Analytical chemistry

Analytical chemistry is the study of the composition of matter. It focuses on

separating, identifying, and quantifying chemicals in samples of matter.

An analytical chemist may use complex instruments to analyze an unknown material

in order to determine its various components.
 The scope of analytical chemistry
➢ In medicine, analytical chemistry is the basis for clinical laboratory tests which help
physicians diagnose disease and chart progress in recovery.

➢ In industry, analytical chemistry provides the means of testing raw materials and for assuring
the quality of finished products whose chemical composition is critical. Many household
products, fuels, paints, pharmaceuticals, etc. are analyzed by the procedures developed by
analytical chemists before being sold to the consumer.

➢ Environmental quality, is often evaluated by testing for suspected contaminants using the
techniques of analytical chemistry.

➢ The nutritional value of food is determined by chemical analysis for major components such
as protein and carbohydrates and trace components such as vitamins and minerals. Indeed,
even the calories in food are often calculated from its chemical analysis.

➢ Analytical chemists also make important contributions to fields as diverse as forensics,

archaeology, and space science.
 Classification of analytical methods
Analytical methods are often classified as being either classical or instrumental. This
classification is largely historical with classical methods, sometimes called wet-chemical
methods, preceding instrumental methods by a century or more.
Classical Methods
Classical methods/ wet chemical methods/ earliest methods of analysis; relied mainly on
chemical properties of analytes. Analytes are treated with reagents to form products that
could be identified. Gravimetric and titrimetric methods were used for quantitative analysis.
Examples:
•Formation of precipitate and measurement of mass.
•Oxidation of analyte and detection of end via the change of color of the analyte.
•Neutralization of analyte and detection of end point using acid- base indicator.
•Complexation of analyte and use of metallochromic indicators to detect end point.
•Separation of analyte from matrix was achieved using precipitation, extraction and
distillation.
Instrumental methods largely rely on physical properties of analyte, thus generally are not destructive.

Techniques, such as spectroscopy potentiometry, voltammetry etc. are the example of instrumental methods.
Both molarity and formality express concentration as moles of solute per liter of
solution. There is, however, a subtle difference between molarity and formality.

Molarity is the concentration of a particular chemical species in solution.

Formality, on the other hand, is a substance’s total concentration in solution

without regard to its specific chemical form. There is no difference between a
substance’s molarity and formality if it dissolves without dissociating into ions. The
molar concentration of a solution of glucose, for example, is the same as its
formality.

For substances that ionize in solution, such as NaCl, molarity and formality are
different. For example, dissolving 0.1 mol of NaCl in 1 L of water gives a solution
containing 0.1 mol of Na+ and 0.1 mol of Cl–. The molarity of NaCl, therefore, is
zero since there is essentially no undissociated NaCl in solution.
The solution, instead, is 0.1 M in Na+ and 0.1 M in Cl–. The formality of NaCl,
however, is 0.1 F because it represents the total amount of NaCl in solution.

The rigorous definition of molarity, for better or worse, is largely ignored in the
current literature, as it is in this text. When we state that a solution is 0.1 M NaCl
we understand it to consist of Na+ and Cl– ions. The unit of formality is used
only when it provides a clearer description of solution chemistry.

Molar concentrations are used so frequently that a symbolic notation is often

used to simplify its expression in equations and writing. The use of square
brackets around a species indicates that we are referring to that species’ molar
concentration. Thus, [Na+] is read as the “molar concentration of sodium ions.”
 Safety in the laboratory and hazards associated with chemicals

Acids and Bases:

Due to their corrosive nature, they can irritate or even burn the eyes, irritate the skin, and
cause respiratory distress. The risk is higher when they are concentrated, but even when
diluted they can be hazardous. Protective equipment, including chemical goggles,
aprons, and gloves, is essential. Examples:

•Acids—hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid
•Bases—sodium hydroxide, potassium hydroxide, ammonia

Compressed Gases

The cylinder should always be kept secured. The cap should always be on when not in use.
The valves and regulators should be routinely checked for leaks.
Examples: Helium, nitrogen, carbon dioxide, hydrogen, oxygen
 Corrosives
These can cause severe burns on contact. It is important to minimize exposure to these by
wearing chemical goggles, aprons, and gloves to prevent damage to the skin or eyes.
Examples:
•Acids—HCl, H2SO4, HNO3
•Bases—NaOH, KOH, NH4OH
•Gases—NO2, NH3
•Oxidizing agents—H2O2, KMnO4, HNO

Cryogenics
These are chemicals stored at very low temperatures. They should be handled with special
cryogenic gloves.

