Reproducibility, definition

Reproducible definition of electrochemicaUy accessible electrode area requires reproducible raw materials, reproducible surface energy of sensor substrate, reproducible dispersion of all electrode components and reproducible viscosity of all media, and transfer of reproducible matrix volumes. Since CGM sensors feature very small electrodes with a typical thickness of 20 pm or less and characteristic electrode dimensions of 500 pm or less, these requirements tend to be more challenging than for BGM sensors. 

The explicit definition of water molecules seems to be the best way to represent the bulk properties of the solvent correctly. If only a thin layer of explicitly defined solvent molecules is used (due to hmited computational resources), difficulties may rise to reproduce the bulk behavior of water, especially near the border with the vacuum. Even with the definition of a full solvent environment the results depend on the model used for this purpose. In the relative simple case of TIP3P and SPC, which are widely and successfully used, the atoms of the water molecule have fixed charges and fixed relative orientation. Even without internal motions and the charge polarization ability, TIP3P reproduces the bulk properties of water quite well. For a further discussion of other available solvent models, readers are referred to Chapter VII, Section 1.3.2 of the Handbook. Unfortunately, the more sophisticated the water models are (to reproduce the physical properties and thermodynamics of this outstanding solvent correctly), the more impractical they are for being used within molecular dynamics simulations. 

Good heat transfer on the outside of the reactor tube is essential but not sufficient because the heat transfer is limited at low flow rates at the inside film coefficient in the reacting stream. The same holds between catalyst particles and the streaming fluid, as in the case between the fluid and inside tube wall. This is why these reactors frequently exhibit ignition-extinction phenomena and non-reproducibility of results. Laboratory research workers untrained in the field of reactor thermal stability usually observe that the rate is not a continuous function of the temperature, as the Arrhenius relationship predicts, but that a definite minimum temperature is required to start the reaction. This is not a property of the reaction but a characteristic of the given system consisting of a reaction and a particular reactor. 

Finally, in this Introduction, it is worthwhile to reproduce one of the several current definitions, in the Oxford English Dictionary, of the word simulate To imitate the conditions or behaviour of (a situation or process) by means of a model, especially for the purpose of study or training specifically, to produce a computer model of (a process) . The Dictionary quotes this early (1958) passage from a text on high-speed data processing A computer can simulate a warehouse, a factory, an oil refinery, or a river system, and if due regard is paid to detail the imitation can be very exact . Clearly, in 1958 the scientific uses of computer simulation were not yet thought worthy of mention, or perhaps the authors did not know about them. 

Precision may be defined as the concordance of a series of measurements of the same quantity. Accuracy expresses the correctness of a measurement, and precision the reproducibility of a measurement (the latter definition will be modified later). Precision always accompanies accuracy, but a high degree of precision does not imply accuracy. This may be illustrated by the following example. 

Discussion. The turbidity of a dilute barium sulphate suspension is difficult to reproduce it is therefore essential to adhere rigidly to the experimental procedure detailed below. The velocity of the precipitation, as well as the concentration of the reactants, must be controlled by adding (after all the other components are present) pure solid barium chloride of definite grain size. The rate of solution of the barium chloride controls the velocity of the reaction. Sodium chloride and hydrochloric acid are added before the precipitation in order to inhibit the growth of microcrystals of barium sulphate the optimum pH is maintained and minimises the effect of variable amounts of other electrolytes present in the sample upon the size of the suspended barium sulphate particles. A glycerol-ethanol solution helps to stabilise the turbidity. The reaction vessel is shaken gently in order to obtain a uniform particle size each vessel should be shaken at the same rate and the same number of times. The unknown must be treated exactly like the standard solution. The interval between the time of precipitation and measurement must be kept constant. 

Secondly, I wish to counteract anticipated despondency which some of the complexities on the present theoretical scene may perhaps provoke. For this purpose, I wish to invoke the decisive simplicity and definiteness of some of the experimental effects observed within the confines of the above, near ideal systems. This, as I often pointed out elsewhere, is unmatched in the field of crystal growth of simple substances. Complicated as polymers may seem, and subtle as some of the currently relevant theoretical issues, this should not obscure the essential simplicity and reproducibility of the core material. To be specific, the appropriate chains seem to want to fold and know when and how, and it is hardly possible to deflect them from it. Clearly, such purposeful drive towards a predetermined end state should continue to give encouragement to theorists for finding out why Those who are resolved to persevere or those who are newly setting out should find the present review a most welcome source and companion. 

