Instrumentation concepts precision

Basic spectroscopic measurements involve the instrumental concepts of bandpass and resolution, signal-to-noise ratio, dynamic range, stray light, wavelength accuracy and precision, and photometric accuracy and precision. These concepts were described in Chapter 1. 

It is just a half-century ago that the concept of real abundance variations became well-established. It is less that 50 years since the famous B2FH paper was published. Quantitative CCD-based spectroscopy is only some 20 years old, while quantitative multi-object spectroscopy has really begun only in the last decade. These rapid observational advances were enabled by impressive advances in instrumentation, combined with increasing software power and complexity. In parallel, significant advances in stellar atmospheric modelling, and the requisite atomic and molecular data, have allowed analyses of superb precision for large numbers of stars. 

In earlier experiments the effect of branching on the second virial coefficient was not seriously considered because the accuracy of measurements were not sufficient at that time. With the refinements of modern instruments a much higher precision has now been achieved. Thus A2 can also now be measured with good accuracy and compared with theoretical expectations. The second virial coefficient results from the total volume exclusion of two macromolecules in contact [3,81]. Furthermore, this total excluded volume of a macromolecule can be expressed in terms of the excluded volume of the individual monomeric units. In the limit of good solvent behavior this concept leads to the expression [6,27] as shown in Eq. (24) ... 

Rigorous correction for instrumental mass bias is required if the precision of an isotope ratio measurement needs to be greater than l%o per mass unit. This concept is well illustrated by the definitive Ca isotope work of Russell et al. (1978), which used a double-spike approach. Prior to the Ca isotope investigation of Russell et al. (1978), natural mass-dependent Ca... 

Chemical techniques of analysis deal with a very large number of atoms and yield averages over the sample. Once the concept of isotopes was accepted, a search for different isotopes of every element was pursued. The key to the success of this search was the development of a precision instrument that sampled the atoms one at a time. It had been known since the development of the cathode ray tube that positive ions were also produced, and early experiments with these particles revealed singly and doubly charged species of the atoms and molectrles that were contained in the tube. Sir J.J. Thomson observed in 1912 that when neon was the background gas, particles of mass ntrmber 20 and 22 were observed. Attempts to obtain pure samples of the two different atoms by fractionation techniques were unsuccessful, but in retrospect this was because they were both neon isotopes. 

History of physical organic chemistry is essentially the history of new ideas, philosophies, and concepts in organic chemistry. New instrumentations have played an essential role in the mechanistic study. Organic reaction theory and concept of structure-reactivity relationship were obtained through kinetic measurements, whose precision depended on the development of instrument. Development of NMR technique resulted in evolution of carbocation chemistry. Picosecond and femtosecond spectroscopy allowed us to elucidate kinetic behavior of unstable intermediates and even of transition states (TSs) of chemical reactions. 

With the exception of the clathrate framework model, all these hypotheses appear to be qualitatively consistent with the available X-ray diffraction data on liquid water. It is argued by some investigators, however, that there are still significant inconsistencies between the most sophisticated statistical thermodynamic models for liquid water and the most sophisticated X-ray and neutron diffraction measurements [734-736]. The interpretation of these data from different experiments, using the concept of pair-correlation functions, shows discrepancies that are considered significant in terms of the instrumental precision, and the definitive answer seems not yet available [737J. 

The claim by G A that only one of these traditions developed techniques to imitate real-world conditions is quite misleading. Both traditions used the cloud chamber to manufacture an artificial environment that approximates known phenomena. For the Cavendish physicists, the cloud chamber became one of the defining instruments of particle physics, precisely because the laboratory phenomena were modeled on the movement of the charged particles. The knotty clouds blended into the tracks of alpha particles and the threadlike" clouds simulate beta-particle trajectories (Galison Assmus, 1989, p. 268). Of course, G A are correct that these physicists aspired to dissect nature into its fundamental components, reflecting the long tradition of the corpuscular conception of matter. 

An understanding of some of the basic vocabulary and principles employed in archaeological chemistry is essential to understanding this field of study. In the following paragraphs a brief discussion of matter and energy includes these relevant concepts. This is followed by a consideration of measurement issues and the very small quantities of elements, isotopes, and molecules we often have to measure in the lab. Finally the meaning of accuracy, precision, and sensitivity provide perspective on the results obtained from scientific instruments. 

A commonly used profile instrument is the Medical Outcomes Study 36-Item Short-Form Health Survey (SF-36). This instrument includes nine health concepts or scales (Table 2-3). The SF-36 can be self-administered or administered by a trained interviewer (face to face or via telephone). This instrument has several advantages. For example, it is brief (it takes about 5-10 minutes to complete), and its reliability and validity have been documented in many clinical situations and disease states. " A means of aggregating the items into physical (PCS) and mental (MCS) component summary scores is available." In addition, an abbreviated version of the SF-36 containing only 12 items (SF-12) has been introduced." However, the scale scores and mental and physical component summary scores derived from the SF-12 are based on fewer items and fewer defined levels of health and, as a result, are estimated with less precision and less reliability. The loss of precision and reliability in measurement can be a problem in small samples and/or with small expected effect sizes for an intervention. 

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