Errors in Quantitative Measurement

In practice, there is error associated with any measurement - that is, the measured value differs
from a theoretical true or actual value. Obviously, we seek to minimize error in measurement
and obtain a value that is as close to the true value as practical or possible. When we report the
result of a measurement, we also report an estimate of the error or uncertainty of the
measurement as a matter of good scientific practice.
There are two types of error that we distinguish - random error and systematic error - and
these can be related to the specific meanings for the terms accuracy and precision earlier
discussed. Random errors are due to the precision of the equipment, and systematic errors are
due to how well the equipment was used or how well the experiment was controlled.

Systematic error Random error

Determinate Errors:

Constant Error
These errors are the same for all measurement
Systematic/Biased Error

 Systematic errors are biases in measurement which lead to a situation wherein the mean
of many separate measurements differs significantly from the actual value of the
measured attribute in one direction.
 A systematic error makes the measured value always smaller or larger than the true value,
but not both. An experiment may involve more than one systematic error and these errors
may nullify one another, but each alters the true value in one way only.
 Accuracy (or validity) is a measure of the systematic error. If an experiment is accurate
or valid, then the systematic error is very small.
 Systematic errors include personal errors, instrumental errors, and method errors.

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Categories of Systematic Errors

Operational error

Errors caused by humans are self-transcending and have nothing to do with experimental
methods or procedures.

Example:

 Non-quantitative treatment from analysts while experimenting

 Less precise quantitative sedimentation
 Heating / sediment heating at temperatures that are less precise
 Cooling the exchange rate is less sufficient before use weigh

Error Instruments and Reagents

This occur when using instruments or choosing reagents.

Example:

 Instruments / tools used are not calibrated before use.

 The fatty / dirty burette is not cleaned before use
 The reagents used are not pure
 Volumetric equipment, such as burets, pipets, and volumetric flasks, frequently deliver
or contain volumes slightly different from those indicated by their graduations.

Method Error

Example:

 Incorrect sampling
 The reaction is not perfect
 The presence of impurities on deposits when using Gravimetry
 Selection of inappropriate indicators to determine the end point of the titration.

Additive and Comparable Errors (Proportional)

The absolute value of the additive error does not depend on the quantity of the constituents of
the substance set, whereas in proportional error it is very influential.

Example 1:

 The loss of the weight of the exchange rate at the time of the annealing will not affect
the quantity of constituent substances placed in the exchange rate later.
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Example 2:

 The presence of impurities in the standard solution causes the increase in the quantity
of constituents linearly or not, so that it can result in an error of normality (N) value of
a standard solution.

Indeterminate/Random/Chance Error
 A random error makes the measured value both smaller and larger than the true value;
they are errors of precision.
 Random errors occur by chance and cannot be avoided.
 Random error is due to factors which we do not, or cannot, control.

How to Minimize Errors in Quantitative Analysis

 Calibrate tools and make corrections

The instrument is calibrated and corrected against standard measurements in order to
determine whether the instrument used is in good condition (not damaged). In
addition to calibration, it is also important to wash glass-sized appliances (eg biuret,
volume pipette) to clean and impurities free.
 Setting the blanks
Make separate assignments to blanks. The objective is to know the presence of
impurities in the reagents and the correction of the standard solution to reach the end
point of the titration. Correction value should not be too big (not correct and not
careful).
 Conducting surveillance
Under identical conditions, determination is made of samples and standards
containing constituents of equal weight as contained in the sample.
 Using comparative analysis methods
Analysis using different methods, e.g. determination of iron content (Fe) in the
sample by Gravimetry in comparison with the Volumetric method. The methods used
are correct if the results obtained do not differ significantly.
 Perform a parallel assignment
Check the results obtained from the analysis and make repeated assignments. For
example, titration is done 3 times not just once to get the right result. However, the
titration volume obtained should not differ much or more than 0.05 (must be
precision).

Meaningful Numbers

In addition to the above, to reduce errors in quantitative analysis is also very important to
understand meaningful numbers using the principles of rounding off.

