Oxyacids of Nitrogen

Nitrous acid, Nitric acid, Hyponitrous acid Oxyacids of Nitrogen: a. Nitrous acid - HNO2 b. Nitric acid - HNO3 c. Hyponitrous acid - H2N2O4 a. Nitrous Acid: HNO2 Preparation: i. By dissolving N2O3 in water N2O3 + H2O 2HNO2

By action of acid on metallic nitrites NaNO2 + HCl ii. NaCl + HNO2

By oxidation of NH3 HNO2 + 4H2O

NH3 + 3H2O2 Properties: iii. iv.

It is a weak acid and does not exist in free state. 2HNO2 3HNO2 NO + NO2 + H2O (Vapour phase) HNO3 + H2O + 2NO (Aqueous solution)

v.

Oxidising property 2HNO2 H2S + [O] 2NO + H2O + [O] H2O + S H2SO4 Fe2(SO4)3 + H2O SnCl4 + H2O 2KOH + l2

SO2 + H2O + [O]

2FeSO4 + H2SO4 + [O] SnCl2 + 2HCl + [O] 2Kl + H2O + [O] vi. Reducing property HNO2 + [O] HNO3

K2Cr2O7 + 4H2SO4 + 3HNO2 2KmnO4 + 3H2SO4 + 5HNO2 Br2 + H2O + HNO2 vii. b. H2NCONH2 + 2HNO2

K2SO4 + Cr2(SO4)3 + 3HNO3 + 4H2O K2SO4 + 2MnSO4 + 3H2O + 5HNO3

HNO3 + 2HBr CO2 + 2N2 + 3H2O

Nitric acid: HNO3 Preparation: i. By heating sodium nitrate with conc. sulphuric acid. 2NaNO3 + H2SO4 2HNO3 + Na2SO4

ii.

Birkeland - Eyde Process N2 + O2 2NO + O2 3NO2 + H2O 2NO 2NO2 2HNO3 + NO

iii.

Ostwald's Process 4NH3 + 5O2 2NO + O2 3NO2 + H2O 2NO2 2HNO3 + NO 4NO + 6H2O

Structure: Properties: Anhydrous acid is a color less fuming liquid. It usually acquires yellow color due to its decomposition by sunlight into NO2. 4HNO3 C12H22O11 + 18[O] Reaction with Metals iv. v. vi. vii. Mg + 2HNO3 (dil) 3Mg + 8HNO3 (conc.) Mg(NO3)2 + H2 3Mg (NO3)2 + 4H2O + 2NO 3Cu(NO3)2 + 4H2O + 2NO Cu(NO3)2 + 2H2O + 2NO2 4NO2 + 2H2O + O2 6H2C2O4 + 5H2O

3Cu + 8HNO3 (cold and dilute) Cu + 4HNO3 (cold and conc.) [Ag, Pb and Bi also react as Cu]

viii. ix. x.

6Hg + 6HNO3 (dilute) Hg + 4HNO3 (conc.) 4Zn + 10HNO3 (very dilute) 4Zn + 10HNO3 (dil) 4Fe + 10HNO3 (very dilute) 4Sn + 10HNO3 (dil.)

3Hg2(NO3)2 + 4H2O + 2NO Hg(NO3)2 + 2H2O + 2NO2

4Zn(NO3)2 + NH4NO3 + 3H2O 4Zn(NO3)2 + N2O + 5H2O 4Fe(NO3)2 + NH4NO3 + 3H2O 4Sn(NO3)2 + NH4NO3 + 3H2O

xi. xii.

xiii.

xiv.

Fe + 6HNO3 (conc.)

Fe(NO3)3 + 3NO2 + 3H2O

Sn + 4HNO3 H2SnO3 + H2O + 4NO2 (conc.) Reaction with non-metals, metalloids and compounds xvi. C + 4HNO3 CO2 + 4NO2 + 2H2O xvii. xviii. xix. xx. xxi. xxii. xxiii. xxiv. S + 6HNO3 l2 + 10HNO3 B + 3HNO3 As + 5HNO3 Sb + 5HNO3 SO2 + 2HNO3 2Hl + 2HNO3 H2SO4 + 6NO2 + 2H2O 2HIO3 + 10NO2 + 2H2O H3BO3 + 3NO2 H3AsO4 + 5NO2 + H2O H3SbO4 + H2O + 5NO2 H2SO4 + 2NO + O2 2NO2 + 3l2 + 2H2O 3Fe2(SO4)3 + 2NO + 4H2O

xv.

