lOMoARcPSD|10378816

ANCH - Errors in Chemical Analyses

Analytical Chemistry (Our Lady of Fatima University)

Scan to open on Studocu

Studocu is not sponsored or endorsed by any college or university

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph)
 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

COURSE OUTLINE: PRELIMS

1. Errors in Chemical Analyses MULTIPLICATION AND DIVISION

REFERENCE • When multiplying and dividing numbers, the answer

• PowerPoint should bear the same number of significant figures
as the given measurement with the least number of
significant figures. Otherwise, the result must be
rounded off
Errors in Chemical Analyses
WHAT IS ERROR?

• Error means difference between true value and

observed value.
• No measurement is perfectly accurate or exact.
“True values” are seldom known. Instrumental,
physical (environmental), as well as human
limitations or interventions may cause
measurements to deviate from their true values. LOGARITHMS AND ANTILOGARITHMS
Such deviations are called” experimental
uncertainties” but more commonly, are known as
ERRORS 1. The number of significant figures in the original
number will be the number of decimal places of the
logarithm of that number.
SIGNIFICANT FIGURES

• The number of significant figures correspond to all

digits that are certain in a measurement plus one
2. The number of decimal places in the original
uncertain digit.
number will be the number of significant figures to
be reported in the antilogarithm of that number.
DETERMINING THE NUMBER OF SIGNIFICANT
FIGURES
1. All initial zeros are not significant.
• Ex. 0.00331 – three significant figures CHEMICAL CALCULATIONS

2. All zeros at the end of a number and follow a • Rounding off should be done in the final step only:
decimal point are significant.
• Ex. 0.00033100 - five significant figures A 3.482-g sample of a solid mixture containing benzoic
acid C6H5COOH (122.123 g/mol), was dissolved and
3. Non zero digits are significant titrated with base to a phenolphthalein endpoint. The
• Ex. 2.11782 - six significant figures acid consumed 41.36mL of 0.2328 M NaOH. Calculate

4. All zeros in between non zero digits are significant

• Ex. 0.002001089923 - ten significant
figures

SIGNIFICANT FIGURES IN CALCULATIONS

ADDITION AND SUBTRACTION

• When adding or subtracting digits, the results shall

have the same number of decimal places as the
given measurement with the least number of
decimal places. Otherwise, the result will have to be the percent benzoic acid (HBz) in the sample
rounded off
DEFINITION OF TERMS
REPLICATES

• 2 or more determinations made on the same

sample

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 1 I gm

 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

Example: A student measures Fe (III) concentration six

times.
6 measurements = 6 replicates
•
MEAN • is simply the absolute error divided by the true value
and can be expressed in percent, ppt or ppm.
• Statistical average or arithmetic mean

PRECISION

• Precision is the closeness of replicate

MEDIAN measurements with each other. It is also referred to
as reproducibility.
• middle value when all values are arranged by size
(either in increasing or decreasing order) Example: The chemist recoded the following
• Note: When evaluating an even number of values, concentrations of Pb: 24.89ppm, 24.22 ppm, 24.56
the average of the 2 middle values would represent ppm, 24.15 ppm and 24.49 ppm
the median.
• Since the values are close to each other, we say
Example: Given a set of values: 17, 15, 12, 13, 18, 19, 21, that the data are precise.
what are the mean and median? • Precision can be expressed as standard deviation,
variance and coefficient of variation.
• “How close are the results that have been obtained
in exactly the same manner”
• The reproducibility is derived from the deviations
• To get the median, arrange the values in increasing from the mean. Some of the measures or
or decreasing order: 12, 13, 15, 17, 18, 19, 21. The indications of precision are:
median in this case is the 4th value. (1) Standard Deviation,
(2) Variance, and
(3) Coefficient of Variation.
Median = 17

ACCURACY ABSOLUTE DEVIATION (D)

• It is the closeness of the measurement to the true or • Absolute Deviation (D) of an element of a data set
accepted value. is the absolute difference between that element
and a given point. Typically, the point from which
Example:
the deviation is measured is the value of either the
Using a reference sample containing 24.54 ppm of lead, a
mean or median of the data set.
chemist found that the concentration of Pb in the sample is
24.26 ppm. We can say that the analysis is ACCURATE
since the result is close to the true concentration of lead in •
the reference sample

MEASURES OF ACCURACY AVERAGE ABSOLUTE DEVIATION / AVERAGE

DEVIATION / MEAN ABSOLUTE DEVIATION (MAD)
ABSOLUTE ERROR
• It is the average of the absolute deviations and is a
• summary statistic of statistical dispersion or
• provides an idea whether the measured value is variability.
higher or lower compared to the true value.

