2019- M.PHIL – CHEMISTRY – PAPER-1- SCIENTIFIC RESEARCH METHODOLOGY(SBG) UNIVERSITY OF MADRAS M. Phil CHEMISTRY – SYLLABUS-2019 Paper I: Scientific Research Methodology (SBG) 1. Introduction Nature and importance of research – Aim, objectives, principles and problems – section of research problem – survey of scientific literature – Primary and secondary sources. 2. Conduct of Research work: Physical properties useful in analysis and methods of separation prior to analysis – Isolation techniques – extraction, crystallization, sublimation, distillation – High vacuum distillation techniques – cyclic distillation, Analytical distillation, thin layer and gas chromatography – Reaction techniques to include high dilution, vacuum line reactions, reactions aided by azeotropic distillation, recycling pyrolysis, Soxhlet extraction, continuous reactions, reactions at low temperature, reaction in non-aqueous media and molten salts, micro-quantity handling use of glove box. Special methods in modern chemistry – methods for vacuum sublimation and quasi sublimation, techniques and apparatus for reactions in inert atmosphere and under low temperature, working with compressed gases, heating under pressure, chemistry of working with hazardous materials – air / water sensitive, corrosive, toxic, explosive and radio active materials. 3. Statistical treatment of analytical results: Page 1 of 94
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2019- M.PHIL – CHEMISTRY – PAPER-1- SCIENTIFIC RESEARCH METHODOLOGY(SBG)
UNIVERSITY OF MADRAS
M. Phil CHEMISTRY – SYLLABUS-2019
Paper I: Scientific Research Methodology (SBG)
1. Introduction
Nature and importance of research – Aim, objectives, principles and problems – section of
research problem – survey of scientific literature – Primary and secondary sources.
2. Conduct of Research work:
Physical properties useful in analysis and methods of separation prior to analysis – Isolation
techniques – extraction, crystallization, sublimation, distillation – High vacuum distillation
techniques – cyclic distillation, Analytical distillation, thin layer and gas chromatography –
Reaction techniques to include high dilution, vacuum line reactions, reactions aided by
azeotropic distillation, recycling pyrolysis, Soxhlet extraction, continuous reactions, reactions at
low temperature, reaction in non-aqueous media and molten salts, micro-quantity handling use of
glove box. Special methods in modern chemistry – methods for vacuum sublimation and quasi
sublimation, techniques and apparatus for reactions in inert atmosphere and under low
temperature, working with compressed gases, heating under pressure, chemistry of working with
hazardous materials – air / water sensitive, corrosive, toxic, explosive and radio active materials.
3. Statistical treatment of analytical results:
Precision and accuracy – reliability – determinate and random errors – distribution of random
errors – normal distribution curve, statistical treatment of finite samples – the students’ t – test
and F – test – criteria for rejection of an observation - the Q test. Significant figures and
computation rules. Data plotting – least square analysis – significance of the correlation
coefficients.
4. Thesis and assignment writing:
Conventions of writing – the general format – page and chapter format – use of quotations and
footnotes – preparation of tables sand figures – referencing – appendices revising, editing and
evaluating the final product – proof reading – meanings and examples of commonly used
abbreviations.
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2019- M.PHIL – CHEMISTRY – PAPER-1- SCIENTIFIC RESEARCH METHODOLOGY(SBG)
UNIT 1
INTRODUCTION TO RESEARCH
1. Nature And Importance Of Research
2. Aim, Objectives, Principles And Problems
3. Section Of Research Problem
4. Survey Of Scientific Literature
5. Primary And Secondary Sources
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2019- M.PHIL – CHEMISTRY – PAPER-1- SCIENTIFIC RESEARCH METHODOLOGY(SBG)
1. In chemistry, most research is first published as primary sources in the form of journal
articles,
2. Other primary sources include patents and reports (for commercially sensitive research),
theses, conference papers and research monographs (a type of book).
3. Secondary sources of information are available to help guide users to the primary
literature, and are reworkings of primary literature into a more digestible form.