6FeSO4 + 3H2SO4 + 2HNO3

Oxyacids of Phosphorus
Hypophosphorus acid, Phosphorus acid, Orthophosphoric acid, Metaphosphoric acid, Hypophosphoric acid, Pyrophosphoric acid Oxyacids of Phosphorus: i. Hypophosphorus acid - H3PO2 ii. Phosphorus acid - H3PO3 iii. Orthophosphoric acid - H3PO4 iv. Metaphosphoric acid - HPO3 v. Hypophosphoric acid - H4P2O6 vi. Pyrophosphoric acid - H4P2O7 a. Phosphorus acid - Orthophosphorus acid - H3PO3 Preparation: i. Phosphorus trichloride when reacted with water gives phosphorus acid. PCl3 + 3H2O ii. H3PO3 + 3HCl

Phosphorus trioxide (P4O6) on reaction with water gives phosphorus acid. 4H3PO3

P4O6 + 6H2O Properties: iii.

Phosphorus acid disproportionates to give PH3 and H3PO4. 4H3PO3 3H3PO4 + PH3

iv.

Phosphorus acid is a disbasic acid. H3PO3 H2PO3

-

H + H2PO3 H + HPO3
+

-2

v.

Phosphorus acid on reaction with phosphorus pentachloride gives phosphorus oxychloride. H3PO3 + 3PCl5 PCl3 + 3POCl3 + 3HCl

b.

Orthophosphoric Acid - H3PO4 Preparation: i. Phosphorus when treated with nitric acid gives H3PO4. P4 + 20HNO3 ii. iii. iv. 4H3PO4 + 20NO2 + 4H2O

Calcium phosphate on reaction with sulphuric acid gives H3PO4 Ca3(PO4)2 + 3H2SO4 2H3PO4 + 3CaSO4

Phosphorus on reaction with excess of oxygen gives oxide which on further reaction with hot water gives orthophosphoric acid.

P4 + 5O2 Properties: v.

P4O10

4H3PO4

Orthophosphoric acid is a tribasic acid and forms series of salts. Primary phosphate - NaH2PO4 Secondary phosphate - Na2HPO4 Tertiary phosphate - Na3PO4

vi. vii.

2H3PO4 H3PO4

H4P2O7 + H2O (HPO3)n metaphosphoric acid + H2O

viii.

H3PO4 on reaction with BaCl2 and AgNO3 gives precipitate. 3BaCl2 + 2H3PO4 3AgNO3 + H3PO4 Ba3(PO4)2 + White ppt Ag3PO4 (yellow) 6HCl

+ 3HNO3

ix.

On heating H3PO4 in presence of nitric acid with ammonium molybdate, a canary yellow precipitate of 3ammonium phosphomolybdate is formed. (test of Po4 ion) H3PO4 + 21HNO3 + 12(NH4)2MnO4 (NH4)3PO4 . 12MoO3 + 21NH4NO3 + 12H2O

Phosphorus (P)
Phosphorus is second number of the "Nitrogen family" with group number 15 and period number 3 Phosphorus (P) Phosphorus Atomic Number : 15 Phosphorus Atomic Mass : 31 2 3 Phosphorus Electronic Configuration : [Ne]3s 3p Phosphorus Group Number : 15 (V A) Phosphorus Period Number :3 Phosphorus Relative Abundance : 11 Phosphorus is second number of the "Nitrogen family" with group number 15 and period number 3. Phosphorus is mostly used in match industry. Occurence of Phosphorus phosphorus being an active element, it is not found free in nature. Phosphorus occurs as phosphate in the rocks and in the soil. The important minerals of phosphorus are

i. ii.

Phosphorite - Ca3(PO4)2 Flourapatite - 3Ca3(PO4)2.CaF2

iii. Chlorapatite - 3Ca3(PO4)2.CaCl2 Other than this, phosphorus is essential constituent of bones, teeth etc. Bone ash contains about 80% of calcium phosphate. Properties of Phosphorus: 1. Phosphorus is a non-metal. 2. 3. Phosphorus though a solid can also convert easily into vapour state. The atomic radius of phosphorus (1.10 ) is higher than nitrogen (0.74 ) and lower than the rest of the family members The first ionisation energy of phosphoprus (253.9 kcal) is lower than nitrogen (336) due to its own bigger size than nitrogen and higher than the rest of the family members Electronegativity of phosphorus (2.1) is lower than the nitrogen but higher than the rest of the members. Phosphorus can exist in discrete tetratomic tetrahedral molecule i.e. P4. Phosphorus can exists in number of allotropic forms like i. ii. iii. iv. v. vi. 8. White or yellow phosphorus Red phosphorus Scarlet phosphorus - Black phosphorus - Black phosphorus Violet phosphorus

4.

5. 6. 7.

