Analytical Chemistry Propagation Error
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Definition Of Error In Analytical Chemistry
in Registration Forgot password Expand/collapse global hierarchy Home Core Analytical Chemistry Quantifying Nature Expand/collapse global location Propagation of sources of error in analytical chemistry Error Last updated 20:33, 14 May 2016 Save as PDF Share Share Share Tweet Share IntroductionDerivation of Exact FormulaDerivation of Arithmetic ExampleCaveats and WarningsDisadvantages of Propagation of Error ApproachTreatment
Errors In Analytical Chemistry Ppt
of Covariance TermsReferencesContributors Propagation of Error (or Propagation of Uncertainty) is defined as the effects on a function by a variable's uncertainty. It is a calculus derived statistical calculation designed to combine uncertainties from multiple variables, in order to provide an accurate measurement of uncertainty. Introduction Every measurement has an air of uncertainty about it, and not all uncertainties error propagation formula are equal. Therefore, the ability to properly combine uncertainties from different measurements is crucial. Uncertainty in measurement comes about in a variety of ways: instrument variability, different observers, sample differences, time of day, etc. Typically, error is given by the standard deviation (\(\sigma_x\)) of a measurement. Anytime a calculation requires more than one variable to solve, propagation of error is necessary to properly determine the uncertainty. For example, lets say we are using a UV-Vis Spectrophotometer to determine the molar absorptivity of a molecule via Beer's Law: A = ε l c. Since at least two of the variables have an uncertainty based on the equipment used, a propagation of error formula must be applied to measure a more exact uncertainty of the molar absorptivity. This example will be continued below, after the derivation (see Example Calculation). Derivation of Exact Formula Suppose a certain experiment requires multiple instruments to carry out. These instruments each have different variability in their measurements. The results of each instrument are given as: a, b, c, d... (For simplification purposes, o
a desired quantity can be found directly from a single measurement, then the uncertainty in the quantity is completely determined by the precision of the measurement. It is not so simple, however, when a quantity must be calculated from two or more
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measurements, each with their own uncertainty. In this case the precision of the final result
Error Propagation Physics
depends on the uncertainties in each of the measurements that went into calculating it. In other words, uncertainty is always present and a measurement’s how to calculate uncertainty in chemistry uncertainty is always carried through all calculations that use it. Fundamental Equations One might think that all we need to do is perform the calculation at the extreme of each variable’s confidence interval, and the result reflecting the http://chem.libretexts.org/Core/Analytical_Chemistry/Quantifying_Nature/Significant_Digits/Propagation_of_Error uncertainty in the calculated quantity. Although this works in some instances, it usually fails, because we need to account for the distribution of possible values in all of the measured variables and how that affects the distribution of values in the calculated quantity. Although this seems like a daunting task, the problem is solvable, and it has been solved, but the proof will not be given here. The result is a general equation for the propagation of uncertainty that http://chemlab.truman.edu/chemlab_backup/DataAnalysis/Propagation%20of%20Error/PropagationofError.htm is given as Eqn. 1.2 In Eqn. 1 f is a function in several variables, xi, each with their own uncertainty, Δxi. (1) From Eqn. 1, it is possible to calculate the uncertainty in the function, Δf, if we know the uncertainties in each variable and the functional form of f (so we can calculate the partial derivatives with respect to each variable). It is easier to understand how this all works by doing several examples. Example 1: f = x + y (the result is the same for f = x – y). Let the uncertainty in x and y be Δx and Δy, respectively. Taking the partial derivatives with respect to each variable gives: and . The uncertainty in f is then , or (2) Example 2: f = x•y (also works for f = x/y) Again let the uncertainty in x and y again be Δx and Δy, respectively. Taking the partial derivatives with respect to each variable gives: and . The uncertainty in f is then . This result is more commonly written by dividing both sides by f = x•y to give (3) Although the idea of error propagation may seem intimidating, you have already been using it since your first chemistry class when you applied the rules for significant figures in calculations. These rules are simplified versions of Eqn. 2 and Eqn. 3, assumi
x, y, or z leads to an error in the determination of u. This is simply the multi-dimensional definition of slope. It describes how changes in u depend http://www.chem.hope.edu/~polik/Chem345-2000/errorpropagation.htm on changes in x, y, and z. Example: A miscalibrated ruler results in a systematic error in length measurements. The values of r and h must be changed by +0.1 cm. 3. Random Errors Random errors in the measurement of x, y, or z also lead to error in the determination of u. However, since random errors can be both positive and analytical chemistry negative, one should examine (du)2 rather than du. If the measured variables are independent (non-correlated), then the cross-terms average to zero as dx, dy, and dz each take on both positive and negative values. Thus, Equating standard deviation with differential, i.e., results in the famous error propagation formula This expression will be used in the Uncertainty Analysis section of every Physical Chemistry laboratory report! in analytical chemistry Example: There is 0.1 cm uncertainty in the ruler used to measure r and h. Thus, the expected uncertainty in V is ±39 cm3. 4. Purpose of Error Propagation · Quantifies precision of results Example: V = 1131 ± 39 cm3 · Identifies principle source of error and suggests improvement Example: Determine r better (not h!) · Justifies observed standard deviation If sobserved » scalculated then the observed standard deviation is accounted for If sobserved differs significantly from scalculated then perhaps unrealistic values were chosen for sx, sy, and sz. · Identifies type of error If ½uobserrved - uliterature½ £ scalculated then error is random error If ½uobserrved - uliterature½ >> scalculated then error is systematic error 5. Calculating and Reporting Values when using Error Propagation Use full precision (keep extra significant figures and do not round) until the end of a calculation. Then keep two significant figures for the uncertainty and match precision for the value. Example: V = 1131 ± 39 cm3 6. Comparison of Error Propagation to Significant Figures Use of significant figures in calculations is a rough estimate of error pr
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