(Chemistry ,Paper-3) PHYSICAL CHEMISTRY भौतिक रसायनविज्ञान UOR B.SC , B.ED Second Year Bilingual book

Unit-I

Thermodynamics-I

Definition of Thermodynamic Terms: System, surroundings, etc. Types of systems, intensive and extensive properties. State and path functions and their differentials. Thermodynamic process, concept of heat and work.

First Law of Thermodynamics: Statement, definition of internal energy and enthalpy, heat capacity, heat capacities at constant volume and pressure and their relationship. Joule’s law. Joule-Thomson coefficient and inversion temperature. Calculation of w, q, dU and dH for the expansion of Ideal gases under isothermal and adiabatic conditions for reversible process.

Thermochemistry: Standard state, standard enthalpy of formation, Hess’s Law of heat, summation and its applications. Heat of reaction at constant pressure and at constant volume. Enthalpy of neutralisation. Bond dissociation energy and its calculation from thermo-chemical data, temperature dependence of enthalpy. Kirchhoff’s equation.

bdkbZ-I

Å"ekxfrdh-I

Å"ekxfrdh 'kCnkoyh dh ifjHkk"kk& fudk;] ifjos'k] vkfnA fudk; ds çdkj] xgu vkSj O;kid xq.kA voLFkk vkSj iFk Qyu vkSj muds varjA Å"ekxfrdh çfØ;k] Å"ek vkSj dk;Z dh vo/kkj.kkA

Å"ekxfrdh dk igyk fu;e& vkarfjd ÅtkZ vkSj ,UFkSYih dk dFku] ifjHkk"kk] Å"ek /kkfjrk] fLFkj vk;ru vkSj nkc ij Å"ek /kkfjrk vkSj mudk laca/kA twy dk fu;eA twy&Fk‚elu xq.kkad vkSj O;qRØe rkiekuA mRØe.kh; çfØ;k ds fy, lerkih vkSj #)ks"e fLFkfr;ksa ds varxZr vkn'kZ xSlksa ds foLrkj ds fy, w, q, dU vkSj dH dh x.kukA

Å"ekjlk;u& ekud voLFkk] fuekZ.k dh ekud ,UFkSYih] gsl dk Å"ek fu;e] ;ksx vkSj blds vuqç;ksxA fLFkj nkc vkSj fLFkj vk;ru ij vfHkfØ;k dh Å"ekA mnklhuhdj.k ,UFkSYihA ca/k fo;kstu ÅtkZ vkSj Å"ejklk;fud MsVk ls bldh x.kuk] ,UFkSYih dh rkieku ij fuHkZjrkA fdjp‚Q dk lehdj.kA

Unit-II

Thermodynamics-II

Second Law of Thermodynamics: Need for the law, different statements of the law. Carnot cycle and its efficiency, Carnot-Theorem. Thermodynamic scale of temperature.

Concept of Entropy: Entropy as a state function, entropy as a function of V and T, entropy as a function of P and T, entropy change in physical change. Clausius inequality and entropy as a criteria of spontaneity and equilibrium. Entropy change in ideal gases and mixing of gases.

Third Law of Thermodynamics: Nernst heat theorem, statement and concept of residual entropy, evaluation of absolute entropy from heat capacity data. Gibbs function (G) and Helmholtz function (A) as: thermodynamic quantities, A and G as criteria for thermodynamic equilibrium and spontaneity, their advantage over entropy change. Variation of G and A with P, V and T.

Chemical Equilibrium

Equilibrium constant and free energy. Thermodynamic derivation of law of mass action. Le Chatelier’s principle. Reaction isotherm and reaction isochore-Clapeyron equation and Calusius-Clapeyron equation, applications.

bdkbZ-II

Å"ekxfrdh-II

Å"ekxfrdh dk nwljk fu;e& fu;e dh vko';drk] fu;e ds fofHkUu dFkuA dkuksZV pØ vkSj bldh n{krk] dkuksZV&çes;A rkieku dk Å"ekxfrdh; iSekukA

