ANCH111: ANALYTICAL CHEMISTRY LECTURE

WEEK 1: Introduction to Analytical Chemistry

2nd SEMESTER I S.Y. 2021-2022
LECTURER: PROF. JERICHA CARINA PASCUA

ANALYTICAL CHEMISTRY ● All zeros to the left of an implied decimal point and to
● Branch of Science that deals with the separation, the right of a non-zero digits are significant.
identification, and determination of the components in a ● Also, when they follow a unit, bar, or scientific notation.
sample ● All zeros to the right of a decimal point and to the right
● Particularly concerned with the questions of “what chemicals of a non-zero digit are significant.
are present, what are their characteristics, and in what
quantities are they present.”
TYPES OF ANALYTICAL CHEMISTRY
● Qualitative Analysis
o Describing
o Asks “what particular sample”
● Qualitative Analysis
o Deals with numbers. Asks “How many drops
o Do not forget the unit of measurement
● Qualitative Chemistry
o What is in the sample?
● Quantitative Chemistry
o How much is the sample?

CLASSIFICATION OF ANALYSIS
● Sample Size
● Extent of Determination
● Nature of Methods
● Materials used

BASED ON SAMPLE SIZE

ACCURACY AND PRECISION
● Accuracy refers to how near it is to the true value
● Precision refers to how near the values are from each
other.
● Ultramicroanalysis - < 1 mg
● Microanalysis – 1 mg - 10 mg
● Semi-Microanalysis – 10 mg - 100 mg
● Macroanalysis – 100 mg - 100 mg
BASED ON THE EXTENT OF DETERMINATION
● Proximate Analysis
o Total amount of a class or a group of active plant
principles in a given sample.
● Ultimate Analysis
o Amount of a specific constituent or a single chemical
species present in the sample.

BASED ON THE NATURE OF METHODS

● Classical method
o Also known as general/ chemical/wet/stoichiometric
method
▪ Titrimetric Analysis
▪ Gravimetric Analysis
● Instrumental method
o Based on specific physical or chemical properties of
the analyte
o Uses a device to do its work and yield results
▪ Spectrometry
▪ Polarimetry
SIGNIFICANT FIGURES ▪ Chromatography
● All non-zero digits are significant. ● Miscellaneous or special method
● Zeros to the left of the expressed decimal point and to o Involves the crude drugs and other natural products
the right of a non-zero are not significant. o Used on molecular level.

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 WEEK#1: [Introduction to Analytical Chemistry]

▪ Acid value o Physical characterization

▪ Ash content ● Polarimeter
▪ Water content o Rotatory power
● Refractometer
o Purity of substance
● Desiccator
BASED ON MATERIALS USED o Moisture content
● Chemical ● Oven
o Titrimetric method o Moisture content
● Physical ● Moisture Balance
o Instruments and special apparata o Moisture content
● Biological ● Chromatography
o Use of microorganism and animals and parts thereof. o Identity and quantity of component
● Spectroscopy
TYPES OF QUANTITATIVE ANALYSIS o Identity and purity
● Volumetric ● Polarography
● Gravimetric o Quality and quantity of components
● Special Methods ● Biological tests
● Physico-Chemical Methods o Determination of amounts required to produce the
desired, definite effect
VOLUMETRIC ANALYSIS
● Analysis involving the measurement of volume of a QUALITATIVE INORGANIC ANALYSIS
solution of known concentration required to react with ● According to their properties, cations are usually
the desired constituent. classified into 5 groups.
● Each group has a common reagent which can be used
DIVISIONS OF VOLUMETRIC ANALYSIS to separate them from the solution
● Neutralization ● The separation must be done in the sequence specified,
otherwise, some ions of 1st group can also react with 2nd
● Precipitation group reagent, so that the solution must not have ay
● Compleximetry ions left from previous groups to obtain meaningful
● Oxidation-Reduction results.
o Permanganate
o Ceric Sulfate 1ST ANALYTICAL GROUP OF CATIONS
o Iodometry ● Consists of ions that form insoluble chlorides
o Iodimetry ● As such, the group reagent to separate them is
o Bromine hydrochloric acid, usually used at a concentration of 1-
o Potassium Iodate 2 M. Concentrated HCl must not be used because it
o Diazotization assay with Nitrite forms a soluble complex ion ([PbCl4]2-) with Pb2+.
● Consequently, the Pb2+ ion would go undetected.
GRAVIMETRIC ANALYSIS ● The most important cations in 1st group are Ag+, Hg2+,
● Analysis involving the accurate measurement of weight and Pb2+. The Chlorides of these elements cannot be
of substance being determined which may be isolated distinguished from each other by their color – they are
in pure form or converted into another substance of all white solid compounds.
known composition by making it react quantitatively with ● PbCl2 is soluble in hot water and can therefore be
another substance, usually a precipitant differentiated easily.
● Ammonia is used as a reagent to distinguish between
SPECIAL METHODS the other two. While AgCl dissolves in ammonia (due to
● Analysis which requires a distinct type of technique such the formation of the complex ion [Ag(NH3)2]+), Hg2Cl2
as analysis of crude drugs, assays of fats and fixed oils, gives a black precipitate consisting of a mixture of
assay of volatile oils, and assay of alkaloids. chloro-mercuric amide and elemental mercury.
Furthermore, AgCl is reduced to silver under light, which
PHYSICO-CHEMICAL METHODS gives samples a violet color.
● Analysis based on some specific physical or chemical ● PbCl2 is far more soluble than the chlorides of the other
property or properties of the substance being analyzed two ions, especially in hot water.
with the use of instruments such as: spectrophotometer, ● Therefore, HCl in concentrations which completely
chromatograph units, polarographer polarimeter, precipitate Hg22+ and Ag+, may not be sufficient to do the
fluorometer. same to Pb2+.
● Higher concentrations of Cl- cannot be used for the
SPECIALIZED ANALYTICAL METHODS AND aforementioned reasons.
EQUIPMENT ● Thus, a filtrate obtained after first group analysis of Pb2+
● Distillation contains an appreciable concentration of this cation,
o Determination of alcohol, protein components, volatile enough to give the test of the second group, viz.
component, alkaloids formation of an insoluble sulfide.
● Microscopy

