle. In general, the distribution of platinum was more uniform on alumina than silica, however, optimal uniformity was not achieved. This observation was based on wide variations In Pt/Sl and Pt/Al ratios measured by EDS. 

EDS compositional analysis with a focused 2nm electron beam of the FEG-TEM in the central part of mother cluster on the Ar-irradiated AuAg sample, gives an Au/ Ag ratio (measured at AuL and AgL) of 1.4 + 0.1, whereas the same ratio measured on the satellite clusters is 2.3+0.8. Similar ratios have been found from EDS analysis on AuAg sample irradiated with He, Ne, or Kr ions. EDS analysis reveals therefore a preferential extraction of Au atoms from the original cluster and this selective dealloying process is independent of the particular system investigated (we obtained similar results for Ne-irradiated AuCu cluster, as previously reported). 

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