Phosphorus can show oxidation state of -3 to +5

Ammonia - HNO3
Ammonia Preparation and Ammonia Properties Ammonia: HNO3 Preparation: i. From Ammonium Salts 2NH4Cl + Ca(OH)2 ii. From nitrides Mg3N2 + 6H2O iii. Haber's Process 3Mg(OH)2 + 2NH3 CaCl2 + 2NH3 + 2H2O

N2 + 3H2 iv. Cyanamide Process CaC2 + N2

2NH3

CaCN2 + C

CaCN2 + 3H2O v. Serpeck's Process Al2O3 + 3C + N2 AlN + 3H2O Properties: i. 4NH3 + 3O2 4NH3 + 5O2 ii. iii. iv. v. vi. vii. 8NH3 + 3Cl2 NH3 + 3Cl2 2Na + 2NH3 Ag+ + 2NH3 Cu
2+

CaCO3 + 2NH3

2AIN + 3CO Al(OH)3 + NH3

2N2 + 6H2O 4NO + 6H2O N2 + 6NH4Cl NCl3 + 3HCl 2NaNH2 + H2 [Ag(NH3)2]

+

+ 4NH3

[Cu(NH3) 4]

+2

2K2Hgl4 + NH3 + 3KOH

H2N.HgO. (Brown ppt)

Hgl + 7Kl + 2H2O

HgCl2 + 2Kl Hgl2 + 2Kl

2KCl + Hgl2 K2Hgl4 Nessler's Reagent

Isolation of Sulphur
Sulphur can be isolated from Frasch Process Isolation of Sulphur Sulphur can be isolated from 1. Frasch Process 2. As by product from i. ii. Alkali waste of Le Blanc's process Spent oxides of gas works

1.

iii. Iron pyrites Frasch Process: i. ii. iii. Three concentric pipes are sunk deep into under ground. Super heated water at around 170 C forced into pipe where sulphur is melted. Compressed air from inner pipe allows sulphur as liquid to come on the surface which further solidified as 99% pure sulphur.

2.

As By product from: i. Alkali waste CaS + H2O + CO2 CaCO3 + H2S

2H2S + O2 ii.

2H2O + S

Spent oxides of Coal gas 2Fe2S3 + 3O2 2Fe2O3 + 6S

iii.

Iron pyrites 3FeS2 3FeS2 + 5O2 FeS + CO2 Fe3S4 + 2S FeO4 + 3SO2 + 3S FeO + CO + S

Sulphur (S)
Sulphur is the sixteenth most abundant element on earth crust Sulphur (S)

Sulphur Atomic Number : 16 Sulphur Atomic Mass : 32 Sulphur Electronic Configuration : [Ne]3s23p4 Sulphur Group Number : 16 (VlA) Sulphur Period Number :3 Sulphur Relative Abundance : 16
1. Sulphur is the sixteenth most abundant element on earth crust. It constitutes 0.034% by weight of the earth's crust. Sulphur is the p-block element and is the second member of "Chalcogen family" after oxygen. The group number of sulphur is 16 and period number is 3.

2. 3.

4. Sulphur is the mostly used in manufacture of SO2, H2SO4, fire works, medicine. Properties of Sulphur 3 1. Sulphur exist as staggered 8-atom ring S8 molecule. Each sulphur atom is in sp -hybridised state. 2. 3. Sulphur is a non metal. The atomic radius, atomic volume and density of sulphur is higher than oxygen but lower than rest of the family members. Electronegativity of sulphur is lower than that of oxygen but higher than rest of the family members. Melting point and boiling point of sulphur are higher than the oxygen due to its bigger size than oxygen but lower than rest of the chalcogen members Catenation property is more pronounced in sulphur as compared to rest of the family members. Sulphur can exhibit the range of -2 to +6 oxidation state due to availability of vacant d-orbital. Sulphur reacts with acid where it itself gets oxidised. S + 2H2SO4 (Conc.) S + 6HNO3 (Conc.) 4S + 6NaOH 9. 3SO2 + 2H2O H2SO4 + 6NO2 + 2H2O

4. 5.

6. 7. 8.

2Na2S + Na2S2O3 + 3H2O

Sulphur undergoes reduction in presence of hydrogen.

H2 + S 10. Cl2 + 2S 11. C + 2S 12. 2As + 3S

H2S S2Cl2 CS2 As2S3 2H2S + SO2

13. 2H2O (steam) + 3S (boiling)

Oxygen (O)
Oxygen is 46.6% by weight in the earth's crust Oxygen (O) Oxygen Atomic Number :8 Oxygen Atomic Mass : 16 2 4 Oxygen Electronic Configuration : [He]2s 2p Oxygen Group Number : 16 (VlA) Oxygen Period Number :2 Oxygen Relative Abundance :1 Oxygen is a most abundant element on earth. Oxygen is 46.6% by weight in the earth's crust. In atmosphere, oxygen is present 21% by volume. Oxygen is the first member of "Chalcogen family". Properties of Oxygen 1. Oxygen is a gas while other family members are solids. 2. 3. Oxygen molecule is diatomic while the other family members exist in polyatomic ring form. Oxygen is non-metal whereas metallic character increases down the group. The non-metallic character of oxygen is due to its high value of electronegativity. Oxygen molecule is highly stable due to higher bond energy of multiple bonds. The atomic radius; atomic volume and density of oxygen are lower than rest of the family members. The ionisation energies of oxygen due to its smaller size is very high compared to that of the other family members. Oxygen is highly electronegative member of its family. It is the second most electronegative element after fluorine (4). The melting point -219 C and boiling point -183 C of oxygen are lower than that of other family members. Oxygen mostly exhibits oxidation state of -2. Oxygen do not have d-orbital hence can't show +4 +6 oxidation state while other family members can.