4. They include databases, reviews, textbooks and encyclopedias (details below).
5. Normally you should reference primary sources.
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UNIT 2. CONDUCT OF RESEARCH WORK:
1. Physical Properties Useful In Analysis2. Methods Of Separation Prior To Analysis 3. Isolation Techniques 4. Extraction,5. Crystallization,6. Sublimation,7. Distillation8. High Vacuum Distillation Techniques 9. Cyclic Distillation,10. Analytical Distillation,11. Thin Layer Chromatography12. Gas Chromatography 13. Reaction Techniques To Include High Dilution,14. Vacuum Line Reactions,15. Reactions Aided By Azeotropic Distillation,16. Recycling17. Pyrolysis, 18. Soxhlet Extraction,19. Continuous Reactions,20. Reactions At Low Temperature,21. Reaction In Non-Aqueous Media And Molten Salts, 22. Micro-Quantity Handling Use Of Glove Box.23. Special Methods In Modern Chemistry24. Methods For Vacuum Sublimation And Quasi Sublimation25. Techniques And Apparatus For Reactions In Inert Atmosphere 26. D Under Low Temperature,27. Working With Compressed Gases,28. Heating Under Pressure, 29. Chemistry Of Working With Hazardous Materials30. Air / Water Sensitive, 31. Corrosive, 32. Toxic,33. Explosive 34. Radio Active Materials.
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135PHYSICAL PROPERTIES USEFUL IN ANALYSIS
235 METHODS OF SEPARATION PRIOR TO ANALYSIS
The separation of components is often performed prior to analysis. Analytical
methods can be separated into classical and instrumental. Classical methods (also
known as wet chemistry methods) use separations such as precipitation, extraction, and
distillation and qualitative analysis by color, odor, or melting point.
335ISOLATION TECHNIQUES
435 EXTRACTION,
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535CRYSTALLIZATION,
6
35SUBLIMATION,
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7
35DISTILLATION
835 HIGH VACUUM DISTILLATION TECHNIQUES
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935 CYCLIC DISTILLATION,
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1035 ANALYTICAL DISTILLATION,
1135 THIN LAYER CHROMATOGRAPHY
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1235 GAS CHROMATOGRAPHY
1335REACTION TECHNIQUES TO INCLUDE HIGH DILUTION,
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1435 VACUUM LINE REACTIONS,
1535 REACTIONS AIDED BY AZEOTROPIC DISTILLATION,
An azeotrope or a constant boiling point mixture is a mixture of two or more liquids whose
proportions cannot be altered or changed by simple distillation
azeotropic distillation usually refers to the specific technique of adding another
component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g.
producing two, immiscible liquid phases), such as the example below with the addition of
benzene to water and ethanol. This practice of adding an entrainer which forms a separate
2019- M.PHIL – CHEMISTRY – PAPER-1- SCIENTIFIC RESEARCH METHODOLOGY(SBG)
2135 REACTION IN NON-AQUEOUS MEDIA AND MOLTEN SALTS,
An inorganic nonaqueous solvent is a solvent other than water, that is not an organic
compound. ... These solvents are used in chemical research and industry for reactions that
cannot occur in aqueous solutions or require a special environment.
1. Sulfur dioxide is a versatile inert solvent widely used for dissolving highly
oxidizing salts.
2. Dry hydrogen fluoride readily dissolves low-valent metal fluorides as well as
several molecular fluorides.
3. Liquid ammonia is the best-known and most widely studied nonaqueous ionising
solvent.
MOLTEN SALTS
When a solid salt melts, it forms a solution of the cations and anions. For example, KOH melts at temperatures above 400 °C and dissociates into K+ and OH- ions which can act as a solvent for chemical reactions.
Because of the autodissociation of the OH- solvent, water is always present in a molten KOH flux, according to the acid-base equilibrium:
Molten hydroxide fluxes can thus be used in the synthesis of oxide crystals, such as the perovskite superconductor (K1-XBaXBiO3). Eutectic mixtures of NaOH and KOH are relatively low melting (≈ 200 °C) and can be used as solvents for crystallizing a variety of basic oxides
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2235MICRO-QUANTITY HANDLING USE OF GLOVE BOX.
