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MODULE - 1
PHYSICAL CHEMISTRY
DIGESTER -1
TYPE OF SOLUTIONS
DIGESTER -2
EXPRESSING CONCENTRATION OF SOLUTIONS
DIGESTER -3
IMPORTANT LAW’S IN SOLUTION
LAW DISCRIPTION
Henary’s law The solubility of a gas in a liquid at a given temperature in directly
proportional to the partial pressure of the gas.
or P = Kh.C
Where,
P = Partial pressure of the gas
C = Concentration of dissolved gas
Raoult’s law Vapour pressure (PA) of a solution containing a non-volatile solute
is directly proportional to the mole fraction of the solvent (XA). The
proportionality constant being the vapour pressure of the pure
solvent (P0A).
PA = P0A XA
Where,
PA = Partial vapour pressure of solution
XA = Mole fraction of solvent
P0A = Vapour pressure of the pure solvent
Dalton’s law of The total pressure exerted by a mixture of gases is equal to the sum
partial of the partial pressures exerted by each individual gas in the
pressures mixture.
Ptotal = ∑ni=1pi (or) Ptotal = P1 + P2 + P3 + …. + Pn
Where,
Ptotal = Total pressure exerted by the mixture of gases
P1, P2,…, Pn are the partial pressures of the gases 1, 2,…, ‘n’ in
the mixture of ‘n’ gases is the total pressure exerted by the
mixture of gases
DIGESTER -4
IDEAL AND NON IDEAL SOLUTION
NON-IDEAL SOLUTION
IDEAL SOLUTION SOLUTION HAVING SOLUTION HAVING
POSITIVE DEVIATION NEGATIVE DEVIATION
They obey Raoult’s law They do not obey Raoult’s They do not obey Raoult’s
law law
A-B = A-A or B-B A-B < < A-A or B-B A-B > > A-A or B-B
interactions interactions interactions
ΔHmix = 0 ΔHmix > 0 ΔHmix < 0
ΔVmix >= 0 ΔVmix > 0 ΔVmix < 0
Does not form an Forms azeotrope mixture Forms azeotrope mixture
azeotrope miture
Example : Benzene and Example : Acetone and Example : Chloroform and
toluene, Carbon disulphide, Benzene,
Hexane and heptane, All Acetone and Benzene, Chloroform and Diether,
the dilute solutions nearly Carbon Tetrachloride and Acetone and Aniline,
behave as an ideal solution Toluene, Nitric Acid and water,
Acetone and Ethanol, Acetic Acid and pyridine,
Ethanol and Water Hydrochloric Acid and
water
DIGESTER -5
COLLIGATIVE PROPERTIES AND THEIR TYPES
DIGESTER -6
IMPORTANT TERMINOLOGY IN THERMODYNAMICS
TERMS DESCRIPTION
System Part of the universe under investigation.
Open System A system which can exchange both energy and matter with its
surroundings.
Example : Tea in cup, Human body, Reaction on container
Closed System A system which permits passage of energy but not mass,
across its boundary.
Example : Hot water in closed vessel
Isolated system A system which can neither exchange energy nor matter with
its surrounding.
Example : Tea in thermal flask
Path functions These depend upon the path followed, Example : Work, Heat
State Functions Property of system which depend only on the state of the
system and not on the path.
Example: Pressure, Volume, Temperature, Internal energy,
Enthalpy, Entropy
Intensive properties Properties of a system which do not depend on mass of the
system.
Example : Temperature, Pressure, Density, Concentration
Extensive properties Properties of a system which depend on mass of the system.
Example : Volume, Energy, Enthalpy, Entropy
DIGESTER -7
LAW OF THERMODYNAMICS
LAW DESCRIPTION
Zero law If the two systems are in thermal equilibrium with a third system then
they are also in thermal equilibrium with each other.
First law Energy can neither be created nor destroyed although it can be
converted from one form to the other.
Q = ΔE + W
Where,
Q = Amount of heat absorbed
ΔE = Change in internal energy
W = work done
Second Law The entropy of the universe is always increasing in the course of every
spontaneous or natural change.
Third law The entropy of a pure crystalline substance approaches zero as the
temperture approaches absolute zero.
Kichoff’s H 2 H 1
equation C p
T1 T 2
Where,
Cp= (Cp of product)- (Cp of reactant)
H2, H1 = Heat of reaction on tempretureT1 T2
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DIGESTER GPAT DISCUSSION CENTER : MAKES STUDY EASY
Hess’s law of The total enthalpy change in a chemical reaction is always constant (at
constant heat constant pressure and constant volume).
summation H = H1 + H2 + H2
DIGESTER -8
THERMODYNAMIC PROCESS
THERMODYNAMIC
DESCRIPTION
PROCESS
Isothermal process Temperature remains constant, i.e., ΔQ = W
Isochoric process Volume remains constant, i.e., ΔQ = ΔE
Isobaric process Pressure remains constant, i.e., ΔQ = ΔE + W
Adiabatic process Heat is not exchanged by system with the surroundings, i.e.,
ΔE = W
Cyclic process System returns to its original state after undergoing a series of
change, i.e., Δ U cyclic = 0; Δ H cyclic = 0
Reversible process A process that follows the reversible path
Irreversible process The process which cannot be reversed and amount of energy
increases. All natural processes are Irreversible.
DIGESTER -9
HEAT CAPACITY
Heat capacity of a Heat Capacity (c) of a system is defined as the amount of heat
system required to raise the temperature of a system by 1° C.
Molar heat capacity It is the heat capacity 1 mole of substance of the system.
Specific heat capacity It is the heat capacity of 1 g of substance of the system
Molar heat capacity at CV = (3 / 2) R
constant volume
Molar heat capacity at Cp = (3 / 2) R + R = (5 / 2)R
constant pressure
Poisson’s ratio γ = Cp / CV = (5 / 3) = 1.66
For monoatomic gas γ = 1.66, for diatomic gas γ = 1.40, for
triatomic gas γ = 1.33
DIGESTER -10
ENTHALPY AND ENTROPY
DIGESTER -11
GIBBS ENERGY
Gibbs Energy or Gibbs Free The energy available for a system at some conditions
Energy (G) and by which useful work can be done. It is a state
function and extensive property.
G = H – TS
Gibbs free energy ΔG = ΔH – TΔS
ΔG > 0 Process is non-spontaneous
ΔG < 0 Process is spontaneous
ΔG = 0 Process is in equilibrium state
Gibbs–Helmholtz equation G
T H
= 2
T T
p
where,
H = Enthalpy
T = Absolute zero temperature
G = Gibbs free energy
EFFECT OF TEMPERATURE ON SPONTANEITY
Sign of ΔH Sign ΔG = ΔH – TΔS Remark
of ΔS
- + - Spontaneous at all
temperature
+ - + Non-spontaneous at all
temperature
+ + + at low temperature Non-spontaneous at
low temperature
- at high temperature Spontaneous at high
temperature
- - - at low temperature Spontaneous at low
temperature
+ at high temperature Non-spontaneous at
high temperature
DIGESTER -12
IMPORTANT TERMIOLOGY IN ELECTROCHEMISTRY
TERM DESCRIPTION
Specific Measure of the ability of that material to conduct electricity.
conductivity SI unit of conductance is S (Siemens).
1
K=
ρ
Where,
K = Conductivity
= Restivity of material
Molar Conductance property of a solution containing one mole of the
conductivity electrolyte.
1000
m = κ ×
Molarity
Equivalent Net conductance of every ion that is produced from one gram
conductance equivalent of a given substance.
1000
eq = κ ×
Normality
Faraday’s First The mass of a substance deposited or liberated at any
Law electrode is directly proportional to the amount of charge
passed.
Eq.Wt
Z=
96500
Where,
Z = Electrochemical Equivalent
Faraday’s Mass of a substance deposited or liberated at any electrode on
Second Law passing a certain amount of charge is directly proportional to
its chemical equivalent weight.
Charge on one mole electrons = 1F = 96487 C
W1 E1
=
W2 E2
Where,
W1 W2 = Weight of substance
E1 E2 = Equivalent weight
Kohlrausch’s Equivalent conductivity of an electrolyte at infinite dilution is equal to the
law sum of the conductance of the anions and cations.
λ eq = λ c + λ a
Where
λ eq = Equivalence conductivity at In finite Dilution
λ c = Conductivity of Cation
λ a = Equivalence conductivity at Anion
EMF series Arrangement of elements in order of their increasing electrode
potential values.
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DIGESTER : PHYSICAL CHEMISTRY DIGESTER
Nernst equation A relation between the cell potential of an electrochemical cell, the
standard cell potential, temperature, and the reaction quotient.
Ecell = E0 – [RT/nF] ln Q
Where,
Ecell = Cell potential of the cell
E0 = Cell potential under standard conditions
R = Universal gas constant
T = Temperature
n = Number of electrons transferred in the redox reaction
F = Faraday constant
Q = Reaction quotient
Electrochemical Are cells in which chemical energy is converted into electrical
cell energy.
Salt bridge An inverted U-tube like structure.
