UNCERTAINTY IN

MEASUREMENTS
CAPE CHEMISTRY UNIT 2
MODULE 2 ( Analytical and Separation
Techniques)
OBJECTIVE 1
Ms. Sarika Chandoo
OBJECTIVES
Uncertainty in measurements
■ It is the quantitative indication of quality of result
■ Numerical data can be divided into two types:
– Data involving exact number ( that is, the values are known exactly- there is no uncertainty)
– Data involving inexact numbers ( for these types there is a degree of uncertainty.
■ When we carry out a particular experiment involving a measurement, there WILL ALWAYS BE
UNCERTAINTY associated with the measured data.
■ With measurements there is a doubt that exists about the result of any measurement. It deals with the
difference between a measured quantity and what is considered to be the true quantity.
■ Every measurement has an error which is unknown and unknownable. This unknown error is called
“measurement uncertainty”
■ It is an estimate of the error in a particular measurement.
■ Uncertainty in measurement is the difference between a measured quantity and what is considered to
be the true or actual quantity. It is an estimate of error in measurements.
■ Two of the most important statistical calculations that can be used to determine the degree of
uncertainty is finding the arithmetic mean or average and the standard deviation for the set of numbers.
Importance of Uncertainty

■ Avoids unnecessary repetition of analysis

■ Consideration of all uncertainty components provides scope for improvement
■ Provides information about quality and reliability of result.
■ Avoids unwarranted or risky decision taken based on only measurement.
Uncertainty in single determinations
■ On a 50 cm3 burette the scale unit is usually 0.1 cm3
■ On a 100 cm3 measuring cylinder the scale unit is 1 cm3
■ On a 10 cm3 measuring pipette the scale unit is 0.1 cm3
■ On a standard laboratory mercury thermometer the scale unit is 1 °C
■ When reading a value from one of these pieces of apparatus you must estimate the value
to one decimal place more than the level of graduation. If the reading coincides with a
scale unit there is a zero in the last decimal place of the reading.
■ If the reading does not coincide with a scale unit, the digit in the last decimal place is the
scale unit divided by 2.
■ The burette reading illustrated in Figure 28.1(a) would therefore be 16.60 cm3 and the
burette reading in Figure 28.1(b) is 16.25 cm3.
■ Recall that burette readings are taken at the lowest point of the meniscus.
■ The thermometer reading illustrated in Figure 28.2(a) is 37.0 °C and in Figure 28.2(b) it is
42.5 °C.
■ The estimated digit in the burette reading of 16.25 cm3 and the thermometer reading of 42.5
°C is the uncertainty in the reading. These readings are therefore correctly written as (16.25
±0.05) cm3 and (42.5 ± 0.5)℃
■ Similarly, the readings which coincide with the scale units are written correctly as (16.0 ±
0.05 ) cm3 and (37.0 ± 0.5)℃
■ Uncertainty in this context is the range which a data value may have because the last digit
which has been read from the instrument scale has been estimated.
 Uncertainty in Addition and Subtration
■ The uncertainty in measured values affects the calculations in which these values are used.
■ We are concerned here only with addition and subtraction, to which a very simple rule applies:
■ The uncertainty in the result of adding or subtracting two numbers is the square root of the
sum of the squares of the uncertainties in the two numbers.
Arithmetic Mean/ Average
■ This is used as an estimate of the true value and is calculated by the sum of all the
values divided by the number of values.
Standard Deviation
■ Standard Deviation (𝜎 𝑜𝑟 𝑠)
Gives a good measure of the level of precision of the data. The value given an indication of the spread of the
values around the mean. If the spread is large then there is a low degree of precision and if the spread is small,
there is a high degree of precision.
Accuracy and Precision
■ Accuracy: is the closeness/correctness of the
experimental measurement to the true or
generally accepted value of the quantity being
measured.