Example: E = 24.26 – 24.54 = -0.28 • \

• A negative absolute error tells us that the calculated

result is lower than the true value. On the other STADARD DEVIATION (σ)
hand, a positive absolute error indicates that the
calculated result is higher than the true value • is a measure of the dispersion of a set of values.

RELATIVE ERROR

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 2 I gm

 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

Example: given a set of values: 5,12,11,7,8, compute

for the mean and standard deviation.

• In tabulated format, (after computing for the

mean):

• Standard deviation measures the spread of data

about the mean. It is useful in comparing sets of TYPES OF ERRORS IN EXPERIMENTAL DATA
data which may have the same mean but different
standard deviations. For example, given two sets RANDOM ERROR (INDETERMINATE ERROR)
of data (15,15,15,14,16) and (2,7,14,22,30). Both
sets will give a mean of 15 however, the 2nd set is
• affects the precision of data sets.
clearly more spread out and will give a higher
• inevitable in measurements and are difficult to
value for the standard deviation.
identify
VARIANCE • causes scattering of data around a mean value

Example: When calibrating a pipet are visual

• is a measure of statistical dispersion. It is the judgements when reading the volume measurements on
average squared deviations around the mean. a pipet, variations in the drainage time and angle of the
Thus, variance is the square of the standard pipet as the fluid drains, temperature fluctuations
deviation. affecting the volume and viscosity of the fluids, and
• Variance = σ2 vibrations and drafts that cause small variations in the
balance readings
COEFFICIENT OF VARIATION (cv)

• is a normalized measure of probability distribution. It SYSTEMATIC ERROR (OR DETERMINATE ERROR)

is defined as the ratio of the standard deviation to
the mean.
• error affects the accuracy of data sets. An analyst
can point out these types of errors, generally
•
classified as:

o Instrumental errors – errors caused by poor

PRECISION AND ACCURACY instrument condition and calibration
o Method errors – caused by poor outcomes
• In analytical chemistry, we need to be both accurate caused by substandard conditions of chemicals
and precise. This can be accomplished by careful and reactions
performance of the procedure to avoid errors in o Personal errors – caused by personal
conducting chemical analysis. limitations of the analyst such as failing to
follow procedures properly, among others

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 3 I gm

 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

• Personal bias (prejudice) – universal source of

personal error
• Improper calculation of results
• These are blunders that can be minimized or
eliminated with proper training and experience
The effect of systematic errors can either be constant errors
or proportional errors.

CONSTANT ERRORS SYTEMATIC ERRORS CAN BE DETECTED BY:

• are those that do not depend on the size of the ANALYSIS OF REFERENCE STANDARDS
sample being measured. The magnitude of error is
the same regardless of the size of the sample
• reference standards are chemicals of known
Example: the loss of precipitate while being washed. concentration and purity.
Constant errors can be minimized by increasing the
amount of the sample. ANALYSIS OF BLANK SAMPLES

PROPORTIONAL ERRORS • blank samples contain all reagents used in the

analysis other than the sample.
• are those errors whose magnitude increases or
decreases depending on the sample size VARIATION OF SAMPLE SIZE

Ex: Cu (II) and Fe (III) reacting simultaneously with KI to • to check for constant or proportional errors.
give out I2 to measure the relative amount of Cu (II).
THIRD PARTY ANALYSIS
SOURCES OF SYTEMATIC ERROR
• allowing other chemists to test or analyze the
INSTRUMENTAL ERRORS sample