,aVª‚ih dh vo/kkj.kk& ,d voLFkk Qyu ds :i esa ,UVª‚ih] V vkSj T ds Qyu ds :i esa ,UVª‚ih] P vkSj T ds Qyu ds :i esa ,UVª‚ih] HkkSfrd ifjorZu esa ,UVª‚ih ifjorZuA Dy‚fl;l vlekurk vkSj lgtrk vkSj larqyu ds ekunaM ds :i esa ,UVª‚ihA vkn'kZ xSlksa esa ,UVª‚ih ifjorZu vkSj xSlksa dk feJ.kA

Å"ekxfrdh dk rhljk fu;e& uuZLV Å"ek çes;] vof'k"V ,UVª‚ih dk dFku vkSj vo/kkj.kk] Å"ek /kkfjrk MsVk ls fujis{k ,UVª‚ih dk ewY;kaduA fxCl Qyu (G) vkSj gsYegksYV~t Qyu (A) ds :i esa& Å"ekxfrdh jkf’k;k¡] A vkSj G Å"ekxfrdh lkE; vkSj lgtrk ds ekunaM ds :i esa] ,UVª‚ih ifjorZu ij mudk ykHkA P, V vkSj T ds lkFk G vkSj A dk ifjorZuA

jklk;fud lkE;

lkE; fLFkjkad vkSj eqDr ÅtkZA nzO;vuqikrh fØ;k ds fu;e dh Å"ekxfrd O;qRifÙkA yk 'kkrSfy, dk fl)karA lerkih vfHkfØ;k vkSj leLFkkfud vfHkfØ;k&DySisj‚u lehdj.k vkSj DykWfl;l&DySisj‚u lehdj.k] vuqç;ksxA

Unit-III

Phase Equilibrium

Statement and meaning of terms; phase, component and degree of freedom, derivation of Gibbs phase rule, phase equilibria of one component system-water, CO₂ and sulphur systems.

Phase Equilibria of Two Component System: Solid-liquid equilibria, simple eutectic-Bi-Cd, Pb-Ag systems, desilverisation of lead.

Solid Solutions: Compound formation with Congruent melting point (Mg-Zn) and incongruent melting point, (NaCl ─ H₂O), System, freezing mixtures, acetone-dry ice.

Liquid-Liquid Mixtures: Idea liquid mixtures. Raoult’s and Henry’s law. Non-ideal system-azeotropes-HCl-H₂O and ethnol-water, systems. Partially miscible liquids-Phenol-water, trimethylamine-water, nicotine-water systems. Lower and upper consolute temperature. Effect of impurity on consolute temperature. Nernst distribution law-thermodynamic derivation, application.

bdkbZ-III

ÁkoLFkk lkE;

'kCnksa dk dFku vkSj vFkZ] ÁkoLFkk] ?kVd vkSj Lora=rk dh dksfV] fxCl ÁkoLFkk fu;e dh O;qRifÙk] ,d ?kVd ç.kkyh&ty] CO₂ vkSj lYQj ra=ksaa ds ÁkoLFkk lkE;A

nks ?kVd ra= ds ÁkoLFkk lkE;& Bksl&æo lkE;] ljy xyuØkafrd-Bi-Cd, Pb-Ag ra=] ysM dk fMflYojhdj.kA

Bksl foy;u& le:i xyukad (Mg-Zn) vkSj vlaxr xyukad (NaCl ─ H₂O) ds lkFk ;kSfxd fuekZ.k] ç.kkyh] fgehdj.k feJ.k] ,lhVksu&'kq"d cQZA

æo&æo feJ.k&  æo feJ.k fl)karA jkmYV vkSj gsujh dk fu;eA vukn’kZ ra=&,tksVªksIl-HCl-H₂O vkSj bFksukWy&ty] ra=A vkaf'kd :i ls feJ.kh; æo inkFkZ&fQuksy&ty] VªkbesfFkykehu&ty] fudksVhu&ty ra=A de vkSj mPp lafoys; rkiekuA lafoys; rkieku ij v'kq)rk dk çHkkoA uuZLV forj.k fu;e&Å"ekxfrdh O;qRifÙk] vuqç;ksxA

Unit-IV

Electrochemistry-I

Electrical transport-conduction in metals and in electrolyte solutions, specific conductance and equivalent conductance, measurement of equivalent conductance, variation of equivalent and specific conductance with dilution.

