Chapter 2

Basic Calculations in
Analytical Chemistry

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Chapter Overview

This chapter provides an

overview of the basic calculations
used in expressing the results of
a quantitative analysis.

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Learning Outcomes
At the end of this lesson, you should be able to

Ø explain the concept of mole

Ø solve problems involving mass- mole conversions
Ø solve problems involving stoichiometry
Ø describe the different types of solutions
Ø explain the ways of expressing concentration of solution
Ø illustrate the proper ways of preparing solutions with specific concentrations
Ø solve problems that involve calculation of the concentration of samples
Ø differentiate the types of errors with their sources, detection and elimination
Ø illustrate the ways of expressing accuracy and precision
Ø carry out calculation in the propagation of errors and uncertainty

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 Review of the fundamentals
The identity of a substance is defined not only by the types of atoms or ions it
contains, but by the quantity of each type of atom or ion, such as the mole.

What is a mole?
The mole is an amount unit similar to familiar units like pair, dozen, gross, etc. It provides
a specific measure of the number of atoms or molecules in a bulk sample of matter.
A mole is defined as the amount of A mole is a standard
substance containing the same scientific unit for measuring
number of discrete entities (atoms, large quantities of very small
molecules, ions, etc.) as the entities such as atoms,
number of atoms in a sample of molecules, or other
pure 12C weighing exactly 12 g. specified particles.

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Review of the fundamentals
The number of entities composing a mole has been experimentally
determined to be 6.02214179×1023, a fundamental constant
named Avogadro’s number or the Avogadro constant in honor of Italian
scientist Amedeo Avogadro.

Consistent with its definition as an amount unit, 1 mole of any element

contains the same number of atoms as 1 mole of any other element. The
masses of 1 mole of different elements, however, are different, since the
masses of the individual atoms are drastically different. The molar mass of an
element (or compound) is the mass in grams of 1 mole of that substance, a
property expressed in units of grams per mole (g/mol).

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Mole-Mass Conversion

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Mass-Particle No. Conversion

1 mole = 6.02×1023 particles

= 6.02×1023 atoms
= 6.02×1023 molecules

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Factor-Label Method
It is easier to write out the solution to a problem so that units in the
denominator of each succeeding term eliminate the units in the numerator
of the preceding one until the units of the answer are obtained.

This method has been referred to as the

factor-label method, dimensional analysis,
or the picket fence method.

It is practical to always use dimensional analysis to set up a

calculation properly. Don’t just memorize a formula.

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Sample Problem 2.1
A biochemist needs 0.100 mol of bilirubin (C33H36N4O6) for
an experiment. How many grams of bilirubin will that be?

Given: 0.100 mol C33H36N4O6

Req’d: g C33H36N4O6
Sol’n:

Calculate the molar mass of bilirubin

584.73 g/mol

!"#.%&'
g C33H36N4O6 = 0.100 mol
()*
g C33H36N4O6 = 58.5 g

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 Sample Problem 2.2
Calculate the number of moles and molecules of 85 grams glucose
C6H12O6 . How many atoms of H are present in the same compound?
Given: 85.0 g glucose
Req’d: H atoms in glucose
Sol’n: 1 mol C6H12O6 = ( 6 x 12 ) + ( 12 x 1 ) + ( 6 x 16 ) = 180 grams
1 mol C6H12O6 = 12 mol H
1 mol H = 6.022 x 1023 atoms

mol C6H12O6 = 85 g C6H12O6 ( 1 mol C6H12O6 .

180 g C6H12O6 . ) = 0.47 mol C6H12O6

Molecules C6H12O6 =.85 g C6H12O6

( 1 mol C6H12O6 .
180 g C6H12O6. )( 6.022 x 1023 C6H12O6 molecules
1 mol C6H12O6
) = 2.84 x 1023 molecules

Atoms of H = . 85 g C6H12O6 ( 1 mol C6H12O6

180 g C6H12O6 )( 12 mol H atoms
1 mol C6H12O6 )( 6.022 x 1023 H atoms
1 mol H atoms ) = 3.41 x 10 atoms
24

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Stoichiometry
Chemical stoichiometry is a section of chemistry that involves using relationships
between reactants and/or products in a chemical reaction to determine desired
quantitative data. In Greek, stoikhein means element and metron means
measure, so stoichiometry literally translated means the measure of elements.

In order to use stoichiometry to run calculations about chemical reactions, it is important

to first understand the relationships that exist between products and reactants and why
they exist, which require understanding how to balance reactions.
A chemical equation is like a recipe for a reaction so it displays all the
ingredients or terms of a chemical reaction. It includes the elements,
molecules, or ions in the reactants and in the products as well as their
states, and the proportion for how much of each particle is create relative
to one another, through the stoichiometric coefficient.
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Stoichiometry
• Write a balanced equation A B
• Convert the given mass in grams
to moles using the molecular mass Mass of Mass of
of the given substance A B

• Calculate the number of moles of Multiply by Molar mass of B

the sought substance using the Divide by Molar Mass of A
coefficient or the mole ratio in the
balanced equation Multiply by Coefficient
• Convert the computed number of of A and B from balanced equation
moles to mass in grams using the
molecular mass of the sought Moles Moles
of A of B
substance

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Mass-Mass Conversion
EXAMPLE: balanced chemical equation: CH4 + 4Cl2 → CCl4 + 4HCl

&'( )*! 0 &'( *)( 1,.0, /

g HCl= _g CH4 +,.-. / + &'( )*! + &'( *)(

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Sample Problem 2.3
Antacids are bases that neutralize acids in the digestive tract. Magnesium
hydroxide [Mg(OH)2] is one such antacid. It reacts with hydrochloric acid in
the stomach according to the reaction: Mg(OH)2 + 2HCl → MgCl2 + 2H2O

How many grams of HCl can a 0.250 g dose of Mg(OH)2 neutralize?

