Random errors accumulation

Random errors accumulated within an analytical procedure contribute to the overall precision. Where the calculated result is derived by the addition or subtraction of the individual values, the overall precision can be found by summing the variances of all the measurements so as to provide an estimate of the overall standard deviation, i.e. 

How to best describe this broadening we expect to occur One way is by analogy to random error in measurements. We know or assume there is a truly correct answer to any measurement of quantity present and attempt to determine that number. In real measurements there are real, if random, sources of error. It is convenient to talk about standard deviation of the measurement but actually the error in measurement accumulates as the sum of the square of each error process or variance producing mechanism or total variance = sum of the individual variances. If we ignore effects outside the actual separation process (e.g. injection/spot size, connecting tubing, detector volume), this sum can be factored into three main influences ... 

Random, or indeterminate, errors exist in every measurement. They can never be totally eliminated and are often the major source of uncertainty in a determination. Random errors are caused by the many uncontrollable variables that are an inevitable part of every analysis. Most contributors to random error cannot be positively identified. Even if we can identify sources of uncertainty, it is usually impossible to measure them because most are so small that they cannot be detected individually. The accumulated effect of the individual uncertainties, however, causes replicate measurements to fluctuate randomly around the mean of the set. For example, the scatter of data in Figures 5-1 and 5-3 is a direct result of the accumulation of small random uncertainties. We have replotted the KJeldahl nitrogen data from Figure 5-3 as a three-dimensional plot in Figure 6-1 in order to better see the precision and accuracy of each analyst. Notice that the random error in the results of analysts 2 and 4 is much larger than that seen in the results of analysts 1 and 3. The results of analyst 3 show good precision, but poor accuracy. The results of analyst 1 show excellent precision and good accuracy. 

In order to provide a means for the precise recalculation of nitrogen chemical shifts reported since 1972, it is necessary to have accurate values of the differences in the screening constants between neat CH3N02 and the large number of reference compounds which have so far been used. Table VII shows the results of precise, 4N measurements (61) which have been carried out in concentric spherical sample and reference containers in order to eliminate bulk susceptibility effects on the shifts. Since the technique adopted (61, 63) involves the accumulation of a large number of individually calibrated spectra with the subsequent use of a full-lineshape analysis by the differential saturation method, (63) the resulting random errors comprise those from minor temperature variations, phase drifts, frequency instability, sweep nonlinearity, etc. so that systematic errors should be insignificant as compared with random errors. 

Since soils are strong accumulators of lead, the analysis of lead in soil is an excellent indicator of accumulated deposition in the vicinity of a source of the metal. In one survey around a secondary smelter [12], concentrations of lead up to 21 000 mg kg" (dry weight) were found in the upper 5 cm of soil adjacent to the smelter with the levels decreasing exponentially with distance from the source. Mean concentrations of lead in soil around the Silver Valley lead smelter [13] (air lead concentrations in Fig. 2.3) are shown in Fig. 4.2. Changes in soil lead between the 1974 and 1975 surveys presumably arise mainly from random errors introduced by minor spatial variability in the lead concentration. 

The use of higher-order algorithms may not always be profitable when the force has some unpredictable quality, for example as a result of cut-off errors, approximation, tabulation error or the explicit use of stochastic terms. In practice algorithms should at least be a 4-value type i.e. they should contain the force derivative (or the force in the previous step) because the second derivative of the potential predominantly has a positive sign for favourably interacting particles and its omission would produce accumulating rather than random errors. The use of still higher derivatives, however, is of questionable practical interest. 

The accumulated effect of indeterminate (random) errors is computed by combining statistical parameters for each measurement (Topic B2). 

The slight overall excess of HF used ( -5%) is in reasonable agreement with the 15% excess indicated by the intensity of the HF band in the Figure 7 spectrum. The total 2.4 mole equivalents of H2 measured as a product is on the low side, probably due to accumulated random error in the measurements combined with the likely systematic error mentioned earlier. 

The discrepancy is due to sources of errors not considered in the above discussion, such as field noise and reproducibility, thermal effects, etc. In particular, thermal effects on the magnet are important since from experience, it shows that the scatter increases when the relaxation field and/or the polarization field are close to the upper limit of the magnet. Since all such contributions are random, prolonged data accumulation reduces both the fitting errors and the scatter. 

After many excitation cycles, the number of counts which have been accumulated in one channel is proportional to the probability of emission at a given time after excitation. The errors on these number of counts are random, independent and follow the well known Poisson distribution The emission decay is recorded alternatively in vertical (Parallel) and horizontal (Perpendicular) polarizations using a computer-commanded rotating Polarizer. 

The Irregularities were considered to be purely random. They were most probably contributed by a steady accumulation of errors with time. 

Often, the quantity of interest in an experiment is not measured directly, but is computed via a mathematical equation or model. Eor example, the overall heat-transfer coefficient (say, C) of a specific heat exchanger might be determined indirectly by measuring the inlet and outlet temperatures. Repeated experiments provide an estimate of the variance of U, but this variance does not account for possible experimental errors (e.g., the thermocouple errors in the temperature measurements). The error in each measurement accumulates in the overall error of a calculated quantity in a manner known as propagation of error. Measurement error can arise from random variability or instrument sensitivity. There is, however, a mathematical approach to deal with these errors. 

If we do not have a well-timed application of the magnetic field component from our RF, then the net magnetization vector will not be effective in tipping the net magnetization vector. In particular, if the RF frequency is not just randomly mistimed but is consistently higher or lower than the Larmor frequency, the errors between when the push should and does occiu will accumulate before too long our pushes will actually serve to decrease the amplitude of the net magnetization vector M s departure from equilibrium. The accumulated error caused by poorly synchronized beats of RF with respect to the Larmor frequency of the spins is well known to NMR spectroscopists and is called pulse roll-off. 

Except for several classic geometric bodies, the integrals in Equations 1.29 and 1.30 with any expression for x must be evaluated numerically. That is done using Monte Carlo schemes, where a large number of gas atoms is shot at an ion with random 0, (p, y, b, their trajectories in the assumed are tracked through the collision event (1.4.3 and 1.4.4) producing x, and contributions to ft are accumulated. As with any Monte Carlo integration, the statistical error scales as (number of... 

Results of an analysis conducted on a hyphenated instrument are typically calculated from two or more experimental data sets, each of which carries some uncertainty due to random noise or experimental errors. It is therefore worthwhile determining the ways various uncertainties accumulate in the final output from a hyphenated instrument. For simplicity, let us assume that two in-line instruments measure two quantities jc and y which depend upon variables p, q, r for x, and s, t, u fory. 

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