The tube is filled with concentrated solution of an inert electrolyte
like KCl, KNO3, NH4NO3, Agar-Agar, K4[Fe(CN)6]
DIGESTER -13
STATE OF MATTER
DIGESTER -14
IMPORTANT GAS EQUATION
EQUATION DESCRIPTION
Graham’s law Under Similar conditions of temperature and pressure, the rates of
of diffusion diffusion of gases are inversely proportional to the square root of their
densities.
r1 d2
= (At same TEMPRETURE and PRESSURE)
r2 d1
r1 M2
= (At same TEMPRETURE and PRESSURE)
r2 M1
Where,
r1 , r2 = Rate of effusion
d1 , d2 = Density gases
M1 , M2 = Molar mass of gases
The kinetic 1
equation
pV = mnu 2
3
Where,
m = Mass of gas
u2 = Root mean square speed of gas
n = Total number of molecule
V = Volume of gas
Van der waals
an 2
equation P + 2 V - nb = nRT
v
Where,
a = Measure of magnitude of attractive force
b = Measure of effective size of the ideal gas molecules
R= Gas constant, T= Temperature, P= Pressure
DIGESTER -15
IMPORTANT MEASURABLE PROPERTIES OF GASES
TERM COMMENT
Mass It is expressed in gram or kg.
Volume It is equal to the volume of the container and is expressed in terms
of liter (L), Milliliter (mL), Cubic centimeter (cm3), Cubic meter (m3)
or Cubic decimeter (dm3).
1 L = 1000 mL = 1000 cm3 = 1 dm3
1 m3 = 103 dm3 = 106 cm3 = 106 ml
Pressure Gas pressure is measured with manometer and atmospheric
pressure is measured by barometer.
1 atm = 76 cm of Hg = 760 mm of Hg = 760 torr
1 atm = 101.325 kPa = 101325 Pa = 101.325 Nm-2 = 1.01325 bar
1 bar = 105 Pa.
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DIGESTER : PHYSICAL CHEMISTRY DIGESTER
DIGESTER -16
IMPORTANT TERMINOLOGY
TERM COMMENT
Dipole A dipole moment is the product of the magnitude of the charge and the
moment distance between the centers of the positive and negative charges. It is
denoted by the Greek letter ‘µ’.
Dipole Moment (µ) = Charge (Q) * distance of separation (r)
Unit of dipole moment is Debye D.
Dipole moment of water is 1.84 D
Symmetrical molecule have zero dipole moment. Example: CO2 , CCl4
Colligative Depend upon only number of molecule.
properties Example: Relative lowering in vapour pressure, Elevation of boiling point,
Depression of freezing point and Osmotic pressure.
Additive Sum of corresponding properties of atoms constituting the molecule.
properties Example: Molecular weight, bond formation enthalpy
Constitutive Depend upon arrangement of atom.
properties Example: Optical activity
Additive and Depend upon the adding the properties of constituent atom but also depend
Constitutive upon arrangement of molecule.
properties Example: Magnetic rotation, Molar refractivity
Refractive The ratio of the speed of light in a vacuum to its speed in a specific medium.
index c Material Refractive index
n=
v
Where, Air 1.0003
n = Refractive index Water 1.333
c = Velocity of light in vacuum Diamond 2.417
v = Velocity of light in a substance Ice 1.31
Specific The specific refraction r of a substance is equal to the substance's
refraction molecular refraction R divided by its molecular weight M.
Molar Product of molar mass (M) of liquid and specific refraction.
refractivity M(n 2 - 1)
A=
ρ(n 2 + 1)
Where,
A = Molar refractivity, ρ = Density, M = Molecular weight
Refractometer A refractometer takes the refraction angles and correlates them to refractive index
(nD) values that have been established. Using these values, you can determine the
concentrations of solutions.
Abbe’s refractrometer – To determine refractive index.
DIGESTER -17
CHEMICAL KINETICS
DIGESTER -18
IMPORTANT GRAPHS RATE V/S TIME
ORGANIC CHEMISTRY
DIGESTER -19
STRUCTURAL ISOMERISM
ISOMERISM DESCRIPTION
Chain Such compounds have the same molecular formula but differ in the
Isomerism order in which the carbon atoms are bonded to each other.
CH3
CH3 CH2 CH2 CH3 CH3 CH CH3
n-Butane (C4H10) Iso butane (C4H10)
Position Positional isomers have same molecular formula but differ in the
Isomerism position of a functional group on the carbon chain.
CH2 CH CH2 CH3 H3C CH CH CH3
But-1-ene But-2-ene
Functional Functional isomers have same molecular formula but differ in
Isomerism functional groups.
CH3 CH2 OH CH3 O CH3
Ethanol (C2H6O) Dimethyl ether (C2H6O)
Metamerism This type of isomerism is due to unequal distribution of carbon
atoms on either side of the functional group. Such compounds are
members of homologous series.
CH3 O CH2 CH2 CH3 CH3 CH2 O CH2 CH3
Methyl propyl ether (C4H10O) Diethyl ether (C4H10O)
Tautomerism This is a special type of functional isomerism in which isomers are
in dynamic equilibrium with each other.
CH3 C CH2 CH3 C CH2
O H O H
keto ane + ol = enol
Ring-Chain The structural isomerism occurring due to the different
Isomerism arrangements of carbon atoms in a ring and in a chain is known as
ring chain isomerism and compounds are called ring chain isomers.
CH3 CH CH2 [open chain]
C3H6 CH2
CH2 CH2 [close chain or ring]
DIGESTER -20
STEREO ISOMERISM
DIGESTER -21
COMPARISON BETWEEN ENANTIOMERS AND DIASTEREOMERS
ENANTIOMERS DIASTEREOMERS
1. They are non-super imposable 1. They don’t have any such relationship.
mirror images. 2. They have different physical properties
2. They have identical physical such as melting
properties such as melting Points, boiling points, densities,
Points, boiling points, densities, solubility’s, etc.
solubility’s, etc. 3. They can be separated by physical
3. They cannot be separated by methods such as fractional
physical methods such as fractional crystallization, fractional distillation,
crystallization, fractional chromatography, etc.
distillation, etc.
DIGESTER -22
TERMINOLOGY IN ORGANIC CHEMISTRY
DIGESTER -23
TYPES OF REACTIONS
(A) Substitution Electrophilic Reaction of aromatic compound
Reaction Substitution
Nucleophilic SN2 nucleophilic reaction = Acid and
Substitution derivative
SN1 substitution reaction = Alkyl
hailide
(B) Addition Electrophilic Addition Alkene, alkyne
reaction Nucleophilic Addition Aldehyde, ketone
Free radical Addition Addition of HBr on alkene
DIGESTER -24
REACTION MEACHNISM
DIGESTER -25
COMPARISON OF E1 AND E2
S.NO CATEGORY E1 E2
1. Kinetics 1st order 2nd order
2. Base Strength Rate independent of base Needs Strong bases
strength
3. Solvent Good ionizing Polarity not important
4. Leaving Group Needs Good LG Needs Good LG
5. Stereochemistry No special geometry Anti-periplanar
6. Rate k[RX] k[RX][B:¯]
7. Substrate 3°>2°>>>1° 3°>2°>1°
8. Rearrangement Possible Not Possible
DIGESTER -26
COMPARISON OF SN1 AND SN2
DIGESTER -27
FUNCTIONAL GROUP AND THEIR PREFIX & SUFFIX
DIGESTER -28
COMMON NAME AND IUPAC NAME OF CARBOXLIC ACID
COOH
Benzoic acid Benzenecarboxylic acid
COOH (Benz+ oic acid)
COOH
DIGESTER -29
DRUGS AND THEIR EFFECTIVE ISOMERS
DIGESTER -30
TYPE OF HYBRIDIZATION & POSSIBLE STRUCTURE
DIGESTER -31
COMPARISON BETWEEN HYBRIDIZATIONS
Sp Sp2 Sp3
Sp hybridization is the Sp2 hybridization is the Sp3 hybridization is the
hybridization that takes mixing of one s atomic mixing of one s atomic
place between an s atomic orbital with two p atomic orbital with three p atomic
orbital and a p atomic orbitals. orbitals.
orbital.
S characteristic percentage S characteristic percentage S characteristic percentage is
is 50%. is 33.33%. 25%.
P characteristic percentage P characteristic percentage P characteristic percentage
is 50%. is 66.66%. is 75%.
Angle between orbitals is Angle between orbitals is Angle between orbitals is
180o C. 120o C. 109.5o C.
Geometry of orbital Geometry of orbital Geometry of orbital
arrangement is linear. arrangement is trigonal arrangement is tetrahedral.
planar.
Results in two Results in one Does not result in any un-
unhybridized p orbitals. unhybridized p orbitals hybridized p orbitals.
DIGESTER -32
BOND LENGTH
DIGESTER -33
BOND ENERGY
DIGESTER -34
IMPORTANT NAME REACTION
5. Baeyer Villiger oxidation Aliphatic ketones undergo oxidation with Caro's acid (per
monosulphuric acid, H2SO4) or per benzoic acid (C6H5CO3H) or m-chloro perbenzoic
acid or per acetic acid (CH3CO3H) or CF3CO3H, etc., to form esters or their hydrolysed
products.