■ Precision: Agreement/closeness among a

series of independent measurements of the
same quantity all carried out in exactly the
same way (under the same experimental
procedure under stipulated conditions)

■ Precision is therefore an indication of

reproducibility.
■ The precision of a group of measurements
can be quantified by calculating the standard
deviation
Accuracy and Precision
Accuracy expresses the correctness of a
measurement while precision expresses the
reproducibility of a measurement.

Precision always accompanies accuracy but a high

degree of precision does not imply accuracy.

Precision is commonly expressed in terms of the

numerical differences between a given experimental
value and the mean of all the experimental results.
Precision:
Reproducibility: How close the values are between
analytic runs ( today, tomorrow, next week, next
month)

Repeatability: How close values are when done all

within the same day.
The smaller the random part of the experimental
errors which affect the results, the more precise the
procedure.
Question

■ Calculate the standard deviation for the values obtained in method A for
the % Cl in the sample.
■ Express the mean value including the standard deviation
■ Which set of values are more precise?
 ERRORS
■ Accuracy can be expressed in terms of errors. There are
two types:
■ Absolute Error ( E)
■ Relative Error( Er)
Absolute Error: E= Xm- Xt
Found by subtracting the true or accepted value from the
measured value.
Can either be a positive or negative value.
Relative Error: Measurement of the absolute error relative to
the true or accepted value.
𝑋𝑚 −𝑋𝑡
Er=
𝑋𝑡

Relative Error can be expressed in Percentage, Parts per

thousand (ppt) or parts per million (ppm)
Significant Figures
■ Number of digits reflecting the precision of a
given measurement.
■ The greater the number of significant figures,
the greater the certainty about the numerical
value of the measured or calculated quantity.
■ It is useful to express the measured parameter
in scientific notation.
■ Multiplication or division: Result should be
expressed based on measurement with
smallest number of SF.
■ Addition or subtraction: Results should be
expressed based on the measurement with the
smallest no. of decimal places
■ Zeros in the middle of a number are significant:
3.708 has four significant figures.
■ Zeros at the beginning of a number are not
significant: 0.003888 has four significant figures
and 0.03708 also has four significant figures.
■ Zeros at the end of a number and after a decimal
place are significant: 37.0 has three significant
figures and 3.850 has four significant figures
Classification of Errors