2335 SPECIAL METHODS IN MODERN CHEMISTRY
2435 METHODS FOR VACUUM SUBLIMATION
Vacuum sublimation requires an apparatus in which the sample is heated to a
sufficiently high temperature in a vacuum that the sample is vaporized and then sublimed
onto a substrate.
1. Place the sample to be sublimed in the bottom of the sublimation apparatus.
2. Lightly grease all joints.
3. Use thick-walled tubing to attach to the vacuum arm, and apply the vacuum.
4. The setup should not hiss or there is a leak.
5. Fill the cold finger, or run water through the condenser.
6. Be sure to apply the vacuum first, then coolant. If cooled before the vacuum,
condensation may occur on the cold finger.
7. Wave a heat gun or Bunsen burner on the apparatus to heat the sample.
8. Sublimation should begin within a few minutes.
9. Coax solid deposited on the side of the glassware toward the cold finger by waving the
heat gun/burner on the sides of the glass.
10. When the sublimation is complete:
11. Remove the coolant.
12. Allow the apparatus to come to room temperature.
13. Remove the cold finger.
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2535 QUASI SUBLIMATION
2635 TECHNIQUES AND APPARATUS FOR REACTIONS IN INERT
ATMOSPHERE
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The main techniques include:
counterflow additions, where air-stable reagents are added to the reaction vessel against a flow
of inert gas.
cannula transfer, where liquids or solutions of air-sensitive reagents are transferred between
different vessels stoppered with septa using a long thin tube known as a cannul
2735 UNDER LOW TEMPERATURE
2835 WORKING WITH COMPRESSED GASES,
A compressed gas is a substance that is a gas at normal room temperature and pressure, and is
contained under pressure, usually in a cylinder.
Some compressed gases (e.g. acetylene) are stabilized in the cylinder by dissolving the gas in a
liquid or solid matrix.
Gases expand to fill the space they are given.
Air.
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Helium. Nitrogen. Freon. Carbon dioxide. Water vapor. Hydrogen. Natural gas
Following these basic general safe practices will help protect you from the hazards of
compressed gases:
Read the MSDSs and labels for all of the materials you work with.
Know all of the hazards (fire/explosion, health, chemical reactivity, corrosivity, pressure) of the
materials you work with.
Know which of the materials you work with are compressed gases and check the label, not the
cylinder colour, to identify the gas.
Store compressed gas cylinders in cool, dry, well-ventilated areas, away from incompatible
materials and ignition sources. Ensure that the storage temperature does not exceed 52°C
(125°F).
Store, handle and use compressed gas cylinders securely fastened in place in the upright position.
Never roll, drag, or drop cylinders or permit them to strike each other.
Move cylinders in handcarts or other devices designed for moving cylinders.
Leave the cylinder valve protection cap in place until the cylinder is secured and ready for use.
Discharge compressed gases safely using devices, such as pressure regulators, approved for the
particular gas.
Never force connections or use homemade adaptors.
Ensure that equipment is compatible with cylinder pressure and contents.
Carefully check all cylinder-to-equipment connections before use and periodically during use, to
be sure they are tight, clean, in good condition and not leaking.
Carefully open all valves, slowly, pointed away from you and others, using the proper tools.
Close all valves when cylinders are not in use.
Never tamper with safety devices in cylinders, valves or equipment.
Do not allow flames to contact cylinders and do not strike an electric arc on cylinders.
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Always use cylinders in cool well-ventilated areas.
Handle "empty" cylinders safely: leave a slight positive pressure in them, close cylinder valves,
or "MT," and store them separately from full cylinders.
Wear the proper personal protective equipment for each of the jobs you do.
Know how to handle emergencies such as fires, leaks or personal injury.
Follow the health and safety rules that apply to your job.
