Analytical chemistry

Analytical chemistry is often described as the area of chemistry responsible for characterizing the composition of matter,
both qualitatively (what is present) and quantitatively (how much is present).
The above definition of “analytical chemistry” best fits in describing the scope of this course. However, the description
could be misleading in totally expressing the essence analytical chemistry. The craft of analytical chemistry is not on in
performing a routine analysis on a routine sample (which is more appropriately called chemical analysis), but in improving
established methods, extending existing methods to new types of samples, and developing new methods for measuring chemical
phenomena.
Here’s one example of this distinction between analytical chemistry and chemical analysis. Mining engineers evaluate
the economic feasibility of extracting an ore by comparing the cost of removing the ore with the value of its contents. To estimate
its value they analyze a sample of the ore. The challenge of developing and validating the method providing this information is the
analytical chemist’s responsibility. Once developed, the routine, daily application of the method becomes the job of the chemical
analyst.

1. Analytical Perspective
What is the “analytical perspective?” Although there are probably as many descriptions of the analytical approach as
there are many analytical chemists, it is convenient for our purposes to treat it as a five-step process: 1. Identify and define the
problem; 2. Design the experimental procedure; 3. Conduct an experiment and gather data. 4. Analyze the experimental data; 5.
Propose a solution to the problem.

Figure 1-Flow diagram for the analytical approach to solving problems

2. Common Analytical Problems

Many problems in analytical chemistry begin with the need to identify what is present in a sample. This is the scope of a
qualitative analysis, examples of which include identifying the products of a chemical reaction, screening an athlete’s urine for
the presence of a performance-enhancing drug, or determining the spatial distribution of lead (Pb) on the surface of an airborne
particulate. However, the most common type of problem encountered in the analytical lab is a quantitative analysis. Examples of
typical quantitative analysis include the elemental analysis of a newly synthesized compound, measuring the concentration of
glucose in blood, or determining the difference between the bulk and surface concentrations of Cr in steel. Much of the analytical
work in clinical, pharmaceutical, environmental, and industrial labs involves developing new methods for determining the
concentration of targeted species in complex samples. Most of the examples in this text come from the area of quantitative
analysis. Another important area of analytical chemistry is the development of new methods for characterizing physical and
chemical properties. Determinations of chemical structure, equilibrium constants, particle size, and surface structure are examples
of a characterization analysis. In conclusion, the purpose of a qualitative, quantitative, and characterization analysis is to solve a
problem associated with a sample. A fundamental analysis, on the other hand, is directed toward improving the experimental
methods used in the other areas of analytical chemistry. Extending and improving the theory on which a method is based, studying
a method’s limitations, and designing new and modifying old methods are examples of fundamental studies in analytical
chemistry.
1. David Harvey: Analytical Chemistry 2.0, Electronic version,
2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)

