OUR LADY OF FATIMA UNIVERSITY

City of Sta. Rosa, Laguna Campus

College of Medical Laboratory Science
Department of Medical Technology

INTRODUCTION TO ANALYTICAL CHEMISTRY

Analytical Chemistry
 It is a branch of chemistry which deals with the study of separation, identification, qualitative
and quantitative determination of the compositions of current substances.
 It facilitates investigation in chemical composition of substances
 It uses the instruments and methods to separate, identify and quantify the matter under study
 it provides chemical or physical information about a sample
 Particularly concerned with the questions “What chemicals are present, what are their
characteristics, and in what quantities are they present?”

Role of Analytical Chemistry

Chemistry

Biology Physics

Engineering
Geology
Analytical
Chemistry
Environmental
Sciences Medicine

Agriculture Materials
Social Science
Sciences

Analytical Chemistry plays a vital role in many of the other sciences. For example, studies on
different analytes during blood chemistry tests (Clinical Chemistry under Medicine) aid the physician in
making a diagnosis or monitoring the treatment of a disease or disease processes.

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

Analytical chemistry uses instruments to:

• Measure physical properties (Quantitation)

-How much is there?

-Expressed in terms of mass, concentration

• Identify Unknowns (Qualitative)

-What is there?

-Expressed in terms of structure, identification, formulas

 Prepare components (Separation)

-How do I get it out?

Classification of Analysis
I. Based on Sample Size: sample size may dictate which method of analysis can be used

1. Ultramicroanalysis: deals with samples <1mg

2. Microanalysis: deals with samples that are 1-10mg or <50µL

3. Semi-microanalysis: deals with samples that are 10-100mg or 50-100µL

4. Meso-/Macroanalysis: deals with samples that are >100mg

II. Based on extent of determination:

1. Proximate analysis: total amount or group of active principles in a given sample

2. Ultimate analysis: amount of a specific constituent or single chemical species in a sample

III. Based on the nature of methods:

1. Classical Method (also known as general/chemical/wet/stoichiometric method-separate the

components of interest)

-Treat separated components with reagents

-Gravimetric measurements – measure mass

-Volumetric (titrimetric) measurement – amount required to react with an analyte

2. Instrumental Analysis/methods

-measure analyte based on a property

-Requires instrumentation to detect

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

Characteristic Properties Instrumental Methods

Emission of radiation Emission spectroscopy (X-ray, UV, visible,
electron, Auger); fluorescence, phosphorescence
and luminescence (X-ray, UV, and visible)
Absorption of radiation Spectrophotometry and photometry (X-ray, UV,
visible, IR); photoacoustic spectroscopy; nuclear
magnetic resonance and electron spin resonance
spectroscopy
Scattering of radiation Turbidimetry; nephelometry; Raman spectroscopy
Refraction of radiation Refractometry; interferometry
Diffraction of radiation X-ray and electron diffraction methods
Rotation of radiation Polarimetry; optical rotary dispersion, circular
dichroism
Electrical potential Potentiometry; chronopotentiometry
Electrical charge Coulometry
Electrical current Amperometry; polarography
Electrical resistance Conductometry
Mass Gravimetry
Mass-to-charge ratio Mass spectrometry
Rate of reaction Kinetic methods
Thermal characteristics Thermal gravimetry and titrimetry; differential
scanning calorimetry; differential thermal
analyses; thermal conductometric methods
Radioactivity Activation and isotope dilution methods.

3. Miscellaneous or Special Method

-based on crude drugs and other natural products

Examples: Acid value, Ash content, Water Content

Specialized Analytical Methods and Equipment

• Distillation -determination of alcohol, protein components, volatile component, alkaloids

• Microscopy – physical characterization

• Polarimeter – rotatory power

• Refractometer – purity of substance

• Dessicator – moisture content

• Oven – moisture content

• Moisture Balance – moisture content

• Chromatography – identity and quantity of component

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

• Spectroscopy – identity and purity

• Polarography – quality and quantity of components

• Biological tests – determination of amounts required to produce the desired, definite effect

Types of Analytical Chemistry

1. Qualitative Analysis

- method of Analytical Chemistry which seeks to find the elemental composition of inorganic
compounds and the functional group of organic compounds.

