Reproducibility condition of measurement

NOTE 2 The specified conditions can be, for example, repeatability conditions of measurement, intermediate precision conditions of measurement, or reproducibility conditions of measurement (see ISO 5725-2 1994). NOTE 3 Measurement precision is used to define measurement repeatability, intermediate measurement precision, and measurement reproducibility. 

Definition Measurement precision under reproducibility conditions of measurement [25]. 

Description Measurement precision is usually expressed numerically by measures of imprecision, such as standard deviation, variance, or coefficient of variation, under the specified conditions of measurement. When a measurement precision is given, it is important to specify the conditions. These conditions can be, for example, repeatability condition of measurement, intermediate precision condition of measurement, or reproducibility condition of measurement (see ISO 5725-3 1994 and see below). The measurement precision is used to define measurement repeatability, intermediate measurement precision, and measurement reproducibiUty. In the VIM, it is mentioned that sometimes measurement precision is erroneously used to indicate measurement accuracy. 

On the other hand, reproducibility is the closeness of the agreement between the results of measurements of the same measurand carried out under changed conditions of measurement . The changed conditions include principle of measurement, method of measurement, observer, measuring instrument, reference standards, location, conditions of use, and time. Such variable conditions are typical for interlaboratory studies (laboratory intercomparisons). 

For a qualitative analysis it is sufficient to be able to apply a test which has a known sensitivity limit so that negative and positive results may be seen in the right perspective. Where a quantitative analysis is made, however, the relation between measurement and analyte must obey a strict and measurable proportionality only then can the amount of analyte in the sample be derived from the measurement. To maintain this proportionality it is generally essential that all reactions used in the preparation of a sample for measurement are controlled and reproducible and that the conditions of measurement remain constant for all similar measurements. A premium is also placed upon careful calibration of the methods used in a quantitative analysis. These aspects of chemical analysis are a major pre-occupation of the analyst. 

Figure 7. Lipophilicity profile of propranolol in liposomes composed of zwitterionic and charged lipids (phosphatidyl ethanolamine (PE), oleic acid (OA), phosphatidyl inositol (PI)). Conditions of measurements are described in [113]. The dotted line indicates the partitioning profile of propranolol in the egg PC liposome system. The bars show the pH-dependent charge profile of propranolol (hatched bars positively charged propranolol) and the lipids in the membrane (black bars negatively charged lipids). Reprinted from [113] Kramer, S. (2001). Liposome/water partitioning , In Pharmacokinetic Optimization in Drug Research, eds. Testa, B. et al. Reproduced by permission of Verlag Helvetica Chimica Acta, Zurich...

Reproducibility means conditions of measurement that includes different locations, operators, measuring systems, and replicate measurements on the same or similar objects. 

Repeatability [2] is defined as the closeness of the agreement between the results of successive measurements of the same measurand carried out under the same conditions of measurement. Repeatability should be distinguished from reproducibility for which the closeness of the agreement concerns the results of measurements (of the same measurand) that are not necessarily made successively and not under the same conditions, by the same method, or in the same laboratory... 

Repeatability closeness of agreement between results of successive measurements carried out under the same conditions (i.e., corresponding to within-run precision). Reproducibility closeness of agreement between results of measurements performed under changed conditions of measurements (e.g., time, operators, calibrators, and reagent lots). Two specifications of reproducibility are often used total or between-run precision in the laboratory, often termed intermediate precision and interlaboratory precision (e.g., as observed m external quality assessment schemes [EQAS]) (see Table 14-2). 

As a result of the reproducibility conditions of these spectra, it is possible to use them for the differentiation of closely related isomers. Thus, Boyd and co-workers [143] were able to characterize polyaromatic hydrocarbon isomers of molecular mass m/z 228 by measuring the ratios of losses of H and H2 from M" " (Table 8). 

Table 3.5. Turnover frequencies (TOFs) for O2 Reduction [e /site.s], Site Densities (SD in [sites/cm ]), and Their Product x 1.6 x 10 [C/e ] = A/cm of Supported Catalyst, at 800mVjj( f. ee for 47 wt% Pt Compared to Activity Requirements for a Costless Catalyst and the Experimental Absolute Activities of Non-Pt Catalysts from Selected References. TOFs are Shown Both at the Conditions of Measurement and Corrected for the Pt Reference Industrial Conditions, Assuming p02 to the First Order and = 54.7 kJ/mol O2, i.e., Corrected Using Parameters for Pt (Reproduced from Ref., with the Permission of Elsevier)...

Toxicity. Toxicity is estabhshed through the Toxicity Characteristic Leaching Procedure (TCLP), which measures the tendency of certain toxic materials to be leached (extracted) from the waste material under circumstances assumed to reproduce conditions of a landfill. The TCLP list includes a relatively small number of industrially important toxic chemicals and is based on the concentration above which a waste is considered hazardous. Failure to pass the TCLP results in classification of a material as a toxic waste. 

This reaction, however, unlike the hydrogen electrode reaction, is not strictly reversible under practical conditions of measurement, and hence the measured potential may vary with time and is not reproducible. The observed potential tends to be less noble than the calculated reversible value. Nevertheless, it is useful to know the direction of expected potential change as, for example, when oxygen pressure is altered. For illustration, consider two oxygen electrodes in an aqueous environment one in contact with O2 at 1 atm (left) and the other with O2 at 0.2 atm (right). The potentials of the left- and right-hand electrodes, respectively, are as follows ... 