• are caused by nonideal instrument behavior, by

faulty calibrations, or by use under inappropriate
conditions. Errors of this type are detectable and
correctable.
• Variation in temperature
• Contamination of the equipment
• Power fluctuations
• Component failure
TYPES OF ERRORS IN EXPERIMENTAL DATA
• All of these can be corrected by calibration or
proper instrumentation maintenance
GROSS ERROR
METHOD ERRORS
• causes large errors leading to outlier data.
• arise from nonideal chemical or physical behavior of
analytical systems. Ex. When the contents of a mixture are spilled when it is
• Slow or incomplete reactions being boiled. The loss brought about by spilling causes
an error in the amount of the analyte present in the
• Unstable species
sample being boiled.
• Nonspecific reagents
• Side reactions
• include an overrun end point during titration,
• These can be corrected with proper method instrument breakdown, loss of a substantial amount
development. of sample, discovery that a “pure” substance was
actually contaminated, etc. When gross error has
PERSONAL ERRORS occurred during measurement, the data obtained is
not used
• result from the carelessness, inattention, or
personal limitations of the experimenter. It occurs • Outlier - the occasional error that obviously differs
when measurements require personal judgment significantly from the rest of the values in the data
• Misreading of data set
• Parallax error
• Improper calibration (due to human intervention)
• Poor technique/sample preparation

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 4 I gm

 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 5 I gm

 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

EXAMPLES The average deviation is 1.09.

MEAN AND MEDIAN
1. CJ finally got her copy of grades for the first semester.
She was so happy seeing 95, 98, 96, 93, 99, 92, and 97 in
the card. Given the set of values, calculate the mean and
what is/are the median?
ABSOLUTE DEVIATION
Absolute deviation is the distance between each value in the
data set and that data set’s mean or median. To find the
distance:
1. Subtract the values. For example, let’s say the
mean of your data set is 10, and you have 5 values:
1, 5, 10, 15 and 19. The absolute deviations are:

1. 10 – 1 = 9
2. 10 – 5 = 5
3. 10 – 10 = 0
4. 10 – 15 = -5
5. 10 – 19 = -9

2. Take the absolute value of the numbers found. The

absolute value of -5 is 5, and -9 is 9. The final list of
values would be 9 ,5, 0, 5, and 9.

Take all of these absolute deviations, find the average, and

you have the mean average deviation.

STANDARD DEVIATION

Example

Find the standard deviation of 4, 9, 11, 12, 17, 5, 8, 12, 14

First work out the mean: 10.222
PRECISION Now, subtract the mean individually from each of the
numbers given and square the result. This is equivalent to
the (x - )² step. x refers to the values given in the question.
ABSOLUTE DEVIATION AND MEAN ABSOLUTE
DEVIATION

Example question: Find the average deviation of the

following set of numbers: 3, 8, 8, 8, 8, 9, 9, 9, 9.
Now add up these results (this is the 'sigma' in the formula):
139.55
Step 1: Find the mean: Divide by n. n is the number of values, so in this case is 9.
(3 + 8 + 8 + 8 + 8 + 9 + 9 + 9 + 9) = 71.9 = 7.89. This gives us: 15.51
And finally, square root this: 3.94
Step 2: Find each individual absolute deviation using the
formula |x – x̄|.

• |3 – 7.89| = 4.89
• |8 – 7.89| = 0.11
• |8 – 7.89| = 0.11
• |8 – 7.89| = 0.11
• |8 – 7.89| = 0.11
• |9 – 7.89| = 1.11
• |9 – 7.89| = 1.11
• |9 – 7.89| = 1.11
• |9 – 7.89| = 1.11

Step 3: Add up all of the values you found in Step 1.

4.89+0.11+0.11+0.11+0.11+1.11+1.11+1.11+1.11= 9.77

Step 4: Divide by the number of items in your data set. There

are 9 items, so:
9.77/9 = 1.09.

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 6 I gm

 lOMoARcPSD|10378816

OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF MEDICAL LABORATORY SCIENCE BATCH 2021-2022
ANALYTICAL CHEMISTRY LECTURE

Downloaded by Karen Jane LEMOSNERO (lemosnero.karenjane@s.msumain.edu.ph) 7 I gm