1
3. Common Languages of Analytical Chemistry
An Analyte is the constituents of interest in a sample and the remainder of the sample is called a matrix. Analysis a
process that provides chemical or physical information about the analyte in the sample or the sample itself. In an analysis we
determine the identity, concentration, or properties of an analyte. To make this determination we measure one or more of the
analyte’s chemical or physical properties. As a result analyzing a sample generates a chemical or physical signal that is propor-
tional to the amount of analyte in the sample.
In order to determine the amount of the analyte, appropriate method should be selected. A method is the application of a
technique to a specific analyte in a specific matrix. The requirements of the analysis determine the best method. In choosing a
method, consideration is given to some or all the following design criteria: accuracy, precision, sensitivity, selectivity, robustness,
ruggedness, scale of operation, analysis time, availability of equipment, and cost.
Accuracy is how closely the result of an experiment agrees with the “true” or expected result. We can express accuracy
as an absolute error, e
e = eperimental result − expected result
or as a percentage relative error, %er,
Experimental result − expected result
%er = × 100
expected result
Precision: When a sample is analyzed several times, the individual results are rarely the same. Instead, the results are
randomly scattered. Precision is a measure of this variability. The closer the agreement between individual analysis, the more
precise the results are.
Sensitivity: The ability to demonstrate that two samples have different amounts of analyte is an essential part of many
analysis. A method’s sensitivity is a measure of its ability to establish that such differences are significant.
Specificity and Selectivity: An analytical method is specific if its signal depends only on the analyte. Although
specificity is the ideal, few analytical methods are completely free from the influence of interfering species. Selectivity is a
measure of a method’s freedom from interferences.
Robustness and Ruggedness: When a method is relatively free from chemical interferences, we can use it on many
analytes in a wide variety of sample matrixes. Such methods are considered robust. If a method’s sensitivity is too dependent on
experimental conditions, such as temperature, acidity, or reaction time, then a slight change in any of these conditions may give a
significantly different result. A rugged method is relatively insensitive to changes in experimental conditions.
Scale of operation: Another way to narrow the choice of methods is to consider three potential limitations: the amount
of sample available for the analysis, the expected concentration of analyte in the samples, and the minimum amount of analyte that
produces a measurable signal. Collectively, these limitations define the analytical method’s scale of operations.
Equipment needs: Methods relying on instrumentation are equipment-intensive and may require significant operator
training. For example, the graphite furnace atomic absorption spectroscopic method for determining lead in water requires a
significant capital investment in the instrument and an experienced operator to obtain reliable results. Other methods, such as
titrimetry, require less expensive equipment and less training.
The time to complete an analysis for one sample is often fairly similar from method to method. This is a significant
factor in selecting a method for a laboratory that handles a high volume of samples.
The cost of an analysis depends on many factors, including the cost of equipment and reagents, the cost of hiring
analysts, and the number of samples that can be processed per hour.
4. Basic Equipments and Instrumentation
Equipments for measuring mass - Analytical balances is an instrument for determine
mass with a maximum capacity that ranges from 1g to few kilograms. The most commonly
encountered analytical balances (Microbalances) have capacity ranging between 160 g to 200
g, and precision of±1 𝑚𝑔. Semi micro analytical balances have a maximum loading of 10 to
30 g with a precision of±0.01 𝑚𝑔. A typical micro-analytical balance has a capacity of 1-3 g
or below and a precision of ±0.001 𝑚𝑔.

Equipments for measuring volume - Examples are shown below; Beakers (A), measuring cylinder (B), volumetric flasks
(C), transfer pipets (D), measuring pipets (E), droplets (F), manual syringes (G) and digital syringes (H) respectively.

A B C D E F G H
1. David Harvey: Analytical Chemistry 2.0, Electronic version,
2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)

2
 Equipment for Drying Samples - Many materials need to be dried (110-140
o
C) prior to their analysis to remove residual moisture. Other materials need to be
heated to much higher temperatures (> 400 oC) to initiate thermal decomposition.

After drying or decomposing a sample, it should be cooled to room

temperature in a desiccator to avoid the re-adsorption of moisture. A desiccator is a
closed container that isolates the sample from the atmosphere. A drying agent, called
a desiccant, is placed in the bottom of the container. Typical desiccants include
calcium chloride and silica gel.

