Physical Chem Notes A. Electron 2. 3.

6th Apr,2012

4. 5. 2. 3.

Energy quantized energy Bohrs model 1. For H 2. +1C nucleus 3. Orbits with discrete energy excited statestransitionrelease of energy (i.e. light or heat) determine I.E. (convergence limit) from atomic spectrum---v/v Electron shell (allowed energy lv.) successive I.E. 1st I.E. of period 2,3,3 pattern orbitals---s, p, d. Electron configuration Successive I.E. Aufbau Principle Pauli exclusion principle Hunds rule (mutual repulsion) Electron attraction/ repulsion Shielding effect Distance/ size Extra stability (uniform distribution of Q) Mutual repulsion Effective nuclear charge (no. of proton) atomic & ionic radii, electronegativity, I.E. Electron distribution Uniform stable Minimum repulsion stable Non uniform in bonding polarity dipole inter- forces

4.

5.

Electronegativity In a bond Attraction on bonding e Accounts for polarity Related to bond length strength

Electron affinity Addition of an e Repulsion is considered

B.

System 1. Nature 1. System is formed lower energy ( from cluster of e) arrangement energetically 2. 3. 4. 5. 6. 7. 2. Each system has both attraction & repulsion Ionic ---big in electronegativity---transfer of electron Covalent ---electron cloud overlapping (localized/ delocalised)-----small E-vity Metallic better shielding effect, delocalized Strength of bonding atomic/metallic/covalent radii + no. of bonding electrons Octet rule

Physical prop of metallic structure 1. M.p---only weakening 2. High B.P.----as all broken 3. Ductility & malleability----mobility of electrons 4. Conductivity ------mobile electrons---------one in, one out // hot cool 5. Shiny ----- close Elv. absorb & re-emit all Packing in metals 1. Min. volume, max. lattice stability( ~Elv.) min energy content 2. CCP(74%) Octahedral & tetrahedral holes (mutually exclusive) 3. HCP

3.

4. 5. 6. 4.

BCC(6 8%) Coordination no.- packing efficiency Packing close more planes for deformation

Packing in ionic crystals 1. *greatest contact between opp. Q 2. Pattern depends on relative size of ions Covalent bonding 1. Bonding environment Bond angle, hybridization, no. of bond pairs& lone pairs If repulsion + short bond length efficiency of overlapping High-s-character overlapping - higher bond strength---bond enthalpy Smaller size of orbitals- high degree of overlapping 2. 3.

5.

Violation of octet rule----expansion of octet if Elv.s are close in energy Formation of bond and shape Valence bond theory + Octet rule I. Covalent bond from overlapping of orbitals (sharing or dative) VSEPR theory I. LP-LP>LP-BP>BP-BP Theory of hybridization---- delocalization I. Separate orbitals mix to give a new set of hybrid orbitals II. Determine no. of bonds & shape III. Purpose: more unpaired e- extra bonds----stable E(excitation) < E(released from extra bonds) IV. Paired orbitals have little participation in bonding V. Types 1. sp One s + one p S character: 50% 2. sp2 One s + two p 33.33333% 3 3. sp One s + three p 25% NB: Increase in s characterdegree of overlappingcloser bonding ebond strength 4. VI. For delocalizationcoplanar Packing efficiency (esp. macromoleculesshort v.d.f.) Symmetry Regularity Rotation

6. Bonding intermediate (1) Ionic -polarising power size-1 charge -polarisablity size charge

(2) Covalent - in Electro-ve -vector sum of dipole moments (universal)

7.

Inter-force 1. DD 2. London dispersion forces 3. H-bond-----------------ENTROPY DECREASE for INTRA- H-bond 4. **state of matter( solid liquid or gas) Inter-forces KE translational motion

C.

Energy 1. definition 1. chemical energy due to breaking/forming of interactions 2. exothermic lower E content VS endo2. key terms 1. 1st law of thermodynamics Conservation of energy i.e. Hsurr= -Hsys H= change in heat content More veenergetically more favourable nd 2. 2 law of thermodynamics Stotal= Ssys +Ssurr >0 S = in disorderness S= no of ways to spread energy out (over more quantized Elv.

3. 4.

5.

6.

less repulsion Hesss law H is independent of the reaction pathways taken Stable Reference to .. Kinetically/ Energetically Spontaneous (feasibility) instantaneous =one way route =may need a push to overcome energy barrier Gibbs Law G<0 = spontaneous

D.

Reaction rate 1. quantities to be monitored gas volume pressure titre volume absorbance mass change intervals of time polarimetry 2. factors conc temp surface area (right orientation) pressure catalyst (/ Ea) 3. relation with conc. Gas: V -Vt [X] ---PVt= kntRT = k( [X]0- [X]t )Vx RT P - Pt [X] Mass: m - mt [X] ---[X] = (MTVT)/V Titre: Vt [X] 4. Order of reaction Keeping other being constant Measure initial rate: clock reaction Quenching

 5.

Mechanism : molecularity

expt. procedures known volume or molarity indication of time control of variables collision theory must collide to react right KE and orientation rate collision freq. Catalyst Alternative pathway Effective Regenerative Specific I. Heterogeneous Low lying vacant d orbital adsorption till satuation Concentrate and provide right orientation Weak interaction desorbs easily Stereospecific II. Homogeneous Various O.S. Intermediate compounds

6.

7.