@ /NEETAIIMSPREPERATION fan eae sass ae Ue Scanned with CamScanetalimspreparation gtsoelesocnemistry is thus process in which Teese cansferted fom one system to another. age Chel eneray — Fleteenersy ci ety Electric energy > Chemical energy el dag Stand Notation for Galvanie Cells sing Direction of e- flow. Ba, Anode half-cell Cathode half-cell Anodepaltcel Zx{s)|Z0"* (aq, IM) || Cu?*(aq) | Culs) sunday Phase boundary | Salt bridge L—Left R= Right 0-+ Oxidation R ++ Reduction A-Anode C+ Cathode N- Negative _ P—» Positive ELECTROCHEMISTRY ——— | Hectrode Potential 0.34 (-0.44) = 0.78 V Oxidation Potential (O.P,) | Reduction Potential (R-P.) n PE to getoxidised _| Tendeney to get reduced 2 x 96500 x 0.78 the OP. then greater | Greater the R.P. greater will willbe tendency to caer Pea 50540 J => 150.5 kJ ‘Megetnsreytoget be tendency to get reds £40 i given then Kis > If By, = #ve AG = -ve => Cell reaction is spontaneous > IPE, =—ve AG = +ve = Cell reaction is non- spontaneous "TPE? is given then AG? is | AG° = -nFE® | Where n= Number of moles of electron | transfered in the reaction. | __F = Faraday constant = 96550 Cimole_ Fy eral Q. AG for the reaction, Cu* + Fe + Fe** + Cus: [wiven: E2,.., = H034V , Ee... = 044V] a 144k b. 180.8 kd c. 150.5 KI d, 28.5 KI no =Eo, EB! Ans. (€) Bly = Edie, Etere "nf Or The Cell/Cell Pot 1 By tial = Eng (anode) + E°., (cathode) Fea = Ey (anode) ~ E?,, (cathode) ¢ Energy Change For Cell (Divi Ns force of chemical reaction are measured by and ( AG ‘ee Energy change) (Cell potential) fe AAFE ey [ace RTbog kK, | where K,, is equilibrium constant redox reaction, E° is positive. i: a. AG is positive, Keay is greater than | b, AG" is positive, Kym i Fess than 1 c. AG! is negative, Kagy i8 greater than 1 4d. AG? is negative, Kygq i8 fess than 1 Ans, (¢) AG? =-nFE" AG" = -2.303 RT log Ky From eq (i) iC E® is positive ocanned WIth GValnocdl200 Bem No reaction then AG" is negative In equation (ii), AG is negative $0; logk > 0= K> 1 1) fom aig seutiOn Of aig Mu My to Cr ee Al steve) Metals Fe H,(u)when react ig (11,0) steam, *dn cr Fe cd Co bl ‘i Sn ee I Pa Vaking T° 298K, Re 8314 Smo K, P= o6sime | "Hn, —o0v as LR eed Sn cf . » 0.059) t Now we wet, [lie = Key mg SRP (tye) r - | SRP value is Where n= number of transfered electron ,(» reaction | WESRPValocis’ increas quotient decrease dency to reduce themselves} | Applications of Nerst equation Oxidising Power} Reactivity of metal | > Tendency to uct oxidising NEET Mo, Nernst Equation for Electrode Potential MM" (aq) + ne = Mis) Ar, | Mos) nb nd > Oxidising power SRP x sop [Maximum SRP — F, (42.87V)] It > Reducing power z SOP 2 ‘educing power af [Minimum SRP — Li (-3.05V)} > Metals which are placed above in series can easily displa which are p ion from their aqueous solution d below in series. Cu + ZnSO,(aq) + No reaction Cu + 2AgNO (aq) ~ CuNO,), + 2Ag(5) > Non-metals which are placed below in series ean sily displace anions of non-metal which are placed above in series. 2A-*B,-12B +A, 298 K and R= 8.314 Jmol g neetaiimsprepara ion canPiuemyt Q. Calculate the emf of half cell : Oh @ [HCL "(10 atm)|(0.1) Mv" =1.36V b.1.27V d.