5. Units of expressing concentration

Concentration is a general measurement unit stating the amount of solute present in a known amount of solution.
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝐶𝑜𝑛𝑐𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 =
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Although the terms “solute” and “solution” are often associated with liquid samples, they can be extended to gas-phase
and solid-phase samples as well. The actual units for reporting concentration depend on how the amounts of solute and solution
are measured. The most common units of concentration will be discussed below.
a) Molarity
Molarity (M) is the concentration of a particular chemical species in solution. It is the number of moles of solute per liter
of solution
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒(𝑛)
𝑀=
𝑙𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑉)
Questions
1. An analyst wishes to add 256 mg of Cl– to a reaction mixture. How many milliliters of 0.217 M BaCl2 should be added?
b) Normality
Normalty makes use of the chemical equivalent, which is the amount of one chemical species reacting stoichiometrically
with another chemical species. Note that this definition makes an equivalent, and thus normality is a function of the chemical
reaction in which the species participates. Although a solution of H2SO4 has a fixed molarity, its normality depends on how it
reacts. The number of equivalents, n, is based on a reaction unit, which is that part of a chemical species involved in a reaction.
The number of equivalents, n, is based on a reaction unit, which is that part of a chemical species involved in a reaction.
In a precipitation reaction, for example, the reaction unit is the charge of the cation or anion involved in the reaction; thus for the
reaction.
Pb2+(aq) + 2I–(aq) ⇌ PbI2(s), n = 2 for Pb2+ and n = 1 for I–.
In an acid–base reaction, the reaction unit is the number of H+ ions donated by an acid or accepted by a base. For the
reaction between sulfuric acid and ammonia
H2SO4(aq) + 2NH3(aq) ⇌ 2NH4+(aq) + SO42–(aq), we find that n = 2 for H2SO4 and n = 1 for NH3.
For a complexation reaction, the reaction unit is the number of electron pairs that can be accepted by the metal or donated
by the ligand. In the reaction between Ag+ and NH3
Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq), the value of n for Ag+ is 2 and that for NH3 is 1.
Finally, in an oxidation–reduction reaction the reaction unit is the number of electrons released by the reducing agent or
accepted by the oxidizing agent; thus, for the reaction
2Fe3+(aq) + Sn2+(aq) ⇌ Sn4+(aq) + 2Fe2+(aq), n = 1 for Fe3+ and n = 2 for Sn2+.
So, Normality is the number of equivalent weights (EW) per unit volume. An equivalent weight is defined as the ratio of a
chemical species’ formula weight (FW) to the number of its equivalents i.e. the mass of a compound containing one equivalent
(EW).
𝐹𝑊
𝐸𝑊 =
𝑛
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐸𝑊𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒(𝐸𝑊)
𝑁=
𝑙𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑉)
The following simple relationship exists between normality and molarity.
𝑁 = 𝑛×𝑀
Questions
1. Calculate the equivalent weight and normality for a solution of 6.0 M H3PO4 given the following reactions:
a. H3PO4(aq) + 3OH–(aq) ⇌PO43–(aq) + 3H2O(l)
b. H3PO4(aq) + 2NH3(aq) ⇌ HPO42–(aq) + 2NH4+(aq)
c. H3PO4(aq) + F–(aq) ⇌ H2PO4–(aq) + HF(aq)
2. A solution of 0.10 M SO42– is available. What is the normality of this solution when used in the following reactions?
a. Pb2+(aq) + SO42–(aq) ⇌ PbSO4(s)
1. David Harvey: Analytical Chemistry 2.0, Electronic version,
2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)

