QUANTITATIVE ANALYSIS - CLASSICAL METHODS,

INSTRUMENTAL METHODS
Quantitative analysis is a chemical analysis performed to find the amount of each component
present in a material. It is done by either a classical or instrumental procedure.
A quantitative investigation means that the amount (quantity) or relative amount of each
component present is determined. In a pure substance, the entire mass, or 100%, is composed of a
single component. In materials composed of two or more substances, a quantitative investigation would
determine the mass or relative mass present for each component within the sample. It is not always
necessary to find quantitative values for all components that make up a substance. In most cases it is
sufficient to analyze the material for one or perhaps more components of interest.

GRAVIMETRY
Gravimetric analysis describes a set of methods in analytical chemistry for the quantitative
determination of an analyte based on the mass of a solid. A simple example is the measurement of
solids suspended in a water sample: A known volume of water is filtered, and the collected solids are
weighed.
In most cases, the analyte must first be converted to a solid by precipitation with an appropriate
reagent. The precipitate can then be collected by filtration, washed, dried to remove traces of moisture
from the solution, and weighed. The amount of analyte in the original sample can then be calculated
from the mass of the precipitate and its chemical composition.
In other cases, it may be easier to remove the analyte by evaporation. The analyte might be collected
perhaps in a cryogenic trap or on some absorbent material such as activated carbonand measured
directly. Or, the sample can be weighed before and after it is dried; the difference between the two
masses gives the mass of analyte lost.
Successful gravimetric procedure:
1. Preparation of the Solution: This may involve several steps including adjustment of the pH of the
solution in order for the precipitate to occur quantitatively and get a precipitate of desired properties,
removing interferences, adjusting the volume of the sample to suit the amount of precipitating agent to
be added.
2.Precipitation: This requires addition of a precipitating agent solution to the sample solution. Upon
addition of the first drops of the precipitating agent, supersaturation occurs, then nucleation starts to
occur where every few molecules of precipitate aggregate together forming a nucleous.
3. Digestion of the Precipitate: The precipitate is left hot (below boiling) for 30 min to 1 hour in order for
the particles to be digested. Digestion involves dissolution of small particles and reprecipitation on

larger ones resulting in particle growth and better precipitate characteristics. This process is called
Ostwald ripening. An important advantage of digestion is observed for colloidal precipitates where large
amounts of adsorbed ions cover the huge area of the precipitate. Digestion forces the small colloidal
particles to agglomerate which decreases their surface area and thus adsorption. You should know that
adsorption is a major problem in gravimetry in case of colloidal precipitate since a precipitate tends to
adsorb its own ions present in excess, Therefore forming what is called a primary ion layer which
attracts ions from solution forming a secondary or counter ion layer. Individual particles repel each
other keeping the colloidal properties of the precipitate. Particle coagulation can be forced by either
digestion or addition of a high concentration of a diverse ions strong electrolytic solution in order to
shield the charges on colloidal particles and force agglomeration. Usually, coagulated particles return to
the colloidal state if washed with water, a process called peptization.
4. Washing and Filtering the Precipitate: It is crucial to wash the precipitate very well in order to remove
all adsorbed species which will add to weight of precipitate. One should be careful nor to use too much
water since part of the precipitate may be lost. Also, in case of colloidal precipitates we should not use
water as a washing solution since peptization would occur. In such situations dilute nitric acid,
ammonium nitrate, or dilute acetic acid may be used. Usually, it is a good practice to check for the
presence of precipitating agent in the filtrate of the final washing solution. The presence of precipitating
agent means that extra washing is required. Filtration should be done in appropriate sized Gooch or
ignition filter paper.
5. Drying and Ignition: The purpose of drying (heating at about 120-150 oC in an oven) or ignition in a
muffle furnace at temperatures ranging from 600-1200 oC is to get a material with exactly known
chemical structure so that the amount of analyte can be accurately determined.
6. Precipitation from Homogeneous Solution: In order to make Q minimum we can, in some situations,
generate the precipitating agent in the precipitation medium rather than adding it. For example, in
order to precipitate iron as the hydroxide, we dissolve urea in the sample. Heating of the solution
generates hydroxide ions from the hydrolysis of urea. Hydroxide ions are generated at all points in
solution and thus there are no sites of concentration. We can also adjust the rate of urea hydrolysis and
thus control the hydroxide generation rate. This type of procedure can be very advantageous in case of
colloidal precipitates.