•Determinate
Systematic Affects accuracy

•Indeterminate
Random Affects Precision
Systematic Errors
■ Definite cause can be assigned and can be corrected.
■ These are errors that can be avoided or whose magnitude can be determined.
■ Operational or personal errors: This is due to the individual analyst.
They are not connected to the procedure and mostly occur when correct analytical technique is
not followed.
Example: Incomplete drying of analytical sample before weighing, colour blindness.
■ Errors of Method: These are very serious errors since they are often difficult to detect as they rise
from non- ideal chemical or physical behaviour of analytical systems eg a wrongly standardized pH
meter, a faulty detector response in spectroscopic and chromatographic methods.
■ Instrumental: These are due to imperfections in measuring devices and instabilities in their power
supplies. E.g faulty constructed balances, the use of uncallibrated or improperly calibrate weights,
graduated glassware or other instruments, the attack of glassware by reagents and the use of
reagents containing impurities.
■ A bias is the measurement of a systematic error associated with analysis. Consistent deviation of
measured value from the true value, caused by systematic error.
■ It has a negative sign if it causes results to be too low and a positive value if results are too high.
This takes place with instrumental and method errors.
■ A method showing good accuracy will bear less systematic errors.
Random Errors
■ Scatter or repeated measurements about their mean value.
■ Affect the level of precision.
■ The sign and magnitude of the error varies at random and cannot be known exactly.
■ They are due to causes that the analyst has no control over even if the greatest care is
taken.
■ They cause the results to be scattered and therefore not precise.
■ These errors manifest themselves by the slight variation that occur in successive
measurements made by the same observer with the greatest care under as nearly identical
conditions as possible.
■ Egs. Temperature fluctuation in the environment.
■ Wind drafts that could affect balance readings.
■ Parallax errors: Improper readings of scales.
■ Reduce errors by repeating experiments and taking the mean of a set of values.
 Error Vs Uncertainty
■ Error is a difference between true value and measured value. Whereas, uncertainty is a range.
■ Any parameter which cannot be expressed with certainty is associated with uncertainty. It exists
in all quantitative measurements.
■ Uncertainty is quantitative indication of the quality of the result.
■ It is the interval around the estimated value between which the true value of the measured
parameter is expected to lie.
Volume
■ Measuring cylinders, volumetric flasks, pipettes, burettes and syringes are all used to measure
volume.
■ Measuring cylinders are the least accurate of these measuring devices and so are not used to
measure liquids for quantitative chemical analysis.
■ Volumetric flasks are used to prepare solutions of known concentration. A volumetric flask is
designated To-Contain (TC) a specific volume of liquid.
■ Volumetric pipettes are used to transfer a specific volume of a solution from one container to another.
■ A volumetric pipette is designated To-Deliver (TD) the volume stated.
■ After the liquid has been delivered from the pipette, some of it remains in the tip and on the inner
surface; the stated TD volume takes account of this, so the liquid in the tip and on the inner surface
should not be blown out.
■ Burettes are used to accurately deliver a variable amount of liquid, as required in titrations.
■ Volumetric glassware must be properly calibrated to avoid introducing systematic errors into the
measurements for which they are used.
■ Calibration is accomplished by very carefully measuring the mass of water that is contained in or
delivered by the volumetric flask, pipette or burette.
■ The mass is then converted to volume, using the density of water at the temperature at which the
mass was measured.
volume = mass/ density
 Glassware and Associated Error
• Pieces of laboratory glassware have calibration marks which
guarantee maximum errors.
• A calibration mark is a line on the glassware that
• shows a particular value of volume, e.g. 100 cm3.
• Class A and Class B instruments.
• Class A have smaller tolerance range and are more accurate.
• Tolerance refers to the total allowable error within an item.
These volumes are usually
measured at a particular
temperature (usually 20 °C)
 Weighing
The terms ‘mass’ and ‘weight’ are often used interchangeably, but they are different properties.
■ Mass is the measurement of the amount of matter in an object.
■ Weight is a force, the pull of gravity on an object by the Earth .
 For making up small quantities e.g. 500 cm3 of solutions for titrations, we need to weigh to an accuracy of
±0.01 g.
 For accurate gravimetric work an accuracy of ± 0.0001g is needed. It is always the loss of mass that is
measured.

Weighing by difference:
Mass of sample: Mass of weighing bottle + sample – mass of weighing bottle after sample has been
transferred. Top Loading Balance Analytical Balance
Accuracy: ±0.01g Accuracy: ±0.0001g
 Recording readings with errors
■ When reading a value from one of these pieces
of apparatus you must estimate the value to one
decimal place more than the level of graduation.
■ If the reading coincides with a scale unit there
is a zero in the last decimal place of the reading.
■ If the reading does not coincide with a scale
unit, the digit in the last decimal place is the
scale unit divided by 2
■ The estimated digit in the burette reading of
16.25 cm3 and the thermometer reading of 42.5
°C is the uncertainty in the reading.
■ These readings are therefore correctly written
as 16.25 ±0.05 cm3 and 42.50±0.5℃
Laboratory Exercise for comparison of the accuracy
and precision among different volumetric
apparatus
■ Accurately weigh three dry labelled vials. Record the masses in your laboratory notebook.
■ Rinse the burette with a small amount of your assigned water sample.
■ Pour approximately 40mL of water sample into the burette and ensure that there are no air
bubbles in the tip.
■ Use the burette to transfer 10 mL of water sample into each of the three vials.
■ Stopper the loaded vials, accurately weigh and record their masses.
■ Pour the water sample from the vials and any remaining in the burette into a 250mL
collection beaker.
■ Please note the tolerance of the burette you are using.
■ To find mass of water transferred from the burette (assuming 1g=1mL): Mass of vial+ water-
Mass of dry vial.
■ Repeat these steps for the measuring cylinder, pipette and volumetric flask (10mL flask)
■ You can then compare the accuracy and precision of the instruments based on your results.
Standards
■ Primary standard: A reagent/ compound of sufficient purity
from which a standard solution can be prepared by direct
weighing of a quantity of it followed by a dilution to give a
definite volume of solution.
■ Standard solution is a solution containing a precisely known
concentration of an element or a substance.
The solid must be able to be
■ A primary standard solution and it should satisfy the following obtained to a very high purity.
requirements: • It must be stable in air.
• It must be readily soluble in
■ It must be easy to obtain, purify, to dry and to preserve in a
water and form a stable
pure state (Condition not met by hydrated substances) solution.
■ The substance should be unaltered in air during weighing • It must give reproducible
(substance should not be hygroscopic- absorbs moisture from results in a titration.
air). It should not be oxidized by air or affected by CO2. The • It should preferably have a
standard should maintain an unchanged composition during high relative molecular mass.
storage.
Standards
■ The substance should be capable of being tested for
impurities by qualitative tests and other tests of known
sensitivity.
■ The substance should have a high relative molecular mass so
that weighing errors are negligible.
The solid must be able to be
■ The substance should be readily soluble under the conditions obtained to a very high purity.
in which it is employed. • It must be stable in air.
• It must be readily soluble in
■ The reaction with the standard solution should be water and form a stable
stoichiometric and practically instantaneous. Titration errors solution.
should be negligible. • It must give reproducible
■ A standard provides a reference that can be used to results in a titration.
determine unknown concentrations or to calibrate analytical • It should preferably have a
instruments. high relative molecular mass.
Examples of Primary standards and
uses
Secondary Standards