3
b. HCl(aq) + SO42–(aq) ⇌ HSO4–(aq) + Cl–(aq)
c. SO42– + 4H3O+(aq) + 2e– ⇌ H2SO3(aq) + 5H2O(l)
c) Molality
Molality is used in thermodynamic calculations where a temperature independent unit of concentration is needed.
Molarity and normality are based on the volume of solution in which the solute is dissolved. Since density is a temperature
dependent property a solution’s volume, and thus its molar and normal concentrations will change as a function of its temperature.
By using the solvent’s mass in place of its volume, the resulting concentration becomes independent of temperature.
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒(𝑛)
𝑚=
𝐾𝑔 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡(𝑉𝑠𝑜𝑙𝑣𝑒𝑛𝑡)
d) Weight, Volume, and Weight-to-Volume Ratios
Weight percent (% w/w), volume percent (% v/v) and weight-to-volume percent (% w/v) express concentration as units
of solute per 100 units of sample. A solution in which a solute has a concentration of 23% w/v contains 23 g of solute per 100 ml
of solution.
𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑤/𝑤% =
100𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑚𝑙 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑣 𝑣% =
100𝑚𝑙 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
g of solute
w v% =
100 ml solution
e) Parts per million (ppm) and parts per billion (ppb)
ppm and ppb are mass ratios of grams of solute to one million or one billion grams of sample, respectively. For example,
steel that is 450 ppm of Mn contains 450 mg of Mn for every gram of steel.
g of solute
𝑝𝑝𝑚 = 6
10 g solution
g of solute
ppb = 9
10 g solution
If we approximate the density of an aqueous solution as 1.00 g/ml, then solution concentrations can be expressed in parts
per million or parts per billion using the following relationships.
𝑚𝑔 𝜇𝑔
𝑝𝑝𝑚 = =
𝑙𝑖𝑡𝑒𝑟 𝑚𝑙
𝜇𝑔 𝑛𝑔
𝑝𝑝𝑏 = =
𝑙𝑖𝑡𝑒𝑟 𝑚𝑙
For gases a part per million usually is a volume ratio. Thus, a helium concentration of 6.3 ppm means that one liter of air contains
6.3 ml of He.
Questions-
1. A concentrated solution of aqueous ammonia is 28.0% w/w NH3 and has a density of 0.899 g/ml. What is the molar
concentration of NH3 in this solution?
2. The concentration of lead in an industrial waste stream is 0.28 ppm. What is its molar concentration?
3. A 250.0 ml aqueous solution contains 45.1 mg of a pesticide. Express the pesticide’s concentration in weight percent, parts
per million, and parts per billion.
4. Commercially available concentrated hydrochloric acid is 37.0% w/w HCl. Its density is 1.18 g/ml. using this information
calculate (a) the molarity of concentrated HCl, and (b) the mass and volume (in milliliters) of solution containing 0.315 mol
of HCl.
6. Preparing Solutions
Preparing a solution of known concentration is perhaps the most common activity in any laboratory. The method for
measuring out the solute and solvent depend on the desired concentration units, and how exact the solution’s concentration needs
to be known.
Material needed to prepare a solution: Pipets and volumetric flasks are used when a solution’s concentration must be
exact; Graduated cylinders, beakers, and reagent bottles suffice when concentrations need only be approximate. Two methods for
preparing solutions are described in this section.
a) Preparing Stock Solutions
A stock solution is prepared by weighing out an appropriate portion of a pure solid or by measuring out an appropriate
volume of a pure liquid and diluting to a known volume. Exactly how this is done depends on the required concentration units. For
example, to prepare a solution with a desired molarity you would weigh out an appropriate mass of the reagent, dissolve it in a
portion of solvent, and bring to the desired volume. To prepare a solution where the solute’s concentration is given as a volume
percent, you would measure out an appropriate volume of solute and add sufficient solvent to obtain the desired total volume.
b) Preparing Solutions by Dilution

1. David Harvey: Analytical Chemistry 2.0, Electronic version,

2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)

4
 Solutions with small concentrations are often prepared by diluting a more concentrated stock solution. A known volume
of the stock solution is transferred to a new container and brought to a new volume. Since the total amount of solute is the same
before and after dilution, we know that
𝐶𝑜 𝑉𝑜 = 𝐶𝑑 𝑉𝑑
Where, Co is the concentration of the stock solution, Vo is the volume of the stock solution being diluted, Cd is the
concentration of the dilute solution, and Vd is the volume of the dilute solution. Again, the type of glassware used to measure Vo
and Vd depends on how exact the solution’s concentration must be known.
Questions
1. Describe how you would prepare the following three solutions:
o 500 ml of approximately 0.20 M NaOH using solid NaOH;
o 1 L of 150.0 ppm Cu2+ using Cu metal; and
o 2 L of 4 % v/v acetic acid using concentrated glacial acetic acid;
o 2 L of 0.108 M BaCl2 from BaCl2.2H2O;
o 500 ml of 0.0740M Cl- solution from solid BaCl2.2H2O
2. A laboratory procedure calls for 250 ml of an approximately 0.10 M solution of NH3. Describe how you would prepare this
solution using a stock solution of concentrated NH3 (14.8 M).
3. Calculate the molarity of a potassium dichromate solution prepared by placing 9.67 g of K 2Cr2O7 in a 100-ml volumetric flask,
dissolving, and diluting to the calibration mark.
7. Standardization and Calibration
Standardization and calibrations are the very important part of analytical procedures. In chemical analysis, a measured
signal usually cannot be interpreted on its own but is often calibrated, i.e. compared to a defined standards or reference value.
Calibration determines the relationship between the analytical signal and the analyte concentration by using chemical
standards. It is accomplished by obtaining the response signal (absorbance, peak height, peak area, pH and so on) as a function of
a known analyte concentration. The signal of the chemical standards are measured and used to prepare a calibration curve,
which is a graph showing how the signal varies with the concentration of the analyte. Almost all analytical methods require some
type of calibration with chemical standards.
a) Standard solution
A standard solution is a reagent of known concentration. It plays a central role in all analytical methods of analysis. The
ideal standard solutions for a titrimetric method will;
 be sufficiently stable so that it is necessary to determine its concentration only once:
 react rapidly with the analyte so that the time required between additions of reagent is minimized
 react more or less completely with the analyte so that satisfactory end points are realized and
 Undergo a selective reaction with the analyte that can be described by a balanced equation.
Based on the above requirements standard solutions can be classified into two: primary and secondary standards.
Primary standard is a highly purified compound that serves as a reference material in volumetric and mass titrimetric methods. It
is standard that is designated or widely acknowledged as having the highest metrological qualities and whose values accepted
without reference to other standards of the same quality. Important requirements for a primary standard are the following:
 High purity
 Atmospheric stability
 Absence of hydrate water so that the composition of the solid does not change with variations in humidity
 Modest cost
 Reasonable solubility in the titration medium
 Reasonably large molar mass so that the relative error associated with weighing the standard is minimized
Very few compounds meet or even approach these criteria and only a limited number of primary-standard substances are
available commercially. As a consequence, less pure compounds must sometimes be used in place of primary standards. These
types of standards are called secondary standards. So a secondary standard is a compound whose purity has been established by
chemical analysis and that serves as the reference material.
There are two methods used to determine the concentration of a standard solution.
1. The direct method involve a carefully weighed quantity of a primary standard is dissolved in a suitable solvent and diluted
to an exactly known volume in a volumetric flask.
2. Standardization, in which the titrant to be standardized is used to titrate
a. a weighed quantity of a primary standard,
b. a weighed quantity of a secondary standard, or
c. a measured volume of another standard solution.
A titrant that is standardized against or against other standard solution is sometimes referred to as a secondary-standard
solution.
b) Determination of specific analyte concentration in solution
There are several ways to determine specific analyte concentration of a sample: The unknown analyte response is
compared with chemical standards are discussed here: the direct comparison technique and the titration procedures.
1. David Harvey: Analytical Chemistry 2.0, Electronic version,
2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)

