Experiment 1-B Evaluation of Analytical Data

Experiment 1-B
EVALUATION OF ANALYTICAL DATA

Objectives
1. To characterize measurements and results
2. To characterize measurement errors

Concepts

Errors in Analytical Measurements

All measurement processes are subject to measurement errors that affect numerical data and which arise
from a variety of sources.

Classification of errors
1. Systematic errors (determinate errors) – generally arise from determinate or identifiable sources causing
measured values to differ from a true or accepted value. These errors can be avoided and the magnitude
could be measured.
a. Operational and personal errors – these are due to factors for which the individual analysts is responsible
and are not connected with the method or procedure
b. Instrumental and reagent errors – these arise from the faulty construction of balances, the use of
uncalibrated or improperly calibrated weights, graduated glassware and other instruments
c. Errors of method – originate from incorrect sampling and from incompleteness of a reaction
d. Additive and proportional errors

2. Random (indeterminate) errors – these arise from a variety of uncontrolled sources and cause small random
variations in a measured quantity when the measurement is repeated a number of times. They are due to
causes over which the analyst has no control.

Measurement of errors
1. Absolute error, EA – is the numerical difference between a measured value and a true or accepted value.
Could be calculated by:
E A = M − T
where xM is the measured value and xT is the true value

2. Relative error, EA - is the absolute error divided by the true or accepted value.
M − T
 ER =
T
Maybe expressed as percentage:
M − T
%E R = x 100
T
3. 
Accumulated errors - Errors are associated with every measurement made in an analytical procedure, and
these will be aggregated in the final calculated result. The overall error for determinate error maybe calculated
using either of the following expression:
a. where only a linear combination of individual measurements is required to compute the result, the overall
 ET, is given by
absolute determinate error,
ET =E1 +E2 +E3 +.......
E1 and E2 etc., being the absolute determinate errors in the individual measurements taking sign into
account

b. where a multiplicative expression is required to compute the result, the overall relative determinate error,
ETR, is given by
ETR =E1R +E2R +E3R +.......

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Experiment 1-B Evaluation of Analytical Data

E1R and E2R etc., being the relative determinate errors in the individual measurements taking sign into
account.

Assessment of Accuracy and Precision

Accuracy is the closeness of an experimental measurement or result to the true or accepted value. It is generally the
more important characteristic of quantitative data to be assessed, although consistency, as measured by precision, is
of particular concern in some circumstances.

Precision is the closeness of agreement between replicated measurements or results obtained under the same
prescribed conditions. Can be assessed in several ways. Spread or range (i.e. the difference between the highest and
lowest value) is sometimes used, but the most popular method is to estimate the standard deviation of the data.
Precision is commonly divided into two categories:
a. Repeatability is the precision obtained when all measurements are made by the same analyst during a
single period of laboratory work, using the same solutions and equipment.
b. Reproducibility is the precision obtained under any other set of con- ditions, including that between
analysts, or between laboratory sessions for a single analyst. Since reproducibility includes additional
sources of variability, the reproducibility of an analysis can be no better than its repeatability.

Figure 1. Illustration of precision and accuracy.

Statistics and Statistical Analysis

Statistics reveal information that is already present in a data set. Statistical analyses allow us to look at our
data in different ways and make objective and intelligent decisions regarding their quality and use.

Terminologies:
Mean, arithmetic mean or average – obtained by dividing the sum of replicate measurements by
the number of measurements in the set:
N

x i
x= i=1
N
where xi represents individual values of x making up a set of N replicate measurements

Median - is the middle result when replicate data are arranged in order of size

Range - is the difference between the largest and smallest values in the data set.
w = x l arg est − x smallest

Deviation, d – determines how far the measured value deviates from the mean.
d = x − xi

Standard deviation, s - measure of the dispersion of data around the mean
(d12 + d2 2 + d3 2 + ...
 s=
n −1
where n is the number of measurements and n-1 is the degrees of freedom

