Errors

In
Chemical
Analysis
SI R KI M MART I N BE LI G O N
C H E M 1 6 - A N A LY T I C A L C H E M I S T R Y
I N ST R U C T O R
C AS- D P S
• Measurements invariably involve errors and uncertainties.
• It is impossible to perform a chemical analysis that is totally free of errors or
uncertainties
• We can only hope to minimize errors and estimate their size with acceptable
accuracy
• Errors are caused by faulty calibrations or standardizations or by random
variations and uncertainties in results.
• Frequent calibrations, standardizations, and analyses of known samples can
sometimes be used to lessen all but the random errors and uncertainties.

The term error has two slightly different meanings.

1) error refers to the difference between a measured value and the “true” or
“known” value.
2) 2) error often denotes the estimated uncertainty in a measurement or
experiment.
A. SYST EMAT IC ERRO RS (Determinate Error)
-causes the mean of a data set to differ from the accepted value.
• have a definite value, an assignable cause, and are of the same magnitude for
replicate measurements made in the same way.
• lead to bias in measurement technique
• may arise from:
1. IN STRUMEN TAL ER RO R S- caused by temperature changes,
fluctuations in current etc., must do calibration.
2. METHO D ER RO R - may be introduced by the non-ideal chemical or
physical behavior of the reagents and reactions upon
which an analysis is based, often difficult to detect.
3. PER SO N AL ER RO R S- may arise from personal judgements,
prejudice or number bias.
 INST RUMENTAL ERRO R

• Caused by nonideal instrument behavior, by faulty calibrations, or

by use under inappropriate conditions
• Pipets, burets, and volumetric flasks may hold or deliver volumes
slightly different from those indicated by their graduations.
• Calibration eliminates most systematic errors of this type.
• Electronic instruments can be influenced by noise, temperature, pH
and are also subject to systematic errors.
• Errors of these types usually are detectable and correctable.
 MET HO D ERRO R

• The nonideal chemical or physical behavior of the reagents and

reactions on which an analysis is based often introduce systematic
method errors.
• Such sources of nonideality include the slowness of some reactions,
the incompleteness of others, the instability of some species, the lack
of specificity of most reagents, and the possible occurrence of side
reactions that interfere with the measurement process.
• Errors inherent in a method are often difficult to detect and hence,
these errors are usually the most difficult to identify and correct.
 PERSO NAL ERRO R
• R esult from the carelessness, inattention, or personal limitations of the experimenter.
• Many measurements require personal judgments.
• Examples include estimating the position of a pointer between two scale divisions, the
color of a solution at the end point in a titration, or the level of a liquid with respect
to a graduation in a pipet or buret.
• Judgments of this type are often subject to systematic, unidirectional errors.
• A universal source of personal error is prejudice, or bias.
• N umber bias is another source of personal error that varies considerably from person to
person.
• The most frequent number bias encountered in estimating the position of a needle on a
scale involves a preference for the digits 0 and 5.
• Also common is a prejudice favoring small digits over large and even numbers over odd.
• Digital and computer displays on ph meters, laboratory balances, and other electronic
instruments eliminate number bias because no judgment is involved in taking a reading.
B. RANDO M ERRO RS (Indeterminate Error)
-causes data to be scattered more or less symmetrically around a mean
value.
• arise when a system of measurement is extended to its maximum sensitivity
• caused by uncontrollable variables

C. GRO SS CARELESS ERRO RS

• These differ from indeterminate and determinate errors.
• They usually occur only occasionally, are often large, and may cause a result to
be either high or low.
• They are often the product of human errors.
• Gross errors lead to outliers, results that appear to differ markedly from all
other data in a set of replicate measurements
 Detection and Elimination of Systematic
(Instrumental and Personal) Errors

1. Periodic calibration of equipment is always desirable because the response of

most instruments changes with time as a result of component aging, corrosion, or
mistreatment.
2. Most personal errors can be minimized by careful, disciplined laboratory work.
3. It is a good habit to check instrument readings, notebook entries, and
calculations systematically.
4. Errors due to limitations of the experimenter can usually be avoided by
carefully choosing the analytical method or using an automated procedure.
 Detection of Systematic (Method) Errors
1. Bias in an analytical method is particularly difficult to
detect.
2. The best way to estimate the bias of an analytical method
is by analyzing Standard reference materials (SR Ms).
 ERRO RS IN CHEMICAL ANALYSIS
1. Central Tendency
a. Mean (x)- is the average value of two or more measurements.
b. Median- is the middle value in a set of data that has been arranged in
order of size