Given: 0.250 g Mg(OH)2
Req’d: g HCl
Sol’n:
Calculate the molar mass of Mg(OH)2 and HCl 58.32 g/mol Mg(OH)2
36.46 g/mol HCl
! "#$ %&$ ().+) ,
g HCl= 0.250 g Mg(OH)2 !"# Mg(OH)2

$%.'( )
' "#$ Mg(OH)2 ' "#$ %&$

g HCl= 0.313 g
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Solutions
Solutions are homogenous mixtures which are governed by solubility principles.

Components
ü Solute – the substance being dissolved;
usually present in smaller amounts. Solubility
ü Solvent – medium into which solutes vqualitative study of solutions
are dissolved; usually present in v defined as the maximum
amount of solute that
greater amounts, thereby determines
dissolves in a given quantity
the resulting phase of the solution of solvent at a specific
temperature

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Types of Solution
Based on the phase of
the solution
Based on the capacity of the
solution to dissolve the solute
Based on the conducting
Saturated Solution nature of the solution
Unsaturated Solution
Supersaturated Solution Based on the amount of
Nonelectrolyte solution solute present
Strong electrolyte solution
Weak electrolyte solution
Dilute solution
Concentrated solution
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Concentration of Solutions
It is not enough to identify a dilute or concentrated solution.
There should be a precise way of expressing the relative amount of solute and
solvent in a solution. This is quantitatively described as solution concentration.

Concentration – a measure of the amount

of solute contained in a given solution

The most common ways to express concentration in analytical chemistry

are molarity, weight percent, volume percent, weight-to-volume percent,
parts per thousand, parts per million and parts per billion.

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Molarity
Molarity refers the number of moles of solute per liter of solution.
The unit of molar concentration is molar, symbolized by M,
which has the dimensions of mol/L, or mol L-1.

Molar analytical concentration (analytical molarity or analytical concentration) is the

total number of moles of a solute, regardless of its chemical state, in 1 L of solution. It
describes how a solution of a given concentration can be prepared.
The molar equilibrium concentration (equilibrium molarity or equilibrium concentration)
refers to the molar concentration of a particular species in a solution at equilibrium.

For example, the molar equilibrium concentration of The analytical molarity

H2SO4 in a solution with a molar analytical concentration, is given by the notation
CH2SO4 = 1.0 M is actually 0.0 M because the strong acid is CX , while equilibrium
completely dissociated into a mixture of ions. molarity is given by [X]
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Percent Concentration
Calculations for solid samples are based on weight.The most common way of expressing the
results of macro determinations is to give the weight of analyte as a percent of the weight
of sample (weight/weight basis). The weight units of analyte and sample are the same.

It is important to note that in such

calculations, grams of solute do not
cancel with grams of sample solution;
the fraction represents grams of
solute per gram of sample.

The same principle is applied to liquid samples whose concentration can be

expressed as volume percent. It can also be expressed as weight (g) by volume (mL).
Whenever a concentration is expressed as a percentage, it should be clearly
specified whether this is wt/vol or wt/wt or vol/vol.
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Percent Concentration
Trace concentrations are usually
given in smaller units, such as
parts per thousand (ppt),
parts per million (ppm), or
parts per billion (ppb).

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Table 2.1 Ways of Expressing Concentration

From: https://chem.libretexts.org
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Table 2.2 Concentrated Solutions of Common Acids and Bases
Chemical Name Molecular Approx. Strength Molarity of Milliliters of Concd. Reagent
Formula of Concd. Reagent Necessary to Prepare 1 Liter
Concd. Reagenta of 1 Normal Soln.c
Acetic Acid, Glacial CH3COOH 99.8 17.4 57.5
Formic Acid HCOOH 90.0 23.6 42.5
Hydrochloric Acid HCl 37.2 12.1 82.5
Hydrofluoric Acid HF 49.0 28.9 34.5
Nitric Acid HNO3 70.4 15.9 63.0
Perchloric Acid HClO4 70.5 11.7 85.5
Perchloric Acid HClO4 61.3 9.5 105.5
Phosphoric Acid H3PO4 85.5 14.8 22.5
Sulfuric Acid H2SO4 96.0 18.0 28.0
Ammonium Hydroxide NH4OH 56.6b 14.5 69.0
Sodium Hydroxide NaOH 50.5 19.4 51.5
Potassium Hydroxide KOH 45.0 11.7 85.5
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Sample Problem 2.4
You can dissolve a precipitate of AgBr by reacting it with Na2S2O3.
AgBr(s) + 2Na2S2O3 (aq) ↔ Ag(S2O3)3- (aq) + Br- (aq) + 4Na+ (aq)
How many mL of 0.0138 M Na2S2O3 do you need to dissolve 0.250 g of AgBr?

Given: 0.0138 M Na2S2O3

0.250 g AgBr

Req’d: mL of Na2S2O3

Sol’n:
' -./ 0123 ! -./ Na2S2O3 '6 ' -6
mL Na2S2O3 = 0.250 g AgBr '45.4 1 0123 ' -./ 0123 7.7'(4 -./ Na2S2O3 '7!" 6
mL Na2S2O3 = 193 mL

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Sample Problem 2.5
(a) Calculate the number of moles of NaOH in 2.50 L of 0.100 M solution.
(b) Calculate the volume (mL) of NaOH needed to prepare 2.5 mmol of 0.100 M solution.

Given: 0.100 M NaOH

(a) 2.50 L (b) 2.50 mol

Req’d: (a) mol NaOH (b) L NaOH

Sol’n:
7.'77 "#$
(a) mol NaOH = 2.50 L = 0.250 567
8

"8
(b) mL NaOH = 2.5 mmol = 25 57
7.'77 ""#$

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Sample Problem 2.6
What is the molarity of a solution prepared by
diluting 5.00 mL of concentrated HNO3 to 0.250 L?
Given: 5.00 mL of concentrated HNO3
final volume = 0.250 L

Req’d: new molarity of HNO3

Sol’n:
molarity of concentrated HNO3 = 15.0 M

()* ,-"# + ,!.. ()* ,

HNO3 = 5.00 m"
+ , (+ + -./!- +
"#$
8
HNO3 = 0.318 M
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Sample Problem 2.7
What is the molarity of a solution prepared by diluting 8.45 mL
of 28.0 % w/w NH3 (density is 0.899 g/mL) to 250.0 mL?