11. Schmidt reaction This is a reaction between a carbonyl compound and hydrazoic
acid in presence of conc. H2SO4 to form alkyl cyanide and N-alkyl formamide.
12. Lederer Manase's reaction When phenol is treated with 40% formaldehyde in
presence of dilute acid or alkali, a mixture of ortho and para-hydroxy benzyl alcohol is
formed.
14. Stephen's reaction Aldehydes are obtained by partial reduction of cyanides with
SnCl2 and HCI and then steam distilled.
15. Finkelstein reaction The corresponding alkyl bromides or chlorides are heated with a
solution of sodium iodide in acetone or methanol. This is a convenient method for the
preparation of alkyl iodides.
16. Wurtz reaction An ether solution of an alkyl halide is treated with sodium which
removes the halogen of alkyl halide and the two alkyl radicals join together to form an
alkane.
17 Corey-House synthesis An alkyl halide is first converted into lithium alkyl which
reacts with cuprous iodide to form lithium dialkyl cuprate, LiR2Cu. It is then treated
with an alkyl halide to give an alkane.
18. Friedel-Crafts reaction Alkyl halides react with benzene in presence of anhydrous
aluminium halides to form a homologue of benzene.
19. Reimer-Tiemann reaction Chloroform reacts with phenol when heated in presence of
sodium hydroxide or potassium hydroxide. The product formed is salicylaldehyde.
20. Bouveault-Blanc reduction The reducing agent used is sodium and ethanol. The
aldehyde, ketones and esters etc., are reduced by nascent hydrogen into corresponding
alcohols.
21. Williamson's synthesis Ethers are formed by heating alkyl halides with sodium or
potassium alkoxides or dry silver oxide. The attacking nucleophile is OR -.
22. Rosenmund's reduction Acid chlorides can be reduced into aldehydes with hydrogen
in boiling xylene using palladium or platinum as a catalyst supported on barium
sulphate. This reaction is called Rosenmund's reduction. Ketones cannot be prepared
by this method.
23. Wacker process This is a recent method for the manufacturing of acetaldehyde from
ethylene. Both aldehydes and ketones can be prepared by this method. Alkenes are
directly oxidised to their corresponding aldehydes and ketones by treating with an
acidified aqueous solution of palladium chloride and cupric chloride in presence of
oxygen or air.
24. Frankland's reaction The method is similar to Wurtz reaction. The alkyl halide is
heated with zinc in inert solvent, higher alkane is formed.
25. Clemmensen's reduction Aldehydes and ketones when reduced with amalgamated
zinc and conc. HCI also yield alkanes. This process is known as Clemmensen
reduction.
27. Hofmann bromamide reaction or Hofmann degradation Amides when heated with
bromine and caustic soda or caustic potash solution, yield primary amines containing
one carbon atom less than the amide. This is an important reaction for reducing a carbon
atom from a compound, i.e., -CONO2 is changed to -NH2 group.
28. Claisen condensation Ethyl acetate (two molecules) undergoes Claisen condensation
in presence of sodium ethoxide involving α-hydrogen atom. Two molecules of ethyl
acetate combine together to form ethyl acetoacetate or acetoacetic ester (α,β-keto ester).
30. Mendius reaction Primary amines can be prepared by reduction of nitriles. The
reduction is done either catalytically with H2 and Raney Ni or with sodium in alcohol or
sodium amalgam and alcohol or with LiAlH4.
31. Curtius degradation The overall reaction which proceeds by the elimination of
nitrogen from acylazide followed by acidic or alkaline hydrolysis to yield primary amine
containing one carbon less, is called Curtius degradation.
32. Mannich Reaction Reduction of N-substituted amides with LiAlH4 yield secondary
amines.
33. Hinsberg's method It involves the treatment of the mixture with benzene sulphonyl
chloride, i.e., Hinsberg's reagent (C6H5SO2Cl). The solution is then made alkaline with
aqueous alkali to form sodium or potassium salt of monoalkyl benzene sulphonamide
(soluble in alkali).
34. Cope reaction When a 3°-amine oxide containing at least one β-hydrogen is heated at
150°C, it decomposes to form an alkene and a derivative of hydroxylamine (Thermal
elimination).
36. From Grignard reagents Alkyl magnesium halides (RMgX) are called Grignard
reagents. These undergo double decomposition reactions with water or ammonia or
alcohol or amines having active H atom (attached to strongly electronegative 0, N, S or
F and triple bond etc.) to give alkane corresponding to alkyl (R -) group of Grignard
reagent.
38. Birch redudion reduction of alkynes with lithiuin or sodium in liquid NH3 (Birch
reduction) yields predominantly trans-alkene.
39. Wittig reaction Conversion of aldehydes and ketones to alkenes with the help of
alkylidene (methylene) triphenyl phosphorus (Wittig reagent) is known as Wittig
reaction.
40. Peterson reaction β-Hydroxy alkyl silane gives elimination reaction in presence of
acid as well as base. It is stereosefective of E- and Z- isomers of alkene.
41. Sabatier-Senderen's reaction Alkenes combine with hydrogen under pressure and in
presence of a catalyst (Ni, Pt, Pd or Rh) to form corresponding alkanes.
44. Blance reaction By heating benzene with formaldehyde solution and HCI in presence
of anhydrous zinc chloride, benzyl chloride is formed and this reaction is called
chloromethylation or Blance reaction.
45. Von Richter reaction When halonitrobenzene is heated with KCN at 150oC, the-,-
NO2 group is expelled and a cyano (or -COOH) group enters the ring at ortho-position
with respect to nitro group.
46. Ulmann biaryl synthesis Iodobenzene, on heating with copper at 200°C in a sealed
tube, forms biphenyl. The reaction is facilitated if a strong electron withdrawing group is
present inortho or para-position.
47. Hunsdieeker's reaction an alkyl halide is formed when the silver salt of
monocarboxylic acid is heated with halogen.
48. Raschig method The vapours of benzene, air and hydrogen chloride are passed over
cupric chloride at about 230°C when chlorobenzene is obtained in sufficient yield.
51. Etard reaction Chromyl chloride dissolved in CS2 or CC14 is made to react with
toluene in CS2 when a brown coloured product is formed. This product is decomposed
with water when benzaldehyde is formed.
52. Perkin reaction When an aromatic aldehyde is heated with an aliphatic acid
anhydride with atleast two α-H atom in presence of Na or K salt of corresponding acid, a
condensation reaction giving α,β-unsaturated acid is formed.
54. Woodward reaction When alkene is treated with iodine and silver acetate, it will
undergo nucleophilic displacement with acetate in the presence of water. The
intermediate product gives the desired diols on hydrolysis.
60. Pfitzner –Moffatt oxidation It is a chemical reaction for the oxidation of primary and
secondary alcohols to aldehydes and ketones, respectively. The oxidant is a combination
of dimethyl sulfoxide (DMSO) and dicyclohexylcarbodiimide (DCC).
O
DMSO. DCC
OH
H
N
H
DIGESTER -35
NAMED REACTIONS
NAME STARTING
CATALYST END PRODUCT
REACTIONS MATERIALS
Wolff Kishner Aldehydes and H2NNH2; C2H5ONa; Methylene group
reduction/ Hung- ketones Glycol
milnon reaction
Meerweili-Ponndorf- Ketones [(CH3)2CHO]3Al; 2o alcohol
Verley (MPV) (CH3)2CHOH
reduction
Pinacol-pinacolone Ketones Mg/ Hg; mineral acid 2,3-dimethyl butane-
rearrangement 2,3-dilol(Pinacol); 3,3-
dimethyl butan-2-one
(Pinacolone)
Beckmann Ketoximes conc. H2SO4, PCl5, N-methyl acetamide
rearrangement H3PO4, SOCl2 or
C6H5SO2Cl
Aldol condensation carbonyl NaOH, Ba(OH)2 or Aldol
compounds K2CO3
Baeyer Villiger Aliphatic ketones (per monosulphuric Esters
oxidation acid, H2SO4) or per
benzoic acid
(C6H5CO3H) or m-
chloro perbenzoic acid
or per acetic acid
(CH3CO3H) or
CF3CO3H
Cannizzaro's Aldehydes (with Conc. Alkali Carboxylic acids
reactions no α-hydrogen)
Tischenko's reaction Aldehydes (with (C2H5O)3Al Ester
or without α-
hydrogen)
Claisen-Schmidt aliphatic aldehyde Dil. NaOH α,β-unsaturated
reaction or ketone (with α- compound
hydrogen)
Schmidt reaction Carbonyl conc. H2SO4 Alkyl cyanide and N-
compounds alkyl formamide
Lederer Manase's Phenol dilute acid or alkali o- and p-hydroxy
reaction benzyl alcohol
Diazotisation aromatic primary NaNO2; HCl Diazonium salt
amine
INORGANIC CHEMISTRY
DIGESTER -36
FEATURES OF INDIAN PHARMACOPOEIA
DIGESTER -37
SOURCE OF IMPURITIES
Raw Materials Pharmaceutical substances are either isolated from natural sources or
synthesized from chemical starting materials which have impurities.