TITRIMETRY
Titration, also known as titrimetry, is a common laboratory method of quantitative chemical
analysis that is used to determine the unknown concentration of an identified analyte. Since volume
measurements play a key role in titration, it is also known as volumetric analysis. A reagent, called the
titrant or titrator is prepared as a standard solution. A known concentration and volume of titrant reacts
with a solution of analyte or titrand to determine concentration. The volume of titrant reacted is called
titration volume.
A typical titration begins with a beaker or Erlenmeyer flask containing a very precise volume of
the analyte and a small amount of indicator (such as phenolphthalein) placed underneath a calibrated
burette or chemistry pipetting syringe containing the titrant. Small volumes of the titrant are then

added to the analyte and indicator until the indicator changes color in reaction to the titrant saturation
threshold, reflecting arrival at the endpoint of the titration. Depending on the endpoint desired, single
drops or less than a single drop of the titrant can make the difference between a permanent and
temporary change in the indicator. When the endpoint of the reaction is reached, the volume of
reactant consumed is measured and used to calculate the concentration of analyte.
Typical titrations require titrant and analyte to be in a liquid (solution) form. Though solids are
usually dissolved into an aqueous solution, other solvents such as glacial acetic acid or ethanol are used
for special purposes (as in petrochemistry).[7] Concentrated analytes are often diluted to improve
accuracy.
Many non-acid-base titrations require a constant pH throughout the reaction. Therefore a
buffer solution may be added to the titration chamber to maintain the pH.

TYPES OF TITRATIONS
There are many types of titrations with different procedures and goals. The most common types of
qualitative titration are acid-base titrations and redox titrations.

ACIDBASE TITRATION
Acid-base titrations depend on the neutralization between an acid and a base when mixed in solution. In
addition to the sample, an appropriate pH indicator is added to the titration chamber, reflecting the pH
range of the equivalence point. The acid-base indicator indicates the endpoint of the titration by
changing color. The endpoint and the equivalence point are not exactly the same because the
equivalence point is determined by the stoichiometry of the reaction while the endpoint is just the color
change from the indicator. Thus, a careful selection of the indicator will reduce the indicator error.

REDOX TITRATION
Redox titrations are based on a reduction-oxidation reaction between an oxidizing agent and a reducing
agent. A potentiometer or a redox indicator is usually used to determine the endpoint of the titration, as
when one of the constituents is the oxidizing agent potassium dichromate. The color change of the
solution from orange to green is not definite, therefore an indicator such as sodium diphenylamine is
used.[16] Analysis of wines for sulfur dioxide requires iodine as an oxidizing agent. In this case, starch is
used as an indicator; a blue starch-iodine complex is formed in the presence of excess iodine, signalling
the endpoint.[17]
Some redox titrations do not require an indicator, due to the intense color of the constituents. For
instance, in permanganometry a slight persisting pink color signals the endpoint of the titration because
of the color of the excess oxidizing agent potassium permanganate.[18] In iodometry, at sufficiently large
concentrations, the disappearance of the deep red-brown triiodide ion can itself be used as an endpoint,
though at lower concentrations sensitivity is improved by adding starch indicator, which forms an
intensely blue complex with triiodide.

GAS PHASE TITRATION

Gas phase titrations are titrations done in the gas phase, specifically as methods for determining
reactive species by reaction with an excess of some other gas, acting as the titrant. In one common gas
phase titration, gaseous ozone is titrated with nitrogen oxide according to the reaction
O3 + NO O2 + NO2.
After the reaction is complete, the remaining titrant and product are quantified this is used to
determine the amount of analyte in the original sample.
Gas phase titration has several advantages over simple spectrophotometry. First, the measurement
does not depend on path length, because the same path length is used for the measurement of both the
excess titrant and the product. Second, the measurement does not depend on a linear change in
absorbance as a function of analyte concentration as defined by the Beer-Lambert law. Third, it is useful
for samples containing species which interfere at wavelengths typically used for the analyte.

COMPLEXOMETRIC TITRATION
Complexometric titrations rely on the formation of a complex between the analyte and the titrant. In
general, they require specialized complexometric indicators that form weak complexes with the analyte.
The commonest example is the use of starch indicator to increase the sensitivity of iodometric titration,
the dark blue complex of starch with iodine and iodide being more visible than iodine alone. Other
complexometric indicators are Eriochrome Black T for the titration of calcium and magnesium ions, and
the chelating agent EDTA used to titrate metal ions in solution.