Given: 8.45mL of 28.0 % w/w NH3

density=0.899 g/mL
final volume=250.0 mL

Req’d: new molarity of NH3

Sol’n:
()* /".- ' 01' -.".. ' ()* ,
NH3 = 8.45 m"
+ ,-- ' (+ ,%.-& ' -./!- +
"#$
8
NH3 = 0.500 M

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Preparation of Solution
A stock solution is prepared by weighing
Preparing Stock Solution out an appropriate portion of a pure solid
or by measuring out an appropriate volume
of a pure liquid, placing it in a suitable flask,
and diluting to a known volume.

Solutions are often prepared by diluting a

more concentrated stock solution.
Preparing Solution by Dilution
A known volume of the stock solution is
transferred to a new container and
brought to a new volume.

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 Preparation of Solution
from Solid Solute

Source: https://chem.libretexts.org/

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Preparation of Solution
Dilution from Stock Solution

Source: https://chem.libretexts.org/ COLLEGE OF SCIENCE

Sample Problem 2.8
Describe how to prepare
(a) 100 mL of approximately 60% (w/v) NaOH from solid NaOH
(b) 50 mL of approximately 0.20 M NaOH using solid NaOH

2- ' 0341 -./- (()* #-.-- ('

( ) *(+,= 100 /" 0 /) *(+,= 50 /"
,-- (+ (+ (()*
: ;<=> = 60 : 5: ;<=>= 400 mg

To prepare 60% (w/v) NaOH , To prepare 0.20 M NaOH,

weigh 60 grams of NaOH in a weigh 400 grams of NaOH in a
beaker and add approximately beaker and add approximately
100 mL of water. 50 mL of water.

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Sample Problem 2.9
Describe how to accurately prepare
(a) 250.0 mL of 5.00 M H2SO4 using the concentrated acid.
(b) 0.100 L of 20.0% ethanol using 75.0% ethanol.

:.77 ""#$ "8

< 5@ A6BA. H2SO4 = 250.0 m@ 5@ conc. H2SO4 = 69.4 mL
"8 '4.7 ""#$

To accurately prepare the solution, we measure out exactly 69.4 mL

of H2SO4 into 250 mL volumetric flask which initially contains approximately
100 mL water. Add enough water to reach the volumetric flask’s calibration
mark. Mix by inverting the flask several times.
!7.7 "8 ;<=% '77 "8 >#$ # ?
F @ EtOH sol’B = 0.100 @
'77 "8 >#$ # ? 5:.7 "8 ;<=%

@ EtOH sol’B = 0.0267 L

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Sample Problem 2.10
A laboratory procedure calls for a standard 5.00 ppm Fe3+. Describe
how you would prepare 1.00 L of this solution using solid ferric sulfate.

:.77 ", Fe3+ ""#8 Fe3+ ' ""#8 @A2(SO4)3 (BB.44 ", '7!" ,
: MN2(SO4)3 = 1.00 @
8 ::.4: ", ! ""#$ Fe3+ ""#$ @A2(SO4)3 ' ",

: MN2(SO4)3 = 0.0179 g

To accurately prepare 5.00 ppm Fe3+, measure out exactly 0.0179 g of MN2(SO4)3 into a
small beaker and dissolve using small portion of water. The resulting solution is
transferred into a 1-L volumetric flask. Rinse the beaker several times with small portions
of water, adding each rinse to the volumetric flask. This process, which is called a
quantitative transfer, ensures that the complete transfer of MN2(SO4)3 to the volumetric
flask. Finally, additional water is added to the volumetric flask’s calibration mark.

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Practice Problems 2.1
1. Exactly 0.2220 g of pure Na2CO3 was dissolved in 100.0 mL of 0.0731 M HCl.
What mass in grams of CO2 were evolved?
2. Calculate the molarity of the following: (a) 1.00 g H2SO4 in 25.0 mL of solution,
(b) 0.600 g NaOH in 50.0 mL of solution, (c) 25.0 g AgNO3 in 1.00 L of solution.
3. Describe how you would prepare each of the following solutions.
a)1.00 L of 0.5844 M NaCl from solid solute
b)0.100 L of 0.030 M K2Cr2O7 from 6.00 M K2Cr2O7
c)0.500 L of 2.00 M H2SO4 from concentrated acid
d)250.0 mL of 70% isopropyl alcohol from absolute alcohol
e)100.0 mL of 0.100 M NaOH from 50.0% (w/v) NaOH pellets
f)0.250 L of 75.0 ppm Zn(NO3)2 from solid Zn(NO3)2
g)100.0 mL of 5.00 ppm Pb2+ from solid Pb3(PO4)2
h) 1.00 L of 6.00 M H3PO4 from a concentrated solution that is 85.1% (w/w)
H3PO4 with a density of 1.69 g/mL
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Errors in Chemical Analysis
Measurements invariably involve errors and uncertainties. It is impossible to
perform a chemical analysis that is totally free of errors or uncertainties. Our
guiding principle will be that no quantitative results are of any value unless
they are accompanied by some estimate of the errors inherent in them.

The term error has two slightly different meanings.

ü Error refers to the difference between a We can only
measured value and the “true” or “known” value. hope to minimize
ü Error often denotes the estimated uncertainty in errors & estimate
a measurement or experiment. their size with
acceptable
The greater the error, the less representative accuracy.
the data are of the population and the less
reliable are the results of the study.
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Types of Errors

Determinate Error
affects accuracy

Indeterminate Error
affects precision

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Systematic Error
Systematic error is a measurement error which is a result of
the variation of a measurement of the true value.

