Chapter 1: Introduction to analytical Chemistry

Analytical Chemistry is the branch of chemistry concerned with determining the qualitative and
quantitative composition of substances. The process of determining the property of a material
system is called analysis. The determination of the identity of chemical species is known as
qualitative analysis. If the identity of a chemical species is known, the concentration of that
species in the sample can be determined by quantitative analysis. The substances that are the
objects of analysis is called analyte while the material in which the analyte is found is called the
matrix of the analyte.
The methods followed while doing a chemical analysis of the sample can be classified as either a
classical (wet) method or an instrumental method. Classical method includes gravimetric
analysis and volumetric analysis, while instrumental methods include spectroscopic,
chromatographic and electroanalytical methods. It is interesting to contrast classical methods
with instrumental methods of analysis. Instrumental methods are usually faster and more
sensitive after the necessary calibration have been established. However, in many cases the
classical methods are more accurate even though much slower than instrumental methods.
Instrumental methods offer improved detection limits over classical methods.
Steps in Chemical Analysis
Selecting chemical analysis method (classical and instrumental) is only one of the several steps
in the total chemical analysis. Before analysis, sample must be collected in a process called
sampling. The obtained sample must undergo chemical or physical pretreatment. After
chemical analysis, the data from the analysis must be mathematically manipulated to provide a
meaningful result and the result must be clearly communicated to interested persons. If any of
the five steps (sampling, sample pretreatment, chemical analysis, data handling and
communication of results) in the total chemical analysis is not performed properly, the analytical
results cannot be expected to be correct.

Application of Chemical Analysis

Analytical chemistry plays a vital role in the development of science. Consider the following
examples:
 The concentrations of oxygen and of carbon dioxide are determined in millions of blood
samples every day and used to diagnose and treat illnesses.
 Smog-control is done by the measurement of quantities of hydrocarbons, nitrogen oxides,
and carbon monoxide in automobile exhaust.

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 Analytical chemistry helps diagnose parathyroid diseases in human’s measurements of
ionized calcium in blood serum.
 Determination of nitrogen in foods establishes their protein content and thus their
nutritional value.
 Analysis of steel during its production permits adjustment in the concentrations of such
elements as carbon, nickel, and chromium to achieve a desired strength, hardness,
corrosion resistance, and ductility.
 Research in all science, biochemistry, biology, chemistry, geology, physics, agriculture,
health and other science.
Errors in Chemical Analysis
Errors in the analytical laboratory are basically of two types: determinate errors and
indeterminate errors. Determinate errors, also called systematic errors, are errors that
were known to have occurred, or at least were determined later to have occurred, in the
course of the lab work. They may arise from avoidable sources, such as contamination,
wrongly calibrated instruments, reagent impurities, instrumental malfunctions, poor sampling
techniques, errors in calculations, etc. Results from laboratory work in which avoidable
determinate errors are known to have occurred must be rejected or, if the error was a
calculation error, recalculated. Determinate errors may also arise from unavoidable sources.
An error that is known to have occurred but was unavoidable is called a bias. Such an error
occurs each time a procedure is executed, and thus its effect is usually known and a
correction factor can be applied. Determinate errors may be divided into four categories:
sampling errors, method errors, measurement errors, and personal errors.
Indeterminate errors, also called random errors, on the other hand, are errors that are not
specifically identified and are therefore impossible to avoid. Since the errors cannot be
specifically identified, results arising from such errors cannot be immediately rejected or
compensated for as in the case of determinate errors. Rather, a statistical analysis must be
performed to determine whether the results are far enough “off-track” to merit rejection.
Examples might include fluctuations in room temperature, fluctuations in line voltage,
mechanical vibrations, cosmic rays, etc.

Statistics establish quality limits for the answers derived from a given method. A given
laboratory result, or a sample giving rise to a given result, is considered “good” if it is within
these limits. In order to understand how these limits are established, and therefore how it is
known if a given result is unacceptable, some basic knowledge of statistics is needed.

