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Evaluation of Analytical Data

Ref:

Holler, Skoog, Crouch, “Principle of Instrumental Analysis”, 6th Ed., Thomson Books/Cole, 2007.

1

Analytical Chemistry

Qualitative & Quantitative Method

• Classical method

– Separation methods: precipitation, extraction,

distillation

– Qualitative methods: color, boiling or melting point,

solubility, odor, optical activities, refractive index

– Quantitative method: gravimetric or titrimetric

measurement

• Instrumental method

– Separation methods: chromatographic, electrophoretic

– Qualitative and Quantitative methods: measurements

of physical and chemical properties of analytes, such

as conductivity, electrode potential, light

absorption/emission, mass-to-charge ratio,

fluorescence etc.

2

electrical. Visible light. mechanical.Types of Instrumental Methods TABLE 1-1 Chemical and Physical Properties Used in Instrumental Methods *Most of the characteristics listed here require a source of energy to stimulate a measurable response from the analyte. or nuclear energy • The stimulus elicits a response from the system under study whose nature and magnitude are governed by the fundamental laws of chemistry and physics. λ sample I I0 (absorption) I/I0 analyte conc. 3 Instruments for analysis • Stimulus: in the form of electromagnetic. 4 .

. e. 3. photodiodes. What are the physical and chemical properties of the sample matrix? 6. What accuracy is required? (time & care?) How much sample is available? (sensitive?) What is the concentration range of the analyte? What components of the sample will cause interference? (selectivity?) 5. How many samples are to be analyzed? (economic? ) 6 . e. electrical charge. 4.g. • Transducer: devices that convert information in nonelectrical domain to the electrical domain and the converse. electrical or chemical device that identifies. . glass electrode… 5 Selecting an analytical method • Defining the problem To answer the following questions is required for selecting an analytical method: 1. 2. T..…. e. • Sensors: devices that are capable of monitoring specific chemical species continuously and reversibly. records or indicates a change in one of the variables in its environment. P.g.Detectors. photomultiers.g. Transducers and Sensors • Detector: a mechanical.

Performance of Characteristics of Instruments TABLE 1-3 Numerical Criteria for Selecting Analytical Methods 7 Precision and Bias • Precision: the degree of mutual agreement among data that have been obtained in the same way TABLE 1-5 Figures of Merit for Precision of Analytical Methods • Bias: μ-xt μ: population mean xt: true value 8 .

or it may be determined by extrapolation. of the analyte. Sbl: signal for a blank (y-intercept) *Analytical sensitivity. or it may be determined by extrapolation. The concentration of the unknown solution may be calculated from the slope m and the intercept b. c: the conc. FIGURE 1-10 Linear calibration plot for the *Two factors limit sensitivity: method of standard additions. *Calibration sensitivity Calibration curve S=mc+Sbl where S: measured signal. as explained in the text. The –The slope of the calibration curve –The reproducibility or precision of the measuring device concentration of the unknown solution may be calculated from the slope m and the intercept b. as explained in the text. c: the conc. of the analyte. m: calibration sensitivity (slope). m: calibration sensitivity (slope). S=mc+Sbl where S: measured signal. γ: γ=m/Ss Ss: the standard deviation of the measurement 9 Calibration curve FIGURE 1-10 Linear calibration plot for the method of standard additions.Sensitivity • Sensitivity: a measure of the ability to discriminate between small differences in analyte conc. Sbl: signal for a blank (y-intercept) 10 .

Detection Limit • Detection Limit (cm): the minimum concentration or mass of the analyte that can be detected at a known confidence level. since S=mc+Sbl cm=(Sm- )/m 11 . • The minimum distinguishable analytical signal Sm: = + ( = ) is the mean blank signal and is the where standard deviation of the blank.

A=mC/mA S=mA(cA+ kB. LOQ = limit of quantitative measurement. cost and availability of equipment. per-sample cost 14 .AcC)+Sbl Example1-2 • Others: speed.A=mB/mA and kC.Dynamic range FIGURE 1-13 Useful range of an analytical method. LOL=limit of linear response.AcB+ kC. ease and convenience. 13 Selectivity and others • Selectivity: the degree to which the method is free from interference by other species contained in the sample matrix. S=mAcA+mBcB+mCcC+Sbl Define selectivity coefficient : kB. skill required for operator.

– To describe the precision: standard derivation. variance.Evaluation of Analytical Data • Precision and Accuracy 15 Precision and Accuracy • Precision: “the reproducibility of results”. coefficient of variation • Accuracy: ”the correctness of an experimental result” – To express the accuracy: *absolute error: *relative error: where : mean of a small set of replicate analyses xt : an accepted value of the quantity being measured 16 . the agreement between numerical values for measurements that have been made in the exactly the same way.

Types of Errors • E a= E r + E s where Er: random error. Es: system error • Random error: where μ: the mean of an infinite collection of data 17 Distribution of Random Error 18 .

• The results cluster symmetrically around this mean value. 20 .Fig a1-1 A No. • Small divergences from the central mean value are found more frequently than are large divergences. the mean of a large set of data approaches the true values. of analyses much larger The size of cell much smaller Fig a1-1 B 19 Characteristics of Gaussian Curve • The most frequently observed results is the mean μ of the set of data. • In the absence of systematic errors.