The presence of this type of error can be

traced and identified in a chemical
measurement; hence, it is also called Instrumental
determinate error. error

If you conduct the experiment again in exactly

the same manner, the error is reproducible
Personal Method
Method
There are three types of systematic errors. error
Errors
error

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Method Errors
Errors due to method are
caused by the nonideal
chemical or physical behavior
of the reagents and reactions
on which an analysis is based.
Errors inherent in a method are
often difficult to detect and hence,
these errors are usually the most
difficult to identify and correct.
Examples:
Ø slowness of some reactions
or incompleteness of others
Ø instability of some species or
lack of specificity of most
reagents
Ø possible occurrence of side
reactions that interfere with
the measurement process
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Instrumental Errors
Instrumental errors are caused
Ø Pipets, burets, and
volumetric flasks may
by nonideal instrument
hold or deliver volumes behavior, by faulty
slightly different from calibrations, or by use under
those indicated by their inappropriate conditions
graduations.
Ø Electronic instruments
q Errors of these types usually are detectable
can be influenced by
and correctable.
noise, temperature, pH
q Calibration eliminates most systematic errors
and are also subject to
of this type.
systematic errors.

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Personal Errors
Ø Include personal judgments such
Personal errors result as estimating the position of a
from the carelessness, pointer between two scale
inattention, or personal divisions, the color of a solution,
limitations of the or the level of a liquid with
respect to a graduation
experimenter.
Ø A universal source of personal
error is prejudice, or bias.
Ø Number bias is another source of
Also called operative errors.
personal error which includes
preference for the digits 0 and 5.

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Personal Errors

Personal Errors

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Effect of Systematic Errors
(1) Constant Errors : magnitude is independent of size of the quantity measured

Example: 500 mg of precipitate → 0.5 mg wash out

50 mg of precipitate → 0.5 mg wash out

0.5
ON7<PQRN NOO6O = − ∗ 100 = −0.1%
500
0.5
ON7<PQRN NOO6O = − ∗ 100 = −1.0%
50

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Effect of Systematic Errors
(2) Proportional Errors : increase or decrease in
proportion to the size of the sample taken for analysis

Example: presence of interfering contaminants in the sample.

Iron can be a contaminant in the analysis of copper.

The size of this error is fixed by the fraction of iron contamination,

which is independent of the size of sample taken.
If the sample size is doubled, for example, the amount of iodine
liberated by both the copper and the iron contaminant is also doubled.
Thus, the magnitude of the reported percentage of copper is
independent of sample size.

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Detection & Elimination
For 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

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Detection & Elimination
For Systematic Method Errors

Systematic error
is a consistent
error that can be
detected and
corrected,
although this may
not be easy.

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Standard Samples
Certified Reference Materials (CRM) The best way to estimate the bias of an
are 'controls' or standards used to analytical method is by analyzing Certified
check the quality and metrological Reference Materials or US Standard
traceability of products, to validate Reference Material. Analytical method
analytical measurement methods, or should produce an answer acceptably close
for the calibration of instruments. to the certified level or there is something
wrong with the accuracy of your method.
Analysis of Standard Samples
Ø The overall composition of a synthetic standard material must closely
approximate the composition of the samples to be analyzed.
Ø Great care must be taken to ensure that the concentration of analyte is
known exactly.

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Independent Analysis
• The independent method should
If standard samples are not available, differ as much as possible from the
another independent and reliable analytical one under study. This practice
method can be used in parallel. minimizes the possibility that some
If results do not agree, there is error common factor in the sample has
in one (or more) of the methods. the same effect on both methods.
• A statistical test must be used
Round robin experiment: Different people to determine whether any
in several laboratories analyze identical difference is a result of random
samples by the same or different methods. errors in the two methods or
Disagreement beyond the estimated due to bias in the method
random error is systematic error. under study.

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Blank Determinations
A blank solution contains the reagents and ümethod blank: taken
solvents used in a determination, but no analyte. through all steps of the
analytical procedure.
Blanks account for interference by other üreagent blank: similar
species in the sample and for traces of analyte to a method blank, but it
found in reagents used for sample has not been subjected
preservation, preparation, and analysis. to all sample
preparation procedures.
If you observe a nonzero result for the blank solution, üfield blank: similar to a
your method responds to more than you intend. method blank, but it has
been exposed to the site
The result of the analysis of blank solutions is applied as a of sampling.
correction (i.e. subtracted) to the sample measurements.

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Variation in Sample Size

As the size of a Sample Size is the number of observations

measurement increases, taken from a population through which
the effect of a constant
error decreases. The more
information you have, the
more accurate your results
are going to be. Thus,
constant errors can often
be detected by varying the
sample size.
statistical inferences for the whole
population are made.
Replicates are
samples of about the
same size that are
carried through an
analysis in exactly the
same way.

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Random Errors
ü No identifiable cause ü arises from natural limitation on our ability
to make physical measurements
ü Always present ü causes data to be scattered more or less
systematically around a mean value
ü Cannot be eliminated ü always present and cannot be corrected
ü has an equal chance of being positive or
ü the ultimate limitation negative
on the determination
of a quantity Example:
reading a scale on an instrument caused by
the finite thickness of the lines on the scale

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Minimizing Random Errors
The sources of
random errors
Sample source: cannot be traced
changes in experimental conditions (indeterminate);
How to minimize them:
these can only be
Take repeated measurements and
evaluated using
use of statistics like mean,
statistics.
standard deviation, variance,
coefficient of variation, etc.
Random error cannot be
eliminated, but it might be
reduced by a better experiment.