5
 Determination of Analyte’s concentration by direct comparison
Some analytical procedures compare the property of the analyte (the product of a reaction with the analyte) with a
standard such that the property being tested matches or nearly match with that of a standard.
Examples:
In early colorimeters, the colors produced as a result of chemical reaction of the analyte was compared with the color
produced by the reaction of standards. If the concentration of the standard is varied by dilution then it was possible to obtain the
exact color match. In some modern instruments, the variation of this analytical procedure is used to determine if the analytical
concentration exceeds or less than some threshold level.
Determination of Analyte’s concentration by reacting with the standard solution (titration)
Titrations are among the most accurate of all analytical procedure. In a titration, the analyte reacts with a standard
solution (the titrant) in a reaction of known stoichiometry. Usually the amount of the titrant is varied until the chemical
equivalence is reached, as indicated by the color change of a chemical indicator or the change in an instrument response (pH).
Example:
The titration of strong acid HCl with strong base NaOH, a standard solution of sodium hydroxide is used to determine the
amount of HCl present.
HCl + NaOH → NaCl + H2O
c) External standard calibration method
An external standard is prepared separately from the sample. By contrast an internal standard is added to the sample itself.
They are used to calibrate the instrument and procedure when there are no interference effects from matrix components in the
analytes solution. A series of such external standards containing the analyte in known concentrations is prepared. Then a
calibration curve is prepared by plotting the data or by fitting them to a suitable mathematical equation, such as the linear
relationship used in the method of least square. The next step is the prediction step, in which the response signal obtained for the
sample is used to predict the unknown analyte concentrations from the calibration curve or best fit equation.
Figure 2 shows a typical multiple-point external standardization. The volumetric flask on the left is a reagent blank and
the remaining volumetric flasks contain increasing concentrations of Cu2+. Shown below the volumetric flasks is the resulting
calibration curve. Because this is the most common method of standardization the resulting relationship is called a normal
calibration curve. Taking strait line equation y = mx + b.

