APPENDIX II: ERRORS IN EXPERIMENTAL MEASUREMENTS EXPERIMENTAL NUMBERS The following types of numbers are encountered in experimental work: • Counted

numbers, e.g. number of beakers, which are integers. • Mathematical numbers, e.g. 2 and n, which appear in mathematical relationships and are accurately known. • Measured numbers, which are the result of experimental measurement of quantities such as length, volume, mass, time, concentration, etc, and which must be quoted with a unit, otherwise the number is meaningless. There is always an upper limit to the certainty with which measured numbers are known. It is usual to quote all digits up to and including the first uncertain digit. This is the number of significant figures. For example, depending on the apparatus used, a measured volume might be quoted as 1.1 mL, 1.12 mL, or 1.1209 mL, corresponding to 2, 3 and 5 significant figures respectively. ACCURACY, PRECISION AND RELIABILITY Uncertainty in measurements can arise from random errors in equipment and procedures. This affects the precision, i.e. how closely repeat measurements agree with one another. Precise measurements have small random error and are highly repeatable. Uncertainty may also be the result of systematic error or bias, e.g. loss of precipitate in gravimetric analysis tends to cause all results to be lower than the true value of the analyte. Similarly a pipette may deliver other than the stated volume. The volume delivered is operator dependent and is determined by calibration. This type of bias affects the accuracy, i.e. how closely the measurements agree with the true or accepted value of a quantity (perhaps obtained by some alternative method). Accurate measurements agree well with the true value; they have small systematic error. Since often the true value is not known, the precision rather than the accuracy has to be used as a guide to the reliability of an experimental quantity. The precision is reported by quoting the error limit after the number. For example, the value (2.500 ± 0.002) mL means that the volume is between 2.498 and 2.502 mL, i.e. there is a range of 0.004 mL. The term ±0.002 mL is called an actual error. The relative error is: ±0.002/2.500 =:±0.0008 or 0.08%. Usually error limits are only reported to one significant figure, although occasionally they may be reported to two. If no error limit is quoted by convention we assume an error of ±1 in the last digit reported, e.g. for the quantities 0.0400 g and 0.04 g this gives (0.0400 ± 0.0001) g and (0.04 ± 0.01) g respectively, i.e. ±1/400 = ±0.25 % and ± 1/4 = ± 25 %. Note that the trailing zeros are significant. If errors are truly random, the most reliable value of a measured quantity is the average, i.e. the arithmetic mean, x, of a series of repeat measurements. If there are n such measurements, xi, then x is given by
x= 1 {x1 + x 2 + x 3 + ......x n } n

The average deviation, ∆x, gives a measure of the precision of the results, i.e. the extent to which the results agree with one another. The average deviation is found by adding the magnitude of the difference between each measurement and the mean and dividing the total of these differences by the number of measurements, i.e.
∆x = 1 x − x1 + x − x 2 + x − x 3 + ..... + x − x n n

{

}

The calculation of the mean and average deviation are illustrated by the example below, where the numbers in the table represent the results of 6 separate determinations of the volume of a 25 mL pipette, and the totals. Values xi 25.04 25.07 25.02 25.08 25.07 25.02 total = 150.30 x = 25.05 (mean) Deviation
x − xi

0.01 0.02 0.03 0.03 0.02 0.03 total = 0.14 ∆x = 0.023 (average deviation)

Hence the volume delivered by the pipette can be said to be 25.05 ± 0.02 mL. For a large number of measurements (say> ~6 in practice), the standard deviation is used instead of the average deviation and confidence limits can be calculated by statistical methods. In addition, there is a welldefined procedure for deciding whether to accept or reject values that differ appreciably from the others. This is not in the scope generally applied to chemistry practicals as the number of measurements of the one property or variable is low. The fewer repeat measurements, the less confidence can be placed in the final result. All values should be included in the mean unless they differ by at least 4 times the average deviation from it. For example, suppose a seventh measurement in the example above gave a value of 24.98 mL for the volume of the 25 mL pipette. This value could not be discarded as the deviation from the mean is 25.05 − 24.98 = 0.07, which is falls less than 4 × average deviation value of (4 x 0.023 =) 0.092. The mean and average deviation should therefore be recalculated including the new values. This gives a new adjusted value of (25.04 ± 0.03) mL for the pipette. For a small number of repeat measurements, for example for triplicates as used in practical work, the average deviation should be compared with the typical error calculated using the errors in the contributing equipment and procedures (see the next section). The larger of the average deviation and the typical error should be used as the estimate of precision. The typical error assumes errors always add which is overly pessimistic, but it is unable to take into account certain types of error, such as the ability to judge the end-point of a titration, which are implicitly included in the average deviation. On the other hand, the results of a small number of repeat measurements may even agree with each other exactly, due to chance or the insensitivity of the instrument to fluctuations, giving an average deviation of zero. However in this case the precision should be set equal to the typical error. For measurements in triplicate, the average deviation is often replaced by the larger of the difference between the average and the highest value and the average and the lowest value.