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Estimation of Errors
Percent Error
Percent error (sometimes referred to as fractional difference) measures the accuracy of a
measurement by the difference between a measured or experimental value E and a true or
accepted value A. The percent error is calculated from the following equation:
| |
% Error =

The reliability of a set of measurements, such as the sequence x1, x2, x3……..xn is specified by
certain measures called errors.
Average deviation /Average error ( )
The average error or average deviation is the arithmetic mean of all individual errors (deviation
from the mean) without regard to sign.

̅ = ∑| |
Where N= Number of measurement (or analysis)

x- = deviation from the mean (individual error)

Standard deviation (or root-mean-square error)
This is the square root of the average of the squares of the deviations from the overall mean.
∑| ̅|
For N≤30 S=

For large value of N, i.e. N ≥ 30, N-1 = N in the above equation

∑( ̅)
S=

S/N x |x- ̅ | | − ̅|

1. 7.2 7.2-7.9= -0.7 −0.7 = 0.49

2. 7.6

3. 7.8

4. 8.0

5. 8.2

6. 8.3

7. 8.2

= 55.3/7 = 7.9

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(i) Coefficient of variation (called the relative standard deviation i.e R.S.D)
This is the ratio of the standard deviationa9 or standard error) to the average of the set
of data.

R.S.D = ̅

Relative standard deviation can be expressed in percentage or in parts per thousand

1. Relative standard deviation (R.S.D)in percentage
R.S.D (%) = ̅ x %

2. Relative standard deviation in parts per thousand

R.S.D (ppt) = ̅ x ‰

(ii) Standard deviation of the mean (or Standard error of the mean,i.e Sm
Sm =
√

(iii) Variance (σ)

σ=
(c) Probable error (r)
A relationship has been established between the root-mean-square error(s), average deviation
( ) and probable error by the formula;
R = 0.6745s= 0.7876
Question
Analyses of a sample of iron ore gave the following percent value for the iron content; 7.08,
7.21, 7.12, 7.09, 7.16, 7.14, 7.07, 7.14, 7.18, 7.11. Calculate the mean, standard deviation,
average deviation, coefficient of variation for the values.

Absolute Error
This is the difference between the true value and the measured value, with regards to sign.
Absolute error (∈ )= Observed value (x)- true value (T)
Thus, we have
∈ = x-T………. for single measurement
∈ = ̅ – T ……… for a set of replicate analyses
Questions
1. The accepted value for the chloride content in a standard milk sample obtained
from extensive previous analysis is 54.20%.The same sample was carried out by
a new instrumental procedure and 54.05% was observed. Calculate the absolute
error.
2. The accepted value for the chloride content in a standard milk sample obtained
from extensive previous analysis is 54.20%. Five analysis of the same sample
were carried out by a new instrumental procedure. The values obtained are 54.01,
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 54.24, 54.05. 54.27 and 54.11%. Calculate the standard deviation and the absolute
error in this new analytical procedure.
Solutions
(a)∈ = x-T
∈ = (54.05 - 54.20) %
= -0.15%, note that absolute error has regard for signs.
(b)
∑ . . . . .
Means, ̅ = = = 54.136 = 54.14%

∑| ̅|
Standard deviation = S=

S/N x |x- ̅ | | − ̅|
1. 54.01 54.01-54.14= 0.13 0.0169
2. 54.24 0.10 0.0100
3. 54.05 0.09 0.0081
4. 54.27 0.13 0.0169
5. 54.11 0.03 0.0009
Summation 270.68 0.0528
∑

∑ | − ̅ | = 0.0528

.
S= = 0.1150%

Absolute error= Mean value – True value

= 54.14 – 54.20 = +0.06%

Relative error (R)

Relative means: considered in relation or in proportion to something else.

Relative error (R) =

∈
R=

From the above example;

.
R= = 0.0011%
.