Method of Reagents employed in the Calcium carbonate contains ‘soluble
Manufacture manufacturing process alkali’ as impurity
Regents used to eliminate Barium is used to remove sulphate from
other impurities potassium bromide, (barium) as
impurity at the end of process.
Solvents Water as solvent, it cotains Ca2+ Mg2+ ,
Na+ ,
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DIGESTER GPAT DISCUSSION CENTER : MAKES STUDY EASY
DIGESTER -38
LIMIT TEST
Limit test is defined as quantitative or semi quantitative test designed to identify and control
small quantities of impurity which is likely to be present in the substance.
SUBSTANCE PRINCIPAL REACTION RESULT
Chloride Chloride ion Produces silver
reacts with silver chloride as white
nitrate in the precipitate.
presence of dilute opalescence
nitric acid. Cl AgNO 3 dil.HCL
AgCl NO 3 produce in sample
Chloride ion (Silver Nitrate) (White Pr ecipitate)
(Siver Chloride)
solution should
not be greater
than standard
solution
Sulphate Sulphate ion Turbidity of test
reacts with solution is less
barium chloride than that of
in the presence of SO BaCl dil. HCl
BaSO4 2Cl standard solution
4 2
dilute (Sulphate
ion)
(Barium
Chlride)
(Barium
Sulphate)
(Chloride ion)
the compound will
hydrochloric acid pass the limit test
and produces of sulphate.
barium sulphate.
Iron Iron Interact with The purple color
CH S OOC
Thioglycolic acid Fe + 2CH S 2+
2
Citric acid 2
2+ Fe produce in sample
Ammonical alkaline
in the presence of COOH Solution COO 2 CH S solution should
(Ferrous (Thyoglycolic (Ferrous
citric acid and ion) acid) glycolate) not be greater
ammonical (Purple coloured than standard
Complex)
alkaline solution. solution.
DIGESTER -39
ACID AND BASE
ACIDS BASES
Definition An acid is a substance that can A base is a substance that can release a
release ion (H+) when dissolved hydroxyl ion (OH-) when dissolve in
in water. water. Base converts red litmus paper
Acid converts blue litmus paper to blue having the pH >7.
to red having the pH <7.
Example: HCl H+ + Cl- Example: NaOH Na+ +OH-
Arrhenius An Acid is a substance that A base is a substance that dissociates to
concept dissociated completely to give give hydroxyl ions when dissolved in
hydrogen ions when dissolved water.
in water. Example: NaOH + Water ⇆ Na+(aq)+
Example: HCl+ Water ⇆ H+(aq) OH- (aq)
+ Cl- (aq)
DIGESTER -40
CONJUGATED ACID AND BASE
DIGESTER -41
pH AND pOH
pH pOH
It is negative logarithm (to the base Negative logarithm (to the base 10) of
10) of hydrogen ion concentration. hydroxyl ion concentration.
Expressed by: pH = -log [H+] Expressed by: pOH = -log [OH-]
Also known as sorensen scale.
[H+] (mol dm-3) pH [OH-](mol dm-3) pOH Acidity, Basicity
100 0 10-14 14 ↑Increasing acidity
10-4 4 10-10 10
10-7 7 10-7 7 Neutral
10-10 10 10-1 1 ↑Increasing basicity
10-14 14 10-0 0
DIGESTER -42
BUFFERS
DIGESTER -43
MAJOR EXTRA AND INTRACELLULAR FLUIDS
DIGESTER -44
DENTAL PRODUCT
DIGESTER -45
GASTROINTESTINAL AGENT
ANTACIDS
CHEMICAL FORMULA PREPARATION USE
Sodium NaHCO3 NH3 + CO2+H2O→ Used as an
bicarbonate NaHCO3 electrolyte
(Baking soda, replenisher
mitha soda)
Calcium CaCO3 CaCl2 + Na2CO3 → Used as fast antacid
carbonate CaCO3 + 2NaCl in calcium
(precipitated deficiency
chalk)
DIGESTER -46
EXPECTORANT AND EMETICS
EXPECTORANTS
CHEMICAL FORMULA PREPARATION USE
Ammonium NH3 + HCl → NH4Cl Used as nitrogen
chloride NH4Cl source in
(Amchlor) fertiliser
Potassium iodide KHCO3 + HI → KI + Used as
H2CO3 ingredient of
KI
expectorant
mixture
Sodium potassium KHC4H4O6 +Na2CO3 Used as laxative
tartrate → used in process of
C4H4NaKO6.4H2O
(Rochelle’s salt) C4H4O6KNa·4H2O silvering of
mirrors
EMETICS
Antimony Emetic
potassium tartrate C4H4O7SbK.1/2H2O treatment of
schitomiasis
Copper sulphate 2Cu + 2H2SO4 + O2 Emetics
(blue vitriol, → 2CuSO4 + used as germicide
bluestone, vitriol CuSO4.5H2O 2H2O
of copper)
Sodium chloride NaCl 2Na + Cl2 → 2NaCl Used as table salt
DIGESTER -47
ANTIMICROBIAL AGENT
ANTIMICROBIAL AGENT
CHEMICAL FORMULA USE
Borax Na2B4O7.10H2O Use externally for eye wash
Boric acid H3Bo3 Antiseptic for minor burns
Hydrogen peroxide H2O2 Antiseptic and a germicide
Potassium KMnO4 Treatment of urethritis
permanganate
Bleaching powder Ca(ClO)2 Used as sanitizer in swimming
pool
Iodine I2 Used as anti hyperthyroidism
Silver nitrate AgNO3 Antiseptic and germicide
Mercury Hg Pharmaceutical aid
DIGESTER -48
IMPORTANT TERMIOLOGY IN RADIOPHARMACEUTICALS
DIGESTER -48
UNITS OF RADIOACTIVITY
UNIT DESCRIPTION
Rutherford (Rd) Amount of a radioactive substance which undergoes 106 dps
Roentagen (R) Unit of exposure, 1R = 2.58 × 10-4 CKg-1
RAD Unit of abosrbed dose, 1rad = 10-2 JKg-1
Bacquerel (Bq) One disintegration per second
DIGESTER -49
NATURE AND TYPE OF RAYS
DIGESTER -51
COMMONLY USED RADIOPHARMACEUTICALS
DIGESTER -52
LIST OF INORGANIC SUBSTANCES ALONG WITH CHEMICAL COMPOSITION AND USES
MEDICINAL CHEMISTRY
DIGESTER -53
DRUG AND STARTING MATERIAL AND SYNTHESIS
DIGESTER -54
DRUG ACTING ON AUTONOMIC NERVOUS SYSTEM
CHOLINERGIC DRUGS
Acetylcholine
Methacholine
Carbachol
Bethanechol
Muscarine
Arecoline
Physostigmine
Neostigmine
bromide
Physostigmine
bromide
Edrophonium
chloride
ANTICHOLINERGIC DRUGS
CLASSIFICATION
1. Solanaceous alkaloids and analogues
Scopolamine
(Hyoscine)
Homatropine
Ipratropium
bromide
Clidinium
Dicyclomine
Glycopyrrolate
bromide
Benztropine
mesylate
4. Amino alcohols
Procyclidine HCl
Trihexyl phenidyl
5. Amino amides
Isopropamide iodide
6 . Diamides
ADRENERGIC DRUGS
CLASSIFICATION BASED ON CHEMICAL STRUCTURES
1. Catecholamines
Noradrenaline
Dopamine
Isoprenaline
Dobutamine
2. Noncatecholamines
Amphetamine
Salbutamol
Naphazoline
Phenylephrine
Xylometazoline
Terbutaline
ADRENERGIC BLOCKERS
CLASSIFICATION
1. Alpha receptor blocking agents
a. Beta halo alkyl amines
DRUG NAME STRUCTURE
Dibenamine
Phenoxybenzamine
b. Imidazole derivatives
Phentolamine
c. Quinazolines
DRUG NAME STRUCTURE
Prazosin
Terazosin
Doxazosin
Oxprenolol
Pindolol
b. Specific -blockers
Timolol
Nadolol
Acebutolol
Atenolol
Metoprolol
Esmolol
Carvedilol
DIGESTER -55
AUTACOIDS AND RELATED DRUGS
CLASSIFICATION
1. H1-Antagonists with classical structures
a. Ethylene diamine derivatives
Pyrilamine
Methapyrilene
Thonzylamine
Zolamine
N
Carbinoxamine -H
Medrylamine -H
Diphenylpyraline
DRUG NAME R1 R2
Cyclizine -H -CH3
Chlorcyclizine -Cl -CH3
Meclizine -Cl
Buclizine -Cl
Chlorpheniramine