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Sample Problem 2.11
Categorize each as a determinate or an indeterminate error and further
classify determinate errors as instrumental, method or personal.

a) An unknown sample being weighed is hygroscopic. Determinate, method

b) One component of a mixture being analyzed quantitatively by GC
reacts with the column packing. Determinate, method
c) A radioactive sample being counted repeatedly without any change in
condition yields a slightly different count at each trial. Indeterminate
d) The tip of the pipet used in the analysis is broken.
Determinate, instrumental
e) In measuring the same peak heights of a chromatogram, two
technician each report different heights. Determinate, personal
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Gross Errors
Ø Gross errors are often the product of human errors.
Ø They usually occur only occasionally, are often large, and may
cause a result to be either extremely high or low.

Gross errors lead to outliers that there is no alternative to

abandoning the experiment and making a completely fresh start.

Examples:
ü complete instrument breakdown
ü accidentally dropping or discarding a crucial sample
ü discovering during the course of the experiment that a supposedly pure
reagent was in fact badly contaminated

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Detecting Outliers
An outlier is an observation that lies outside the overall pattern of a
distribution. It is product of gross error so it should be excluded from the data.

Evaluating an outlier

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Grubb’s Test
Table
Table 2.3 2.3

Grubbs’ test – ISO recommended

test for outliers. This test compares
the deviation of the suspect value
from the sample mean with the
standard deviation of the sample.
̅
/2324567 89:35;=/
!= 2> Source: Miller and Miller, 2010

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Dixon’s Test/Q-test
Dixon’s test (also called Q-test) - the test
Table
Table 2.3 2.4 assesses a suspect measurement by
comparing the difference between it and
the measurement nearest to it in size with
the range of the measurements.

/:<Y/
W=
O<B:N
/Z[ZYNAP R<7[N − BN<ONZP R<7[N/
W=
7<O:NZP R<7[N − Z5<77NZP R<7[N
Source: Harris, 20106

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Dixon’s Test/Q-test
Example:: Is 167 an outlier in this set of data? 167, 180, 188, 177, 181, 185, 189

Step 1: Sort your data into ascending order (smallest to largest).

167, 177, 180, 181, 185, 188, 189
Step 2 :Find the Q statistic using the following formula:
!"#$ =
/'(')*"+ ,#$(* − .*#/*'+ ,#$(*/ /167 − 177/
$#/0*'+ ,#$(* − '1#$$*'+ ,#$(* W = W = 0.455
189 − 167
Step 3: Find the Q critical value in the Q table. For a sample size of 7 and an alpha level
(confidence level) of 5%, the critical value is 0.568.
Step 4: Compare the Q statistic from Step 2 with the Q critical value in Step 3.
If the Q > Q critical value, the point is an outlier, the value should be rejected.
Answer: Qcal 0.455 < Qcrit 0.568, so the value 167 is not an outlier at an alpha level of 5%.
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Sample Problem 2.12
The following values are the reported masses (in milligrams) from a chloride analysis
of a serum sample: 10.2, 10.7, 10.1, 10.6, 13.0. One value appears suspicious.
Determine if it can be ascribed to gross error at the 95% confidence level.

/Z[ZYNAP R<7[N − `/
̅ `̅ = 10.92 sd = 1.19
Grubbs’ test ^A<7 =
Za
^A<7 =
/'(.7D'7.B!/
= 1.75 Gcal = 1.75 Gcrit < Gcal
'.'B Gcrit = 1.72
Q test
/Z[ZYNAP R<7[N − BN<ONZP R<7[N/ /'(.7D'7.5/ WA<7 = 0.79 Qcrit < Qcal
W= W= = 0.79
7<O:NZP R<7[N − Z5<77NZP R<7[N '(.7D'7.' Qcrit = 0.71

Both test revealed that the value 13.0 is an outlier. It is a product of gross error.

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L

Table 2.4 Comparison of Random and Systematic Errors

Source: Miller and Miller, 2010. COLLEGE OF SCIENCE

Accuracy

It is often more difficult to

Accuracy indicates the
determine be because the true
closeness of the
value is usually unknown.
measurement to the
true or accepted value.
An accepted value must be
used instead.

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Measure of Central Tendency
The mean, also called the arithmetic
mean or the average, is obtained by
dividing the sum of replicate
measurements by the number Measures of central
of measurements. tendency are measures
of the location of the
middle or the center of a
The median is the middle distribution.
value in a set of data that has
been arranged in numerical order.
The median is used advantageously
when a set of data contain an outlier.

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Expressing Accuracy
Absolute Error
The absolute error of a measurement is the difference
between the measured value and the true value. If
The higher the the measurement result is low, the sign is negative; if
absolute or the measurement result is high, the sign is positive.
relative error, the b = `E -`<
lower the
accuracy. Relative Error
The relative error of a measurement is the absolute
error divided by the true value. It may be expressed in
percent, parts per thousand, or parts per million,
depending on the magnitude of the result.
Er=xi -xt/xt *100%

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Precision

Precision describes the

agreement among
several results obtained
in the same way.
Source: Skoog, et.al., 2010. Fundamentals of Analytical Chemistry

Illustration of accuracy and precision using the

pattern of darts on a dartboard. Note that we can
have very precise results (upper right) with a mean
that is not accurate and an accurate mean (lower
left) with data points that are imprecise.
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Types of Precision

Instrument precision, also called injection precision, is the reproducibility

observed when the same quantity of one sample is repeatedly introduced
(>10 times) into an instrument.
Intra-assay precision is evaluated by analyzing aliquots of a homogeneous
material several times by one person on one day with the same equipment.
Intermediate precision, formerly called ruggedness, is the variation
observed when an assay is performed by different people on different
instruments on different days in the same lab.
Interlaboratory precision, also called reproducibility, is the most general
measure of reproducibility observed when aliquots of the same sample are
analyzed by different people in different laboratories.