4. 5. 6.

7.

8. 9.

10. Oxygen reacts with metal to form basic oxide. K + O2 2Mg + O2 KO2 (Potassium super oxide) 2MgO (Magnesium oxide)

11. It reacts with non-metal to form acidic oxide. C + O2 S + O2 4P + 5O2 CO2 SO2 P4O10

12. It reacts with some metals to form amphoteric oxides (acidic as well as basic) 4Al + 3O2 2Be + O2 2Zn + O2 2Al2O3 2BeO 2ZnO

13. It reacts-with some non-metals to form neural oxide C+ O2 CO

N2 + O2

2NO

14. It acts as oxidising agent. It is trequired for combusion. It is used for roasting of sulphide ores. CS2 + 3O2 2ZnS + 3O2 CO2 + 2SO2 2ZnO + 2SO2

Isolation of Oxygen & Compounds of Oxygen

Oxygen is pale blue gas having a strong characteristic smell. It is neutral to litmus Isolation of Oxygen: In laboratory it is prepared by heating KMnO4 or KClO3 in presence of MnO2. 2KClO3 (s) 2KMnO4 2KCl + 3O2 K2MnO4 + MnO2 + O2

It can also be prepared by reaction of H2O on Na2O2 2Na2O2 + 2H2O(l) 4NaOH + O2

On large scale it is prepared by fractional distillation of liquid air. Pure oxygen is prepared by electrolysis of water. Oxygen is also manufactured by i. Brine's Process: BaO is heated at 500 C in air. It is converted into BaO2, which on further increase in temperature upto 800 C decomposes to give oxygen. ii. By electrolysis of water: Electrolysis is done by using alkaline water using nickel or platinum electrode which gives hydrogen and oxygen.

Compounds of Oxygen: Ozone - O3: Preparation: It is prepared by subjecting pure oxygen to silent electric discharge 3O2 2O3 H = + 284.5 kJ mole
-1

Properties: It is pale blue gas having a strong characteristic smell. It is neutral to litmus.

1. 2. 3. 4. 5. 6. 7. 8.

O3 H2S + O 2Ag + O 2Hg + [O]

O2 + O H2O + S Ag2O Hg2O 2HIO3 H2SO4 2H3PO4

l2 + H2O + 5[O] S + H2O + 3[O] 2P + 3H2O + 5[O]

It is better oxidising agent as compared to H2O2. H2O2 + O3 BaO2 + O3 H2O + 2O2 BaO + 2O2

It is condensed to blue liquid (Boiling point 161.2 K) It condenses to a violet-black solid (m. pt 80.6 K), Ozone has angular structure. Both the O-O bonds are of equal bond length due to resonance.

Test of Ozone In presence of O3, mercury loses its meniscus and starts sticking to glass. This is known as telling of mercury. It does not release iodine from Kl in presence of FeSO4. In this way it is different from H2O2.

Hydrogen Bonding
Type of H-Bonding, Modern Concept of Covalent Bonding In formed when H-atom of one molecules combines with the electronegative atom of other molecule by dipoledipole interaction (N, O, F and electron cloud exhibit H-bonding) Type of H-Bonding 1. Intermolecular H-Bonding: Formed between H and electronegative element of two different or same molecule

It increase the boiling point, solubility in water and viscosity. 2. Intramolecular hydrogen bonding: Formed between H and electronegative element present in the same molecule.

3. It increases volatile nature, decreases boiling point and solubility. Modern Concept of Covalent Bonding Valence bond theory: Formed by overlapping of half filled atomic orbitals. Main Characters: 1. Greater the overlapping higher the strength of the bond. 2. Electron density is maximum between the two atom where overlapping takes place. 3. p-orbitals will form stronger bond than s-orbital. 4. When overlapping of orbital takes place along their axis the bond formed is (sigma) bond. 5. When overlapping of orbital takes place laterally or sidewise the bond formed is bond.

Hybridization
Hypothetical concept of hybridization is introduced The VBT theory fails to explain shape of the molecules. So hypothetical concept of hybridization is introduced. According to this any number of atomic orbitals of the atom which differ in energy with each other to form new orbital called hybrid orbital. It only includes bond (along with lone pair).