Brompheniramine
Triprolidine
DRUG NAME R
Promethazine
hydrochloride
Trimeprazine
Methdilazine
Aspirin O
Sodium salicylate
Salsalate
Sulfasalazine
Diflunisal
Phenacetin
Paracetamol
DRUG NAME R R1
Phenylbutazone –H –C4H9
Oxyphenbutazone –OH –C4H9
Sulphinpyrazone –H –(CH2)2SOC6H5
4. Anthranilic acid derivatives
DRUG NAME STRUCTURES
Flufenamic acid
Mefenamic acid
Meclofenamate
sodium
Zomepirac
Ibuprofen
Diclofenac
Naproxen
Carprofen
Fenoprofen
Ketoprofen
Flurbiprofen
Ketorolac
Etodolac
Ibufenac
6. Oxicams
DRUG NAME STRUCTURES
Meloxicam
Tenoxicam
Piroxicam
Celecoxib
Rofecoxib
Valdecoxib
Nabumetone
Nimesulide
Analgin
Allopurinol
Probenecid
DIGESTER -56
DRUGS ACTING ON ENDOCRINE
ORAL HYPOGYLCAEMIC DRUGS
Classification
1. Sulphonylureas
a. First-generation drugs
DRUG NAME R R1
Carbutamide –C4H9 –NH2
Tolbutamide –C4H9 –CH3
Chlorpropamide –C3H7 –Cl
Tolazamide –CH3
Acetohexamide –COCH3
Glibenclamide
(Glyburide)
Glipizide
–CH3
Gliclazide
–CH3
Glibornuride
2. Biguanides
DRUG NAME R R1
Phenformin -H
DRUG NAME R
Pioglitazone
Rosiglitazone
ANTITHYROID DRUGS
CLASSIFICATION
1. Thioureylenes
a. Thiouracil derivatives
Propylthiouracil
b. Imidazoles
Carbimazole
Methimazole
DIGESTER -57
DRUG NAME R R1 R2
Mephenesin –CH3 –H –H
Mephenesin carbamate –CH3 –CONH2 –H
Guaifenesin –OCH3 –H –H
Methocarbamol –OCH3 –CONH2 –H
Chlorphenesin carbamate –H –CONH2 –Cl
LOCAL ANAESTHETICS
CLASSIFICATION
1. Benzoic acid derivatives
NAME R1 R2
Isobucaine –H
Piperocaine –H
NAME R1 R2 R3 R4 R5
Benzocaine –H –H –H –CH2–CH3 –
Butamben –H –H –H –(CH2)3 CH3 –
Procaine –H –H –H –CH2–CH2– –N(C2H5)2
Chloroprocaine –H –H –Cl –CH2–CH2– –N(C2H5)2
Tetracaine –C4H9 –H –H –CH2–CH2– –N(CH3)2
Butacaine –H –H –H –CH2–CH2–CH2 –N(C4H9)2
NAME R1 R2
Lidocaine/Lignocaine –CH3 –CH2–N(C2H5)2
–CH3
Mepivacaine
–H
Prilocaine
–CH3
Bupivacaine
DIGESTER -58
DRUG ACTING ON CENTRAL NERVOUS SYSTEM
Butabarbital –H –C2H5
Pentobarbital –H –C2H5
Cyclobarbital –H –C2H5
Heptabarbital –H –C2H5
Benzodiazepines
R1
R2
9 N1
8 2
3 R3
X 7 6 N
5 4
R2'
Prazepam =O –H –Cl –H
Nitrazepam –H =O –H –NO2 –H
Nordiazepam –H =O –H –Cl –H
Nimetazepam –CH3 =O –H –NO2 –H
Flunitrazepam –CH3 =O –H –NO2 –F
Flurazepam –(CH2)2N (C2H5)2 =O –H –Cl –F
Quazepam –CH2CF3 =S –H –Cl –F
Halozepam –CH2CF3 =O –H –Cl –H
Temazepam –CH3 =O –OH –Cl –H
Lorazepam –H =O –OH –Cl –Cl
Clonazepam –H =O –H –NO2 –Cl
Doxefazepam –CH2OH =O –OH –Cl –F
ANTICONVULSANTS/ ANTIEPILEPTICS
1. Hydantoins
ANTIPARKINSONISM AGENTS
1. Anticholinergic agents
a. Piperidine analogues
DRUG NAME R1 R2
Biperiden
Cycrimine
Trihexyphenidyl HCl
b. Pyrrolidine analogues
DRUG NAME STRUCTURE
Procyclidine HCl
c. Phenothiazine analogues
DRUG NAME STRUCTURE
Ethopropazine HCl
Diphenhydramine
TRANQUILLIZERS/ ANTIPSYCHOTICS
CLASSIFICATION
1. Phenothiazine derivatives
NAME R2 R10
Propyl dialkylamino side chain
Promazine –H
Chlorpromazine –Cl
Triflupromazine –CF3
Mesoridazine O SCH3
Trifluoperazine –CF3 =
Perphenazine –Cl
Fluphenazine –CF3 =
Acetophenazine =
NAME R1 X
Chlorprothixene –Cl –N(CH3)2
Clopenthixol –Cl
Flupenthixol –CF3 =
Thiothixene –SO2N(CH3)2
ANTIDEPRESSANTS
Phenelzine
Tranylcypromine
Clorgyline
DRUGS NAME R R1 R2
Imipramine –H –H – CH3
Desipramine –H –H –H
Trimipramine –H –CH3 – CH3
Clomipramine –Cl –H – CH3
Nortryptyline
Fluoxetine
Fluvoxamine
Paroxetine
Sertraline
OPIOID ANALGESICS
CLASSIFICATION
RO
O
N R"
R'O
DRUG NAME R R’ R’’
Morphine –H –H –CH3
Ethyl morphine –C2H5 –H –CH3
Codeine –CH3 –H –CH3
Heroin –COCH3 –COCH3 –CH3
Nalorphine –H –H CH2–CH=CH2
a. Hydromorphone derivatives
O
N R"
R'
O
DRUG NAME R R’ R’’
Hydromorphone –OH –H –CH3
Oxymorphone –H –OH –CH3
Hydrocodone –OCH3 –H –CH3
Oxycodone –OCH3 –OH –CH3
b. Dihydromorphine derivatives
RO
O
N CH3
HO
DRUG NAME R
Hydromorphone –H
Oxymorphone –CH3
2. Meperidine analogues
R1
6
N1
2
5 3
4
R2 R3
DRUG NAME R1 R2 R3
Meperidine –CH3 –C6H5 –COO C2H5
Bemidone –CH3 –C6H4OH –COOC2H5
Properidone –CH3 –C6H5 –COOCH(CH3)2
Ketobemidone –CH3 – C6H4OH –COC2H5
Anileridine –C6H5 –COOC2H5
CH2 CH2 NH2
Fentanyl –H
Lofentanil –COOCH3
Sufentanil –CH2OCH3
Alfentanil –CH2OCH3
3. Methadone analogues
DRUG NAME R1 R2 R3 R4
–COC2H5 -CH2CH(CH3)N(CH3)2
Methadone
–COC2H5 -CH(CH3)CH2N(CH3)2
Isomethadone
Dipanone –COC2H5
Phenadoxone –COC2H5
4. Morphinan analogues
RO
N R"
R'
DRUG NAME R R1
Pentazocine –CH2–CH=C(CH3)2 –CH3
Phenazocaine –CH2–CH2–C6H5 –CH3
Cyclazocine –CH3
Ketazocine =O
NARCOTIC ANTAGONISTS
HO HO
HO
O O
N CH2 CH CH2 N CH2 CH CH2 O
N CH2
OH
O Allyl group HO Allyl group OH
O Cyclo propyl
Oxymorphone methyl
N-allyl normorphine Oxymorphone
CNS STIMULANTS
CLASSIFICATION
1. Psychomotor stimulants or central stimulants (sympathomimetics)
a. –Phenylethylamine derivatives (Amphetamine and related drugs)
DRUG NAME R R1 R2 R3 R4
Amphetamine(+) –H –H –H –H –H
Dextroamphetamine(+) –H –H –H –H –H
Methamphetamine(+) –CH3 –H –H –H –H
Phentermine –H –H –CH3 –H –H
Benzphetamine –CH3 –CH2C6H5 –H –H –H
Fenfluramine –H –C2H5 –H –H m-CF3
b. Methylxanthines
O R7
7
R1 1 6
5 N
N 8
2
4 9N
O 3N
CH3
DRUG NAME R1 R7
Caffeine –CH3 –CH3
Theophylline –CH3 –H
Theobromine –H –CH3
Etophylline –CH3 –CH2CH2OH
Proxyphylline –CH3
DIGESTER -59
CARDIOVASCULAR DRUGS
ANTIANGINALS
DRUG NAME R1 R2 R3 X
Amlodipine –CH2O(CH2)2NH2 –C2H5 –CH3 2–Cl
Felodipine –CH3 –C2H5 –CH3 2, 3–Cl
Nifedipine –CH3 –CH3 –CH3 2–NO2
Nitrendipine –CH3 –CH3 –C2H5 3–NO2
Nimodipine –CH3 –CH2CH2OCH3 –CH(CH3)2 3–NO2
Nisoldipine –CH3 –CH2CH(CH3)2 –CH3 2–NO2
DRUG NAME STRUCTURE
Isradipine
Benidipine
Nicardipine
b. Diphenyl alkylamines
c. Benzothiazepine derivatives
ANTIHYPERTENSIVE DRUGS
α-Methyldopa
Guanabenz
Nifedipine
Diltiazem
Felodipine
Amlodipine
Nicardipine
Nitrendipine
Irbesartan
Candesartan
Telmisartan
Valsartan
d. ACE inhibitors
i. Sulfhydryl containing ACE inhibitors
DRUG NAME STRUCTURE
Captopril
Enalaprilat –CH3 –H
Lisinopril –(CH2)4NH2 –H
STRUCTURE
DIGESTER -60
DRUGS ACTING ON KIDNEY
DIURETICS
1. Non m er cu r i al d i u r et i cs
a. T h i azi de der ivat ives
DRUG NAME R1 R2
Chlorothiazide -H -Cl
Benzthiazide -CH2-S-CH2-C6H5 -Cl
Flumethiazide -H -CF3
b. Hydrothiazides
DRUG NAME R1 R2 R3
Hydrochlorothiazide -H -H -Cl
Bendroflumethiazide -H -CH2C6H5 -CF3
Cyclothiazide -H -Cl
Hydroflumethiazide -H -H -CF3
Cyclopenthiazide -H -Cl
Methazolamide
Amiloride
Bumetanide
Torsemide
Piretanide
DIGESTER -61
DRUGS AFFRCTING BLOOD AND BLOOD FORMATION
ANTICOAGULANTS
Anticoagulants are drugs that prevent the clotting of blood.
