04-Accuracy and Precision

Accuracy, Precision, Mean
There are certain basic concepts in analytical chemistry that are helpful to
the analyst when treating analytical data. This section will address
accuracy, precision, mean as related to chemical measurements in the
general field of analytical chemistry.
Accuracy
In analytical chemistry, the term 'accuracy' defines as "closeness of the
agreement between the result of a measurement and a true value." In
theory, a true value is that value that would be obtained by a perfect
measurement. Since there is no perfect measurement in analytical
chemistry, we can never know the true value.
For example, lets call a measurement we make XI and give the symbol µ
for the true value. We can then define the error in relation to the true
value and the measured value according to the following equation:
error = XI - µ (1)
We often speak of accuracy in qualitative terms such a "good," "expected,"
"poor," and so on. However, we have the ability to make quantitative
measurements. We therefore have the ability to make quantitative
estimates of the error of a given measurement. Since we can estimate the
error, we can also estimate the accuracy of a measurement.
In addition, we can define error as the difference between the measured

result and the true value as shown in equation (1) above. However, we
cannot use equation (1) to calculate the exact error because we can never
determine the true value. We can, however, estimate the error with the
introduction of the 'conventional true value' which is more appropriately
called either the assigned value, the best estimate of a true value, the
conventional value, or the reference value.
Therefore, the error can be estimated using equation (1) and
the conventional true value.
Errors in analytical chemistry are classified as systematic (determinate)
and random (indeterminate). The definitions of error, systematic
error, and random error follow:
 Error - the result of a measurement minus a true value of the
measurand.
 Systematic Error - the mean that would result from an infinite
number of measurements of the same measurand carried out under
repeatability conditions, minus a true value of the measurand.
 Random Error - the result of a measurement minus the mean that
would result from an infinite number of measurements of the same
measurand carried out under repeatability conditions.
e. For example, if we need to dispense 25.0 mL of dilute HCl, then
dispensing 24.9 mL is more accurate then dispensing 25.7 mL.
Accuracy usually is reported as a percent error
% error = actual value − expected value/ expected value × 100
A systematic error is caused by a defect in the analytical method or by an

improperly functioning instrument or analyst. A procedure that suffers from
a systematic error is always going to give a mean value that is different
from the true value.
The term 'bias' is sometimes used when defining and describing a
systematic error. The measured value is described as being biased high or
low when a systematic error is present and the calculated uncertainty of the
measured value is sufficiently small to see a definite difference when a
comparison of the measured value to the conventional true value is made.
Some analysts prefer the term 'determinate' instead of systematic because

it is more descriptive in stating that this type of error can be determined.
A systematic error can be estimated, but it cannot be known with certainty
because the true value cannot be known. Systematic errors can therefore
be avoided, i.e., they are determinate.
Sources of systematic errors include spectral interferences, chemical