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 Statistical Analysis of Data
The procedure used to determine whether a given result is unacceptable involves running a series
of identical tests on the same sample, using the same instrument or other piece of equipment,
over and over. In such a scenario, the indeterminate errors manifest themselves in values that
deviate, positively and negatively, from the mean (average) of all the values obtained. Given this
brief background, let us proceed to define some terms related to elementary statistics.
1. Mean
In the case in which a given measurement on a sample is repeated a number of times, the average
of all measurements is called the mean. It is calculated by adding together the numerical values
of all measurements (Xi) and dividing this sum by the number of measurements (n). In this text,
we give the mean the symbol m. The true mean, or the mean of an infinite number of
measurements (the entire population of measurements), is given the symbol µ, the Greek letter
mu.
Xi ,
m
n
2. Deviation
How much each measurement differs from the mean is an important number and is called the
deviation. A deviation is associated with each measurement, and if a given deviation is large
compared to others in a series of identical measurements, there is problem with the analysis.
Such a measurement is called an outlier. Mathematically, the deviation is calculated as follows:
d = |m – e|
in which d is the deviation, m is the mean, and e represents the individual experimental
measurement. (The bars refer to absolute value, which means the value of d is calculated without
regard to sign.)
3. Standard deviation
The most common measure of the dispersion of data around the mean is the standard deviation:

The term n is the number of measurements, and n – 1 is referred to as the number of degrees of
freedom. The term s represents the standard deviation. The significance of s is that the smaller it
is numerically, the more precise the data (the more the measurements are “bunched” around the

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mean). For an infinite number of measurements (where the mean is µ), the standard deviation is
symbolized as σ (Greek letter sigma) and is known as the population standard deviation. An
infinite number of measurements is approximated by 30 or more measurements.
4. Relative standard deviation
One final deviation parameter is the relative standard deviation (RSD). It is calculated by
dividing the standard deviation by the mean and then multiplying by 100 or 1000:

Relative % standard deviation = RSDx100

Relative parts per thousand standard deviation = RSDx1000
Relative standard deviation relates the standard deviation to the value of the mean and represents
a practical and popular expression of data quality.
Example: The following numerical results were obtained in a given laboratory experiment:
0.09376, 0.09358, 0.09385, and 0.09369. Calculate the relative parts per thousand standard
deviation.
Solution

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 5. Normal Distribution
For an infinite data set (in which the symbols µ and σ apply), a plot of frequency of occurrence
vs. the measurement value yields a smooth bell-shaped curve. It is referred to as bell-shaped
because there is equal drop-off on both sides of a peak value, resulting in a shape that resembles
a bell. The peak value corresponds to µ, the population means. This curve is called the normal
distribution curve because it represents a normal distribution of values for any infinitely
repeated measurement. The normal distribution curve is a picture of the precision of a given data
set. The more points there are bunched around the mean and the sharper the drop-off away from
the mean, the smaller the standard deviation and the more precise the data.

Figure: The normal distribution curve

6. Variance (V)

The term that is sometimes useful in statistics is the variance (V). This is the square of the
standard deviation. The sample variance is given by

V = s2

7. Precision, Accuracy, and Calibration

Precision refers to the repeatability of a measurement. If you repeat a given measurement over
and over and these measurements deviate only slightly from one another, within the limits of the
number of significant figures obtainable, then we say that the data are precise, or that the results
exhibit a high degree of precision. The mean of such data may or may not represent the real
value of that parameter. In other words, it may not be accurate.

Accuracy refers to the correctness of a measurement, or how close it comes to the correct value
of a parameter. For example, if an analyst has an object that he or she knows weighs exactly

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1.0000 g, the accuracy of a laboratory balance (weight measuring device) can be determined.
The object can be weighed on the balance to see if the balance will read 1.0000 g. If a series of
repeated weight measurements using this balance are all between 0.9998 and 1.0002 g, we say
the balance is both precise and accurate. If, on the other hand, a series of repeated weight
measurements using this balance are all between 0.9983 and 0.9987 g, we say that the balance is
precise, but not accurate. If repeated weight measurements using this balance are all between
0.9956 and 0.9991 g, the data are neither precise nor accurate. Finally, if repeated weight
measurements using this balance are all between 0.9956 and 1.0042 g, such that the mean is
1.0000 g, then the balance is not precise but it appears to be accurate. These facts on accuracy
and precision are illustrated further in the following Figure.

If it is established that a measuring device provides a value for a known sample that is in
agreement with the known value to within established limits of precision, that device is said to be
calibrated. Thus, calibration refers to a procedure that checks the device to confirm that it
provides the known value.

Confidence interval is range of results around a mean value that could be explained by random
error. In general, we can write

where the factor z accounts for the desired level of confidence.

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Table: Confidence Intervals for Normal Distribution Curves between the Limits m ± zs

Example: What is the 95% confidence interval for the amount of aspirin in a single analgesic
tablet drawn from a population where m is 250 mg and s2 is 25?

SOLUTION
According to the above Table, the 95% confidence interval for a single member of a normally
distributed population is

Xi = m ± 1.96s = 250 mg ± (1.96)(5) = 250 mg ± 10 mg

Thus, we expect that 95% of the tablets in the population contain between 240 and 260 mg of
aspirin.