a. Coumarin derivatives
DRUG NAME STRUCTURE
Dicoumarol
Phenprocoumon
Warfarin
Acenocoumarol
b. Indandione derivatives
Brimonidine
ANTIHYPERLIPIDAEMIC AGENTS
CLASSIFICATION
1. HMG CoA—Reductase Inhibitors
DRUG NAME R1 R2 R3
Metastatin -H -H
Lovastatin -H -CH3
Pravastatin -H -OH
Atorvastatin
DRUG NAME R1 R2
Clofibrate -Cl -C2H5
Fenofibrate -CH(CH3)2
Ciprofibrate -H
Bezafibrate -H
DIGESTER -62
DRUGS ACTING ON DIGESTIVE SYSTEM
ANTIULCER AGENTS
CLASSIFICATION
1. Reduction of gastric acid secretion
a. H2-antihistamines
DRUG NAME STRUCTURES
Nizatidine
Cimetidine
Famotidine
Ranitidine
Lansoprazole
Pantoprazole
Rabeprazole
DIGESTER -63
ANTIMICROBIAL DRUGS
ANTIBACTERIAL SULPHONAMIDES
DRUG NAME R R’
Sulphanilamide -H -H
Sulphapyridine -H
Sulphathiazole -H
Sulphacetamide -H -COCH3
Sulfadiazine -H
Sulphadimidine -H
Sulphasomidine -H
Sulfisoxazole -H
b. Intermediate-acting Sulphonamides
DRUG NAME R R’
Sulphasomizole -H
Sulphamethoxazole -H
c. Long-acting Sulphonamides
DRUG NAME R R’
Sulphamethoxy -H
pyridazine
Sulphamethoxy -H
diazine
Sulpha -H
dimethoxine
Sulphaphenazole -H
d. Extra-long-acting Sulphonamides
DRUG NAME R R’
Sulphalene -H
Sulphormethoxine -H
QUINOLONE ANTIBACTERIALS
Effective antibacterial quinolone derivatives
DRUG NAME X R6 R1 R7
Nalidixic acid -N -H -CH2CH3 -CH3
Norfloxacin -CH -F -CH2CH3
Ciprofloxacin -CH -F
Sparfloxacin -CF -F
Gatifloxacin -COCH3 -F
-LACTAM ANTIBIOTICS
CLASSIFICATION
DRUG NAME R
Penicillin G
(Benzyl penicillin)
Penicillin V
(Phenoxy methyl penicillin)
a. Penicillinase-susceptible Penicillins
DRUG NAME R
Penicillin G
CH2
Penicillin-V
O CH2
Phenethicillin CH3
O CH
Oxacillin
N
O CH3
Methcillin OCH3
OCH3
Ampicillin
CH
NH2
Amoxicillin
HO CH
NH2
Cloxacillin Cl
N
O CH3
b. Aminopenicillins
DRUG NAME R
Ampicillin
Amoxicillin
CLASSIFICATION OF CEPHALOSPORINS
1. First-generation Cephalosporins
DRUG NAME R1 R2 R3
Cephaloridine -H
Cephalothin -H
Cephapirin -H
Cephalexin -CH3 -H
Cephaloglycine -H
Cefadroxil -CH3 -H
HO CH
NH2
Cefradine -CH3 -H
Cefazolin -H
2. Second-generation Cephalosporins
DRUG NAME R1 R2 R3
Cefamandole -H
Cefoxitin -OCH3
Cefuroxime -H
Cefaclor -Cl -H
Cefonicid -H
3. Third-generation Cephalosporins
DRUG NAME R1 R2 R3
Ceftizoxime -H -H
Cefotaxime -H
Ceftazidime -H
Ceftriaxone -H
Cefmenoxime -H
4. Fourth-generation Cephalosporins
DRUG NAME R1 R2 R3
Cefepime -H
Cefpirome -H
TETRACYCLINE ANTIBIOTICS
CLASSIFICATION OF TETRACYCLINE
1. Natural tetracyclines
DRUG NAME R1 R2 R3
Tetracycline -H -CH3 -H
Chlortetracycline -Cl -CH3 -H
Oxytetracycline -H -CH3 -OH
Bromotetracycline -Br -CH3 -H
Dexamethyltetracycline -H -H -H
Dexamethylchlortetracycline -Cl -H -H
2. Semisynthetic tetracyclines
DRUG NAME R1 R2 R3 R4
Doxycycline -OH -H -CH3 -H
Minocycline -H -H -H -N-( CH3)2
Methacycline -OH =CH2 - -H
Meclocycline -OH =CH2 - -Cl
Sancycline -H -H -H -H
ANTILEPROTIC DRUGS
CLASSIFICATION
1. Sulphones
DRUG NAME STRUCTURE
Dapsone
Acedapsone
Solapsone sodium
Sulfoxone sodium
Gluco sulfone
sodium
Clofazimine
ANTIFUNGAL AGENTS
CLASSIFICATION
1. Antibiotics
DRUG NAME STRUCTURE
Amphotericin B
Griseofulvin
Nystatin
2. Azole antifungals
DRUG NAME STRUCTURE
Miconazole
Econazole
Ketoconazole
Clotrimazole
Fluconazole
Butoconazole
Bifonazole
CLASSIFICATION
1. Nucleoside RT inhibitors
a. Purine nucleosides and nucleotides
DRUG NAME STRUCTURE
Aciclovir
Ganciclovir
Valaciclovir
Vidarabine
Penciclovir
Famciclovir
Abacavir
b. Adamantane amines
DRUG NAME R
Amantadine -NH2
Rimantadine -CH-NH2CH3
ANTIMALARIALS
CLASSIFICATION
1. Cinchona alkaloids
DRUG NAME R
Quinine –OCH3 (–) isomer
Quinidine –OCH3(+) isomer
(used as antiarrhythmic)
Cinchonine –H (+) isomer
Cinchonidine –H (–) isomer
2. 7-Chloro-4-Amino Quinolines
DRUG NAME R R1
Chloroquine -CH(CH3)(CH2)2-N(C2H5) 2 -H
Amodiaquine -H
Hydroxychloroquine -H
3. 8-Amino Quinolines
DRUG NAME R
Primaquine -CH(CH3)-(CH2)3-NH2
Pamaquine -CH(CH3)-(CH2)3-N(C2H5)2
Pentaquine -(CH2)5-NH-CH(CH3)2
phosphate
Isopentaquine -CH(CH3)-(CH2)3-NH-CH(CH3)2
Quinocide HCl -(CH2)3-CH(CH3)-N(C2H5)2
4. Acridine derivatives (9-amino acridine derivatives)
DRUG NAME R
Quinacrine -CH(CH3)(CH2)3-N(C2H5)2
Acriquine -(CH2)4-N(C2H5)2
5. Antifolates
a. Biguanides
DRUG NAME R R’
Proguanil -Cl -H
Chloroproguanil -Cl -Cl
Bromoguanil -Br -H
Nitroguanil -NO2 -H
b. Diamino pyrimidines
DRUG NAME STRUCTURE
Pyrimethamine
Trimethoprim
DRUG NAME R
Sulphadoxine
Sulfadiazine N
N
Sulfamethoxazole
Sulphalene
7. Miscellaneous drugs
DRUG NAME STRUCTURE
Mefloquine
Dapsone
Artemether,
Artemotil
Artesunate
ANTIAMOEBIC AGENTS
CLASSIFICATION
1. Mixed Amoebicides
DRUG NAME STRUCTURE
Metronidazole
Tinidazole
Ornidazole
ANTHELMINTICS
1. Benzimidazoles
DRUG NAME R
Albendazole -S-CH2CH2CH3
Mebendazole -COC6H5
DIGESTER -64
ANTINEOPLASTIC AGENTS
CLASSIFICATION
1. Alkylating agents
a. Nitrogen mustards
DRUG NAME STRUCTURE
Mechlorethamine
Ifosfamide
Cyclophosphamide
Melphalan
Chlorambucil
b. Alkyl sulphonate
DRUG NAME STRUCTURE
Busulfan -CH3SO2O(CH2)4OSO2CH3
c. Nitrosoureas
DRUG NAME R
Carmustine -CH2CH2Cl
Lomustine
Semustine
Azathioprine
Trimetrexate
2. Antibiotics
a. Anthracyclines
DRUG NAME R1 R2 R3 R4
Daunorubicin -OCH3 -H -OH -H
Doxorubicin -OCH3 -H -OH -OH
Carminomycin -OH -H -OH -OH
Idarubicin -H -H -OH -H
Epirubicin -OCH3 -OH -H -OH
3. Plant products
a. Camptothecin Derivatives
DRUG NAME R R’
Camptothecin -H -H
Irinotecan -C2H5
PHARMACEUTICAL ANALYSIS
DIGESTER -65
TYPES OF ERROR
Error is the difference between the true result (accepted true result) and the measured
result.