2935 HEATING UNDER PRESSURE,
3035CHEMISTRY OF WORKING WITH HAZARDOUS MATERIALS
3135AIR / WATER SENSITIVE
WATER EXPOSURE SENSITIVE
Water reactive chemicals can develop pressure, generate flammable, explosive, corrosive or toxic gases, or ignite or explode when exposed to water or moisture. Examples of water exposure sensitive chemicals include:
alkali and alkaline-earth metals (sodium, lithium, calcium, potassium, magnesium)
aluminum chloride
anhydrous metal halides (aluminum tribromide, germanium tetrachloride)
Air exposure-sensitive chemicals can develop pressure, generate flammable or explosive gases, ignite, or explode when exposed to air. Examples of air exposure sensitive chemicals include:
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alkyl metal derivatives (ethoxydiethylaluminum and dimethylbismuth chloride)
analogous derivatives of nonmetals including diborane, dimethylphosphine, triethylarsine,
dichloro(methyl)silane
carbonyl metals (pentacarbonyliron and octacarbonyldicobalt)
finely divided metals (calcium, titanium)
metal hydrides (potassium hydride and germane)
partially or fully alkylated metal hydrides (diethylaluminum hydride, triethylbismuth)
sodium methoxide
sec-butyl lithium
triethylaluminum
white phosphorus
3235CORROSIVE Chemicals
Corrosives are one of the most commonly encountered hazards in the laboratory. The major classes of corrosive chemicals are:
strong acids and bases
dehydrating agents
oxidizing agents
Sulfuric acid
Nitric acid
The halogen acids include hydrofluoric (HF), hydrochloric (HCl), hydrobromic (HBr), and hydriotic acid (HI).
Perchloric acid
Acetic acid
Phenol
Sodium and potassium hydroxides
Laboratory Use of Corrosives
1. Always investigate the additional hazards such as flammability and reactivity before using.
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2. Purchase only the amount needed; small quantities are recommended for easier handling and storage.
3. Bottle carriers or some other means of containment should be used when moving chemicals between floors.
4. Store separately from incompatible materials.
5. Wear appropriate protective equipment, as described in Section 4.5.
6. Always add chemicals slowly and always add concentrated acid to water.
7. Keep ignition sources away from inorganic acid spills (that may produce flammable hydrogen gas on contact with metals), and from glacial acetic acid, which as an organic acid is a combustible material.
8. When neutralizing corrosives, never add a concentrated acid to base or a concentrated base to acid.
3335TOXIC,
3435 EXPLOSIVE
3535 RADIO ACTIVE MATERIALS.
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UNIT 3. STATISTICAL TREATMENT OF ANALYTICAL RESULTS:
1. Precision And Accuracy
2. Reliability
3. Determinate And Random Errors
4. Distribution Of Random Errors
5. Normal Distribution Curve,
6. Statistical Treatment Of Finite Samples
7. The Students’ T – Test
8. F – Test
9. Criteria For Rejection Of An Observation
10. The Q Test.
11. Significant Figures And Computation Rules.
12. Data Plotting
13. Least Square Analysis
14. Significance Of The Correlation Coefficients.
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114PRECISION AND ACCURACY
Precision refers to the closeness of two or more measurements to each other.
For example , If we weigh a given substance five times, and get 3.2 kg each time, then the
measurement is very precise.
Accuracy refers to the closeness of a measured value to a standard or known value.
For example, if we obtain a weight measurement of 3.2 kg for a given substance, but the actual
weight is 10 kg, then the measurement is not accurate.
Precision is independent of accuracy.
we can be very precise but inaccurate, we can also be accurate but imprecise.
For example, if on average, the measurements for a given substance are close to the known
value, but the measurements are far from each other, then the measurement has accuracy
without precision.
Measurements that are close to the known value are said to be accurate, whereas measurements
that are close to each other are said to be precise
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214 RELIABILITY
Reliability is the degree of consistency of a measure.
A test will be reliable when it gives the same repeated result under the same conditions.
314 DETERMINATE AND RANDOM ERRORS
Error:
Deviation from the absolute value is called error.