- answers the question “What is in the sample?”

- includes the Identification of chemicals present, determination of composition and ascertainment

of impurities of a szample material.

2. Quantitative

- measurements of the amount of substances produced in the reaction rather than just noting the
nature of reactions.

- answers the question “How much is in the sample?”

- includes determination of the proportion of components present in a sample.

Types of Quantitative Analysis

1. Volumetric Analysis - analysis involving the measurement of volume of a solution of known
concentration required to react with the desired constituent.

Divisions of volumetric analysis:

I. Neutralization
II. Precipitation
III. Compleximetry
IV. Oxidation-reduction
-permanganate
-ceric sulfate
-iodometry
-iodimetry
-bromine
-potassium iodate
-diazotization assay with nitrite

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

2. Gravimetric Analysis - analysis involving the accurate measurement of weight of substance

being determined which may be isolated in pure form or converted to another substance of known
composition by making it react quantitatively with another substance usually a precipitant.

3. Special Methods - analysis which require a distinct type of technique such as analysis of crude
drugs, assay of fats and fixed oils, assay of volatile oils and assay of alkaloids.

4. Physico-Chemical Methods - Analysis based on some specific physical or chemical property or

properties of the substance being analyzed with the use of instruments such as:
spectrophotometer, chromatograph units, polarographer, polarimeter, flourometer.

Types of Qualitative Analysis

- Types of ion that are present in the solution

- For the purpose of qualitative analysis, the metals (cations) are divided into groups according to
their behavior toward certain reagents known as group reagents or group precipitants which
precipitate all the metals belonging to a certain group. This classification is based on the difference
in solubility of their salts which permit the precipitation and separation of one group to another.
These group reagents are added, one after another in the specific order and will separate all the
common metals, commonly known as basic constituents or cations into five groups.

Detecting Cations

- According to their properties, cations are usually classified into five groups.

- Each group has a common reagent which can be used to separate them from the solution.
The separation must be done in the sequence specified, otherwise, some ions of 1st group
can also react with 2nd group reagent, so that the solution must not have any ions left from
previous groups to obtain meaningful results.

Five group classification:

1st analytical group of cations

- consists of ions that form insoluble chlorides.

- They are precipitated by hydrochloric acid (HCl) or ammonium chloride (NH4Cl) from their
aqueous or dilute acid solutions: silver (Ag+), mercurous (Hg22+), lead (Pb2+)

Most important cation in 1st analytical group:

Ag, Hg, Pb

*Important notes:

- Chlorides of these three elements cannot be distinguished from each other by their color because
they are all white solid compounds.

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

Differentiation:

1. PbCl2 - is soluble in hot water, and can therefore be differentiated easily.

2. AgCl – dissolves in ammonia (due to the formation of the complex ion [Ag(NH3)2]+)
3. Hg2Cl2 - gives a black precipitate consisting of a mixture of chloro-mercuric amide and
elemental mercury.

2nd analytical group of cations

- consists of ions that forms acid-insoluble sulfides.

- They are precipitated by H2S (Hydrogen sulfide)

Most important cation in 2nd analytical group:

Cd, Bi, Cu, Sn

(Cd2+, Bi3+, Cu2+, As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ )

*Important Notes:

- Pb2+ is usually also included here in addition to the first group.

- The reagent can be any substance that gives S 2- ions in such solutions; most commonly
used are H2S (at 0.2-0.3 M), CH3CSNH2 (Thioacetamide/ATK) (at 0.3-0.6 M).
- The test with the sulfide ion must be conducted in the presence of dilute HCl.
- Its purpose is to keep the sulfide ion concentration at a required minimum, so as to allow
the precipitation of 2nd group cations alone.
- If dilute acid is not used, the early precipitation of 4th group cations (if present in solution)
may occur, thus leading to misleading results.

