Physical Chemistry I (Chem 235) Tentbooks 1. Principles/Fundamentalsof Physical Chemistry By. . Maron and C.F. Prutton/J. Lando 2. Elements of Physical Chemistry ByS, Glasstone and D. Lev 3, Principles of physical Chen By. M. Hague and M. A. Nawa Contents Electrolytic Conductance: metallic and electrolytic conduction, specific, equivalent and molar conductance, migration of ions, Ionic mobiliy, theories of electrolytic conductance, conduetometic titrations Tonic Eguilbria: salt hydrolysis, Debye-Huckel theory, activity and activity coelficient, ionic strength, dilution law, salt effect and solubility, buffer solution and buffer capaci Electrochemical Cells; Reversible and irreversible cells, types of electrodes, Nernst eqn, concenteation cells, application of emf measurement: determination of activityNotes taken by hands improves your capacity to explain the concept covered in the lecture. It involves you in active learning process. Note-Taking Guidelines Record the date of the lecture, topicrtitle of the lecture Take your own notes on each and every topic /class (sufficient time will be given) and you will be benefited in the long rundio: put aside the idea re Playing and replaying recorded audio can improve your language skills: listening and comprehension. ic ideas are d Avoid VERBATIM no s much as possible. Use your own words to improve your cognitive skills on the subject Review your notes after classes but do not rely merely on notes, use (standard) textbooks Group discussion and sharing ideas / notes are encouraged Source: https://www-bbe.com/worklife/article/202009 10-the-henefits-of note-taking-by-hand (1 1th September 2020) hitps://www.bbe.com/futurefarticle/20191122-when-the-best-way-to:Electrolytes: Substances that form ions in solution and conduct an electric current Strong electrolytes: shows good conductance and high degree of dissociation in solution Weak electrolytes: shows poor conductance and low degree of dissociation in solution 1:1 type: NaCl, KCL 1:2 type: H,SO, ;Na,SO, 2:1 type: BaCl, ; Mg(NO,), type: CuSO, ; ZnSO,Metallic Conduction Current carried by electrons Velocity of electrons is very large Specific conductance is very high Temp. coefficient is usually -veElectrolyte solutions conducts electrical current by movement of the ions to the electrodes. >The conductance of electrolyte solutions may be measured by Ohms law EB R=7,R=resistance, E=potental difference, I=currente: resistance of a solution held between the electrodes 1 cm? in area and 1 cm apart R=S~; S=specific resistance a reciprocal of specific resistanc conductance 1 w=, K=specific condutance is called specificsd e: resistance of a solution held between the electrodes 1 cm* in area and 1. cm apart R=S-; S=specific resistance am a Le reciprocal of specific resistance is called specific conductance » K-=specific condutance Equi cond Specific conductance multiplied by the volume in ml. that contains 1 gram equivalent of the electrolyte.Sar mc, Increases with increasing the concentration of electrolytes. No. of ions increases with increasing concentration ale tance: Increases with decreasing the concentration —_ of electrolytes. Decrease in specific conductance is more than compensated by the increase in the value of VC on dilution, and hence L goes up.phere: The average spherical non-zero charge distribution around an ion is called the ionic atmosphere laxation effect: The first of these arises from the fact that any central ion and its atmosphere are oppositely charged, i.e., when the central ion is positively charged the atmosphere is negative, and v central positive ion will tend to move toward the cathode while i e versa. Thus a sionic atmosphere will tend toward the anode. Electrophor ffect: The electrophoretic effect arises from the fact that an ion, in moving through the solution, does not travel through a stationary medium, but through one that moves in a direction opposite to that of the ion. Ions are generally solvated, and when these move, they carry with them solvent. A=A,-BYC Se eeSpecific conductance, molar conductance and equivalent conductance may be determined by measuring the conductance of the electrolyte solution Cell constant :For a particular cell 'cell constanta EE. ‘Tanz 11-6. Koutaavscn’s Law or Inszeexonyr Micnarion or Ions Blectrolyte Difference | Blectrolyte Difference Ka uel 34.9 KNO, LiNOs KOH oHDetermination of A, of weak electrolytes: CH,COOH Bou = Reayeoo + %, ‘aixeoon ~ “cu,coo~ t Au" +4 Fre4 4 4 OH ion also follows the above mechanism 0.030 (0300 (already explained)= Mg -~ 0.030 10.300 (already explained)a eiWeak Acid vs Strong BaseSar Mixture of Weak Acid and Strong Acid vs Strong Base HCI#+!CH,COOH#NaOH = NaCl + CH,COONa + H,0Sar Weak Acid vs. Weak Base Example; CH,COOH + NH,OH =CH,COONH, + H,0reSar mc, 1000xx ee Ago =127 ohm? em? mol * A, 1000xx __1000xx 2... =160 ohm "em? mol! c= —1000%K : A Ky +ky Problem: The conductivity of a saturated solution of silver chloride in water of conductivity 