• The laws of statistics apply strictly to populations only. or universe. we must assume that the sample is truly representative of the population.System Error—Bias Method A has no bias Method B has a bias : • Three types of systematic errors: instrumental. 21 Statistical Treatment of Random Errors • Statisticians call the handful of data a sample and view it as a subset of an infinite population. 22 . when applying these laws to a sample of laboratory data. personal and method. of data that in principle exists.

• Relative Standard Deviation (RSD) and Coefficient of Variation (CV) Z=2. when the RSD is given as a percent. then the total variance σt2 is given by the relationship 23 Some Terms Used in Statistics (2) • Sample Standard Deviation (s) and Sample Varince (s2) : the sample mean (N-1): the number of degree of freedom. If there are n independent source of random error in a system.Some Terms Used in Statistics (1) • Population Mean (μ) • Population Standard Deviation (σ) and the Population Variance (σ2) Statistician prefer to express the precision of data in terms of variance. 24 .

Symmetrical distribution of positive and negative deviations about this maximum 3. whose values lie in the region x to (x+dx) is given by • Figure a1-3 b: the Normal Error Curve 25 The Normal Error Curve • This type of plot yields a single curve regardless of the magnitude of the standard deviation of the data. Zero deviation from the mean occurring with maximum frequency 2. • The general properties of this curve: 1. Exponential decrease in frequency as the magnitude of the deviations increases 26 . dN/N.The Normal Error Law • The normal error law states the fraction of a population of observations.

3% of a population of data lie within ±1σ of its mean value – 95.. the average strength of the noise is constant and independent of the magnitude of the signal. effect of noise ↑ as signal ↓ 28 .Areas Under Regions of the Normal Error Curve • The area under the curve in Figure a1-3 where erf(b) is error function • The area under the curve between z=1 and z=-1 (±1σ) – 68. 5-1b never be realized in the lab. • In most measurement.9 ×10-15 A direct current.7% lie within ±3σ 27 Signal to Noise FIGURE 5-1 Effect of noise on a current measurement: (a) experimental stripchart recording of a 0. because some types of noise raise from thermodynamic and quantum effect. • Fig.5% lie within ±2σ and 99. (b) mean of the fluctuations.

including noise • Noise for each measurement: Sx – Si –Mean-square noise = (variance of signal) –Root-mean-square (rms) noise = (standard deviation of the signal) • Signal to noise ratio: 30 . i=1. it becomes impossible to detect signal when the signal-to-nose ratio becomes less than about 2 or 3. FIGURE 5-2 Effect of signal-to-noise ratio on the NMR spectrum of progesterone: A. the mean of the measurement Signal to noise ratio. S/N = 4. B.2….. S/N = 43.Signal to Noise Ratio (S/N) • • • Signal to noise ratio (S/N): for describing the quality of an analytical method or the performance of an instrument For a dc signal (fig5-1a) Noise: the standard deviation s of numerous measurements of the signal strength Signal: .. a dc signal The mean value: where Si.n are the individual measurements of the signal.3. S/N = mean/ standard deviation = 1 / RSD where RSD: relative standard deviation • As a general rule. 29 Signal to Noise Ratio (S/N) • Make n repetitive measurements of S.

but the signal itself accumulates Thus. Random fluctuations in the signal tend to cancel as the number of scans increases.Signal to Noise Ratio multiply by n: S/N is proportional to FIGURE 5-10 Effect of signal averaging. 31 S/N Enhancement by Software Methods • Ensemble averaging (coaddition) FIGURE 5-9 Ensemble averaging of a spectrum. Note that the vertical scale is smaller as the number of scans increases. the S/N increases with an increasing number of scans. The signal-to-noise ratio is proportional to √n. 32 .

Boxcar Averaging • assumptions: irregularities are the consequence of noise. the inverse Fourier transform of part (d) with most of the high-frequency noise removed. 34 . (d) product of part (b) and part (c). 33 Fourier Transform Procedure Upper-cutoff frequency FIGURE 5-12 Digital filtering with the Fourier transform: (a) noisy spectral peak. the analog analytical signal varies as only slowly with time and the average of a small number of adjacent points is a better measure of the signal than any of the individual points FIGURE 5-11 Effect of boxcar averaging: (a) original data. (c) low-pass digital-filter function. (b) the frequencydomain spectrum of part (a) resulting from the Fourier transformation. (b) data after boxcar averaging.

smoothed data (▲).Least-Squares Polynomial Smoothing (1) * Unweighted data smoothing FIGURE 5-13 The operation of an unweighted moving average smoothing function: noisy spectral data (•). The basic unweighted smoothing function gives too much weight to points that are well removed from the central point. 36 . (b) firstderivative cubic five-point integers. 35 Least-Squares Polynomial Smoothing (2) A1=(-3*A01+12*A02+17*A03+12*A04-3*A05)/35 FIGURE 5-14 Least-squares polynomial smoothing convolution integers: (a) quadratic five-point integers. See text for a description of the smoothing procedure. (c) second-derivative quadratic five-point integers.

(B) quadratic 5-point smooth of the data in A. (C) fourth-degree 13point smooth of the same data. (D) tenth-degree 77-point smooth of the data.Least-Squares Polynomial Smoothing (3) FIGURE 5-15 Effect of smoothing on a noisy absorption spectrum of tartrazine: (A) Raw spectrum. 37 . Users of smoothing must recognize that noise reduction has to be balanced against possible distortion of the signal.

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