standards, volumetric wares, and analytical balances where an improper
calibration or use will result in a systematic error, i.e., a dirty glass pipette
will always deliver less than the intended volume of liquid and a chemical
standard that has an assigned value that is different from the true value will
always bias the measurements either high or low and so on.
Random errors are unavoidable. They are unavoidable due to the fact that
every physical measurement has limitation, i.e., some uncertainty.
Using the utmost of care, the analyst can only obtain a weight to the
uncertainty of the balance or deliver a volume to the uncertainty of the
glass pipette.
For example, most four-place analytical balances are accurate to ± 0.0001
grams. Therefore, with care, an analyst can measure a 1.0000 gram weight
(true value) to an accuracy of ± 0.0001 grams where a value of 1.0001 to
0.999 grams would be within the random error of measurement.
If the analyst touches the weight with their finger and obtains a weight of
1.0005 grams, the total error = 1.0005 -1.0000 = 0.0005 grams and the
random and systematic errors could be estimated to be 0.0001 and 0.0004
grams respectively.
Note that the systematic error could be as great as 0.0006 grams, taking
into account the uncertainty of the measurement.
A truly random error is just as likely to be positive as negative, making the
average of several measurements more reliable than any single
measurement. Hence, taking several measurements of the 1.0000gram
weight with the added weight of the fingerprint, the analyst would eventually
report the weight of the finger print as 0.0005 grams where the random
error is still 0.0001 grams and the systematic error is 0.0005 grams.
However, random errors set a limit upon accuracy no matter how many
replicates are made.
Precision
The term precision is used in describing the agreement of a set of results
among themselves. Precision is usually expressed in terms of the deviation
of a set of results from the arithmetic mean of the set (mean and standard
deviation). Good precision does not mean good accuracy.
Why doesn't good precision mean we have good accuracy?
We also know that the total error is the sum of the systematic error and
random error. Since truly random error is just as likely to be negative as
positive, we can reason that a measurement that has only random error is
accurate to within the precision of measurement and the more precise the
measurement, the better idea we have of the true value, there is no bias in
the data. In the case of random error only, good precision indicates good
accuracy.
The top left image shows the target hit at high precision and
accuracy. The top right image shows the target hit at a high accuracy
but low precision. The bottom left image shows the target hit at a high
precision but low accuracy. The bottom right image shows the target
hit at low accuracy and low precision.
We know that systematic error will produce a bias in the data from the true
value. This bias will be negative or positive depending upon the type and
there may be several systematic errors at work. Many systematic errors
can be repeated to a high degree of precision. Therefore, it follows that
systematic errors prevent us from making the conclusion that good
precision means good accuracy. When we go about the task of determining
the accuracy of a method, we are focusing upon the identification and
elimination of systematic errors. Don't be misled by the statement that
'good precision is an indication of good accuracy.' Too many systematic
errors can be repeated to a high degree of precision for this statement to
be true.
 Repeatability (of results of measurements) - the closeness of the
agreement between the results of successive measurements of the
same measurand carried out under the same conditions of
measurement.
Additional Notes:
1. These conditions are called repeatability conditions.
2. Repeatability conditions include the same measurement procedure, the
same observer, the same measuring instrument, used under the same
conditions, the same location, and repetition over a short period of time.
 Reproducibility (of results of measurement) - the closeness of the
agreement between the results of measurements of the same
measurand carried out under changed conditions of measurement.
Additional Notes:
1. A valid statement of reproducibility requires specification of the
conditions changed.
2. The changed conditions may include principle of measurement, method
of measurement, observer, measuring instrument, reference standard,
location, conditions of use, and time.
When discussing the precision of measurement data, it is helpful for the
analyst to define how the data are collected and to use the term
'repeatability' when applicable. It is equally important to specify the
conditions used for the collection of 'reproducibility' data.
Mean
The definition of mean is, "an average of n numbers computed by adding
some function of the numbers and dividing by some function of n." The
central tendency of a set of measurement results is typically found by
calculating the arithmetic mean (x̄) and less commonly the median or
geometric mean.
The mean is an estimate of the true value as long as there is no systematic
error. In the absence of systematic error, the mean approaches the true
value (µ) as the number of measurements (n) increases.
The frequency distribution of the measurements approximates a bell-
shaped curve that is symmetrical around the mean. The arithmetic mean is
calculated using the following equation:
x̄ = (X1 + X2 + ···Xn) / n (2)
Typically, insufficient data are collected to determine if the data are evenly
distributed. Most analysts rely upon quality control data obtained along with
the sample data to indicate the accuracy of the procedural execution, i.e.,
the absence of systematic error(s). The analysis of at least one QC sample
with the unknown sample(s) is strongly recommended. Even when the QC
sample is in control it is still important to inspect the data for outliers.
There is a third type of error typically referred to as a 'blunder'.

This is an error that is made unintentionally. A blunder does not fall in the
systematic or random error categories.
It is a mistake that went unnoticed, such as a transcription error or a spilled
solution. For limited data sets (n = 3 to 10), the range (X n-X1), where Xn is
the largest value and X1 is the smallest value, is a good estimate of the
precision and a useful value in data inspection.
In the situation where a limited data set has a suspicious outlier and the QC
sample is in control, the analyst should calculate the range of the data and
determine if it is significantly larger than would be expected based upon the
QC data.
If an explanation cannot be found for an outlier (other than it appears too
high or low), there is a convenient test that can be used for the rejection of
possible outliers from limited data sets.
Q test.
The Q test is commonly conducted at the 90% confidence level but the
following table (3) includes the 96% and 99% levels as well for your
convenience. At the 90% confidence level, the analyst can reject a result
with 90% confidence that an outlier is significantly different from the other
results in the data set. The Q test involves dividing the difference between
the outlier and it's nearest value in the set by the range, which gives a
quotient - Q.
The range is always calculated by including the outlier, which is

automatically the largest or smallest value in the data set. If the quotient is
greater than the refection quotient, Q0.90, then the outlier can be rejected.
Table 3: The Q Test
n Q0.90 Q0.96 Q0.99
3 0.94 0.98 0.99
4 0.76 0.85 0.93
5 0.64 0.73 0.82
6 0.56 0.64 0.74
7 0.51 0.59 0.68
8 0.47 0.64 0.53
9 0.44 0.51 0.60
10 0.41 0.48 0.57
Example: This example will test four results in a data set--1004, 1005,
1001, and 981.
 The range is calculated: 1005 - 981 = 24.
 The difference between the questionable result (981) and its nearest
neighbor is calculated: 1001 - 981 = 20.
 The quotient is calculated: 20/24 = 0.83.
 The calculated quotient is compared to the Q 0.90 value of 0.76 for n=4
(from table 14.3 above) and found to be greater.
 The questionable result (981) is rejected.

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Accuracy, Precision, Mean

In addition, we can define error as the difference between the measured

A systematic error is caused by a defect in the analytical method or by an

Some analysts prefer the term 'determinate' instead of systematic because

Sources of systematic errors include spectral interferences, chemical

There is a third type of error typically referred to as a 'blunder'.

The range is always calculated by including the outlier, which is

n Q0.90 Q0.96 Q0.99

3 0.94 0.98 0.99

4 0.76 0.85 0.93

5 0.64 0.73 0.82

6 0.56 0.64 0.74

7 0.51 0.59 0.68

8 0.47 0.64 0.53

9 0.44 0.51 0.60

10 0.41 0.48 0.57

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