CLS571 Fall 2022-23

Introduction to Analytical Chemistry

American University of Science and Technology

Nina Esipenko, Ph.D.

1
 Introduction
• Analytical chemistry is a measurement science consisting
of a set of powerful ideas that are useful in all fields of
science and medicine.
• The aim is to separate, identify and determine the relative
amounts of substances in samples of matter.
• Qualitative analysis: Reveals the identity of the elements
and compounds in a sample. “What is present?”
Quantitative analysis: Indicates the amount of each
substance in a sample. “How much is present?”
• Analytes: The components of a sample that are to be
determined.

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• Analytical chemistry is often called the central science.
• Analytical chemistry is at the core of chemistry and play an
important role in nearly all aspects.

3
 Steps in Quantitative Analysis

1. Define the problem and select

the method of analysis
accordingly
2. Obtain representative samples
3. Prepare laboratory samples
4. Define replicate samples
5. Prepare solutions of the
samples
6. Eliminate interferences
7. Calibrate and measure
8. Calculate the results
9. Evaluate the quality of the
results using statistical analysis
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 1. Define the Problem and Select the Method
of Analysis Accordingly

• The selected method usually

represents a compromise
between accuracy (quality)
required and the time and
money available for analysis.

• The sample size will also depend on the factors above as well
as the complexity of the sample and the number of
components in the sample.
• Depend on the facilities, equipment and instruments available,
sensitivity and precision required and cost.
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 2. Obtain Representative Samples /
Acquiring Samples
• To produce meaningful information, an analysis must be
performed on a sample that has the same composition as
the bulk (population) of material from which it was taken.

• Sampling is the process of collecting a small mass of a

material whose composition accurately represents the bulk
(population) of the materials being analyzed.

• When the bulk is large and heterogeneous (parts can be

distinguished) great effort is required to get a representative
sample.

• When the bulk is homogeneous, the sample population is

reduced in size to an amount that can be conveniently handled
in the laboratory. 6
 3. Prepare Laboratory Samples
• Depending on the sample, sometime sample processing is
required.
• Keep the INTEGRITY of the sample !
• A solid sample is ground to decrease particle size, mixed to
ensure homegeneity, and stored before analysis. Precaution:
Control the water adsorption content.
• For liquid samples. Precaution: avoid volume changes and
cross-contamination.
• For gas dissolved in a liquid. Precaution: Isolate the
container and avoid contamination.
• The reliability of the final results will be often limited by this
step.

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 4. Define Replicate Samples
• Replicate samples or replicates are portions of a
material of approximately the same size that are
carried through an analytical procedure at the same
time and in the same way.
• Quantitative measurements on replicates are usually
averaged, and various statistical tests are performed
on the results to establish reliability.

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 5. Prepare Solutions of the Samples
(Physical and Chemical Changes)

• Analysis is usually performed on solution of the

sample.
• Conversion of the analyte to a soluble form is
important in most cases.
• A sample should have properties that are
proportional to the analyte concentrations or else we
convert quantitatively the sample using chemical
means in order to measure the concentration.
• Inorganic material may be dissolved in various
acids, redox or complexing media.
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 6. Eliminate Interferences

• An interference or interferent is a species that

causes an error in an analysis by enhancing or
attenuating the quantity being measured.
• The matrix, or sample matrix, is all of the
components in the sample containing an analyte.
• An interferent, if present in the sample matrix,
should be eliminated from the sample being
analyzed.
• This is done by selectively isolating the analyte of
concern from the sample matrix before analytical
measurements.

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7. Calibration and Measuring Concentration
• Measurement (X) of a physical or chemical property that
vary in a known and reproducible way with the
concentration (CA) of an analyte (A).

Calibration curve
A4

A3
Property

A2

A1

C1 C2 C3 C4
Concentration

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 8. Calculating Results

• These computations are based on the raw

experimental data collected in the measurement step.
• These numbers are usually characteristics of
 The physical/chemical property
 The measurement instruments
 The stoichiometry of the analytical reaction

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9. Evaluate the Quality of the Results Using
Statistical Analysis

• An analytical result should always be associated

with an estimate of reliability and measure of the
uncertainty associated with the computed data.

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 Type of Analysis

• Samples are analyzed to determine the identity and

amount of analytes.
• The analysis is complete when all constituents of the
sample matrix are determined.
• The analysis is partial when only selected constituents
of the sample matrix are determined.
Partial analysis is more common than complete
analysis.