Examples: dry ice (solid CO2), liquid nitrogen

Electrical Hazards
Electricity has long been recognized as hazardous. It can cause electric shock,
electrocution, burns, fires, and even explosions. Ideally, all of the electrical circuits in a
science laboratory should include ground fault circuit interrupters (GFCIs), which are
designed to protect people from electrical hazards. Any electrical circuits used for
measuring conductivity, or similar circuits, unless they are battery-powered, must contain a
momentary switch. The teacher should ensure that all electrical devices are functioning
properly and that the electrical cords are in good condition.
Examples: hot plates, magnetic stirrers, any equipment plugged into an electrical outlet

Flammables
These are most commonly used in the laboratory as solvents. Never use any type of open
flame or any source of ignition around flammable chemicals.
Note: It is the vapors from flammable liquids that are flammable, and when one opens a
bottle of flammable liquid, the first thing that leaves the bottle is the vapor (flammable part)
from the top of the bottle.
Examples: acetone, ethanol, ethyl acetate, hexane, methanol
Halogens
These elements are highly reactive, toxic, corrosive, and capable of irritating the skin
Examples: fluorine, chlorine, bromine, iodine
Note: Fluorine is extremely poisonous and requires special equipment and handling.
Hydrocarbons and Volatile Organic Compounds
These compounds are combustible or flammable and can irritate the skin . Used in a
confined space, they can cause asphyxiation, They should always be used in a well-
ventilated area or hood, and away from any open flames. Flammables and combustibles must
never be heated on a hot plate.
Examples: hexane, pentane, petroleum ether, acetone, methanol, ethanol
Mercury
Mercury is a serious chronic health hazard. Although it is not readily absorbed through the
skin, its greatest health hazard is due to inhalation of its vapors, usually as a result of a spill.
Mercury compounds (e.g., alkyl mercury) are extremely toxic and must be handled with
extreme care.
Examples: mercury-in-glass thermometers and barometers
Oxidizing Agents/Oxidizers and Reducing Agents
An oxidizing agent is a substance that causes oxidation, or the loss of electrons from an
atom, compound, or molecule. A reducing agent is a substance that causes reduction, or the
gain of electrons. Oxidation and reduction always occur together. Oxidation-reduction
reactions tend to release heat, so oxidizers and reducing agents can cause other materials to
combust more readily. Always store oxidizing and reducing agents away from each other
and from flammable materials.
Note: Mixing oxidizing agents (nitric acid) with organic materials in waste bottles has
resulted in many explosions.

Examples:
•Oxidizing agents—chlorates, chromates, dichromates, hypochlorites, nitrates, nitric acid,
nitrites, perchlorates, permanganates, peroxides
•Reducing agents—alkali metals, alkaline earth metals, hydrogen gas, carbon monoxide
Peroxides
These are a group of chemicals that have an oxygen-to-oxygen bond (R–O–O–R). Care
must be taken when handling inorganic or organic peroxides, since they tend to be unstable
and can, depending on the compound, decompose violently. Some peroxides are used as
reactants, but peroxides as contaminants in other chemicals are also a concern. Peroxides
that contaminate organic solvents are of particular concern. Peroxides form slowly in some
organic solvents, and as their concentrations increase they present a greater hazard.

Examples:
•Common peroxides used in the pre-college setting—hydrogen peroxide, H2O2
•Peroxide-forming substances to avoid—ethers, alkenes, secondary alcohols, ketones,
alkali metals
Pyrophorics
These are substances that readily ignite and burn in air spontaneously. They should be
handled only by chemists with the knowledge and skills to work with them safely.
Examples: white phosphorus, alkali metals and their compounds
 Errors in Chemical Analysis

Accuracy indicates the closeness of the measurement to the true or accepted value and
is expressed by the error. Note that accuracy measures agreement between a result and
the accepted value.

Precision, on the other hand, describes the agreement among several results obtained
in the same way. We can determine precision just by measuring replicate samples.

Accuracy is often more difficult to determine because the true value is usually
unknown. An accepted value must be used instead.

Accuracy is expressed in terms of either absolute or relative error.

 Types of Error

There are two principal types of error in analysis: determinate or systematic error
and indeterminate or random error.

Broadly speaking, determinate errors are caused by faults in the analytical

procedure or the instruments used in the analysis. The name determinate error
implies that the cause of this type of error may be found out and then either avoided
or corrected. Determinate errors are systematic errors; that is, they are not random.

A particular determinate error may cause the analytical results produced by the
method to be always too high; another determinate error may render all results too
low. Sometimes the error is constant; all answers are too high (or too low) by the
same amount. If the true results for three samples are 25, 20, and 30 mg/L of
analyte, but the measured (or determined) results are 35, 30, and 40 mg/L,
respectively, the analysis has a constant error of 10 mg/L.