Migration of ions and Kohlrausch law, Arrhenius theory of electrolyte dissociation and its limitations, weak and strong electrolytes. Ostwald’s dilution law, its uses and limitations. Debye-Huckel-Onsager’s equation for strong electrolytes (elementary treatment only). Transport number, definition and determination by Hittorf ’s method and moving boundary method.

Applications of Conductivity Measurements

Determination of degree of dissociation, determination of K_a of acids, determination of solubility product of a sparingly soluble salt. conductometric titrations.

bdkbZ-IV

fo|qr jlk;u-I

fo|qr ifjogu&/kkrqvksa vkSj fo|qrvi?kV~; foy;uksa esa pkyu] fof'k"V pkydrk vkSj rqY;kadh pkydrk] rqY;kadh pkydrk dk ekiu] ruqdj.k ds lkFk rqY;kadh vkSj fof'k"V pkydrk esa ifjorZuA

vk;uksa dk vfHkxeu vkSj dksgyj‚'k fu;e] fo|qrvi?kV~; fo;kstu dk vkgsZfu;l fl)kar vkSj bldh lhek,¡] nqcZy vkSj izcy fo|qrvi?kV~;A vksLVokYM dk ruqrk fu;e] blds mi;ksx vkSj lhek,¡A izcy fo|qrvi?kV~; ds fy, fMckbZ&gdy&v‚ulsxj dk lehdj.k ¼dsoy çkFkfed vfHkfØ;k½A fgV‚QZ dh fof/k vkSj py lhek fof/k }kjk vfHkxeukad] ifjHkk"kk vkSj fu/kkZj.kA

pkydrk ekiu ds vuqç;ksx

fo;kstu dh dksfV dk fu/kkZj.k] vEyksa ds K_a dk fu/kkZj.k] de ?kqyu'khy yo.k ds foys;rk xq.kuQy dk fu/kkZj.kA pkydrkferh; vuqekiuA

Unit-V

Electrochemistry-II

Types of Reversible Electrodes: Gas-metal ion, metal-metal ion, metal-insoluble salt anion and redox electrodes, electrode reactions, Nernst equation, derivation of cell E.M.F. and single electrode potential, standard hydrogen electrode-reference electrodes, standard electrode potential, sign conventions, electrochemical series and its significance.

Electrolytic and Galvanic cells-reversible and irreversible cells, conventional representation of electrochemical cells.

EMF of a cell its measurements. Computation of cells EMF. Calculation of thermodynamic quantities of cell reactions, (DG, AH and K). polarization, over potential and hydrogen overvoltage.

Concentration cell with and without transport, liquid junction potential, application of concentration cells, Valency of ions, solubility product and activity coefficient, potentiometric titrations.

Definition of pH of and pK_a, determination of pH using hydrogen quinhydrone and glass electrodes, by potentiometric methods.

bdkbZ-V 

fo|qr jlk;u-II

mRØe.kh; bysDVªksM ds çdkj& xSl&/kkrq vk;u] /kkrq&/kkrq vk;u] /kkrq&v?kqyu'khy yo.k vk;u vkSj jsM‚Dl bysDVªksM] bysDVªksM vfHkfØ;k,¡] uuZLV lehdj.k] lsy E.M.F vkSj ,dy bysDVªksM foHko dh O;qRifÙk] ekud gkbMªkstu bysDVªksM&lanHkZ bysDVªksM] ekud bysDVªksM foHko] fpUg ifjikVh] fo|qr jklk;fud Js.kh vkSj bldk egRoA

fo|qrvi?kVuh vkSj xSYosfud lsy mRØe.kh; vkSj vuqRØe.kh; lsy] fo|qr~ jklk;fud lsy dk ikjaifjd fu:i.k