V = No. of valence shell electrons in ground state to central atom. G = No. of monovalent atom attached to central atom. a = Magnitude of charge on anion. c = Magnitude of charge on cation. H value 2 3 4 4 5 6 7 Hybridization sp 2 sp 3 sp 2 dsp 3 3 sp d or dsp 2 2 2 3 sp d or d sp 3 3 3 3 sp d or d sp Shape of molecule Linear Plane triangular Tetrahedral Square planar Trigonal bipyramidal Octahedral bipyramidal Pentagonal bipyramidal Bond angle 180 120 109 28 90 120 & 90 90 72 & 90

Chemical Bonding
Cause of Chemical Bonding & Type of Bonding Chemical Bond is defined as the force that acts between two or more atoms to hold them together as a stable molecule. Cause of Chemical Bonding 1. To decrease potential energy 2. To complete octet or duplet Type of Bonding 1. Electrovalent or Ionic Bonding: Formed by the transfer of one or more electrons from one atom to another atom. Conditions: large cation + small anion + low charge on ions (Also called Fajan's rule)

Characteristics of ionic compounds i. ii. iii. iv. 2. Crystalline in nature Have high melting and boiling point Do not conduct electricity in solid state but conduct electricity in molten state and in aq. medium. Soluble in polar solvent like water.

Covalent Bond: Formed by mutual sharing of electrons between two or more atoms, it may be single, double or triple bond. Polar and non-polar Covalent bonds XA - XB XA - XB 0 the bond is polar covalent bond. 0 the bond is non-polar covalent bond.

Characteristics of Covalent Compounds i. ii. iii. iv. Generally exist as gases or liquids under normal condition of temperature and pressure. Bad conductor of electricity. Insoluble in polar solvent like water but soluble in non-polar solvent. Generally low melting and boiling temperature than ionic compound.

Co-ordinate or Dative Compound Formed when shared pair of electrons, is contributed by one of the two atoms. The bond is represented by an arrow Characteristics of Co-ordinate Compound Have higher melting and boiling points than purely covalent compounds. They are sparingly soluble in polar solvent like water but readily soluble in non-polar solvents. Molecular Orbital Theory According to this theory all the atomic orbitals of the atom participating in molecule formation get disturbed when the concerned nuclei comes closer. They all get mixed up to give rise to an equivalent number of new orbitals that belong to the molecules. Linear Combination of Atomic Orbitals (LCAO) 1. Overlapping of atomic orbitals is the overlapping of waves. 2. In phase overlapping results in Bonding molecular orbital and out of phase over lapping results in anti bonding molecular orbital. Energy levels of these orbitals is increasing energy sequence is 1s < * 1s < Ne2 molecules 2s < * 2s < 2pz < =E 2px = 2py < * 2px = * 2py < * 2pz for O2, F2 and

3.

Note: For B2, C2, N2 molecules, E Bond Order

2px

2py

< E 2pz

Higher the bond order smaller the bond length

B. Order Stability (Molecule) < 0 Unstable and does not exist = 0 Does not exist 0.5 Exist but unstable 1 A stable molecule with single bond 2 A stable molecule with double bond 3 A stable molecule with triple bond

Fractional bond order indicates paramagnetic nature of molecule. Dipole Moment: Is defined as the product of the magnitude of charge (q) on the atom and the distance between the atom (d). =qxd Its unit is debye (D) 1D = 10
-18

esu-cm

e.g., CO2, CS2, CH4, BF3, XeF4 Polar molecule have non-zero dipole moment e.g., NH3, PCl3, H2O, SF4, XeF6 Resultant Dipole Moment

Periodic Table and Periodicity

There are 7 periods (Horizontal rows) and 18 groups (vertical columns) Periodic Table and Periodicity History 1. Doebereiner discovered group of three elements having similar properties and called them triads. The atomic mass of the central element was the arithmetic mean of the atomic mass of other two elements e.g., Li, Na, K 2. Newlands law of Octaves: He arranged elements in their increasing atomic weights of the elements and properties of first element was found to be similar to that of eighth element. Lother Meyer plotted graph between atomic volumes and atomic weight of the elements. Elements with similar properties had the similar position on the curve. Mendeleev stated that "Physical and chemical properties of elements are periodic function of their atomic weight". Only 57 elements were known at that time. Modern periodic Law: Moseley stated that physical and chemical properties of elements are periodic function of their atomic number. Bohr given long form of periodic table. Long Form of Periodic Table There are 7 periods (Horizontal rows) and 18 groups (vertical columns)

3.

4.

5.

6.