1.6:10°* ohm ‘cm? equiv tis 3.41 10°° ohm cm? equiv at 25°C What is the solubility of the salt at this temperature? Ans:1P m: The conductivity of a saturated solution of BaSO, is 3.48 * 10 ~° Sicm. The conductivity of pure water is 0.50 * 10 ~® S/cm. Calculate the solubility product of BaSO, (Limiting molar conductance of Ba and SO,2- are 127.26 and 160.04 $ cm? mol, respectively) 1000xXK WeKnow, A, =——— 1000%(K%,., Ak ‘at T Aco or,c= orc 04x10 * moll * _1000x(3.48x10 * —0.510 *) 127.26 + 160.04 Here, Kuso, =3-48%10* Sem IK;,9 = 05010 *Scm ts =127.26Scm*mol * oy 22, =160.04S cm*mol *5 e om Co Arrhenius ascribed the decrease in A with increasing concentration to variation of the degree of dissociation of the electrolyte. Then, it can be shown that the degree of dissociation @ must be given by the ratio A/ A A_ ou, +H) (1) |“#=ionic mobility xX Hote If the mobilities of the ions at any finite concentration are the same as at infinite dilution, then Hy YH FH) ann) Then from Eq(1) and (2), we get, a= xReceived the Nobel Prize in Chemistry in 1909 Contributions Catalysis Chemical Equilibria Reaction Velocities. Intr Friedrich Wilhelm Ostwald (1853-1932)Weak electrolytes dissociates partially into ions. Consider the dissociation of the electrolyte MA, = MA=M*+A~ IMA) [MA] Ifq@ isthe degree of dissociation, and c isthe conc.in molL”’ then. The equilibrium constant, K,. = -@ (M*]=[A"] =c@and[MA]=G—@)¢ -____ ©.Eq(1) becomes,K, =-2°'" - © ___ (a) c(i-@) 1-@ A MP /-When a=—-, Eq(2) becomes,k, =! ate 4:Multiplying eq(3) by ewe get, AL (cA) 1 { cA) Af cA WLAN) KA) ALATransport Number: The fraction of the current carried by each ionic species is called the transport number of that ion, It is given by t, (cation) or t (anion) Consider two Parallel plates d cm apart, across which a potential £ volt is applied and between which contain some volume ofan el Average Speed of cation = v, cm/s Charge of the cation No. of cation: rly ‘Average Speed of anion = v_ cm/s Charge of the anion No.of anionCurrent carried by the cation, I, =” d Current carried by theanion, 1. =" Total current, =I, +1 = ‘Thecondition of electronutrality of thesoltion, n,z, =z nz,ev, +nz,ev__m,z,eV, +) 2-Bq(3): = ae Eq(3) d d (4) From eq(1)and (4): t, 2-2 nz.ev, +7)rT Fromeq(2)and(4): ¢ =<—--—"=** n,z,ev,+¥_) L n,z,ev, I n,z,ev,+v) v i 6) ‘ @+¥) © From eqn (5) and (6) we get: ‘Therefore, transport gumber of an ion is directly proportional to their absolute velocities. Hittorf’s methodtod he mur oh haga TeConsider pair of electrodes d cm apart, across which a potential E volt is applied. An electrolyte A,B, in a volume contains the solution, If a is the degree of dissociation, then AxBy=xA" + yB™ l-a@ xa + ya The number of +ve ions present between the electrode mn, = xotN. where, N= Avogadro's number . ‘The current flowing between the plates is given by, I= xaNz, ev, +¥_)Sar a (xz, v, +v_) ort d v2) fF = Ne] One mole of A,B, corresponds to xz, equivalents of the substance. ‘Therefore, if Cis the conc. in gram equiv per 1000 mL of solution, the vol. per equiv is 1000/C. and per mol xz,1000/C, The latter volume is Ad where, A is the area of one of the parallel plates.Sar a A=ar(y, +p. )--——{12)_ [and pare ionic mobilities of tons] At infinite dilution, N= Fy; + Fy! ———(13) q ie ° Mees tee ASK, M,=H, and p= 4) N=2,4+2————(14) — (Koblrausch's law) Fromeq(13)and (14) weget, 2, = Fu, and 2. =Fys z Zz, ows and p= wa alae <-lonic mobility of an ion is directly proportional to its ion conductnaceConsider pair of electrodes d cm apart, across which a potential E volt is applied. One mole of an electrolyte A,B, in a volume contains the solution. If o is the degree of dissociation, then A,B, =xA" + yB° 1-@ xa + ya The number of +ve ions present between the electrodes n, = xoiN. where, N= Avogadro's number ‘The current flowing between the plates is given by, I= xaNz, ev, +¥_)d where, A is the area of on IFC is the conc. in gram equiv per 1000 mL of the solution, thevolume per equiv =1000C. And thevolume per mol =xz,1000/C. where A is the area of oncof the platesSar 1000x., c Equiv.conductnace, A = ACA _ ACA Prom eq(4)and (5) we get, L= att A. nd 8) we Boy = 000 a Brom eq(3) and (6) we get, L= = A From Ohm's law: =1=EL R From eg(7)and(8)wege, 1="!s) From eq(2)and (5) weget, “AE _ GPE 4¥) aayThe deviation ofa solution from ideal behavior is commonly represented in term of the quantities commonly known as the activity and activity coefficient Consideran electrolyte M.A, ionizes inthe manner: M.A, = deviation from ideal behavior, {molality20 mc, (1875-1946) was a professor of UC, Berkeley ‘was nominated 41 times but never won the Nobel Prize in Chemistry a major Nobel Prize controversy Contributions: Acid-base theory Thermodynamics (Introduced Thermodynamics in Physical Chem.) Electrochemistry (a, 7and 40) First isolated D,O Showed the formation of tetraoxygen (O,)Sar mc, (W) Molality of K’ =02mx2=0.4m Molality of SO? =0.2mx1=0.2m Tonic Strength, 42 hed = HMloames*)+(02m2")}= 0.6m