COMBINATION OF ERRORS: CALCULATION OF TYPICAL ERRORS No calculation of an experimental property can be more precise than the least precise quantity used in the calculation. For quantities which are multiplied or divided this means that if the least number of significant figures in the data is n, then the final result can only be quoted to n significant figures, at most. The size of the typical error gives a better estimate of how many figures should be quoted in the final result. However you must retain at least one more significant figure throughout your calculations to avoid accumulation of rounding errors, and not round off until the end. How to calculate the typical error is illustrated below for two independently measured quantities x and y, with actual errors ∆x and ∆y, which are combined in various ways to obtain a final result, R, i.e. R = f(x,y). As a result of the errors in x and y, R will contain an actual error, ∆R. If R = x + y or R = x - y
∆R = ∆x + ∆y ; add actual errors;

If R = xy or R = x/y

 ∆x ∆y  ∆R ∆x ∆y ; add relative errors; so that ∆R =  = +  x + y ×R  R x y  

These principles are illustrated below by an example from an experiment in first year practical work. The concentration of hydrochloric acid is determined by standardisation against solid mercuric oxide. The equation for the reaction is: 2HCl + HgO → HgCl2 + H2O An accurate balance is used to weigh a mass of HgO which is then titrated with the HCl solution ie. HCl is in the burette. From the chemical equation, the number of moles of HCl = 2 x number of moles of HgO. Therefore the mathematical equation is:
[HCl] = 2 × m(HgO) 1000 × MW (HgO) VHCl

The relative error in [HCl] is given by:
∆[HCl] ∆m ∆VHCl = + [HCl] m VHCl

There is an error of ±0.0002 g in every reading of the accurate balance and so an error of ± 0.0004 g in every mass. The HCI is in the burette and there is an error of ± 0.02 mL in every burette reading and so an error of at least ± 0.04 mL in every titre. The error in the formula mass is negligible. Substituting some typical values yields
[HCl] = 2 ×
0.2185 1000 × = 0.09288 M 216.6 21.72

∆[HCl] 0.0004 0.04 = + = 0.0018 + 0.0018 = 0.0036 [HCl] 0.2185 21.72

Hence the actual error in [HCl] is ∆[HCl] =±0.09288 × 0.0036 = ±0.0003 ∴the experimentally determined value of [HCl] = 0.0929 ± 0.0003 M

The hydrochloric acid is then used to standardise an unknown solution of sodium hydroxide ∴number of moles of NaOH = number of moles of HCl and
[NaOH] = [HCl] × VHCl VNaOH

The HCl is again in the burette. The NaOH is dispensed from a 20 mL pipette which may vary by ± 0.05 mL from the manufacturer's specification. Substituting some typical values yields:
[NaOH] =
0.09288 × 19.60 = 0.09118 M 20.00

∆[NaOH] 0.0003 0.04 0.05 = + + = 0.0036 + 0.0020 + 0.0025 = 0.0081 [NaOH] 0.09288 19.60 20.00

Hence the actual error in [NaOH] is ~[NaOH] = ±0.09118 × 0.0081 = ± 0.0007 ∴ the experimentally determined value of [NaOH] = 0.0912 ± 0.0007 M.

ERRORS IN VOLUMETRIC GLASSWARE Systematic Error in pipettes (class B) Capacity Tolerance ± mL 1 0.02 2 0.02 5 0.03 10 0.04 20 0.05 25 0.06 50 0.08 100 0.12

Systematic Error in standard flasks (class B) Capacity Tolerance: ± mL 5 0.03 10 0.03 25 0.04 50 0.06 100 0.1 200 0.2 250 0.2 500 0.3 1000 0.4 2000 0.6

Systematic Error in Measuring cylinders Capacity Tolerance: ± mL Reading errors 10 0.2 50 0.5 100 1.0

Burette:
reading error = ±0.02 mL minimum error in titre =:±0.04 mL

Analytical balance:
reading error = ± 0.0002 g minimum error in mass = ± 0.0004 g

Top-loading balance:
reading error =:±0.02 g minimum error in mass =±0.04 g

Instruments with a digital readout:
reading error due to fluctuations =± ½ × (max reading - min reading)

Instruments with an analogue scale:
reading error =:± ¼ × scale graduation

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