The main purposes of the System of accreditation is to ensure reproducibility of measurements, harmonisation of rules and procedures of the National system of accreditation with guidelines of international organizations and national systems of different countries, creation of conditions for mutual recognition of the results of testing, calibration, attestation. 

The concept of equilibrium is central in thermodynamics, for associated with the condition of internal eqmlibrium is the concept of. state. A system has an identifiable, reproducible state when 1 its propei ties, such as temperature T, pressure P, and molar volume are fixed. The concepts oi state a.ndpropeity are again coupled. One can equally well say that the properties of a system are fixed by its state. Although the properties T, P, and V may be detected with measuring instruments, the existence of the primitive thermodynamic properties (see Postulates I and 3 following) is recognized much more indirectly. The number of properties for wdiich values must be specified in order to fix the state of a system depends on the nature of the system and is ultimately determined from experience. 

The literature contains many references to the use of notched, as opposed to pre-cracked or plain, specimens in laboratory studies of stress corrosion, for reasons of improved reproducibility, inability to crack plain specimens under otherwise identical conditions or ease of measuring some parameter such as crack growth rate when the crack location is predetermined. However, the developments in fracture mechanics (see Section 8.9), have resulted in a whole new field of stress-corrosion testing involving the use of specimens... 

Campbell (6) was perhaps the first to investigate the relationship between tenderometer values for raw peas and the texture characteristics of collateral samples after freezing and cooking. A high degree of correlation was observed. The investigations of Nielsen and co-workers (31) indicate the usefulness of the instrument for estimation of maturity in peas intended for freezing preservation. In order to secure consistent and reproducible results, the instrument requires standardization and calibration, and the measurements must be made under standardized conditions of temperature and interval after harvest. 

Though the literature is replete with methods of measuring the moisture content, truly accurate as well as practical methods are virtually nonexistent in the food field. The situation is well illustrated in what is probably the best compendium on this subject, the Official and Tentative Methods of Analysis of the Association of Official Agricultural Chemists (2). It becomes apparent from an examination of this volume that the stress is laid not so much on accuracy as on reproducibility and practicability of a method. Though these last two factors are for the most part the only ones of importance in the control of processing procedures and in standardization of products of commerce, the factor of accuracy is, nevertheless, of extreme importance to the research worker who endeavors to establish broad quantitative generalizations for the conditions that govern the stability of foods. 

Although liquid Hg would never be used as a reference (model) surface in surface physics because its liquid state and high vapor pressure do not allow appropriate UHV conditions, this metal turns out to be a reference surface in electrochemistry for precisely the same reasons reproducibility of the surface state, easy cleaning of its surface, and the possibility of measuring the surface tension (surface thermodynamic conditions). In particular, the establishment of a UHV scale for potentials is at present based on data obtained for Hg. 

The precision of an analytical procedure expresses the closeness of agreement (degree of scatter) between a series of measurements obtained from multiple sampling of the same homogeneous sample under the prescribed conditions. Precision may be considered at three levels repeatability (within run) intermediate precision (over time) and reproducibility (inter-laboratory). 

Figure 2. The binding and dissociation of FLPEP and receptor on intact neutrophils at 37 C The data are plotted as the specific binding of FLPEP (pmoles/10 cells) on a log plot versus time. Experimental details 10 cells/mL were exposed at time 0 to 1 nAf FLPEP. At 15, 30, 60, or 120 s, antibody to fluorescein is added to each sample. Fluorescence is monitored continuously during the additions. The data ate derived from a point-by-point comparison of the fluorescence measured under conditions of receptor binding and receptor blockade. Data are representative of observations in more than 10 separate experiments. (Reproduced with permission from reference 22. Copyright 19S7 Journal of Biological Chemistry.)...

Some Chemical Considerations Relevant to the Mouse Bioassay. Net toxicity, determined by mouse bioassay, has served as a traditional measure of toxin quantity and, despite the development of HPLC and other detection methods for the saxi-toxins, continues to be used. In this assay, as in most others, the molar specific potencies of the various saxitoxins differ, thus, net toxicity of a toxin sample with an undefined mixture of the saxitoxins can provide only a rough approximation of the net molar concentration. Still, to the extent that limits can be placed on variation in toxin composition, the mouse assay can in principle provide useful data on trends in net toxin concentration. However, the somewhat protean chemistry of the saxitoxins makes it difficult to define conditions under which the composition of a mixture of toxins will remain constant thus, attaining a reproducible level of mouse bioassay toxicity is difficult. It is therefore useful to review briefly some of the chemical factors that should be considered when employing the mouse bioassay for the saxitoxins or when interpreting results. Similar concepts will apply to other assays. 

One distingnishes practical and standard reference electrodes. A standard RE is an electrode system of particnlar confignration, the potential of which, nnder specified conditions, is conventionally taken as zero in tfie corresponding scale of potentials (i.e., as the point of reference nsed in finding tfie potentials of otfier electrodes). Practical REs are electrode systems having a snfficiently stable and reproducible value of potential which are nsed in the laboratory to measure the potentials of other electrodes. The potential of a practical reference electrode may difier from the conventional zero potential of the standard electrode, in which case the potential of the test electrode is converted to this scale by calculation. 

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