-1.27V 0.0591 E=B°- Jog, LL n Be Che) in electric current to bring about s called electrolysis. Faraday’s Ist Law of Electrolysis The mass of substance deposited is directly proportional to charge passed through electrolyte, m= Q, where Q is charge. where Lis current in ampere, *t’is time insecond, *7" is electro chemical equivalent. Equivalent mass (E) : Mass of any substance produced when 1 mole of e° are passed through the solution Q. What is the time required (in seconds) for depositing all the silver present in 125 mL of 1 M AgNO, solution by passing a current of 241.25 A [IF = 96500 C]? a. 10sec b. 50sec c, 1000 see d. 100 see Ans, (b) 1000 mL of AgNO, solution conta 108 g Ag 2. 125 mL of AgNO, solution will contain 108125 1000) sited by 96500 C *. 13.5 of Ag is deposited by neetaiimspreparation Faraday’s second law of electrolysis It states when equal charge is passed through different electrolytes, amount of substance deposited is proportional to their equivalent weights. EQ w=79-—2” 2 36500 Ls Age W, = (= same) ——————— Electrolytic Conductance Formula S.Lunit v ‘Ohms Resistance: R=— 7 Siemens Conduetance: (8) (mho or oo) Qm ee pe(Length) SpeciticResistance(p): R= 2S pecific Resistance (p): Nae ‘snr Specific conductance/conductivity () U a =GxG" p AxR (G*-cell constant) Molar conductivity A,, =«¥ mot! molarin Sem? eq? Equivalent conductivit __«x1000 Normality nd molar conductivity Variation of conductivity with concentration > Conduetivity always decreases with the decrease in concentration both for weak and strong electrolytes. ) Molar conductivity increases with decrease in concentration. This is because the total volume, V of solution containing one mole of electrolyte also increases. ocanneIPI ET PI nA circa era ‘A increases slowly with > Strong Electrolyt dilution and can be represented by the equation = A-AS- ACI? > Weak electrolytes (i) Weak electrolytes like acetic acid have lower Wn at higher concentration degree of dissocii and hence for such electrolytes. concentration ¢ — zero) Atinfinite dilution (i electrolyte dissoci completely (a= 1) 400-7 cH,COOH, ‘A, /Sem® mol" 8 02 04 c°H(moV/L)" Molar conductivity versus ¢! for weak and strong electrolyte in aqueous solutions. Effect of Dilution > Specific conductivity (x) decreases with dilution because of decrease in no. of ions per cm? of electrolyte. > The magnitude of increase in molar conductance for weak electrolyte is much larger than that for a strong electrolyte because strong clectrolytes are almost completely ionised in all concentration and increase in A,, (or) A,, with dilution is only due to decrease in interionic attractions. The condu of all Effect of ‘Temperature electrolytes increases with increase in temperature. et ‘Kohlrauch’s Law, “The equivalent conductance at infinite dilution (A,,) of an electrolyte is equal to the algebric sum of equivalent condutances (or) mobilities of anion (25) and cation (4) of the electrolyte at infinite dilution” [Ao (electrolyte)= Ay +p (ions) Age eg. (i) Ak neetaiimspreparation sill PONE ke en ust Tip equivalent conductance of y of anions ig = — Q. At infinite dilution the equivalent ee of Aland SO? ions are 189 and 1600 em2 eq”! respectively. Calculate the equivalent conductivity at infinite dilution of Al,(SO,),. ee 2 is [A | given then Ay eS Lye AMS. ey al,(S0,)5) = 374? ‘SOF x 194% 160 = 14307 'cmeq” Applications : > Molar conductivity of an electrolyte at infinite dilution Ay = xx Ay" E PX AGS ©.8 Naacty = Apgar +24C- > Determination of A, for weak electrolytes Eg:A,(NH,OH)=A,(NH,CI)+A,(NaOH)-A,(NaC) > Degree of ionisation of weak electrolyte Am (ane where, Ay, = equivalent / molar conductivity at given concentration A®,, = limiting equivalent / molar conductivity > Calculation of dissociation constant of weak electrolytes. Q. Equivalent