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Repeatability/Reproducibility
Repeatability - describes the precision of within-run replicates;
nearness of each result with the same:
ü set of solutions
ü glassware would be used throughout
ü preparation of indicator would be added to each titration flask
ü temperature, humidity and other lab conditions would remain much the same

Reproducibility - describes the precision of between-run replicates;

nearness of result with:
ü the titrations performed by different staff on five different occasions
in different laboratories
ü using different pieces of glassware and different batches of indicator

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Expressing Precision
An ideal measure of precision must have been the following attributes:
(1) It must be independent of sample size.
(2) It must be useful in quantitative comparisons of different data sets.
(3) The experiments must be able to combine different sets of data, regardless
of size, to obtain betters estimates of the precision.

sd range
!5678 rsd cv s2

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 Standard Deviation
Standard deviation: measure spread or dispersion around the mean of a data set

For a small number of replicate measurements,

∑$ (= ; ̅
=) % ∑$
!"#(=! ;A)
%
$= !"# !
#=
C;D C

S : sample standard deviation σ: population standard deviation

x : measured mean for the small set μ: population mean (true value)

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Range and Pooled SD
Spread or Range (w) = difference between the highest and lowest value.
w=/ highest – lowest /

Pooled Standard Deviation

When several small sets have the same sources of indeterminate error
(i.e., the same type of measurement but different samples) the standard
deviations of the individual data sets may be pooled to more accurately
determine the standard deviation of the analysis.

2#% C# ;D F2%% (C% ;D)

%4EE:5> = C# ;C% ;G

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RSD and CV
Relative Standard Deviation (rsd) – standard deviation divided by the mean; often
used to compare the precision of results which have different units or magnitude
'
&'( =
*̅
c
rsd = d̅ ∗ 1000 ++,
Coefficient of Variation (cv) - relative standard deviation expressed as percentage
c
cv = ̅ ∗ 100%
d

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Variance and Smean
Variance – square of the standard deviation; a more statistically
useful measure of the scatter particularly for random errors

variance = ' e = '(e

Standard deviation of the mean - standard deviation divided by the square root of
the sample size; sometimes referred to as the standard error
'(
'!"#$ =
-

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Sample Problem 2.13
Replicate water samples are analyzed for water hardness with the following
results; 102.2, 102.8, 103.1, 101.8 and 102.3 ppm CaCO3. Calculate
(a) mean
(b) standard deviation
(c) relative standard deviation
(d) variance
(e) coefficient of variation

(a) Mean x = 102.4

(b) standard deviation sd = 0.5128
(c) relative standard deviation rsd = 0.005008
(d) Variance s2 = 0.2630
(e) coefficient of variation cv = 0.5008%

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Sample Problem 2.14
Identify the data set with the highest (a) precision and (b) accuracy.

Data set Certified Mean Standard Coefficient Percent

true value deviation of variation Error
1 0.500 0.444 0.041 9.2% 11%
2 1.00 1.33 0.253 19% 33%
3 50.00 45.20 0.041 0.091% 9.6%
4 100.0 99.1 3.22 3.2% 0.90%

highest precision = data set 3 (lowest coefficient of variation)

highest accuracy = data set 4 (lowest percent error)

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Errors and Uncertainty
Error is the difference between a single measurement or result
and its expected value. In other words, error is a measure of bias.
Uncertainty expresses the range of possible values for a
measurement or result.

q Uncertainty accounts for all errors—both determinate and

indeterminate—that reasonably might affect a measurement
or a result.
q Although we always try to correct determinate errors before
we begin an analysis, the correction itself is subject to
uncertainty.

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Uncertainty
Absolute Uncertainty (AU): margin of uncertainty associated An uncertainty of
with a measurement. ±0.02 mL means
Example: a buret reading : 12.35±0.02 mL that, when the
Relative Uncertainty (RU) : comparing the size of the absolute reading is 13.33 mL,
uncertainty to the size of its associated measurement. the true value could
be anywhere in the
range 13.31 to
<FZ67[PN [BANOP<QBPh
fg = 13.35 mL.
5<:BQP[aN 6i 5N<Z[ON5NBP

0.02 5@
fg = = 0.002 = 2YYP = 0.2%
12.35 5@

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Propagation of Uncertainty

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Propagation of Uncertainty
from Random Error

Uncertainty is usually expressed as the standard deviation of calculated

results or as a confidence interval. These parameters are based upon a series
of replicate measurements.

- The most likely uncertainty in the result is not the sum of individual errors,
because some of these are likely positive and some negative. We expect some
cancellation of errors .

- The uncertainty for glassware expressed as the tolerance.

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 Table 2.5 Type A Glassware Tolerance

Source: Harvey (2016) COLLEGE OF SCIENCE

Propagation of Uncertainty
Uncertainty is
A propagation of propagated when
uncertainty allows solving data involving
us to estimate the
Addition or subtraction NF = N'! + N!! + N(! + …
uncertainty in a
result from the
uncertainties in Multiplication or division %N = (%N' )! +(%N! )! + ⋯
F
the measurements
used to calculate Powers and roots % Nh = < (%N`)
that result. NG
Logarithm NF = 0.43429
NF `
= (7B 10) NG = 2.3036 NG
h I
$
qH = J
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Addition/Subtraction
Example :Uncertainty in a Buret Reading
The volume delivered by a buret is the difference between final and initial readings.
If the uncertainty in each reading is what is the uncertainty in the volume delivered?

Solution Suppose that the initial reading is0.05(±0.02) and the final reading is
17.88 ±0.02 5@. The volume delivered is the difference:

17.77(±0.02) NF = N'! + N!! + N(!

- 0.05(±0.02)
17.83(±N) N = 0.02! + 0.02! = 0.024 ≈ 0.03
Regardless of the initial and final readings, if the uncertainty in each one is
± 0.02 5@, the uncertainty in volume delivered is ±0.03 5@.
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 Multiplication/Division
%N+ = (%N' )! +(%N! )! +(%N( )!