Testing for Significance

i. Student's t-test: Comparison of two means

Among the most commonly used statistical significance tests applied to small data sets
(population samples) is the series of Student's tests. One of these tests is used for the comparison
of two means, which is commonly applied to many cases. Typical examples are:

Example 1: Comparison of analytical results obtained with the same method on samples A and
B, in order to confirm whether both samples contain the same percentage of the measured
analyte or not.

Example 2: Comparison of analytical results obtained with two different methods A and B on the
same sample, in order to confirm whether both methods provide similar analytical results or not.

The outcome of these tests is the acceptance or rejection of the null hypothesis (H0). The null
hypothesis generally states that: "Any differences, discrepancies, or suspiciously outlying results
are purely due to random and not systematic errors". The alternative hypothesis (Ha) states
exactly the opposite.

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The null hypothesis for the aforementioned examples is: The means are the same, i.e. in Example
1: both samples contain the same percentage of the analyte; in Example 2: both methods provide
the same analytical results. The differences observed (if any) are purely due to random errors.

The means are significantly different, i.e. in Example 1: each sample contains a different
percentage of the analyte; in Example 2: the methods provide different analytical results (so at
least one method yields systematic analytical errors).

To compare two means using student’s t-test, the two means and the corresponding standard
deviations are calculated by using the following equations (nA and nB are the number of
measurements in data set A and data set B, respectively):

nA nB
Xi Xi
XA  
i 1 n A
and X B  n
i 1 B

nA nB

 ( X A  X i )2 (X B  X i )2
SA  i 1
and S B  i 1
nA  1 nB  1

Then, the pooled estimate of standard deviation SAB is calculated:

(n A  1) S A  (nB  1) S B
2 2
S AB 
n A  nB  2

XA  XB
texp 
1 1
S AB 
n A nB

texp value is compared with the critical (theoretical) tth value corresponding to the given degree

of freedom N (in the present case N = nA + nB - 2) and the confidence level chosen. Tables of
critical t values can be found in any book of statistical analysis, as well as in many quantitative
analysis textbooks. If texp > tth then H0 is rejected else H0 is retained.

F-test: Comparison of Precision Measurement

An F-test is a simple calculation to compare the precision of two sets of measurement. An F-test
can provide insights into two main areas: 1) Is method A more precise than method B? 2) Is there
a difference in the precision of the two methods? To calculate an F-test, the standard deviation of
the method which is assumed to be more precise is placed in the denominator, while the standard
deviation of the method which is assumed to be least precise is placed in the numerator.

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 2
S1
F 2
S2

Comparing the calculated F with tabulated F, if the F-table value is smaller than the calculated
value, you can reject the null hypothesis.

Q-Test - Rejection Test

In a set of replicate measurements of a physical or chemical quantity, one or more of the

obtained values may differ considerably from the majority of the rest. An outlier is defined as an
observation that is generated from a different model or a different distribution than was the main
"body" of data. The rejection of suspect observations must be based exclusively on an objective
criterion and not on subjective or intuitive grounds. This can be achieved by using statistically
sound tests for "the detection of outliers". Q-test is the simpler test of this type, and this test
allows to examine if one (and only one) observation from a small set of replicate observations
can be "legitimately" rejected or not.

The test is very simple and it is applied as follows:

(1) The N values comprising the set of observations under examination are arranged in ascending

order: x1 < x2 < . . . < xN

(2) The statistic experimental Q-value (Qexp) is calculated. This is a ratio defined as the
difference of the suspect value from its nearest one divided by the range of the values (Q:
rejection quotient). Thus, for testing x1 or xN (as possible outliers) we use the following Qexp
values:

X 2  X1 X  X N 1
Qexp  or Qexp  N
X N  X1 X N  X1

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(3) The obtained Qexp value is compared to a critical Q-value (Qcrit) found in tables. This critical
value should correspond to the confidence level (CL) we have decided to run the test (usually:
CL=95%).

(4) If Qexp > Qcrit, then the suspect value can be characterized as an outlier and it can be rejected,
if not, the suspect value must be retained and used in all subsequent calculations.

Table of critical values of Q

N Qcrit (CL: 90%) Qcrit (CL: 95%) Qcrit (CL: 99%)

3 0.941 0.970 0.994
4 0.765 0.829 0.926
5 0.642 0.710 0.821
6 0.560 0.625 0.740
7 0.507 0.568 0.680
8 0.468 0.526 0.634
9 0.437 0.493 0.598
10 0.412 0.466 0.568

Example: The following replicate observations were obtained during a measurement and they are
arranged in ascending order: 4.85, 6.18, 6.28, 6.49, 6.69. Can we reject observation 4.85 as an
outlier at a 95% confidence level?