conductance of IM of CH,COOH 10 ohm em?eq-! and that at infinite dilution is 200 ohmr!emPeqr! . Hence the % ionization of CH,COOH is a. 5% c. 4% b. 2% d. 1%‘Ans. (8) A, = 2000hm 'om?eq"' Az, © 100hm"em? eg’! Nickel dioxide | KOH soln Degree of lonisation Wbiaideerg caatlose H,-0, | Porous C | Porous carbon | Cone. aq. fuel cell | containing | containing | NaOH soln. catalysts | catalysts (O, (H, passed) | passed) cr Primary E.g., Dry cell ‘Corrosion ICell-» Secondary E-¢., Lead Storage > Corrosion is the slow eating away of metals when exposed to the atmosphere Fuel Cell Energy (Combustion) —+ Electric energy > Corrosion of Iron (Rusting): Isis an electrochemical a henomenon and oxygen occurs in the presence of Name of P g Thecell | Atode | Cathode | Electrolyte! Prom nd O88 Dry cell | Zine Graphite: NH,CI> At anode: Fe,, — Fe, Mn0,+C — |znc, Ateathiode : Oy,, + 4H", + de” —+ 2H, Oy, Mercury |Zn/tig [Paste of gO [Paste of | Overall reaction: 2s, +0,,+4, —2Fe +H. cell | Amalgam | & carbon KOH & Methods used for prevention of corrosion are barrier elec prev i roby | 200, protection, sacrificial protection, anti-rust solutions. NaOH). cctrolyte Scanned with CamScanSta i 1, What will be standard cell potential of galvanic cell with the following reaction? 2Cr{s) + 3Ca(aq) —+ 2Cr™(aq) + 3Cals) (Given: E¥.,. , =-0.74V and E?...., =-0.4V] a. 0.70V b. 14 V ©. 034V 4. -034V 2 IES... =0.25V.E%.., “OVE... =08V and ES... =-0.76V, then which of the following reactions under standard condition will not take place in the specified direction spontaneously ? & Cu(s)+Ni* (aq) > Cu’* (aq) +Ni(s) b. Cu(s)+2Ag* (aq) > Cu** (aq) +2Ag(s) © Cu(s)+ Zn’ (aq) > Cu**(aq) +Zn(s) d. Both (a) & (c) 3. Arrange the following in the order of their decreasing electrode potentials: Mg, K, Ba,Ca a. K>Ba>Ca> Mg b. Ba>Ca>K> Mg ©. Ca>Mg>K>Ba @. Mg>Ca>Ba>K 4. The standard reduction potentials of Cu, Ag’, Hg” and Mg ate 0.34V, +0.80V, +0.79V and -2.37V respectively. With increasing voltage, the sequence of deposition of metals on the cathode from a molten mixture containing all those ion: a. Ag, Hg, Mg,Cu _b, Cu, He, Ag, Mg c.AgHg,CuMg —— d. Cu, Hg, Mg, Ag . E2, for the reaction, 2,0 + H,0' + OH at 25°C is'.0.8277 V. The equilibrium const reaction is: a 10" c. 107 wn ant for the b. 108 107) 6, The Nemst equation giving dependenc electrode reduction potential on concentra on is o , 2.303 RT [mM] BT be Tay of 2303 RT og [mM] nF [M] c. E=E° 2303 Toft] nF 303 RT) _[M] nF [Mm] 7. AG? for the cell with cell reaction: Zn(s) + Ag, Os) + H,O(0) — Zn?*(aq) + 2Ag{s) + 20H (aq), is TEx.ony = +0348, ES. = a. 2.13 « 10°J mol ¢. 1.06 * 10° J mol" b. E=E°— d. E=E°+ 76) b, -2.13 « 108 J mot! . =1.06 « 105 J mot 8. Which of the following is always true regarding the spontaneity of reaction occuring in a galvanic cel? a. Ely > 0,AG° K, b. Ely > 0,AG° 0,AG° > OandQ>K, d. Ely > 0,AG" 2Fe(aq) + L,(aq) £2, = 0.24 V at 298 K. The standard Gibbs energy (A.G°) of the cell reaction is: (2019) {Given that Faraday constant F = 96500 C mot] a, 46.32 kJ mol! b, -23.16KI mol ©. 46.32 kJ mol" 4. 23.16 Ki mol rene Nernst Equation 2. Fora cell involving one electron E°eell = 0.59 V at 298 K, the equilibrium constant for the cell (NaCl, HCl and NH,OH) is plotted against (@ RS 3 VC — Which of the following options is correct? 1 2 3 a. NaCl HCI NH,OH b. NH,OH NaCl HCL c. HCI NaCl NH,OH d. NH,OH HCI NaCl 30. for 50. min, 18» metal deposits, the equivalent mass of metal is a 93 b. 19.3 ©. 