EXAMPLE:
Calculate the mean and median for each of the following set of data:
Set A Set B
6.37 6.37
6.33 6.33
6.41 6.41
6.80 6.93
2. Precision- describes the reproducibility of measurements
- it is the closeness of data to other data that have been obtained in
exactly the same way

a. Standard D eviation

b. Variance

c. Relative Standard D eviation

d. Coefficient of Variation

e. Spread or Range
3. Accuracy- is the closeness of a measurement to its true or accepted value

Express by:

a. Absolute Error- is the difference between the measured value and the
true value. If the measurement result is low, the sign
is negative; if the measurement result is high, the sign is positive.

b. Relative Error- is the absolute error divided by the true value. R elative
error may be expressed in percent, parts per thousand, or parts
per million, depending on the magnitude of the result.
EXAMPLE:
The following results were obtained in the replicate analysis of a blood sample for its lead (Pb)
content:
Pb (ppm)
0.752
0.756
0.752
0.751
0.760

Calculate the:
1. Mean
2. Median
3. Standard Deviation
4. Variance
5. R SD @ ppt
6. CV
7. R ange
STANDARD DEVIAT IO N of CO MPUT ED RESULT S (Uncertainties)
Type of Calculation Example Standard Deviation of Y

Addition & Subtraction y= a+ b+ c Sy= 𝑆𝑆𝑆𝑆2 + 𝑆𝑆𝑆𝑆2 + 𝑆𝑆𝑆𝑆2

Multiplication & Division y= a • b 𝑆𝑆𝑆𝑆 2 2 2

= 𝑆𝑆𝑎𝑎 𝑆𝑆𝑆𝑆 𝑆𝑆𝑐𝑐
𝑦𝑦 + +
c 𝑎𝑎 𝑏𝑏 𝑐𝑐

Exponentiation y= ax 𝑆𝑆𝑦𝑦 𝑆𝑆𝑒𝑒

= 𝑥𝑥
𝑦𝑦 𝑎𝑎

Logarithm 𝑆𝑆𝑎𝑎
y= log10a Sy= 0.434
𝑎𝑎

Antilogarithm 𝑆𝑆𝑦𝑦
y= antilog10a = 2.303 Sa
𝑦𝑦
Standard D eviation for Sums and D ifferences

Consider the summation:

+ 0.50 (± 0.02)
+ 4.10 (± 0.03)
- 1.97 (± 0.05)

N ote: (The numbers in parenthesis re absolute standard deviations)

The Standard Deviation of the result is:

Sy= 𝑆𝑆𝑆𝑆2 + 𝑆𝑆𝑆𝑆2 + 𝑆𝑆𝑆𝑆2

Sy=

And the sum should be reported as ______________________.

Standard D eviation of P roducts and Q uotients

Consider the following computations:

4.10 ±0.02 × 0.0050 ±0.0001

1.97 ±0.04
The Standard Deviation of the result is:
𝑆𝑆𝑆𝑆 𝑆𝑆𝑎𝑎 2 𝑆𝑆𝑆𝑆 2 𝑆𝑆𝑐𝑐 2
= + +
𝑦𝑦 𝑎𝑎 𝑏𝑏 𝑐𝑐
Standard D eviation of Exponential Calculation
The standard deviation in measuring the diameter of a sphere is ± 0.02 cm. What is the
standard deviation in the calculated volume V of the sphere if d= 2.15 cm?

4 𝑑𝑑 3
V= 𝜋𝜋
3 2

The Standard Deviation of the result is:

𝑆𝑆𝑆𝑆 𝑠𝑠𝑒𝑒
= 𝑥𝑥
𝑦𝑦 𝑎𝑎
Standard D eviation of Logarithm and Antilogarithm

A. y= log [2.00 (± 0.02) x 10-4]

𝑆𝑆𝑎𝑎
Sy= 0.434
𝑎𝑎

B. y= antilog [1.200 (± 0.003)]

𝑆𝑆𝑦𝑦
= 2.303 Sa
𝑦𝑦