INSTRUMENTAL CHEMISTRY
SPECTROSCOPY
Spectroscopy measures the interaction of the molecules with electromagnetic radiation. Spectroscopy
consists of many different applications such as atomic absorption spectroscopy, atomic emission
spectroscopy, ultraviolet-visible spectroscopy, x-ray fluorescence spectroscopy, infrared spectroscopy,
Raman spectroscopy, nuclear magnetic resonance spectroscopy, photoemission spectroscopy,
Mssbauer spectroscopy, Circular dichroism spectroscopy, and so on.

MASS SPECTROMETRY
Mass spectrometry measures mass-to-charge ratio of molecules using electric and magnetic fields.
There are several ionization methods: electron ionization, chemical ionization, electrospray, fast atom
bombardment, matrix-assisted laser desorption/ionization, and others. Also, mass spectrometry is
categorized by approaches of mass analyzers: magnetic-sector, quadrupole mass analyzer, quadrupole
ion trap, time-of-flight, Fourier transform ion cyclotron resonance, and so on.

CRYSTALLOGRAPHY
Crystallography is a technique that characterizes the chemical structure of materials at the atomic level
by analyzing the diffraction patterns of electromagnetic radiation or particles that have been deflected

by atoms in the material. X-rays are most commonly used. From the raw data the relative placement of
atoms in space may be determined.

ELECTROCHEMICAL ANALYSIS
Electroanalytical methods measure the electric potential in volts and/or the electric current in amps in
an electrochemical cell containing the analyte.[1][2] These methods can be categorized according to which
aspects of the cell are controlled and which are measured. The three main categories are potentiometry
(the difference in electrode potentials is measured), coulometry (the cell's current is measured over
time), and voltammetry (the cell's current is measured while actively altering the cell's potential).

THERMAL ANALYSIS
Calorimetry and thermogravimetric analysis measure the interaction of a material and heat.

SEPARATION
Separation processes are used to decrease the complexity of material mixtures. Chromatography and
electrophoresis are representative of this field.

HYBRID TECHNIQUES
Combinations of the above techniques produce "hybrid" or "hyphenated" techniques.[3][4][5][6][7] Several
examples are in popular use today and new hybrid techniques are under development.

MICROSCOPY
The visualization of single molecules, single biological cells, biological tissues and nanomaterials is very
important and attractive approach in analytical science. Also, hybridization with other traditional
analytical tools is revolutionizing analytical science. Microscopy can be categorized into three different
fields: optical microscopy, electron microscopy, and scanning probe microscopy. Recently, this field is
rapidly progressing because of the rapid development of the computer and camera industries.

LAB-ON-A-CHIP
Devices that integrate multiple laboratory functions on a single chip of only a few square millimeters or
centimeters in size and that are capable of handling extremely small fluid volumes down to less than
picoliters.
WHY IS QUANTITATIVE ANALYSIS IMPORTANT?
It's important to know the quantity of all or part of a sample for several reasons.
1. First, if you're performing a chemical reaction, quantitative analysis helps you predict how much
product to expect and to determine your actual yield.
2. Another reason quantitative studies are important is because some reactions take place when
the concentration of one component reaches a critical level. For example, an analysis of a
radioactive material might indicate there is enough of a key component for the specimen to
undergo spontaneous fission!
3. Quantitative analysis is crucial to the formulation and testing of food and drugs, as it is used to
measure nutrient levels and provide an accurate accounting of dosage.

4. Quantitative analysis is critical in determining the level of contaminants or the impurity of a

sample. While qualitative analysis might be able to determine the presence of lead in the paint
on a toy, for example, it is quantitative analysis that detects how the concentration of lead.
5. Medical tests rely on quantitative analysis for information about a patient's health. For example,
quantitative analysis could determine blood cholesterol levels or the ratio of lipoproteins in
plasma or the amount of protein excreted in urine. Here again, quantitative analysis
complements qualitative analysis, since the latter identifies the nature of a chemical while the
former tells you how much there is.
6. Quantitative tests of a mineral may be used to determine whether it's practical to mine it for a
specific element or compound.
7. Quantitative tests are used to verify products meet manufacturer or regulatory specifications.