1st period : Very short period (only two elements H11 and He42) 2nd period : Short period (8 elements 3Li - 10Ne) 3rd period : Short period (8 elements 11Na - 18Ar) 4th period : Long period (18 elements 19K - 36Kr) 5th period : Long period (18 elements 37Rb - 54Xe) 6th period : Longest period (32 elements 55Cs - 86Rn) 7th period : Incomplete period (26 elements 87Fr - 112Uub)
In the long form of periodic table elements can also be classified as: a. s-Block Elements: Elements of group 1 and 2 having general electronic configuration ns 1 ns - Alkali metal (Li to Cs) Fr is radioactive 2 ns - Alkaline earth metal (Be to Ba)
1-2

b.

p-Block Elements: Elements of group 13, 14, 15, 16, 17 and 18 having electronic configuration ns np . Elements of group 18 are also called as inert gases. d-Block Elements: Also called as transition element having electronic configuration (n-1)d 2 (except 46Pd)
1-10

1-6

c.

ns

1-

f-Block Elements: Also called as inner transition element, having electronic configuration (n-2) f 1 2 ns . It includes 4f or lanthanoid (Ce to Lu) 5f or actinoid (Th to Lr) The elements are broadly divided into three types i. ii. iii.

d.

1-14

(n-1) d

0-

Metals comprise more than 78% of the known elements. Non-metals are less than twenty (C, N, P, O, S, Se, H, F, Cl, Br, l, He, Ne, Ar, Kr, Ar, Kr, Xe and Rn) Elements which lie in the border line between metals and non metals are called metalloids. (B, Si, Ge, As, Sb, Te, Po, At) Periodicity is observed in a number of properties which are directly or indirectly or linked with electronic configuration. Effective nuclear charge increase across each period and remain almost constant down the group. Zeff = Z where 'Z' is nuclear charge is shielding effect

Atomic radii (is generally taken as covalent radii)

n = Principal quantum number of outer orbit It generally decreasing across a period and increases down the group. It is of three types i. Covalent radius ii. Metallic radius iii. van der Waal radius Order: van der waal's radius > Metallic radius > Covalent radius Ionic Radii

Cationic radii is smaller than anionic radii for some atom. Cationic radii < Atomic < anionic radii Elements of 2 and 3 transition series belonging to same group are similar in size and properties due to lanthanide contraction. Ionisation Enthalpy is the energy required to remove the most loosely held electron from the gaseous isolated atom
nd rd

Ionisation enthalpy generally decreases down the group. Successive I.E of an atom have higher values. IE1 < IE2 < IE3 .......

Electron gain enthalpy is the enthalpy change taking place when an electron is added to an isolated gaseous atom of the element. The I electron gain enthalpy of most of the elements is negative as the process is exothermic. Electron gain enthalpy becomes more negative from left to right in a period and less negative from the top to bottom in a group. Successive electron gain enthalpies are always positive. Electro negativity is the tendency of an atom to attract the shared pair of electron towards itself in a molecule. 1. Electro negativity increases across the period and decreases down the groups. 2. Metals have low electro negativity and non-metals have high electro negativities.
st

3. Application of Electro negativity 2 1. Percentage ionicity = 16 (XA ~ XB) + 3.5 (XA ~ XB) 2. For oxides Xo ~ X element higher the difference more basic the oxide

Classifications of Organic Reactions - Organic Chemistry

On the basis of the products of the reactions; organic reactions are classified as... Classifications of Organic Reactions Organic Reactions have been broadly classified into two types on the basis of bond cleavage, i. free radical reaction (hemolytic cleavage) ii. ionic reactions (heterolysis cleavage) On the basis of the products of the reactions; organic reactions are classified as,

a.

Addition Reactions

b.

Substitution Reactions

c. d.

Elimination Reactions Rearrangement

Addition Reactions - Organic Chemistry

A reaction in which the substrate and the reagent add up to form a product... Addition Reactions A reaction in which the substrate and the reagent add up to form a product is called addition reaction. Compounds having multiple bonds such as, etc. undergo addition reactions. I. Electrophilic Addition Reaction: This is a characteristic reaction of unsaturated hydrocarbons,

On bromination trans-2- butene gives meso-dibromide and cis-2- butene gives recemic (dl) modification. Thus, addition of Br2to the -bond is the trans (or anti) addition. The reaction is, therefore, stereoselective. The relative rates of addition of some substituted alkenes are as;

Electron withdrawing groups will have reverse effect. Markownikov Rule: In case of addition of unsymmetrical reagents (i.e., HX) to unsymmetrical alkenes, the negative part of the addendum is added to that doubly bonded carbon which is less hydrogenated. In the presence of organic peroxide or under conditions of radical formation, anti-Markonikov addition results. The peroxide converts into a free radical which generates a bromine-free radical from HBr. Free radical addition of HF, Hl or HCl is energetically not favorable. Addition of Br2 to Conjugated dienes

The 1,2 product predominates at lower temperature and 1,4-product predominates at higher temperature. This may be due to stabilization of 1, 4-product by hyper conjugation. II. Addition to Alkynes: Alkenes are less reactive than alkenes because the -electrons are more tightly held by the carbons. Electrophilic addition to alkynes resembles those of alkenes.

In the hydration of alkynes with sulphuric acid, the catalyst (such as mercuric salt) is necessary.