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The significance of s is that the smaller it is numerically, the more precise the data (the more the
measurements are “bunched” around the mean). For an infinite number of measurements (where
the mean is ), the standard deviation is symbolized as (Greek letter sigma) and is known as
the population standard deviation. 30 or more measurements approximate an infinite number of
measurements.
N

 (x i − ) 2
= i=1
N
Variance - The square of the standard deviation, 2, or estimated standard deviation, s2, is used
in a number of statistical computations and tests, such as for calculating accumulated (propagated)
errors or when comparing the  precisions of two sets of data.
Relative standard deviation - relates the standard deviation to the value of the mean and
represents a practical and popular expression of data quality. It is calculated by dividing the
standard deviation by the mean and then multiplying by 100 or 1000:

s
RSD =
x
relative % standard deviation = RSD x 100
relative parts per thousand standard deviation = RSD x 1000


Normal Distribution Curve

For an infinite data set (in which the symbols and apply), a plot of frequency of occurrence vs. the
measurement value yields a smooth bell-shaped curve. It is referred to as bell-shaped because there is
equal drop-off on both sides of a peak value, resulting in a shape that resembles a bell. The peak value
corresponds to , the population mean. This curve is called the normal distribution curve because it
represents a normal distribution of values for any infinitely repeated measurement. The normal distribution
curve is a picture of the precision of a given data set.

Uncertainty – is the range of possible values for a measurement.

Confidence Interval

This is the range of values around an experimental result within which the true or accepted value is expected
to lie with a defined level of probability.

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When the standard deviation is already known from past history, the confidence limits are given by the
equation:
z
CL( ) = x 
N
where z is a statistical factor related to the probability level required

Table 1. Confidence Levels for Various Values of z

Confidence Level, % z Confidence Level, % z
50 0.67 95.4 2.00
68 1.00 99 2.58
80 1.29 99.7 3.00
90 1.64 99.9 3.29
95 1.96

Where an estimated standard deviation is to be used, is replaced by s, which must first be calculated
from the current data. The confidence limits are then given by the equation
ts
CL( ) = x 
N
where z is replaced by an alternative statistical factor, t, also related to the probability level but in addition
determined by the number of degrees of freedom for the set of data, i.e. one less than the number of results.


Table 2. Values of t for Various Levels of Probability

Factor for Confidence Interval
Degrees of Freedom
80% 90% 95% 99% 99.9%
1 3.08 6.31 12.7 63.7 637
2 1.89 2.92 4.30 9.92 31.6
3 1.64 2.35 3.18 5.84 12.9
4 1.53 2.13 2.78 4.60 8.60
5 1.48 2.02 2.57 4.03 6.86
6 1.44 1.94 2.45 3.71 5.96
7 1.42 1.90 2.36 3.50 5.40
8 1.40 1.86 2.31 3.36 5.04
9 1.38 1.83 2.26 3.25 4.78
10 1.37 1.81 2.23 3.17 4.59
11 1.36 1.80 2.20 3.11 4.44
12 1.36 1.78 2.18 3.06 4.32
13 1.35 1.77 2.16 3.01 4.22
14 1.34 1.76 2.14 2.98 4.14
 1.29 1.64 1.96 2.58 3.29

Standard Deviation of Computed Results

Table 3. Error Propagation in Arithmetic Calculations

Type of Calculation Example Standard Deviation of y

Addition or subtraction y = a+b −c sy = sa 2 + sb 2 + sc 2

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 
Experiment 1-B Evaluation of Analytical Data

sy  sa  2  sb  2  sc  2
Multiplication or division y = a x bc =   +  + 
y a b c
sy s
Exponentiation y = ax =x a
y a

 sa
Logarithm y = log10 a sy = 0.434
 a
 sy
Antilogarithm y = antilog10 a = 2.303sa
y
 

Reporting Computed Data

1. Report your data in proper 
significant figures and level of uncertainty.

Procedure

Use the data that will be obtained in Exercise 2 parts I and IV to determine the following:
A. Mean
B. Median
C. Range
D. Standard deviation
E. Variance
F. Accuracy
G. Precision
H. Absolute error
I. Relative Error
J. Confidence intervals for sample

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