Errors in Chemical Analysis

Lecture 1

Data quality
Measurements invariably involve errors and uncertainties.
Uncertainties can never be completely eliminated, measurement data can give us only an estimate of the true value.

Reliability can be assessed in several ways:

Experiments designed to reveal the presence of errors Compared with the known compositions Consult to the chemical literature Equipment Calibration Statistical tests

Representative Data
Chemists usually carry two to five portions (replicates) of a sample through an entire analytical procedure.
Replicates are samples of about the same size that are carried through an analysis in exactly the same way.

One usually considers the best estimate to be the central value for the set:
Usually, the mean or the median is used as the central value for a set of replicate measurements. The variation in data allows us to estimate the uncertainty associated with the central result

The Mean and Median

The most widely used measure of central value is the mean, . The mean, also called the arithmetic mean, or the average,

where xi represents the individual values of x making up the set of N replicate measurements.

The median is the middle result when replicate data are arranged according to increasing or decreasing value.

EXAMPLE 5-1 Calculate the mean and median for the data shown in Figure 5-1.

Because the set contains an even number of measurements, the median is the average of the central pair:

Precision
Describes the reproducibility of measurements Or, the closeness of results that have been obtained in exactly the same way. Three terms are widely used to describe the precision of a set of replicate data:
standard deviation; variance; coefficient of variation.

Deviation from the mean:

Accuracy
Indicates the closeness of the measurement to the true or accepted value Expressed in terms of either absolute or relative error. Absolute error:
where xt is the true or accepted value of the quantity We retain the sign in stating the absolute error.

Relative error:

The difference between accuracy and precision

Types of Errors in Experimental Data

The precision of a measurement is readily determined by comparing data from carefully replicated experiments. To determine the accuracy, we have to know the true value, which is usually what we are seeking in the analysis.

 Analyst 1: relatively high precision & high accuracy Analyst 2: poor precision but good accuracy Analyst 3: excellent precision & significant error in the numerical average for the data Analyst 4: poor precision & poor accuracy

Types of Errors
Random (or indeterminate) error:
Affect measurement precision Causes data to be scattered more or less symmetrically around a mean value.
Analysts 1 and 3 is significantly less than that for analysts 2 and 4.

Systematic (or determinate) error:

Affect the accuracy of results Causes the mean of a data set to differ from the accepted value.
Analysts 1 and 2 have little systematic error; Analysts 3 and 4 show systematic errors of about -0.7% and -1.2%.

 Gross error:
Often the product of human errors. usually occur only occasionally, are often large, and may cause a result to be either high or low. lead to outliers, results that appear to differ markedly from all other data in a set of replicate measurements.

Systematic Errors
Lead to bias in measurement results
Bias affects all of the data in a set in the same way and that bears a sign

Three types:
Instrumental errors are caused by nonideal instrument behavior, by faulty calibrations, or by use under inappropriate conditions. Method errors arise from nonideal chemical or physical behavior of analytical systems. Personal errors result from the carelessness, inattention, or personal limitations of the experimenter.

Instrument Errors
All measuring devices are potential sources of systematic errors. Calibration eliminates most instrumental systematic errors. Electronic instruments are subject to instrumental systematic errors.
Ex: low battery voltage, noises In many cases, errors of these types are detectable and correctable.

Method Errors
The nonideal chemical or physical behavior of the reagents and reactions on which an analysis is based Ex: the slowness of some reactions, the incompleteness of others, the instability of some species Errors inherent in a method are often difficult to detect and are thus the most serious of the three types of systematic error.

Personal Errors
Many measurements require personal judgments. Judgments of this type are often subject to systematic, undirectional errors. Analytical procedures should always be adjusted so that any known physical limitations of the analyst cause negligibly small errors. A universal source of personal error is prejudice, or bias. Number bias is another source of personal error that varies considerably from person to person.

Effect of Systematic Errors on Analytical Results

Systematic errors may be either constant or proportional. Constant errors
Independent of the size of the sample being analyzed. The absolute error is constant with sample size, but the relative error varies when sample size is changed. The excess of reagent required to bring about a color change during a titration is an example. The effect of a constant error becomes more serious as the size of the quantity measured decreases.

 Proportional errors
Decrease or increase in proportion to the size of the sample. The absolute error varies with sample size, but the relative error stays constant with changing sample size. A common cause of proportional errors is the presence of interfering contaminants in the sample.

Systematic Instrument and Personal Errors Detection

Instrument errors
Some systematic instrument errors can be found and corrected by calibration. Periodic calibration of equipment is always desirable because the response of most instruments change with time as a result of wear, corrosion, or mistreatment.

Personal errors
Most personal errors can be minimized by care and self-discipline. It is a good habit to check instrument readings, notebook entries, and calculations systematically.

Systematic Method Errors Detection Take one or more of the following steps to recognise and adjust for a systematic error:
Analysis of Standard Samples Independent Analysis Blank Determinations Variation in Sample Size

Analysis of Standard Samples

The best way of estimating the bias of an analytical method is by the analysis of standard reference materials.
Standard Reference Materials (SRMS):
Materials that contain one or more analytes at known concentration levels. Can sometimes be prepared by synthesis. Can be purchased from a number of governmental and industrial sources. Ex: National Institute of Standards and Technology (NIST); Sigma Chemical Co.

Independent Analysis & Variation in Sample Size

Independent Analysis
A second independent and reliable analytical method can be used in parallel with the method being evaluated. A statistical test must be used to determine whether any difference is a result of random errors in the two methods or due to bias in the method under study.

Variation in Sample Size

As the size of a measurement increases, the effect of a constant error decreases. Constant errors can often be detected by varying the sample size.

Blank Determinations
A blank contains the reagents and solvents used in a determination, but no analyte. Many of the sample constituents are added to simulate the analyte environment, often called the sample matrix. In a blank determination:
All steps of the analysis are performed on the blank material. Blank determinations reveal errors due to interfering contaminants from the reagents and vessels used in the analysis.