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 Calculations Using Analytical Chemistry
SI Units (International System Of Units):
• Metric units of kilograms (kg), grams (g), milligrams
(mg) or micrograms (µg) are used.
• Volumes of liquids are measured in units of liters (L),
milliliters (mL) and sometimes microliters (µL).
1 L = 1 dm3 = 10-3 m3
1 mL = 1cm3 = 10-6 m3

• Angstrom unit Å is a non-SI unit of length that is

widely used to express the wavelength of very short
radiation such as X-rays and interatomic distances in a
crystal lattice (1Å = 0.1 nm = 10-10 m).
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 Solutions and Their Concentrations

The molar concentration Cx is the number of moles of that

species that is contained in 1 L of the solution, molarity (M),
expressed in mol/L

n (mol)
C (mol/L) =
V (L)

• Density expresses the mass of a substance per unit volume, in kg/L

or, g/mL.

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 Solutions and Their Concentrations
Analytical Molarity

• The analytical molarity of a solution gives the total number

of moles of a solute initially dissolved, regardless of its
chemical state, in 1 L of the solution (or the total number of
millimoles in 1 mL).

• A sulfuric acid solution that has an analytical concentration

of 1.0 M can be prepared by dissolving 1.0 mol, or 98 g , of
H2SO4 in water and diluting to exactly 1.0 L.

• So, the analytical molarity represents the noumber moles of

solute initially dissolved in 1 L of solution.

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 Solutions and Their Concentrations
Equilibrium Molarity
• The equilibrium molarity/species concentration
expresses the molar concentration of a particular species in
a solution at equilibrium.
• For example, the species molarity of H2SO4 in a solution
with an analytical concentration of 1.0 M is 0.0 M because
the sulfuric acid is entirely dissociated into a mixture of H+,
HSO4-, and SO42 - ions; no H2SO4 molecules as such are
present in this solution. So for our solution of H2SO4 with an
analytical concentration of 1.0 M, we can write
[H2SO4] = 0.00 [H+] =1.01 M
[HSO4-] = 0.99 [SO42-] = 0.01 M

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 Solutions and Their Concentrations
Calculate the analytical and equilibrium molar concentration of the
solute species in an aqueous solution that contains 285 mg of
trichloroacetic acid, Cl3CCOOH (163.4 g/mol) in 10.0 mL (the acid is
73% ionized in water)

Analytical concentration: C = m / (M × V) = 285 × 10-3 g / (163.4

g/mol × 10 × 10-3 L ) = 0.174 M
On this solution, 73% of the HA dissociates giving H+ and A-
The species molarity of HA is then 27%
Thus [HA] = 0.174 × 0.27 = 0.047 M

The species molarities of H+ and A- are equal to 73 % of the

analytical concentration HA:
[A-] = 0.174 × 0.73 = 0.127 M
[H+] = [A- ] = 0.127 M

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 Solutions and Their Concentrations
Concentrations in terms of percent
weight solute
Weight percent (w/w) = × 100 %
weight solution
nitric acid is sold as a 70 % solution, which means that the reagent contains
70 g of HNO3 per 100 g of solution.

volume solute
Volume percent (v/v) = × 100 %
volume solution
5 % aqueous solution of methanol is prepared by diluting 5.0 mL of pure
methanol with enough water to give 100 mL.

weight solute, g
Weight / Volume percent (w/v) = × 100 %
volume solution, mL
5 % aqueous silver nitrate prepared by dissolving 5 g of silver nitrate in
sufficient water to give 100 mL of solution.
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 Solutions and Their Concentrations
ppm and ppb are used for very dilute
solutions
Parts per Million (ppm)
mass of solute
Cppm = × 106 ppm
mass of solution

ppm = 1 mg/L or 1 µg/mL

Parts per Billion (ppb)

mass of solute
Cppb = × 109 ppm
mass of solution

ppb = 1 µg/L 22
 Errors of Chemical Analysis
Statistical Data Treatment and Evaluation
 Introduction
• Measurements invariably involve errors and
uncertainties.
• True value of a measurement is never known
exactly.
• Errors result from faulty calibrations or standardizations
or random variations and uncertainties in results.
• Errors are reduced by performing replicate
measurements and determining the mean or average.
• Data of unknown precision and accuracy is
worthless.
• The maximum error that you can tolerate dictates the
method.
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 Results from 6 replicate determinations of iron in
aqueous samples of a standard solution containing
20 ppm iron (III)