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 WEEK#1: [Introduction to Analytical Chemistry]

o For this reason, Pb2+ is usually also included in the 2nd ● Caution should be taken to properly
analytical group. separate all lower analytical groups
beforehand, as many of cations in previous
2ND ANALYTICAL GROUP OF CATIONS groups also form insoluble carbonates.
● The 2nd analytical group of cations ● Most important ions in the 4th group: Ba2+,
consists of ions that forms acid-insoluble Ca2+, and Sr2+. After separation, the
sulfides. easiest way to distinguish these ions is by
● Cations in the 2nd group include: Cd2+, testing flame color: barium gives a yellow
Bi3+, Cu2+, As3+, As5+, Sb3+, Sb5+, Sn2+, -green flame, calcium orange-red and
Sn4+ and Hg2+. strontium deep red.
● Pb2+ is usually also included here in
addition to the first group. 5TH ANALYTICAL GROUP OF CATIONS
● The reagent can be any substance that gives S2- ● Cations which are left after carefully
ions in such solutions; most commonly used are separating previous groups are considered
H2S (at 0.2-0.3 M), CH3CSNH2 to be in the fifth analytical group.
(Thioacetamide/ATK) (at 0.3-0.6 M). ● The most important ones are Mg2+, Li+,
● The test with the sulfide ion must be conducted Na+, K+ and NH4+.
in the presence of dilute HCl.
● Its purpose is to keep the sulfide ion QUALITATIVE INORGANIC ANALYSIS
concentration at a required minimum, so as to
allow the precipitation of 2nd group cations DETECTING ANIONS
alone.
● Halides are precipitated by silver nitrate; they
● If dilute acid is not used, the early can be further identified by color.
precipitation of 4th group cations (if
present in solution) may occur, thus
● Sulfates can be precipitated by barium
chloride.
leading to misleading results.
● Acids beside HCl are rarely used. Sulfuric
● Nitrates can be reduced to ammonia.
acid may lead to the precipitation of the
4th group cations, while nitric acid directly 1ST ANALYTICAL GROUP OF ANIONS
reacts with the sulfide ion (reagent), ● The 1st group of anions consist of CO32-,
forming colloidal sulfur. HCO3-, CH3COO-, S2-, SO32-, S2O32- and
● The precipitates of these cations are NO2-.
almost indistinguishable, except for CdS ● The group reagent for Group 1 anion is
which is yellow. HCl (dil) or H2SO4.
● All the precipitates, except for HgS, are
soluble in dilute mineral acids. HgS is MODERN TECHNIQUES
soluble only in aqua regia, which can be ● Qualitative inorganic analysis is now used
used to separate it from the rest. only as a pedagogical tool.
● The action of ammonia is also useful in ● Modern techniques such as atomic
differentiating the cations. absorption spectroscopy and ICP-MS
● CuS dissolves in ammonia forming an (Inductively coupled plasma mass
intense blue solution, while CdS dissolves spectrometry) are able to quickly detect
forming a colorless solution. the presence and concentrations of
● The sulfides of As3+, As5+, Sb3+, Sb5+, elements using a very small amount of
Sn ,2+
Sn 4+
are soluble in yellow sample.
ammonium sulfide, where they form
polysulfide complexes.
GOODLUCK MGA BEVS MWA
3RD ANALYTICAL GROUP OF CATIONS “The great aim of education is not knowledge but action”
● 3rd analytical group of cations includes
ions that form sulfides which are insoluble
in basic solution.
● The reagents are similar to these of the
2nd group, but separation is conducted at
pH of 8–9. Occasionally, a buffer solution
is used to ensure this pH.
● Cations in the 3rd group are, among
others: Zn , Ni , Co2+, Mn2+, Fe2+, Fe3+,
2+ 2+

Al3+, and Cr3+.

4TH ANALYTICAL GROUP OF CATIONS

● Ions in 4th analytical group of cations form
carbonates that are insoluble in water.
● The reagent usually used is (NH4)2CO3 (at
around 0.2 M), the pH should be neutral or
slightly basic.

ANCH 111 | OLFU-VAL BMLS ‘25