Figure 2- Normal calibration curve for the hypothetical data in showing the regression line.
When a calibration curve is a straight-line, as it is in Figure 2 the slope of the line gives the value of “m”. However
because of the indeterminate errors in the measurement process, not all the data fall exactly on the line. Thus the investigator must
try to obtain the best strait line equation among the data points by using the least-square method. Two assumptions are made in
using the method of least squares. The first is that a linear relationship actually exists between the measures response, y, and the
standards analyte concentration, x. The mathematical relationship describing this assumption is called the regression model, which
may be represent as y=mx + b. where b is the y intercept (the value of y when x is 0) and m is the slope of the line. The second
assumption is that any deviation of the individual points from the strait line arises from error in the measurement. That is, we
assume that there is n o error in the x values of the points (concentration). Both these assumption are appropriate for many
analytical methods, but bear in mind that whenever there is significant uncertainty in the x data, basic linear least-square analysis
my not give the best strait line.
d) Finding the least square line
As shown in the above Figure 2 the vertical deviation of each point from the straight line is called a residual. The least square
methods find the sum of the squares of the residuals SSresid as;
𝑁
2
Sum of the squares of the residuals = 𝑆𝑆𝑟𝑒𝑠𝑖𝑑 = 𝑦𝑖 − (𝑏 + 𝑚𝑥𝑖
𝑖=1
𝑥𝑖
𝑀𝑒𝑎𝑛 𝑜𝑓 𝑥 = 𝑋 =
𝑁
1. David Harvey: Analytical Chemistry 2.0, Electronic version,
2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)

6
 𝑦𝑖
𝑚𝑒𝑎𝑛 𝑜𝑓 𝑦 = 𝑦 =
𝑁
𝑁
2
𝑥𝑖
𝑆𝑥𝑥 = (𝑥𝑖 − 𝑥 )2 = 𝑥𝑖 2 −
𝑁
𝑖=1
𝑁
2
𝑦𝑖
𝑆𝑦𝑦 = (𝑦𝑖 − 𝑦 )2 = 𝑦𝑖 2 −
𝑁
𝑖=1
𝑁
𝑥𝑖 𝑦𝑖
𝑆𝑥𝑦 = (𝑥𝑖 − 𝑥)(𝑦𝑖 − 𝑦 ) = 𝑥𝑖 𝑦𝑖 −
𝑁
𝑖=1
𝑆𝑥𝑦
1. The slope of the line, m; 𝑚=
𝑆𝑥𝑥
2. The intercept, b: 𝑏 = 𝑦 − 𝑚𝑥
3. The standard deviation about regression (also called standard error of the sample), S r: is the standard
deviation for y when the deviations are measured not from the mean of y but from the straight line that
results from the least-squares prediction.
𝑆𝑦𝑦 − 𝑚2 𝑆𝑥𝑥 𝑆𝑆𝑟𝑒𝑠𝑖𝑑
𝑆𝑟 = = “𝑁 − 2” in referred to as the numbers of degrees of freedom.
𝑁−2 𝑁−2
𝑆𝑖2
4. The standard deviation of the slope, Sm: 𝑆𝑚 =
𝑆𝑥𝑥
1
5. The standard deviation of the intercept, Sb: 𝑆𝑏 = 𝑆𝑟 2
𝑥𝑖
𝑁−
𝑥 𝑖2
𝑆𝑆 𝑟𝑒𝑠𝑖𝑑
6. The coefficient of determination (R2) 𝑅2 = 1 − 𝑆𝑦𝑦
The closer R2 to unity, the better the linear
model explains the y variations.

Example
The table below represents the calibration datas for the determination of isooctane in hydrocarbon mixture. Carryout a least square
analysis of the experimental data provided in the table. In doing so, calculate the slope, intercept, and define the least square line,
standard deviation about regression, standard deviation of the slope, and standard deviation of the intercept. Finally calculate the
coefficient of determination for the chromatographic data.
Ca 0 0.1 0.2 0.3 0.4 0.5
Smeas 0.1 12.36 24.83 35.91 48.79 60.42

1. David Harvey: Analytical Chemistry 2.0, Electronic version,

2. David Harvey: Modern Analytical Chemistry, 2nd edition, DePauw University, 2000
3. D. A. Skoog, D. M. West, F. J. Holler: Fundamentals of analytical Chemistry, 7th Edition, Harcourt college publisher, 1996. (Found in science library)