Fig. 1. Definition of Euler angles. Reproduced from Polymer by permission of the publishers, Butterworth Co. (Publishers) Ltd. (C)...

While there are no problems in the definition of the configuration leading to 0, difficulties are encountered in the procedure to reproduce the electrochemical situation. In fact, Eq. (17) has meaning only if the M/S interface has exactly the same structure during the measurement of E (relative to a reference electrode-electrochemical configuration) as well as during the measurement of 0. ... 

In a similar way, electrochemistry may provide an atomic level control over the deposit, using electric potential (rather than temperature) to restrict deposition of elements. A surface electrochemical reaction limited in this manner is merely underpotential deposition (UPD see Sect. 4.3 for a detailed discussion). In ECALE, thin films of chemical compounds are formed, an atomic layer at a time, by using UPD, in a cycle thus, the formation of a binary compound involves the oxidative UPD of one element and the reductive UPD of another. The potential for the former should be negative of that used for the latter in order for the deposit to remain stable while the other component elements are being deposited. Practically, this sequential deposition is implemented by using a dual bath system or a flow cell, so as to alternately expose an electrode surface to different electrolytes. When conditions are well defined, the electrolytic layers are prone to grow two dimensionally rather than three dimensionally. ECALE requires the definition of precise experimental conditions, such as potentials, reactants, concentration, pH, charge-time, which are strictly dependent on the particular compound one wants to form, and the substrate as well. The problems with this technique are that the electrode is required to be rinsed after each UPD deposition, which may result in loss of potential control, deposit reproducibility problems, and waste of time and solution. Automated deposition systems have been developed as an attempt to overcome these problems. 

As an example of the interest to scrutinise the UHF solution, one may quote the Bea problem [19]. The bond is weak but it takes plaee at short interatomic distance and is definitely not the dispersion well which one might expect from two closed shell atoms (and which occurs in Mga and heavier eompounds). Quantum chemical calculations only reproduce this bond when using large basis sets and extensive Cl calculations [20]. It is amazing to notice that the UHF solution gives a qualitatively correct behaviour, and suggests a physical interpretation of this bond since in... 

It can be seen from Figures 3.7 and 3.8 that the calculations reproduce very well not only the experimental spectra but also the experimentally observed isotopic shifts indicating a high reliability of the computational method. According to this comparison, definite attribution can be made for even the difficult Raman bands that cannot be assigned based solely on the experimental results. It is, however, necessary to mention at this point that the calculated Raman spectrum provided directly by the ab initio computations correspond to the normal Raman spectrum with the band intensity determined by the polarizability of the correlating vibration. Since the intensity pattern exhibited by the experimentally recorded resonance Raman spectrum is due to the resonance enhancement effect of a particular chromophore, with no consideration of this effect, the calculated intensity pattern may, in many... 

Figure 4.30 Definition of the peak separation function P - f/g. (Reproduced with permission fron ref. 479. Copyright Elsevier Scientific Publishing Co.)...

Trying to determine which column is ideal for a specific analysis can be difficult with over 1000 different columns on the market [74]. A proper choice implies a definition of parameters such as column material, stationary phase (polarity), i.d., film thickness and column length. Guides to column selection are available [74,75]. The most important consideration is the stationary phase. When selecting an i.d., sample concentration and instrumentation must be considered. If the concentration of the sample exceeds the column s capacity, then loss of resolution, poor reproducibility and peak distortion will result. Film thickness has a direct effect on retention and the elution temperature for each sample compound. Longer columns provide more resolving probe, increase analysis times and cost. 

Chemists have been working for a long time with particles having sizes of nanometers. The novelty of recent developments concerns the ability to make nanostructured substances with uniform particle sizes and in regular arrays. In this way it becomes feasible to produce materials that have definite and reproducible properties that depend on the particle size. The development began with the discovery of carbon nanotubes by Ijima in 1991 (Fig. 11.15, p. 116). 

Figure 23.44 The definition of cogeneration efficiency and site power-to-heat ratio. (From Varbanov P, Perry S, Makwana Y, Zhu XX and Smith, 2004, Trans IChemE, 82A 784, reproduced by permission of the Institution of Chemical Engineers.)...

Figure 5-1. Definition of chair conformation in /J-glucopyranose. Reproduced with permission from reference [66]. Copyright Elsevier 2004...

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