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 Mean and Median
Mean (X ): the most widely used measure of central value
average or arithmetic mean. Often used as a central value.
N

N
Xi – individual values of X making up the set of N replicate
measurements (n - number of repetitions)

Calculate the mean for the following se of data: 19.4, 19.6, 19.5, 20.1,
19.8, 20.3

X = (19.4 + 19.5 + 19.6 + 19.8 + 20.1 + 20.3) / 6 = 19.8

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 Mean and Median
Median: middle result when replicate data are arranged in
increasing or decreasing order. For an odd number of
measurements median is a middle value; for an even number -
the median is the average of the two middle values.
• In ideal case mean and the median are identical
• The median is used advantageously when a set of data contains
an outlier
• An outlier is a result that significantly differ from the others
• An outlier has a significant effect on the mean but not on the
median

19.4, 19.5, 19.6, 19.8, 20.1, 20.3

Since the data contains an even number of measurements (n=6),

the median is the average of the central pair:
Median = (19.6 + 19.8) / 2 = 19.7
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 Precision and Accuracy
Precision

• Reproducibility of results
• How close are the results to each other.
• Three terms used to describe the precision of a set of
replicate data: standard deviation, variance and
coefficient of variation.
• All three are functions that describe how much an
individual result xi differs from the mean; deviation from
the mean di. “Covered later”

Deviation from mean = di = │Xi - X │

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 Accuracy
• How close are the results to the true or accepted value.
• Expressed by an error:
Absolute error (difference between the measured value and the
true value)

E = Xi - Xt
Where Xt is the true or accepted value

Xi - Xt
% Relative error : Er = ×100%
Xt
Relative error in ppt: Er × 1000 ppt or % Er x 10

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Accuracy and Precision

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 Accuracy
Richand and Willard determined the atomic mass of lithium and
collected the following data:
Experiment Molar Mass, g/mol
1 6.9391
2 6.9407
3 6.9409
4 6.9399
5 6.9407
6 6.9391
7 6.9406

a) Find the mean atomic mass determined by these workers

b) Find the median atomic mass
c) Assuming that the currently accepted value for the atomic
mass of lithium (6.9410 g/mol) is the true value , calculate
the absolute error and the present relative error of the
mean value determined in the experiment 31
 Accuracy
a) Find the mean atomic mass determined by these workers
X = (6.9391 + 6.9407 + 6.9409 + 6.9399 + 6.9407 + 6.9391 + 6.9406)
/ 7 = 6.9401

b) Find the median atomic mass

6.9391 6.9391 6.9399 6.9406 6.9407 6.9407 6.9409

c) Assuming that the currently accepted value for the atomic

mass of lithium (6.9410 g/mol) is the true value, calculate the
absolute error and the present relative error of the mean
value determined in the experiment

E = 6.9401 – 6.9410 = - 0.0009 = 0.0009 (absolute value)

Er = (6.9401 – 6.9410) / 6.9410 ×100% = 0.013 % = 0.13 ppm
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 Types of Errors
• Random (indeterminate): causes data to be scattered
symmetrically around the mean value and affects precision;
eg. temperature fluctuations.
• Systematic (determinate): causes the mean of a data set to
be different than the true or accepted value and affects
accuracy; eg. faulty calibration of a balance.
• Gross error: causes data to be too high or too low and is
the result of human mistakes. Leads to outliers → Outliers
are results that are markedly different than all other data in
a set of replicate measurements.

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 34
NE
The identification of outliers

Is the data point that “looks/seems wrong” is a true outlier?

Q or Dixon test

Organize results in ascending order, including the point in question

Gap – difference between that point and the next closest one
Range – spread from low to high, including the data point is question

Qcalc > Qtable, the data point can be rejected with 95% confidence.
Qcalc < Qtable, the data point accepted

Example: Are there any outliers in these data at the 5% level (95% confidence)? Take any such
outliers into account if necessary, and report the mean, %RSD, and 95% confidence interval for
the results.
For outlier testing, the data are sorted in order such that potential outliers
are easily located. Here, the questionable value is the last one: 59.6 ppb. It
seems far removed from the others, but can we justify removing it from the
data set? gap
Dixon’s Q test:
 35
NE

Grubb’s test
recommended by the International Organization for Standardization (ISO) and ASTM
International, formerly known as the American Society for Testing and Materials (ASTM),
is another approach to the identification of outliers

Same Example:
Q or Dixon test

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 Systematic Errors
The errors with a definite value of the same magnitude, made
in the same way
1- Instrumental errors: caused by nonideal instrument
behavior, wrong calibration, by use under inappropriate
conditions

2- Method errors: arise from nonideal chemical or

physical behavior of analytical system

3- Personal errors: result from the carelessness,

inattention or personal limitations of the experimenter.