Determinate Determinate errors are caused by faults in the analytical procedure
Error or the instruments used in the analysis.
Determinate errors are systematic errors.
Indeterminate Indeterminate errors are not constant or biased. They are random
Error in nature and are the cause of slight variations in results of replicate
samples made by the same analyst under the same conditions
Gross Error Gross errors differ from indeterminate and determinate errors.
They usually occur only occasionally, are often large, and may cause
a result to be either high or low. They are often the product of
human errors.
Absolute error Absolute error = Observed value – True or most probable value
Relative error Relative error = Absolute error /True value1000 per thousand
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ACCURACY AND PRECISION
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PRECISION MEASURE
deviation s=
N
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ELECTROMAGNETIC SPECTRUM
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CHARACTERISTICS OF WAVE
CHARACTERISTICS DESCRIPTION
Frequency Number of waves per unit time.
Expressed in cycle per second (cps)/Hertz/Fresnel
Wavelength Distance between two nearest parts of wave in the same phase
Expressed in nm/ A°/μm
Wave number Number of waves per unit length
Expressed in cm-1 or Kaiser
Max-Plank E = h.ν = h c/λ
Equation Where E = energy of photon ν = frequency
h = Plank constant (6.6 × 10–27 erg-sec)
c = velocity of light , λ = wavelength
DIGESTER -70
CLASSIFICATION OF SPECTROSCOPIC TECHNIQUES
DIGESTER -71
ANALYTICAL TECHNIQUE AND MOLECULAR CHANGE
DIGESTER -72
SPECTROSCOPY AND THEIR PRINCIPLE
DIGESTER -73
SPECTROSCOPIC TECHNIQUES AND THEIR SOURCE OF RADIATION SOUCE
DIGESTER -74
SPECTROSCOPIC TECHNIQUES AND THEIR SOLVENTS
TECHNIQUES SOLVENTS
UV spectroscopy Ethanol, Methanol, Cyclohexane, Ether, Water
IR spectroscopy Cyclohexane, Xylene, Chloroform, Acetone, CCl4
Mass spectroscopy Methanol, Acetonitrile
NMR spectroscopy CDCL3, CCl4, DMSO4 , CS2 , D2O
ESR Methyl cyclohexane, Isooctane, Toluene
DIGESTER -75
SPECTROSCOPIC TECHNIQUES AND THEIR DETECTOR
DIGESTER -76
ANALYTICAL TECHNIQUE AND THEIR REFRENCE STANDARD
DIGESTER -77
UV -VISIBLE SPECTROSCOPY
DIGESTER -78
WOODWARD FIESER RULE
H 3C CH3
Parent value for Homoannular diene =
253 nm Two alkyl substituents = 2 × 5 = 10 nm
Two alkyl substituents = 2 × 5 = 10 nm Three ring residue = 3 × 5 = 15 nm
Two ring residue = 2 × 5 = 10 nm One exocyclic double bond = 5 nm
Total calculated λmax = 253 + 10 + 10 = Total calculated λ max = 214 + 10 + 15 + 5 =
273 nm 244 nm
Parent 215 nm
R = H (Aldehyde) 207 nm
Values X = OH, OR (Acid or Ester) 193 nm
X = alkyl (Ketone) or six membered ring 215 nm
Homoannular conjugated diene +39 nm
Increment Exocyclic double bond +5 nm
Double bond extending conjugation + 30 nm
Br OH
parent value for acyl benzene (Ketone) Parent value for aromatic carboxylic acid
derivative= 246 nm derivative = 230 nm
Br atom at para position = 15 nm Br atom at two ortho position = 2 × 2 = 4 nm
Total calculated λmax = 246 + 15 = 261 nm OH group at para position = 25 nm
calculated λmax = 230 + 04 + 25 = 259 nm
DIGESTER -79
INFRA RED SPECTROSCOPY
TYPE OF VIBRATION
Stretching Bond length Symmetrical Two bends increase or decrease in
vibration altered. length symmetrically.
Asymmetrical Two bends increase or decrease in
length asymmetrically.
Bending Bond angle In plane bending Scissoring Bond angle decrease.
vibration altered. Rocking Bond angle maintained
but both bonds move
within the plane.
Out of plane Wagging Both atoms move to one
bending side of plane
Twisting One atom is above the
plane and the other is
below the plane.
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ABSORPTION PEAK WITH INTENSITY OF SOME SELECTED FUNCTIONAL GROUP
DIGESTER -81
NMR SPECTROSCOPY
DIGESTER -82
SOME COMPOUNDS WITH THEIR NMR SIGNAL
DIGESTER -83
ABSORPTION POSITION OF SOME PROTON
O 2 to 2.7
CH C OH
O 9 to 10
R C H
R NH2 1 to 5
DIGESTER -84
MASS SPECTROSCOPY
Molecular ion Ion formed from a molecule by removal of one electron of lowest
peak (parent ionization potential.
peak) Height of parent peak = Aromatic˃ Acylic ˃ Ketone ˃ Amine ˃ Ether ˃
Carboxylic acid
Base peak Most intense peak.
It is considered as 100%
Most abundant peak
Fragment ion The ions produced from the molecular ion by cleavage of bonds are
called fragment ions.
Metastable Mass spectrum of molecule shows sharp peaks at m/z integrals.
Ions
M+1 peak It occurs due to presence of C13 , H2 , N13
M+2 peak It occurs due to presence of O18 , S34 , l37 ,Br31
DIGESTER -85
TYPE OF MASS ANALYZER AND THEIR WORKING
DIGESTER -86
TYPE OF IONIZATION SOURCE AND THEIR PRINCIPLE
DIGESTER -87
MC-LAFFERTY REARRANGEMENT REACTION
Molecular ion
DIGESTER -88
COUPLING CONSTANT
DIGESTER -89
INFORMATION FROM PMR
DIGESTER -90
X RAY
DIGESTER -91
COMPARISON OF ATOMIC ABSORPTION AND FLAME EMISSION SPECTROSCOPY
DIGESTER -92
COMPARISON OF NEPHELOMETRY AND TURBIDIMETRY
NEPHELOMETRY TURBIDIMETRY
Nephelometry deals with measurement of Turbidimetry deals with measurement of
Intensity of scattered light Intensity of transmitted light
In Nephelometry, the intensity of the Turbidimetric measurements are made at
scattered light is measured, usually at right 180o from the incident light beam.
angles to the incident light beam.
Similar to Fluorimetry because both Similar to Colorimetry because both
measure scattered radiations but elastic measure transmitted radiations but light
scattering in Fluorimetry while non-elastic intensity decreased by scattering in
scatter in Nephelometry. Turbidimetry while by absorption in
Colorimetry.
Low concentrated suspension High concentrated suspension
DIGESTER -93
COMPARISON OF FLUORESCENCE AND PHOSPHORESCENCE
FLUORESCENCE PHOSPHORESCENCE
Life time Short, < 10-5 Sec Long, Several Seconds
Electron spin No Yes
Excited states Singlet Triplet
Quantum yield High Low
Temperature Most Temperature Proffered in Low Temperature
DIGESTER -94
APPLICATION OF ANALYTICAL TECHNIQUE
TECHNIQUE APPLICATION
Detection of impurities
UV VISIBLE Structure elucidation of organic compounds
Distinction between conjugated and non-conjugated system
Identification of functional group
Study of polymer
IR Structure determination
Distinction between inter and intramolecular H-bonding
Study of keto-enol Tautomerism
Identification of Geometrical isomer
Detection of H-bonding
NMR Detection of aromaticity
Distinction between cis-trans isomer
Detection of electronegative atom
Molecular mass determination
Identification of unknown compound
MASS Drug metabolism study
Clinical, toxicological and forensic application
Presence of isotopes
AAS It can be used to determine Al, Mg, Cu, Zn, Pub, and Ni.
Estimation of trace elements in biological fluids (blood).
ESR Study of free radical.
Determination of reaction rate and mechanism.