In case of aromatic compounds (e.g., benzene) addition reaction is energetically not favorable due to loss of resonance energy. III. Nucleophilic Addition Reaction: Electron-releasing groups conjugated to carbon-carbon multiple bonds favor electrophilic addition while electron withdrawing groups conjugated to carbon-carbon multiple bonds favor nucleophilic addition.

Polar functional groups, e.g., addition.

etc., also undergo nucleophilic

Substitution Reactions - Organic Chemistry

A reaction in which one group or atom is replaced by another... Substitution Reactions A reaction in which one group or atom is replaced by another is called a substitution reaction. i. Free Radical Substitution: Alkenes undergo free radical substitution in the presence of light CH4 + Cl2 CH3Cl + HCl

Light energy or heat causes homolytic fission of chlorine producing chlorine radicals which attack methane to methyl chloride. When the ratio of CH4 to Cl2 is high, CH3Cl is formed predominantly and when Cl2 is in excess, all the hydrogens are replaced to give CCl4. Ratio of rate of substitution.

In Cl2 : In Br2 :
ii.

1H 1 1

2H : 3.8 : 82

3H :5 : 1600

The number of types of H present in an alkane is equal to the number of monohalogen substituted products obtained by the halogenation of that alkane. For example, Isopentane has 4 types of H, hence, isopenthane on chlorination will give four alkyl chlorides.

iii.

Nucleophilic Substitution: The reaction which involves displacement of a nucleophile by another nucleophile is called nucleophilic substitution (SN) reaction. For example, hydrolysis of alkyl halide.

iv.

Electrophilic (aromatic) Substitution: Due to having negative -electron cloud, benzene ring discourages the nucleophilic attack and encourages electrophilic attack. The typical reactions of benzene and its derivatives are electrophilic substitution.

Tautomerism - Organic Chemistry

A very common form of tautomerism is that between a carbonyl compound... Tautomerism A very common form of tautomerism is that between a carbonyl compound containing an -H and its enol form.

In simple cases, the equilibrium lies well to the left. In certain cases, however, a larger amount of the enol form is present. There are three main types of the more stable enols: i. Molecules in which the enolic double bond is on conjugation with another double bond. For example, carboxylic esters have a much smaller enolic content than ketons. In molecules like acetoacetic ester, the enol is also stabilized by intramolecular hydrogen bonding.

ii.

Molecules that contain two or three bulky aryl groups. For example, in case of 2, 2-dimesitylethenol, the keto content at equilibrium is only 5%. In this case steric hindrance destabilizes the keto form.

iii.

Highly Fluorinated enols: The extent of enolization is greatly affected by solvant, concentratiom and temperature. Thus, acetoacetic ester has an enol content of 0.4% in water and 19.8% in toluene. In this case, water reduces the enol content by hydrogen bonding with the carbonyl, making this group less available for intramolecular bonding. Other Proton-Shift Tautomerism 1. Phenol-keto Tautomerism

For most simple phenols, the equilibrium lies well to the side of the phenol, since only on that side is there aromaticity.

2.

Nitroso-Oxime Tautomerism

This equilibrium lies far to the right, and as a rule nitroso compounds arestable only when there is no hydrogen. 3. Nitro-acinitro Tautomerism Primary and secondary nitroalkanes containing -H undergo tautomerism.

4.

Imine-enamine Tautomerism

Enamines are normally stable only when there is no hydrogen on the nitrogen (such as R2C = CR NR2). Otherwise, the imine from predominates. Factors Influencing Reactivity 1. Inductive Effect The electron pair forming the -bond is slightly displaced towards the more electronegative atom. This permanent state of polarization is called the inductive effect. l effect (i.e., electron-withdrawing effect) : NO2 > F > COOH > Cl > Br > l > OH > OR > C6H5 + l effect (electron-releasing effect) : Me3C - > Me2CH - > MeCH2 - > CH3 2. Electromeric Effect On the close approach of a reagent, the electronic system of an unsaturated molecule is deformed. When the reagent is removed, the electronic system reverts to the original state. This kind of polarizability of multiple bonds is known as electronic effect. Electromeric effect is temporary

3.

Mesomeric Effect The permanent polarization of a group conjugated with a -bond or a set of alternate -bonds is transmitted through the -electrons of the system resulting in a different distribution of electrons in the unsaturated chain. This is called mesomeric effect. + M effect possessing groups are : M effect possessing groups are :

4.

Hyperconjugation The ability of the -bond electrons of an is called hyperconjugation.

-C

H bond to undergo conjugation with the adjacent -electrons

The ortho-and para-directing effect of methyl group in toluene is attributed to electron release by hyperconjugation.