D.HI ±K.KL ∗D.NO (±K.KG)

For example: = 5.64 ± +Q
K.PO (±K.KG)

First, convert absolute uncertainties to percent relative uncertainties.

1.76 ±1.7% ∗ 1.89 (±1.1%)
= 5.64 ± N+
0.59 (±3.4%)
%N+ = (1.7)! +(1.1)! +(3.4)! = 4.0% 4.0% ∗ 5.64 = 0.040 ∗ 5.64 = 0.23

Two expressions of final result: 5.6 ±0.2 <FZ67[PN [BANOP<QBPh

5.6 (±4%) (ON7<PQRN [BANOP<QBPh)
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Multiplication/Division
The Real Rule for Significant Figures
The first digit of the absolute uncertainty is the last significant digit in the answer.
For example, in the quotient
0.002364 (±0.000003) / 0.02500 (±0.00005)=0.0946 (±0.0002)

The uncertainty occurs in the fourth decimal place. Therefore, the answer 0.094 6 is
properly expressed with three significant figures, even though the original data have
four figures. The first uncertain figure of the answer is the last significant figure.

The quotient 0.821(±0.002)/0.803 (±0.002)=1.022 (±0.004)

is expressed with four figures even though the dividend and divisor each
have three figures.

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Powers and Roots
The uncertainty in the function

y = xa is % RS = ( (%RV)

Example:
%
&
-.--, 9 ,--
[3.1415 (±0.001)]1/2 %ey = = 0. 0159%
&.,#,!

WRX(YZ[R \]^RWY(Z]YS: 1.7724 (±0.02%)

(0bcX\YR \]^RWY(Z]YS: 1.7724 (±0.0004)

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Logarithm
' A% A%
h = 76:` ⇒ NF = $?'7 G
≈ 0.043429 G

Example: log[2.0 (2.0 ± 0.02 ` 10D+ ]= -3.699 ± ey

R9 0.02 V 10;#
R: = 0.43429 = 0.43429 = 0.00434
V 2.0 V 10 − 4
<FZ67[PN [BANOP<QBPh: −3.699 (±0.004)
A&
Y = antilog x F
= (7B 10) NG = 2.3036 NG
Example:
yBPQ76: [1.2(±0.003)] = 15.849 ± ey
NF
= 2.3036 NG = 2.3036 (0.003)(15.849) = 0.1
h
absolute uncertainty: 15.8 (±0.1)
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Logarithm
&H
Uncertainty for natural logarithm: " = $% & ⇒ (% =
'
Example:
)*[3.1415(±0.0011)] = 1.14470 ± 7<
(±+.++--)
7( = = 0.00035
/.-0-1

89!:);<7 ;*=7><8?*<@: 1.14470 (±0.00035)

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Propagation of Uncertainty

from Systematic Error Other than the normal distribution,

uncertainties can be assume to have
Systematic error occurs in
some common situations,
Rectangular Distribution
and is treated differently
from random error in
arithmetic operations.

Triangular Distribution

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Rectangular Distribution
q Also called uniform distribution
q Proposes a uniform (rectangular shape) distribution between the
limits of ±x, in which each result between the limits is equally likely.
q Example with a uniform distribution is when a coin is tossed. The
likelihood of getting a tail or head is the same.
q For a uniform distribution the estimated standard deviation, sd, is
!
!"=
"
This is the most conservative estimate of uncertainty as it gives the
largest estimate for the standard deviation.

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Rectangular Distribution

Example:
Rectangular distribution for atomic mass.
The standard uncertainty interval
(standard deviation) shown in color is
equal to the uncertainty given in the
periodic table divided by 3 .
The atomic mass of oxygen in the
periodic table is 15.999 4 ± 0.0003.
The standard uncertainty is
±0.0003/ 3 = ±0.00017.

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Triangular Distribution
q Typically used as a subjective description of a population for which there is
only limited sample data, and especially in cases where the relationship
between variables is known but data is scarce.
q It is based on a knowledge of the minimum and maximum and an "inspired
guess” as to the modal value. For these reasons, the triangle distribution has
been called a "lack of knowledge" distribution.
q It is the choice when the manufacturer provides a tolerance range without
specifying a level of confidence and when there is a good reason to believe
that results near the center of the range are more likely than results at the
ends of the range.
q For a triangular distribution the estimated standard deviation z
./= {
This is a less conservative estimate of uncertainty as, for any value of x, the
standard deviation is smaller than that for a uniform distribution.
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Triangular Distribution
Multiple deliveries from one pipet
A 25 mL pipet is certified to deliver 25.00 ± 0.03 mL.
The volume delivered by a pipet is reproducible, but
can be in the range of 24.97 ~ 25.03 mL, depending
on a pipet. However, the manufacturer works hard to
make the volume close to 25.00 mL. There is the
highest probability that the pipet will deliver 25.00
mL. The probability falls off approximately in a linear
manner as the volume deviates from 25.00 mL. There Triangular distribution
is negligible probability that a volume outside of for volumetric
25.00 ± 0.03 mL will be delivered. The standard glassware including
uncertainty (standard deviation) in the triangular volumetric flasks and
K.KL transfer pipets.
distribution is |= = 0.012 mL.
M

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Multiple deliveries from a pipet
If you use an uncalibrated 25-mL Class A volumetric pipet four times to deliver a total
of 100 mL, the standard uncertainty is 4 * ± 0.012 = ± 0.048 mL, not
0.012! + 0.012! + 0.012! + 0.012! = 0.024 mL, because the uncertainty is a
systematic error, not random error.

The difference between 25.00 mL and the actual volume delivered by a particular
pipet is a systematic error. It is always the same, within a small random error. You
could calibrate a pipet to eliminate the systematic error.