Study of inorganic compound.
X-ray Determination of crystalline structure
Determination of particle size
Property of metal
Raman Structure elucidation of molecules
spectroscopy Presence of Tautomerism
Study of ionic equilibrium and chemical bond
DIGESTER -95
ELECTRO ANALYTICAL TECHNIQUE
DIGESTER -96
TYPES OF ELECTRODE
DIGESTER -97
THERMO ANALYTICAL TECHNIQUE
DIGESTER -98
TYPE OF TITRATION
DIGESTER -99
INDICATORS FOR ACID BASE TITRATION
COLOUR ON COLOUR ON
INDICATOR PH RANGE OF
ACIDIC SIDE BASIC SIDE
Methyl Violet 0.0 to 1.6 Yellow Violet
Bromophenol Blue 3.0 to 4.6 Yellow Blue
Methyl orange 3.1 to 4.4 Red Yellow
Methyl red 4.4 to 6.2 Red Yellow
Phenol red 6.8 t0 8.4 Yellow Red
Cresol red 7.2 to 8.8 Yellow Red
Naphtholphthalein 7.3 to 8.7 Yellow Blue
phenolphthalein 8.3 to 10.0 Colourless Pink
Alizarin yellow 10.1 to 12.0 Yellow Red
DIGESTER -100
INDICATORS FOR COMPLEXOMETRIC TITRATION
DIGESTER -101
PRIMARY STANDARD
DIGESTER -102
POINTS IN COMPLEXOMETRIC TITRATION
DIGESTER -103
NON AQUEOUS TITRATION TYPES OF SOLVENT
DIGESTER -104
CHRMATOGRAPHIC TECHNIQUES
PRINCIPLES TECHNIQUES
Thin Layer Chromatography (TLC)
High Performance Liquid Chromatography (HPLC)
Adsorption Column Chromatography
Adsorption
Gas Solid Chromatography
Partition Paper Chromatography
Gas Liquid Chromatography
Ion-Exchange Ion Exchange Chromatography
Based on molecular size Size-Exclusion Chromatography
(Exclusion) Gel Filtration and Gel-Permeation
Chromatography (GPC)
Analyte and ligand interaction Affinity Chromatography
is utilized for the separation.
DIGESTER -105
CLASSIFICATION OF CHROMATOGRPHIC SEPARATIONS
DIGESTER -106
NORMAL PHASE V/S REVERSE PHASE
DIGESTER -107
TYPE AND THEIR STATIONARY AND MOBILE PHASE
DIGESTER -108
VISUALIZING AGENT
DIGESTER -109
TYPE OF STATIONARY PHASE
DIGESTER -110
PURE CELLULOSE PAPERS (WHATMAN PAPERS)
These types of papers are prepared from cotton linters selected to be especially low in
organic and inorganic impurities and uniform in physical characteristics.
Components Percentage
α Cellulose 98-99
β Cellulose 0.3-1.0
Pentosans 0.4-0.8
Ether soluble matter 0.015-0.03
Ammonia 0.001-0.06
Organic nitrogen <0.01
Inorganic material 0.008-0.06
Mostly used whatmann chromatographic filter papers are
Whatmann 31ET Used for separation of substances having
sufficiently wide apart Rf
Whatmann 3MM Generally used for preparative purposes
Whatmann 20 Slow paper
Whatmann 540-42 Acid washed paper
DIGESTER -111
COMPARISON ON COLUMN, HPLC AND GAS CHROMATOGRAPHY
DIGESTER -112
COMPARISON BETWEEN TLC AND HPTLC
DIGESTER -113
DETECTORS IN HPLC
DETECTORS DESCREPTION
Uv-visible spectroscopic Measures the ability of solutes to absorb light at a
detectors particular wavelength(s) in the ultraviolet (uv) or visible
(vis) wavelength range.
Refractive index detector Measures the molecule’s ability to deflect light in a flowing
mobile phase in a flow cell relative to a static mobile phase
contained in a reference cell.
Photo diode array detector Monitoring absorbance of solutes at several different
wavelengths
Fluorescence detectors Sensitivity depends on the fluorescence properties of the
components in the elute
Electrical conductivity Conductivity detectors measures electronic resistance and
detector measured value is directly proportional to the
concentration of ions present in the solution.
DIGESTER -114
DETECTORS IN GAS CHROMATOGRAPHY
SUPPORT
DETECTORS TYPE SELECTIVITY DETECTABILITY
GASES
Flame ionization Mass flow Hydrogen Most organic 100pg
(FID) and air compounds
DIGESTER -115
IMPORTANT POINT IN GAS CHROMATOGRAPHY
Parameter
Retention time Difference between point of injection and
appearance of peak maxima.
Retention volume Volume of carrier gas required to elute
50 % of component from the column.
HETP (Height equivalent to If HETP is less – column is more efficient
theoretical plate) If HETP is more – Column is less efficient
Number of theoretical plate If number of theoretical plate is high than column is
highly efficient
If number of theoretical plate is less than column is
less efficient
B
Van Deemter Equation H = A + + Cμ
μ
Where, H = Height of theoretical plate,
= Average liner velocity of mobile phase
A = Eddy diffusion
B = Longitudinal or ordinary diffusion term
C = Non equilibrium or resistance to mass transfer
Van Deemeter plots • The term ‘A’ is independent of flow of
the mobile phase
12
• The term B/u decrease drastically in
10
the beginning with increase in the
HETP-AB/v+Cv
08 flow rate of mobile phase. Increase in
Cv the flow rate beyond particulars
HETP (mm)
06
value , leads to slow decrease value
04 in the value of B/u
B/v
02
• The term Cu increase with increase
A in the rate
00
0 10 20 30 40 50 60 70 80
DIGESTER -116
CHIRAL CHROMATOGRAPHY
DIGESTER -117
SIZE EXCLUSION CHROMATOGRAPHY
Size Exclusion Chromatography - Larger molecule unable to fit into pores are eluted
first while small molecules enters into pores and are eluted later.
Gel Permeation Stationary phase used are semi-rigid or rigid gel.
Example: Cross-linked polystyrene, Alkylated Dextran,Controlled
porosity Glass beads
Gel Filtration- Stationary phase used are cross-linked carbohydrates.
Example: Sephadex (Cross linked dextran), Agarose (Sepharose),
Polyacrylamide (Bio-gel)
DIGESTER -118
ION EXCHANGE RESINS
DIGESTER -119
IMPORTANT POINTS TO REMEMBER
Edge effect The solvent front in the middle of TLC plates moves faster than that
edge. Therefore the spot are distorted and not regular.
Preparation of (a) Pouring
thin layer plate (b) Spraying
(c) Dipping
(d) Spreding (Best technique) Spreder is 0.25 mm
Retention factor Distance travelled by solute/ Distance travelled by solvent.
(Rf ) Rf Value cannot be greater than 1.
Mobile phase in CCl4 , Cyclohexane, Ether, Acetone, Benzene, Toluene, Chloroform,
TLC Alcohol
Hydrophilic Isopropanol : Ammonia : Water (9:1:2)
Mobile phase in n-Butanol : glacial acetic acid : Water (4:1:5)
paper Methanol : Water (3:1)
chromatography Hydrophobic Kerosene : 70% Isopropanol
Dimethyl ether : Cyclohexane
Elution technique (a) Isocratic elution – Single solvent run through column.
(b) Gradient elution – Solvents with increasing polarity
Detection of (a) Uv-visible detector
compound in (b) Fluorescence detector
column (c) Flame ionization detector
chromatography (d) Refractive index detector
Pump used in (a) Pneumatic pump
HPLC (b) Reciprocating pump
(c) Displacement pump
DIGESTER -120
NON AQUEOUS TITRATIONS
DIGESTER -121
COMPLEXOMETRIC TIRATIONS
DIGESTER -122
ACID BASE TITRATIONS
DIGESTER -123
REDOX TITRATIONS
DIGESTER -124
NITRITE TITRATIONS
DIGESTER -125
POTENTIOMETRIC TITRATIONS
DIGESTER -126
ARGENTOMETRIC TITRATIONS
DIGESTER -127
IODOMETRY & IODIMETY TITRATIONS
DIGESTER -128
DRUGS ANALYZED BY GRAVIMETRIC ANALYSIS
DIGESTER -129
DRUGS ANALYZED BY HPLC
DIGESTER -130
MICROBIOLOGICAL ASSAYS
DIGESTER -131
SPECTROMETRY
DIGESTER -132
MISCELLANEOUS
NAME OF THE DRUG TITRANT
Thiomersal 0.1 M ammonium thiocyanate
Sodium stilbogluconate 0.05 M ferric ammonium SO42-
Sodium lauryl sulphate 0.04 Benzethomium Cl-
Phenyl mercuric acetale 0.1 M amm thiocyanate
Isoniazid 0.0167 M KBrO3
Desferrioxamine mesylate 0.1 M ferric ammonium sulphate
Cyclophosphamide 1.1 M AgNO3
Cloxacillin sodium 1.2 M mercuric NO -3
Cetrimide 0.05 M KIO3
Captopril 0.025 M KIO3
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