Relative error can be expressed in percentage or in parts per thousand as follows

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 (i) Percentage relative error
∈
R (%) = x %

(ii) Relative error in Parts Per Thousand

∈
R (ppt) = x ‰

Relative Accuracy (RA)

This is the measured value or mean (in case of a set of measurements) expressed as a
percentage or in part per thousand of the true value.
( )
Relative Accuracy (RA) =

From the above examples

(RA) = OR (RA) =
.
(i) (RA) = = (RA) = .
= 0.9972 %
.
(ii) (RA) = = (RA) = .
= 0.9989 %

(a). RA expressed in Percentage

( )
RA (%) = x %

(b). RA expressed in Part Per Thousand

( )
RA (ppt) = x ‰

Rules for Combination of Errors

Maximum errors or maximum deviations (E) combine according to different rules from
standard errors or standard deviation.
(i) For maximum error, the absolute (or relative errors in case of products, quotients
and power) are added
E.g. In Addition and Subtraction
Z= A + B – C
Maximum error in Z, i.e. EZ
EZ = EA + EB + EC…………….
Where, EA, EB, EC are maximum error in A, B and C respectively.
Multiplication and Division

Z= the maximum error in Z, i.e. EZ

= + +

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 EZ = Z ( + + )

Product, Quotient and Power

Z=

Maximum error in Z, .i.e. EZ

= + +

EZ = Z ( + + )

(ii) Standard error

Addition and Subtraction
Z= A + B – C
Standard error in Z, .i.e. ∆
(∆ ) = (∆ ) +(∆ ) +(∆ )
∆ = (∆ ) + (∆ ) + (∆ )

Multiplication and Division

Z=

Standard error in Z, i.e. ∆

∆ ∆ ∆ ∆
( ) = ( ) +( ) +( )

∆ ∆ ∆ ∆
( )= ( ) + ( ) + ( )

∆ ∆ ∆
∆ =Z( ( ) + ( ) + ( ) )

Product, Quotient and Power

Z=
∆ ∆ ∆ ∆
( ) = ( ) + ( ) + ( )

∆ ∆ ∆ ∆
( )= ( ) + ( ) + ( )

∆ ∆ ∆
∆ =Z( ( ) + ( ) + ( ) )

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 Examples
Given the summation below:
y = 1.05 (±0.02) + 4.10 (±0.03) − 1.97(±0.05) where the values in the parenthesis
are the limits estimate of standard errors. Calculate (i) absolute standard error in y (ii)
percentage relative error in y.
Recall;
Z= A + B – C
Standard error in Z, .i.e. ∆
(∆ ) = (∆ ) +(∆ ) +(∆ )
∆ = (∆ ) + (∆ ) + (∆ )
Thus;
(∆ ) = (±0.02) +(±0.03) +(±0.05)
∆ = (±0.02) + (±0.03) + (±0.05)

= ±(0.0004 + 0.0009 + 0.0025) = √±0.0038 =

=±0.06
∆
(iii) % relative error= x %
y= 1.05 + 4.10 – 1.97 = 3.18
.
% relative error = .
x %

= 1.89%
For more Examples; consult Fundamental Physical Chemistry, Series A , by Olajire
Abbas
Question
Solve this question
The unit of viscosity is called poise ( ). Viscosity is determined experimentally by
measuring the time (t) for certain volume (v) under a pressure (P) according to the
Poiseeuille equation:

= ,

If there is an error of Δ ,Δ Δ ,Δ Δ
. ℎ %
. What are the unit of poise in S. I. units?

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 References
1. Abass A. Olajire 2008: Fundamental University Physical Chemistry, Series A.
2. https://courses.lumenlearning.com/boundless-statistics/chapter/measurement-error/
3. Chapter 5: Errors in Chemical Analyses
http://web.iyte.edu.tr/~serifeyalcin/lectures/chem201/cn_5.pdf
4. Theory of Errors in Quantitative Analysis.
https://steemit.com/science/@manah/theory-of-errors-in-quantitative-analysis
5. ‘Experimental Methods. An Introduction to the Analysis and Presentation of Data.’ Les
Kirkup, Wiley, (1994).
6. ‘Data Reduction and Error Analysis for the Physical Sciences.’ Philip R. Bevington,
McGraw Hill (1969). ‘

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