Answer: Qexp = (6.18 - 4.85) / (6.69 - 4.85) = 0.722. Qexp > Qcrit at CL: 95% for N=5). Therefore
we can reject 4.85.

SOLUTIONS AND THEIR CONCENTRATION

A solution is a homogeneous mixture, which means that it is uniform throughout in appearance

and composition. It consists of two classes of components:

 Solute – the component(s) in smaller quantity; and

 Solvent – the component in major quantity.

Aqueous solutions are solutions in which the solvent is water. For every solution, there is a limit
to the amount of solute that can be dissolved in the solvent. For example, if we add salt to water,
it will dissolve. If we add more salt to the water, it too will dissolve. However, at a certain point,
no more salt will dissolve and any additional salt will simply fall to the bottom of the container.
At this point, the solution is said to be saturated. A saturated solution is one which has the
maximum amount of solute dissolved in the solvent. A solution that has not reached the
maximum limit of dissolved solute is said to be unsaturated. The amount of solute dissolved in
the solvent can be referred qualitatively as concentrated if it has a large amount of solute. A
solution which has only a relatively small amount of dissolved solute is termed dilute.

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Three common ways of expressing the relative amounts of solute to solvent are as follow:

 Mole fraction (or mole percent);

 Mass fraction (or mass percent); and
 Molarity.

They are defined as follows:

Here the subscript i refer to any member of the solution.

Example: Suppose that 5.00 g calcium chloride is dissolved in 40.0 g water. Calculate the mole
and mass fractions of calcium chloride in the solution.

Solution:

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Example: Calculate the mole and mass fractions of a solution made by dissolving 9.0 g ethanol
in enough water to make 200.0 g solution.

Solution:

Calculations Involving Molarity

By far the most common method used chemists to express the concentration of a solution is
through the molarity of the solution. The term, molar concentration is also used to refer to the
molarity. According to its definition, the molarity is

Example: Calculate the molar concentration of a solution made by dissolving 42.3 g glucose in
250.00 mL water.

Solution: By defination, M  n
V

Mole of glucose: Molar mass of glucose (C6H12O6): 6.(12.011) + 12.(1.008) + 6.(16.00) = 180.16

n = 42.3g = 0.235 mol

180.16 g / mol

Molarity: M  n = 0.235mol = 0.939 M

V 0.250 L

Example: What mass of sodium hydroxide (NaOH) is needed to make up 0.5 L of a 0.5M
solution? [Atomic mass: Na = 23, O = 16, H = 1].

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Dilution

Dilution is the addition of solvent (or other substances) to a solution, thereby reducing the solute
concentration. Dilution is important in the chemical laboratory because of:

 Storage considerations – it is usually not feasible to store large volumes of solutions in a

lab. Normally a solution of high concentration (called the stock solution) is stored and
later some of this solution is diluted to the desired concentration as needed,
 Creating mixtures – when solutions are mixed the volume of the new solution is greater
than the volume of the individual solutions before mixing.

The first step involved when two or more solutions are mixed is to recalculate the
concentration(s) in the mixture. The following generic example will serve to illustrate the
procedure: Suppose that two solutions, A and B, are mixed. The volumes and concentrations of
A and B are (VA, [A]0), and (VB, [B]0) respectively. Note that the subscript “0” means here that
this is the concentration of the original solution.

Step 1: Calculate the moles of each substance present:

Step 2: Calculate the concentrations of each substance in the mixture.

Final solution volume: V = VA + VB

New concentrations in the mixture:

Example: If 25.00 mL of a 0.1223 M standard solution of NaOH is added to 420.0 mL water,

Calculate the concentration of the final solution.

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Normality of Solution

Parts Per Million of Solution

Preparation of Solution: to prepare standard solution, it is possible to start with

solid or liquid samples.
Preparation of Molar Solutions
If solute is a pure solid (or liquid) that will be weighed,
grams to weigh = VL x M x M.mass
If solute is already dissolved, but the solution is to be diluted,

C A xVA
VB 
CB

If concentration given in percentage and specific density of the solute given, to calculate
10 xsdx%
molarity, M 
M .mass

Preparation of Normal Solutions

If solute is a pure solid (or liquid) that will be weighed,
grams to weigh = VL x M x EWsol
If solute is already dissolved, but the solution is to be diluted,

C A xVA
VB 
CB

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