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 Random Errors in Chemical Analysis

In this chapter we will discuss:

• Sources of random errors
• Determination of error magnitude
• Error effects on chemical analysis

Random errors exist in every measurement and can never

be eliminated.

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 Random Errors
Gaussian curve (normal error curve) is a bell-shaped curve
that represents the symmetrical distribution of data around the
mean of an infinite set of measurements.
It represents a plot of the relative frequency of various
deviations from the mean against the deviation from the mean (a
plot of the frequency of a deviation vs the magnitude of the
deviation)

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 Random Errors
Calibration of 10-mL pipet. Ten milliliters of water were transferred in
the flask and weight (50 repetitions).

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41
 Random Errors
Sources of random errors in the calibration of a pipet include:
• Visual judgment (level of water with respect to the marking
on the pipet)
• Temperature fluctuations (affect the volume of the pipet, the
velocity of liquid, performance of balance)
• Vibrations and drafts that cause small vibrations in the
balance reading

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 Statistical Treatment of Random Errors
• Population: entire material to be tested or entire collected
measurements (in some cases population is finite and real,
while in others is hypothetical or conceptual in nature)
• Sample: portion of the population

Example: In the determination of the % Ca in a river, the

river represents the population while 10 x 1 mL represent
the sample.

? Multivitamin tablets production

? Blood sample

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Statistical Treatment of Random Errors

Population mean µ

Sample mean X

Population standard deviation σ sigma

Sample standard deviation s

Measured value Xi

Number of measurements N

Variance s2 or σ2

Number of degrees of freedom N-1

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 Statistical Treatment of Random Errors

Sample mean Population mean

N N

µ
N N
N – number of measurements N – total number of
in a sample set measurements in the population

If there is no systematic error, the population mean µ is the true

value of the measured quantity

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 46
Statistical Treatment of Random Errors NE

Standard deviation (STDEV)

The standard deviation is the average deviation from the mean and
measures the spread of the data

Population STDEV, σ Sample STDEV, s

small standard deviation - replicate measurements

are close to each other

large standard deviation - replicate measurements

are spread out over a larger range of values.
 47
NE
%RSD (% relative standard deviation)
of coefficient of variation (CV or %CV)

Sample variance (v)

V = S2

Range

Range of a set of data is the difference between the largest and smallest values

As an example, suppose that copper determination has a standard

deviation (s) of 2 mg. If the sample has a mean value of 50 mg of
copper, the CV for this sample is 4% (2/50×100%). For a sample
containing only 10 mg, the CV is 20%.
 Error

Random Systematic

• Generally small • Predictable

• Due to inescapable Large • Detected using laboratory
variations due to random error checks and quality control
uncertainties large %RSD procedures
(CV)
• Cannot be completely
eliminated • Can be eliminated
in some cases
• Large absolute error and %
Gross error relative error (% error)

Presence of an outlier

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Standard Deviation of Calculated Results
Standard Deviation of a Sum or Difference
For addition and subtraction:

y = a (± sa) + b (± sb) - c (± sc)

Consider the summation:

+ 0.50 (± 0.02)
+ 4.10 (± 0.03)
- 1.97 (± 0.05)
2.63 (0.02)2 + (0.03)2 + (0.05)2 = 0.06

Answer: 2.63 (± 0.06) 49

 Standard Deviation of Calculated Results
Multiplication or Division

Consider the following computation:

4.10 (± 0.02) × 0.0050 (± 0.0001)
= 0.010406 (± ?)
1.97 (± 0.04)
2 2 2
0.02 0.04 0.0001
( ) (
+
1.97
+) (
0.0050
) = 0.0289
4.10

Sy = y × 0.0289 = 0.010406 × 0.0289 = 0.000301 50

 Standard Deviation of Calculated Results
Calculate the standard deviation of the result of:

[ 14.3 (± 0.2) – 11.6 (± 0.2) ] × 0.050 (± 0.001)

= 1.725 (± ?) × 10-6
[ 820 (± 10) + 1030 (± 5) ] × 42.3 (± 0.4)

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