Elimination Reactions - Organic Chemistry

When two groups or atoms from adjacent carbons are eliminated... Elimination Reactions When two groups or atoms from adjacent carbons are eliminated with the formation of unsaturated compounds (alkene or alkyne), the reaction is called elimination reaction. Huckel's rule: Huckel's rule based on molecular orbital calculations, predicts that electron rings will constitute an aromatic system only if the number of electrons in the ring is of the form, (4n + 2) electron system, where n is zero or any positive integer. The rule predicts that rings of 2, 6, 10, 14 etc., electrons will be aromatic, while rings of 4, 8, 12, etc., will not be aromatic, while rings of 4, 8, 12, etc., will not be. Antiaromaticity: Electron rings will constitute an antiaromatic system, if the number of electrons in the ring is of the form, 4n electron system, where n is any positive number. For aromaticity and antiaromaticity, the molecule must be planar.

e.g.,

is an antiaromatic compound.

Cyclooctatetraene is not planar but tub-shaped. Hence, it is neither aromatic nor antiaromatic. The reason for the lack of planarity is that a regular octagon has angles of 135 .

Stereoisomerism - Organic Chemistry

Stereoisomerism It is due to the difference in arrangement of atoms or group in space. It is classified into two types 1. Configurational Isomerism 2. Conformational Isomerism Configurational Isomerism is further classified into (I) Geometrical Isomerism (II) Optical Isomerism. 1. Geometrical Isomerism In this, the isomer have different spatial arrangement of atoms or group around the double bonded carbon atom.

Necessary Condition i. Carbon-carbon rotation must be restricted either double bond or by cyclic structure. ii. The group attached to doubled bonded carbon atom must be different. iii. Triple bonded carbon does not have stereogenic centre so it does not exhibit Geometrical isomerism. The isomers which have similar group on the same side of the doubly bonded carbon are called 'cis' isomers and the isomers which have similar group on the opposite sides are called 'trans' isomers.

In aldoxime and ketoxime the prefix 'syn' and 'anti' indicates 'cis' and 'trans' isomer respectively. If four different groups are attached to carbon atom then 'E' and 'Z' system is used if higher groups are on same side then 'Z' system is used and if higher groups are on opposite side then 'E' system is used. vi. Geometrical isomer shows different physical properties. There chemical properties are similar but not identical. vii. Cis-isomer is more polar and have higher boiling point that trans-isomer. viii. Trans-isomer are more stable and have higher melting point then cis-isomer. 2. Optical Isomerism These isomers resembles in their chemical properties but shows different behavior towards plane polarized light. Necessary Condition i. Organic molecules must have chiral centre when all the group bonded to carbon are different then the carbon is called as chiral carbon or assymetric carbon. ii. Organic molecules must show enantiomerism i.e. non-super imposable mirror images. For this, molecules must have chiral centre and must not have plane symmetry. Optical isomer may be dextrorotatory or laevo rotatory depending upon the rotation of plane polarized light. Representation of the structure (Fischer Projection) iii. Most oxidised carbon is arranged vertically at the top. iv. Group attached to carbon atom are assigned a priority which is divided on the basis of atomic number. v. Rotate the molecule such that the group of lowest priority is directed away. If rotation is clockwise the configuration is 'R' and if the rotation is anticlockwise then configuration is specified as 'S'.

iv. v.

vi. vii.

If group of lowest priority is at the top of vertical line then rotate the molecule through180 to bring atom of lowest priority at the bottom. If group of lowest priority is on the lefts hand side, then position of atoms are group are changed in anticlockwise direction to bring the group of lowest priority at the bottom except changing the position of the group present at the top and vice versa, if the group of lowest priority is present on the right hand side.

Properties of Enantiomers viii. They have almost identical physical properties. ix. They rotate the plane polarized light in opposite direction to same extent. x. They have identical chemical properties. Diastereomer: Stereomers which are not the mirror image of each other are called as diastereomers. They have different physical properties, they may or may not be optically active. Meso Compounds: These compounds are optically inactive inspite of the presence of chiral carbon atoms . This is due to presence of plane symmetry. Racemic mixture: It is equimolar mixture of (+) and (-) enantiomers. This mixture is optically inactive due to external compensation. Resolution: It is the mtehod of separation of Racemic mixture. The mixture is treated with a suitable optically active reagent which give a mixture of two diastereomers which are separated by fractional crystallization. Number of possible Stereoisomers in a compound. xi. If molecule can not be divided into two equal halves n No. of 'd' and 'l' form = 2 No. of meso form = 0 Where 'n' is number of assymetric carbon. xii. When molecule can be divided into equal halves n = even (n-1) No. of d and l form = 2 No. of meso form = xiii. If n = odd No. of 'd' and 'l' form = 2
n-1

No. of meso form = Conformational Isomerism It arises due to the rotation through single bond. This results in staggered and eclipsed structures. e.g., ethane

All other conformation between eclipsed and staggered form may be obtained by rotating the two adjacent carbon to 60 C. Staggered > Gauche > Partially eclipsed > Fully eclipsed.