lsy dk EMF vkSj mldk ekiuA lsy EMF dh x.kukA lsy vfHkfØ;kvksa dh Å"ekxfrdh jkf’k;ksa dh x.kuk] (DG, AH vkSj K½A /kzqohdj.k] vf/kfoHko vkSj gkbMªkstu vf/koksYVrkA

ifjogu ds lkFk vkSj fcuk lkaærk lsy] æo taD'ku foHko] lkaærk lsy dk vuqç;ksx] vk;uksa dh la;kstdrk] foys;rk xq.kuQy vkSj lfØ;rk xq.kkad] iksVsaf'k;ksesfVªd vuqekiuA

pK_a vkSj pH dh ifjHkk"kk] gkbMªkstu fDougkbMªksu vkSj dk¡p bysDVªksM dk mi;ksx djds pH dk fu/kkZj.k] foHkoekih fof/k;ksa }kjkA

CH-204 Chemistry Practical

¼ CH-204  HkkSfrd jlk;ufoKku Á;ksxkRed½

Physical Chemistry

1) Transition Temperature

a) Determination of the transition temperature of the given substance by thermometric dilatometric method, e.g., MnCl₂×4H₂O/SrBr₂×2H₂O

2) Thermochemistry

a) To determine the solubility of benzoic acid at different temperatures and to determine ΔΗ of the dissolution process.

b) To determine the enthalpy of neutralization of a weak acid weak base versus strong base strong acid and determine the enthalpy of ionization of the weak acid weak/weak base.

c) To determine the enthalpy of solution of solid calcium chloride and calculate the lattice energy of calcium chloride from its enthalpy data using Born-Haber cycle.

3) Phase Equilibrium

a) To study the effect of a solute, (e.g., NaCl, succinic acid) on the critical solution temperature of two partially miscible liquids, e.g., phenol-water system) and to determine the concentration of that solute in the given phenol in water system.

b) To construct the phase diagram of two components, e.g., diphenylamine-benzophenone system by cooling curve method.

4) Distribution Law

a) To study the distribution of iodine between water and CCl₄.

b) To study the distribution of benzoic acid between benzene and water.

HkkSfrd jlk;u

1) laØe.k rkieku

a) FkeksZesfVªd MkbySVksesfVªd fof/k }kjk fn, x, inkFkZ ds laØe.k rkieku dk fu/kkZj.k] mnkgj.k ds fy,] MnCl₂×4H₂O/SrBr₂×2H₂O

2) Å"ekjlk;u

a) fofHkUu rkiekuksa ij csatksbd vEy dh ?kqyu'khyrk fu/kkZfjr djuk vkSj fo?kVu çfØ;k dk ΔΗ fu/kkZfjr djukA

b) ,d nqcZy vEy nqcZy {kkj cuke izcy {kkj izcy vEy ds mnklhuhdj.k dh ,UFkSYih fu/kkZfjr djuk vkSj nqcZy vEy nqcZy @ nqcZy {kkj ds vk;uu dh ,UFkSYih fu/kkZfjr djukA

c) Bksl dSfY'k;e DyksjkbM ds foy;u dh ,UFkSYih fu/kkZfjr djuk vkSj cksuZ&gScj pØ dk mi;ksx djds blds ,UFkSYih MsVk ls dSfY'k;e DyksjkbM dh tkyd ÅtkZ dh x.kuk djukA

3) ÁkoLFkk lkE;

a) nks vkaf'kd :i ls feJ.kh; æo inkFkksaZ] tSls] fQuksy&ty ra=½ ds Økafrd foy;u rkieku ij ,d foys;] ¼tSls] NaCl] lfDlfud vEy½ ds çHkko dk v/;;u djuk rFkk fn, x, fQuksy&ty ra= esa ml foys; dh lkaærk fu/kkZfjr djukA

b) 'khryu oØ fof/k }kjk nks ?kVdksa] tSls] MkbQsfuykehu&csatksQhuksu ra= ds ÁkoLFkk vkjs[k dk fuekZ.k djukA

4) forj.k fu;e

a) ty vkSj CCl₄ ds chp vk;ksMhu ds forj.k dk v/;;u djukA

b) csathu vkSj ty ds chp csatksbd vEy ds forj.k dk v/;;u djukA