If a calibrated pipet delivers a mean volume of 24.991 mL with a standard uncertainty

of ± 0.006 mL, and you deliver four aliquots, the volume delivered is 4 x 24.991 =
99.964 mL. The uncertainty (± 0.006 mL) is random error. So the standard uncertainty
is 0.006! + 0.006! + 0.006! + 0.006! = ± 0.012 mL.
For an uncalibrated pipet, the standard uncertainty is 4 * ± 0.012 mL. = ± 0.048 mL.
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Sample Problem 2.15
Estimate the standard deviation of the following calculations:
a) [(90.31±0.08)-(89.32±0.06)]+(0.200±0.004)
b) [163(±0.03) x 10-14] / [1.03(±0.04) x 10-16]
c) [2.45(±0.02) x 10-2 – 5.06(±0.06) x 10-3] / (23.2±0.7 + 9.11±0.08)
d) (2.78±0.04)(0.00506±0.00006) / (30.2±0.2)
e) [(25.0±0.1)(0.0215±0.0003) – (1.02±0.01)(0.112±0.001)] (17.0±0.2)

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Sample Problem 2.16
For a concentration technique, the relationship between the signal and the an
analyte’s concentration is

S =k C +S
total A A mb

What is the analyte’s

concentration, CA,
and its uncertainty if
Stotal is 24.37 ± 0.02,
Smb is 0.96 ± 0.02, and
kA is 0.186 ± 0.003
ppm–1?

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Sample Problem 2.17
The formula weight (FW) of a gas can be determined using the form
of the ideal gas law: FW= PV

where g is the mass in grams, R is the gas constant, T is

the temperature in Kelvin, P is the pressure(atm) and V
is the volume in liters.
In a typical analysis the following data are obtained g =
0.118 g (± 0.002 g)
R = 0.082056 L atm mol-1 K-1 (a) What is the compound’s formula weight
(± 0.000001 L atm mol K )
-1 -1
and its estimated uncertainty? (b) To which
T= 298.2 K (± 0.1 K) variable(s) should you direct your attention
P= 0.724 atm (± 0.005 atm) if you wish to improve the uncertainty in the
V= 0.250 L (± 0.005 L) compound’s molecular weight?

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a) What is the compound’s
formula weight and its
estimated uncertainty?
b) To which variable(s)
should you direct your
attention if you wish to
improve the uncertainty in
the compound’s molecular
weight?

b) The two with the largest relative uncertainty are the mass in grams and
the volume in liters; these are the measurements where an improvement in
uncertainty has the greatest impact on the formula weight’s uncertainty.
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Sample Problem 2.18
What is the uncertainty in 100 mL if you use an uncalibrated 25 mL pipet
four times to deliver of 100 mL ?
K.KL
The uncertainty is a systematic error. So the standard uncertainty = ± 4 x
M

= ±} ∗ ~. ~Ä = ±~. ~}Å ÇÉ

So the uncalibrated pipet volume = 100.00 ± 0.05 mL
The difference between 25.00 mL and the actual volume delivered by a particular
pipet is a systematic error. In other words, it is always the same, within a small
random error.
You could calibrate the pipet by weighing the water it delivers to eliminate a
systematic error. In such case, the pipet always delivers, say, 24.991 ± 0.006 mL.
The uncertainty (± 0.006 mL) is random error.
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Sample Problem 2.19
What is the uncertainty in 100 mL if you use a calibrated pipet which delivers
a mean volume of 24.991 mL with a standard uncertainty of ± 0.006 mL ?

You deliver four times, so the volume is 4 x 24.991 mL = 99.964 mL

But the uncertainty ± 0.006! + 0.006! 0.006! + 0.006! = ±0.012 5@
We use equations for random error, because the uncertainties in four delivered
aliquots are independent of each other. One might be positive and one might
be negative because they are random error.
So calibrated pipet volume = 99. 964 ± 0.012 mL

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Sample Problem 2.20
Which of the following is the best way to dispense 100.0 mL if we wish to
minimize the uncertainty: (a) use a 50-mL pipet twice; (b) use a 25- mL pipet
four times; or (c) use a 10-mL pipet ten times?

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 Problem Set 2.2
1. A chemist working in a hospital clinical laboratory obtained the following values for uric acid in
blood serum: 4.63, 4.58, 4.72, 4.21, 4.67 and 4.65 %. (a) Use the 95% confidence level to test any
dubious values. What value should be reported as the b) mean? c) sd? d) CV?
2. Quantitative analysis student Ana Lytical analyzed an ore sample for its lead content and
obtained a mean of 4.75% Pb for five measurements. If the certified true value is 4.50%, what is the
(a) percent error? (b) percent accuracy?
3. Which of the following methods for preparing a 0.0010 M solution from a 1.0 M stock solution
provides the smallest overall uncertainty?
a) A one-step dilution that uses a 1-mL pipet and a 1000-mL volumetric flask.
b) A two-step dilution that uses a 20-mL pipet and a 1000-mL volumetric flask for the first dilution,
and a 25-mL pipet and a 500-mL volumetric flask for the second dilution.
4. You prepared HCl solution by diluting 8.00 (±0.04) mL of 37.7 (±0.5) % w/w HCl [density = 1.19
'
±0.01 ] up to 500.0 (±0.2) mL. Find the resulting molarity and uncertainty. The molecular
()
mass of HCl has negligible uncertainty relative to other uncertainties in this problem.
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References
ü Christian, G. (2014). Analytical Chemistry, 7th ed. USA:
John Wiley & Sons.

ü Harris, D. (2016). Quantitative Chemical Analysis, 9th edition.

New York: W.H. Freeman and Company.

ü Harvey, D. (2016). Analytical Chemistry 2.0. Electronic version

ü https://chem.libretexts.org/

ü Miller and Miller. (2010). Statistics and Chemometrics for

Analytical Chemistry, 6th ed. Canada: Pearson Education.

ü Skoog et al. (2014). Fundamentals of Analytical Chemistry, 9th

edition. Canada: Brooks/Cole Publishers Company.

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