Differentiation:

1. The precipitates of these cations are almost indistinguishable, except for CdS which is yellow.
2. Action of ammonia is also useful in differentiating the cations
CuS – dissolves in ammonia forming an intentse blue solution
CdS – dissolves forming a colorless solution
As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ - sulfides of this elements are soluble in yellow
ammonium sulfide, where they form polysulfide complexes.
3. Action of sodium sulfide (Na2S)
Copper subgroup - sulfides are insoluble in sodium sulfide (Na2S) reagent: copper
(Cu2+), Cadmium (Cd2+), lead (Pb2+), bismuth (Bi3+)

Tin subgroup – sulfides are soluble in sodium sulfide (Na2S) reagent: arsenic (As3+,
As5+), antimony (Sb3+, Sb5+), tin (Sn2+, Sn4+)

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

3rd analytical group of cations

- They are precipitated by OH- (Hydoxide)

- those metals whose chlorides are soluble in water and dilute acids. Sulfides and hydroxides
of these metals are soluble in dilute acids but are insoluble in ammoniacal (alkaline)
solutions. They are therefore not precipitated by HCl nor H 2S from their dilute acid
solutions, but are precipitated by hydrogen sulfide (H2S) or ammonium sulfide [(NH4)2S]
from their ammoniacal solutions. It includes cations whose sulfide compounds are
decomposed into hydrogen sulfide and insoluble hydroxides. The group is further
subdivided into:

Aluminum subgroup – sulfides and hydroxides are soluble in excess sodium hydroxide (NaOH)
and sodium peroxide (Na2O2) mixture: aluminum (Al3+), chromium Cr3+), zinc (Zn2+)

Iron subgroup – sulfides and hydroxides are insoluble in sodium hydroxide (NaOH) and
sodium peroxide (Na2O2) mixture: manganese (Mn2+), iron (Fe2+, Fe3+), Nickel (Ni2+), Cobalt
(Co2+).

4th analytical group of cations

- They are precipitated by CO32- (Carbonate)

Most important ions in the 4th group:

Ba2+, Ca2+, and Sr2+

*Improtant Notes:

After separation, the easiest way to distinguish these ions is by testing flame colour:
1. Barium - yellow-green flame
2. Calcium - orange-red
3. Strontium - deep red

- metals whose chlorides, sulfides, and hydroxides are soluble in acids and ammoniacal
solutions and are therefore not precipitated by the reagents mentioned earlier. Their
carbonates however, are insoluble in water containing excess ammonium carbonate
[(NH4)2CO3] reagent: barium (Ba2+), strontium (Sr2+), calcium (Ca2+), magnesium
(Mg2+). Carbonates of this group are completely precipitated by the addition of 95% ethyl
acohol (CH3CH2OH, C2H5OH, EtOH).

ANCH111 LECTURE-MJV
 OUR LADY OF FATIMA UNIVERSITY
City of Sta. Rosa, Laguna Campus
College of Medical Laboratory Science
Department of Medical Technology

5th analytical group of cations

- FLAME TEST
- metals whose chlorides, sulfides, hydroxides, and carbonates are soluble in water and
therefore not precipitated by any of the group precipitating reagents above. Their ions may
be found in the last filtrate after precipitation of the first four groups. As such, this group is
commonly referred to as the soluble group.

Ions in the 4th group:

sodium (Na+), potassium (K+), lithium (Li+)

Although not a metal, also included in this group is the polyatomic cation ammonium (NH4+)

- Cations which are left after carefully separating previous groups are considered to be in
the fifth analytical group.

The most important ones are:

Mg2+, Li+, Na+, K+ and NH4+.

Distinguish:

1. Sodium – yellow flame

2. Potassium – violet flame
3. Lithium – Red flame

Qualitative Inorganic Analysis

Detecting Anions

- Halides are precipitated by silver nitrate; they can be further identified by color.
- Sulfates can be precipitated by barium chloride.
- Nitrates can be reduced to ammonia.

1st analytical group of anions

- The 1st group of anions consist of CO32-, HCO3-, CH3COO-, S2-, SO32-, S2O32- and NO2-.
- The group reagent for Group 1 anion is HCL(dil) or H2SO4.

Modern techniques

- Qualitative inorganic analysis is now used only as a pedagogical tool. Modern techniques
such as atomic absorption spectroscopy and ICP-MS (Inductively coupled plasma
mass spectrometry) are able to quickly detect the presence and concentrations of
elements using a very small amount of sample.

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