383 4.399 IESTIONS. » 2303RT Given that 2019) a. 1.0% 10? c. 1.0 109 b. 1.0 « 10 d. 1.0 10% 3. The pressure of H, required to make the potential of H, electrode zero in pure water at 298 K (2016) a. 10% atm b. 10" atm, c. 10" atm d. 10" atm, ‘ssereeeecrmeraceereemeneaes Cell & Batteries eS, 4. A device that converts energy of combustion of fuels like hydrogen and methane, directly into electrical energy is known as: (2015) &. Electrolytic cell, Dynamo ©. Ni-Cd cell 4, Fuel cell ocanned with camstaEw 100 Fe y.40—(-0.74) = -9.40-+ 0.74 =0.34V sje 10H hs higher standard reduction ince, 7 10a al than NiINi & Zn"IZn, mu? gets reduced faster than Ni”? & Zn’, ayng> o> Ba> Ks This isthe order of SRP 3 . ‘qo cueannot displace MgCl, due to high SRP. 46 on 4) 28,0 ~ H,0" + OF 9.0591 og K 2 Etyxn _ -0.8277x1 Wek=Joso1 0.0591 sosrt,_ [M"*] log —* oF [M] This nemst equation is showing dependency of electrode reduction potential on concentration. a= K=10" 6,(0) E=E*— 18) Bea = Bagong Een = 0.344 - (-0.76) 1.104. V AG? = nFE® =-2 « 96500 * 1.104 =-2.13 x 10° J mol 4 (@) EMPshould be positive AG should be negative K, greater than reaction quotient 1 5.) gion te [H"] B, _0.0591 Tle [x it gl"), O then E,. <0 Fh a 10. (d) In electrochemical series Zn is present above H,, So; it liberates hydrogen gas from dilute HCV H,SO, but HINO, is oxidising agent. So, it oxidises H, and NO; is itself reduced. 1 (a) Bag? 2030B8T og nF (Ni) 0.0591, [1 E=-025- ae 2 al =~0.25~0.03 «1 0.28 12, (d) 2H* + 2e > H, According to nemst equation, =0 297} togttP) =~0.0591(-log(H"]) =-0.0591 pH Jog [H"}-pH] 13. (d) Cu(s)+2Ag* (aq) > Cu" (aq)+2Ag(s) E=0.46 v at 298 K 0.059 E log, 046 = jog, log K,,= 15.56 K. = antilog 15.56 = 3.89 10!5=4 x 10'8 14, (b) 1 F deposits 108 g of Ag (Ag +e > Ag) 1p 54 g of Ag will be deposited by ie s4= 2 3 F deposited 27 g of Al (AB* + 3" > Al) er ag Zh 1p will deposit =x =4.5 g of Al. SF will deposit x5 = 4.5 g of 15. (¢) Electricity passed = 9.65 coulomb ‘The amount of silver deposited =? We know that 96500 coulomb electricity deposits Ag = 108g mol -. 9,65 coluomb electricity deposits Ag 9.65 108 = 108x107 g = 10.8 96500" eo etbine ocanned with val v16, (¢) Cr,0-5 —+ 2Cr* Change in O.S. Change required = 6F ; 17.(¢) The quantity of charge to obtain one mole of aluminium from ALO, is equal to number of electron required to reduce Al,O, to Al. Al (aq) > Als) 18. (c) As the concentration of ions decreases so do the ion-ion interactions. These weaken interactions together with the ion-solvent and solvent-solvent } | Hence, total 3 F is required. ' i i ractions contribute to the increasing conductivity of the electrolytic solution, A x 19, (a) @ ALi we know that Ay = 20, (6) A,, = 21000 _ 0401521000 "™M O15) 1000 =1010"'em mor" a) A, _LOxi 01 mmol 22. (b) AQNaBr = ALNaCl+ ALKBr—A°KCI 23. (a) Aj HCOOH = 404.2 Sem? mol Ag _ 461 AY 404.2 0.886 1 edi) 0.025 0.114 0.114 3.6710 mol L 24. (b) BaCl, + Ba + 2C1 7 +76(@ temfeq”!) emeeq (d) Fuel cells are more efficient, fixe pollution and they run tll reactants are acne 26. (d) All the given methods ean be used to preven, corrosion. 27. ©) Avqaso,) =A. $x,-2n, 28. (c) According to Std. R.P. the ECS is So. correct order of deposition on cathode is Ag. Hg. Cu. H,, Mg So correct order is Ag. Hg. Cu 29. (©) HCL and NaCl are strong electrolytes. They are totally dissociated when dissolved in water to form separated hydrated ions. : NHOH isa weak electrolyte. Eit_ _ Ex3x50x60 96500 30. (b) Wray = 96500 — 96500% W 60x 3) ESS ee