■ A secondary standard has already been standardized against a primary standard.

■ A secondary standard is a substance which may be used for standardization and whose

content of the active substance have been found against a primary standard.

■ A secondary standard is a solution in which the concentration of a dissolved solute have not

been determined from the weight of the compound dissolved but by reaction ( eg. Titration) of

a volume of the solution against the measured volume of a primary standard.

Making Standards
To prepare a solution of known concentration, we need to weigh out the solute to the required degree of accuracy
and use a volumetric flask to prepare the solution.
■ To make 200cm3 of a solution of known concentration, the procedure is:
■ Tip the solid from the weighing bottle into a 200cm3 beaker. Add about 50cm3 of pure water.
■ Sir/ Shake well to dissolve the solid.
■ Wash out the volumetric flask with a little pure water.
■ Pour the solution from the beaker into the volumetric flask using a funnel.
■ Wash out the beaker several times with pure water and add the washings to the volumetric flask.
■ Wash out any liquid remaining in the funnel into the volumetric flask with a little pure water.
■ Fill the volumetric flask with pure water to just below the meniscus.
■ Add water drop wise( using a dropper) until the bottom of the meniscus is on the calibration mark.
■ Put the stopper (bung) on the flask and gently invert to mix the contents of the flask.

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 Calibration Curves
■ A calibration curve determines the relationship between the analytical

response and the analyte concentration.

■ The process is accomplished by using a set of chemical standards.

■ The operator prepares a series of standard solutions across a range of

concentration, near the expected concentration of the analyte in the

unknown.

■ When using spectroscopic methods it is necessary to carry out a

calibration procedure by using a series of standards each having a

known concentration of the analyte to be determined.

Calibration Curves
■ A series of standards is prepared containing analyte of known
concentration. At least three such standards are used in the
calibration process.
■ Calibration is accomplished by obtaining the response signal
eg absorbance as a function of the known analyte
concentration.
■ A calibration curve is constructed by measuring the
instrument signal eg absorbance for each standard and
plotting this result against concentration.
■ Provided the same experimental conditions are used for the
measurement of the standards and for the test sample, the
conc of the test sample may be determined from the
calibration curve by graphical interpretation.
■ Once curve has been plotted, the conc of the unknown can be
determined by placing it on the curve based on its
absorbance.
Videos On calibration Curves

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■ https://www.youtube.com/watch?v=DIIA7ywx7G4
■ https://www.youtube.com/watch?v=9iUrjW6vHps